CN101864119B - Preparation method of polyacrylic ester/montmorillonoid composite material - Google Patents
Preparation method of polyacrylic ester/montmorillonoid composite material Download PDFInfo
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- CN101864119B CN101864119B CN2010102203958A CN201010220395A CN101864119B CN 101864119 B CN101864119 B CN 101864119B CN 2010102203958 A CN2010102203958 A CN 2010102203958A CN 201010220395 A CN201010220395 A CN 201010220395A CN 101864119 B CN101864119 B CN 101864119B
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Abstract
The invention relates to a preparation method of a polyacrylic ester/montmorillonoid composite material, which comprises the following steps: a, pre-emulsification of a nuclear layer monomer; b, pre-emulsification of a shell layer monomer; and c, preparation of acrylic ester emulsion which comprises the following steps: adding pre-emulsion of the nuclear layer monomer and pre-emulsion of the shell layer monomer in a reactor containing pre-emulsion of seed monomer in step a, and dropwise adding three groups of initiator solution of different components in the process to prepare acrylonitrile-butyl acrylate-styrol copolymer (AAS) emulsion; adding montmorillonoid solution into the obtained product and stirring to prepare the polyacrylic ester/montmorillonoid composite emulsion, carrying out demulsification, washing and drying to prepare polyacrylic ester/montmorillonoid copolymer powder; and then adding SAN resin of which the mass is 4 times of that of the powder, and blending to preparethe polyacrylic ester/montmorillonoid composite material. The polyacrylic ester/montmorillonoid composite material of the invention has excellent dispersion property of the montmorillonoid, the impact property of the polymeric matrix is improved by 120%, and the tensile property is improved by 110%, thereby improving the properties of the polymer composite greatly.
Description
Technical field
The present invention relates to a kind of preparation method of polyacrylic ester/montmorillonite composite material, belong to the polymer-modified field of compound material of mineral filler.
Background introduction
Polymer composites is meant a class material of the mineral filler and the matrix material blend preparation of various forms (fiber, whisker, sheet, granular), at mechanical property, thermal property, and aspect such as flame retardant properties all is significantly improved, it is considered to have a class type material of huge applications potentiality, it has become one of focus of current polymer materials fundamental research and Application and Development for the alternative of the application of polymkeric substance in special dimension in providing very on a large scale.
Nano composite polymer-montmorillonoid material is present emerging a kind of polymer base inorganic nano-composite material, compare with conventional matrix material, have following characteristics: need the packing volume mark few, have good thermostability and dimensional stability, a cost performance height.So polymkeric substance/montmorillonite nano-composite material becomes one of focus of studying in the novel material and field of functional materials in recent years.Because its special structure of MMT, MMT plays a part very important in the preparation field of nanocomposite materials.Polynite (Montmorillonite is called for short MMT) mining deposits is very abundant, cheap, and excellent property can be used for multiple industries such as light industry, oil, metallurgy, desertification control, sewage disposal, medicine, is described as by people " universal material ".Natural montmorillonite is the earthy mineral of the hydrous alumino silicates of a kind of laminate structure, plate crystal, and main component is silicon oxide and aluminum oxide, and its chemical general formula is (Al
2-xMgx) Si
4O
10(OH)
2(MnH
2O) (M=Na wherein
+, Ca
2+, Mg
2+Deng).Its typical constructional feature is that each unit cell is by alumina octahedral wafer of two silicon-oxy tetrahedron wafer sandwich, be connected by shared Sauerstoffatom between tetrahedron and the octahedron, form the accurate two-dimentional wafer of high-sequential, the structure cell parallel stacked, belong to 2: 1 type three-layer sandwich structures, have very high rigidity, interlayer is easy glide not.The about 1nm of the yardstick of each structural unit is thick, long * wide be 100 * 100nm
2Lamella, the structure cell surface-area is up to 700～800m
2/ g.Because its special structure, MMT plays a part very important in the preparation field of nanocomposite materials.But because inherent character of MMT own and existing dispersing method make its dispersion in polymeric matrix bad, too much MMT can reunite and make its raising to the polymeric matrix performance also very limited.
Summary of the invention
The objective of the invention is at dispersed bad, the amount of the MMT that exists in the current techniques in polymeric matrix many easily reunite, to the unconspicuous deficiency of polymkeric substance mechanical property modified effect, a kind of method for preparing polyacrylic ester/montmorillonite composite material is proposed, this method adopts seed emulsion semi-continuous process, has synthesized be that nuclear, vinylbenzene (St) and vinyl cyanide (AN) multipolymer are polyacrylic ester/ester/montmorillonite composite emulsion of shell, outermost layer introducing MMT at butyl polyacrylate (PnBA).The adding of polynite can be significantly improved to the tensile property and the impact property of polymeric matrix.
Technical scheme of the present invention is:
A kind of preparation method of polyacrylic ester/montmorillonite composite material may further comprise the steps:
A. the pre-emulsification of nuclear layer monomer
Seed stage
Material is formed and proportioning is:
Composition quality/g
Emulsifying agent 0.5
Deionized water 140
Acrylic ester monomer 10
At first, in reactor, add above-mentioned emulsifying agent and deionized water, mix and stir 20min; In reactor, add above-mentioned acrylic ester monomer again, mix and stir 10min, promptly obtain the seed monomer pre-emulsion, standby;
Nuclear is grown up the stage
Material is formed and proportioning is:
Composition quality/g
Emulsifying agent 1.4
Linking agent 0.57
Acrylic ester monomer 114
Above-mentioned composition is added in the container, stirs 20min and make its thorough mixing, promptly obtain the nuclear layer monomer pre-emulsion, standby;
B. pre-emulsification of shell monomer
Material is formed and proportioning is:
Composition quality/g
Emulsifying agent 0.95
Vinylbenzene 57
Vinyl cyanide 19
Said components is joined in the reactor, stir 20min and make its thorough mixing, promptly obtain the shell monomers pre-emulsion, standby;
Emulsifying agent used among described step a, the b is anionic emulsifier;
C. preparing acrylate emulsion
Feed nitrogen in a step fills the reactor of seed monomer pre-emulsion, behind the dispersed with stirring 10min, add initiator solution I, the polyreaction of seed stage begins, and behind the seed stage polyreaction 55min, adds initiator solution II; The seed stage polyreaction finishes after continuing reaction 5min, drips the nuclear layer monomer pre-emulsion by a step preparation immediately in reactor, continues the growth polyreaction of stratum nucleare; After the nuclear layer monomer pre-emulsion dropwises, cooling also drips the monomer pre-emulsion that is made of shell vinylbenzene, vinyl cyanide and emulsifying agent, before dripping 30min at last, monomer drips initiator III, stopped reaction behind the insulation 1h made vinyl cyanide-n butyl acrylate styrene (AAS) emulsion after the shell monomers pre-emulsion dripped;
D. will join in the deionized water of 150ml for the polynite of the mass percent 0.2%-0.8% of stratum nucleare and shell reaction monomers sum that top each step adds, leave standstill after the stirring, get the 140ml upper solution and it is joined in the AAS emulsion that makes make polyacrylic ester/ester/montmorillonite composite emulsion after stirring, after breakdown of emulsion, washing, drying, make polyacrylic ester/polynite copolymer powder;
E. get the copolymer powder that the step obtains, add the SAN resin of its 4 times of quality again, mixing in mill under 165 ℃, make polyacrylic ester/montmorillonite composite material;
Wherein, used initiator is a persulphate among the step c, in use is configured to the initiator solution of different concns with deionized water, and concrete proportioning is as follows:
Quality/the g of the quality of persulphate/g water
Initiator solution I 0.14～0.44 20
Initiator solution II 0.11 10
Initiator solution III 0.051 10
The concrete quality of above material is not the qualification to invention, in the actual production, enlarges or dwindles according to above-mentioned mass ratio is whole according to the desired product amount.
Used anionic emulsifier is a dodecyl biphenyl ether sulfonic acid sodium among above-mentioned steps a, the b.
Used linking agent is an allyl methacrylate(AMA) among the above-mentioned steps a.
Used acrylic ester monomer is a butyl acrylate among the above-mentioned steps a.
Used persulphate is a Potassium Persulphate among the above-mentioned steps c.
The invention has the beneficial effects as follows: different with the method for polymer composites in the past with on twin screw, carrying out blend after the MMT modification, this experimental technique is MMT have been synthesized the back in the AAS emulsion just it is added in the emulsion, and stir for some time so that MMT and emulsion thorough mixing, then carrying out breakdown of emulsion, carrying out blend with the SAN matrix, this method was promptly saved this step of MMT surface modification, again because of it added in the emulsion stage, and made its degree of scatter in polymkeric substance better.This method can be good at unmodified polynite is distributed in the polymeric matrix, thereby make the good nano composite polymer-montmorillonoid material of polynite dispersing property, the adding of polynite has improved 120% to the impact property of polymeric matrix, tensile property has been improved 110%, made the performance of polymer complex that good raising be arranged.
Description of drawings
Fig. 1 is the influence curves of different MMT content to the mechanical property of matrix material
Embodiment
Embodiment 1
A. the pre-emulsification of nuclear layer monomer
At first, in the 500ml four-hole boiling flask, add 0.5g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium and 140g deionized water, and mix and stir 20min; In reaction flask, add the 10g butyl acrylate again, and mix and stir 10min, promptly obtain nuclear layer monomer seed pre-emulsion, standby.
In the 500ml beaker, add 1.4g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 0.57g allyl methacrylate(AMA) and 114g butyl acrylate, and mix and stir 20min; Promptly obtain the nuclear layer monomer pre-emulsion, standby.
B. pre-emulsification of shell monomer
Get the beaker of 1 500ml, 0.95g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 57g vinylbenzene and 19g vinyl cyanide are added in the beaker successively, be placed on then to mix on the induction stirring and stir 20min, promptly obtain the shell monomers pre-emulsion; Leave standstill after making with pre-emulsion, standby.
C. preparing acrylate emulsion
Used initiator is a Potassium Persulphate.Need in use to add deionized water, and initiator solution is made in abundant dissolving on magnetic stirrer with certain proportion.Concrete proportioning is as follows:
Quality/the g of Potassium Persulphate quality/g water
Initiator solution I 0.44 20
Initiator solution II 0.12 10
Initiator solution III 0.051 10
To a step fill stratum nucleare seed monomer pre-emulsion four-hole boiling flask in feed nitrogen, logical water of condensation is warming up to 80 ℃ under whipped state, rotating speed is controlled at 150～250 to be changeed.After treating homo(io)thermism, add initiator solution I 20.44g; The polyreaction of seed stage begins.Behind the seed stage polyreaction 55min, add initiator solution II.The seed stage polyreaction finishes after continuing reaction 5min.After the seeding polymerization stage finishes, drip a nuclear layer monomer pre-emulsion in step immediately in flask, the speed that splashes into 30g with every 30min drips, and continues the growth polyreaction of stratum nucleare.After treating that the nuclear layer monomer pre-emulsion dropwises, bath temperature is reduced to the shell monomers pre-emulsion in dropping b step after 73 ℃.Splash into the speed dropping of 30g equally with every 30min, before dripping 30min at last, monomer pre-emulsion drips initiator III with identical speed simultaneously, the shell monomers pre-emulsion drips back insulation 1h, obtains 300g vinyl cyanide-BA-St (AAS) emulsion;
D. the preparation of polyacrylic ester/ester/montmorillonite composite emulsion.
The polynite (interlamellar spacing is 1.48nm) of 0.4g is joined in the 150mi deionized water, and with leaving standstill 1h behind the magnetic stirrer 5h, (bottom is the impurity in the polynite) gets upper solution 140ml, it is joined in the whole AAS emulsion that makes above make polyacrylic ester/ester/montmorillonite composite emulsion after stirring 1h, through making the AAS emulsion particle 250g after imvite modified behind Tai-Ace S 150 breakdown of emulsion, deionized water wash, 60 ℃ of dry 3h of loft drier.
E. the preparation of polyacrylic ester/montmorillonite composite material.
25g is gone up AAS emulsion particle after the MMT modification and the 100gSAN resin (styrene-acrylonitrile copolymer that the step obtains, Taiwan Qimei Industry Co., Ltd., specification PN117, following examples are together) in being mixing in the two roller mills of LG-160 under 165 ℃, make polyacrylic ester/montmorillonite composite material in the diligent machine plant in Shanghai model.
Comparative Examples
A. the pre-emulsification of nuclear layer monomer
At first, in the 500ml four-hole boiling flask, add 0.5g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium and 140g deionized water, and mix and stir 20min; In reaction flask, add the 10g butyl acrylate again, and mix and stir 10min, promptly obtain nuclear layer monomer seed pre-emulsion, standby.
In the 500ml beaker, add 1.4g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 0.57g allyl methacrylate(AMA) and 114g butyl acrylate, and mix and stir 20min; Promptly obtain the nuclear layer monomer pre-emulsion, standby.
B. pre-emulsification of shell monomer
Get the beaker of 1 500ml, 0.95 anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 57g vinylbenzene and 19g vinyl cyanide are added in the beaker successively, be placed on then to mix on the induction stirring and stir 20min, promptly obtain the shell monomers pre-emulsion; Leave standstill after making with pre-emulsion, standby.
C. preparing acrylate emulsion
Used initiator is a Potassium Persulphate.Need in use to add deionized water, and initiator solution is made in abundant dissolving on magnetic stirrer with certain proportion.Concrete proportioning is as follows:
Quality/the g of Potassium Persulphate quality/g water
Initiator solution I 0.44 20
Initiator solution II 0.12 10
Initiator solution III 0.051 10
To a step fill stratum nucleare seed monomer pre-emulsion four-hole boiling flask in feed nitrogen, logical water of condensation is warming up to 80 ℃ under whipped state, rotating speed is controlled at 150～250 to be changeed.After treating homo(io)thermism, add initiator solution I 20.44g; The polyreaction of seed stage begins.Behind the seed stage polyreaction 55min, add initiator solution II.The seed stage polyreaction finishes after continuing reaction 5min.After the seeding polymerization stage finishes, drip a nuclear layer monomer pre-emulsion in step immediately in flask, the speed that splashes into 30g with every 30min drips, and continues the growth polyreaction of stratum nucleare.After treating that the nuclear layer monomer pre-emulsion dropwises, bath temperature is reduced to the shell monomers pre-emulsion in dropping b step after 73 ℃.Splash into the speed dropping of 30g equally with every 30min, before dripping 30min at last, monomer drips initiator III, the shell monomers pre-emulsion drips back insulation 1h, obtain 400g vinyl cyanide-BA-St (AAS) emulsion, the above AAS emulsion that obtains is made AAS emulsion particle 250g behind Tai-Ace S 150 breakdown of emulsion, deionized water wash, 60 ℃ of dry 3h of loft drier.
D. the preparation of polyacrylic ester contrast material.
25g is gone up AAS emulsion particle that the step obtains and 100gSAN resin in being mixing in the two roller mills of LG-160 in the diligent machine plant in Shanghai model under 165 ℃, make the polyacrylic ester contrast material.
Embodiment 2～5 concrete steps are with embodiment 1, but MMT content difference, its content and letex polymerization parameter such as table 1 among the embodiment 2～6
Embodiment 6～9 concrete steps are with embodiment 1, but are initiator I content difference, its content and letex polymerization parameter such as table 2,
The different MMT content of table 1 list factor emulsion polymerization process parameter
Table 2 initiator I different content emulsion polymerization process parameter
The test of composite materials property
Is that CMT6104 microcomputer control electronics universal testing machine and model are that the balance weight impact testing machine of ZBC-4 stretches and shock test with the batten that makes in the Shenzhen City Xinsansi Metering Technology Co., Ltd model, test-results is as figure (1), and the adding of visible polynite is significantly improved to impact and the tensile property of AAS.
As can be seen from Table 1: MMT content changes from 0%-1%, initiator I content changes by 0.14～0.44, and the final transformation efficiency of monomer is all more than 95%, the polydispersity coefficient of latex particle size (PDI)＜0.0900, coagulum＜5%, this explanation letex polymerization monomer conversion height; Emulsion system is comparatively stable.Fig. 1 is that the polynite of different content is to the stretching of polyacrylic ester/montmorillonite composite material and the influence of shock strength.As we can see from the figure, along with the increase of polynite content, the tensile strength of matrix material is first increasing and afterwards reduces trend, and the polymeric matrix shock strength that does not add polynite as seen from the figure only is 8.7KJ.m
2, tensile strength is 29.37MPa.The shock strength that adds MMT reaches as high as 19.33KJ.m
2, the tensile strength maximum can reach 61.79MPa.The MMT that adds with the common process method polymeric matrix is impacted and the raising of tensile property all between 30%-40%, reach 50% and be almost the limit, and the impact property of polymeric matrix has been improved 120% with present method MMT, tensile property has been improved 110%, the superiority of visible present method.
Claims (3)
1. the preparation method of a polyacrylic ester/montmorillonite composite material is characterized by and may further comprise the steps:
A. the pre-emulsification of nuclear layer monomer
Seed stage
Material is formed and proportioning is:
At first, in reactor, add above-mentioned emulsifying agent and deionized water, mix and stir 20min; In reactor, add above-mentioned acrylic ester monomer again, mix and stir 10min, promptly obtain the seed monomer pre-emulsion, standby;
Nuclear is grown up the stage
Material is formed and proportioning is:
Above-mentioned composition is added in the container, stirs 20min and make its thorough mixing, promptly obtain the nuclear layer monomer pre-emulsion, standby;
B. pre-emulsification of shell monomer
Material is formed and proportioning is:
Said components is joined in the reactor, stir 20min and make its thorough mixing, promptly obtain the shell monomers pre-emulsion, standby;
Emulsifying agent used among described step a, the b is anionic emulsifier;
C. preparing acrylate emulsion
Feed nitrogen in a step fills the reactor of seed monomer pre-emulsion, behind the dispersed with stirring 10min, add initiator solution I, the polyreaction of seed stage begins, and behind the seed stage polyreaction 55min, adds initiator solution II; The seed stage polyreaction finishes after continuing reaction 5min, drips the nuclear layer monomer pre-emulsion by a step preparation immediately in reactor, continues the growth polyreaction of stratum nucleare; After the nuclear layer monomer pre-emulsion dropwises, cooling also drips the monomer pre-emulsion that is made of shell vinylbenzene, vinyl cyanide and emulsifying agent, before dripping 30min at last, monomer drips initiator solution III, stopped reaction behind the insulation 1h made vinyl cyanide-n butyl acrylate styrene (AAS) emulsion after the shell monomers pre-emulsion dripped;
D. will join in the deionized water of 150ml for the polynite of the mass percent 0.2%-0.8% of stratum nucleare and shell reaction monomers sum that top each step adds, leave standstill after the stirring, get the 140ml upper solution and it is joined in the AAS emulsion that makes make polyacrylic ester/ester/montmorillonite composite emulsion after stirring, after breakdown of emulsion, washing, drying, make polyacrylic ester/polynite copolymer powder;
E. get the copolymer powder that the step obtains, add the SAN resin of its 4 times of quality again, mixing in mill under 165 ℃, make polyacrylic ester/montmorillonite composite material;
Wherein, used initiator is a persulphate among the step c, in use is configured to the initiator solution of different concns with deionized water, and concrete proportioning is as follows:
Wherein, used linking agent is an allyl methacrylate(AMA) among the above-mentioned steps a; Used acrylic ester monomer is a butyl acrylate among the step a.
2. the preparation method of polyacrylic ester/montmorillonite composite material according to claim 1 is characterized by that used anionic emulsifier is a dodecyl biphenyl ether sulfonic acid sodium among above-mentioned steps a, the b.
3. the preparation method of polyacrylic ester/montmorillonite composite material according to claim 1 is characterized by, and used persulphate is a Potassium Persulphate among the above-mentioned steps c.
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| CN102206395B (en) * | 2011-03-31 | 2013-01-30 | 广东工业大学 | Preparation method and application of nano-montmorillonite/polyacrylate composite material |
| CN104322489B (en) * | 2014-09-18 | 2016-09-21 | 北京理工大学 | A kind of montmorillonite Composite pesticide dispersing agent and its preparation method and application |
| CN104448112B (en) * | 2014-11-11 | 2016-06-08 | 河北工业大学 | The nylon 6 low temperature toughening modifying preparation method of functionalization poly acrylate composite emulsion |
| CN104387521B (en) * | 2014-11-27 | 2016-08-17 | 武汉工程大学 | A kind of montmorillonite and the preparation method of methacrylic acid compound modified acrylic ester core-shell emulsion |
| CN105399893B (en) * | 2016-01-12 | 2017-03-22 | 河北工业大学 | Preparation method of acrylate polymer/montmorillonite composite particles for toughening makrolon |
| CN105418836B (en) * | 2016-01-12 | 2017-08-29 | 河北工业大学 | The preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle |
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