CN103214604B - Inorganic-organic compound dispersing agent for suspension polymerization and application of inorganic-organic compound dispersing agent - Google Patents
Inorganic-organic compound dispersing agent for suspension polymerization and application of inorganic-organic compound dispersing agent Download PDFInfo
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Abstract
The invention relates to an inorganic-organic compound dispersing agent for suspension polymerization. The inorganic-organic compound discharging agent is characterized in that inorganic mineral powder is used as a host agent, a polyvinyl alcohol is used as an auxiliary agent, wherein the mass of the auxiliary agent accounts for 10-30 percent of that of the host agent; and the main agent comprises the following components in percentage by mass: 70-90 percent of kieselguhr powder and 10-30 percent of calcined kaolin powder. The inorganic-organic compound dispersing agent can be used for effectively preventing oil-phase reaction drops in polymer suspension polymerization from being adhered, improving the dispersibility of polymer beads and preventing polymer products from being adhered to rods and kettles.
Description
Technical field
The invention belongs to Polymer Synthesizing and chemical technology field, be specifically related to a kind of inorganic-organic hybrid dispersion agent for suspension polymerization and application method thereof.
Background technology
The use of dispersion agent is most important for suspension polymerization.Suspension polymerization is by strong stirring and under the effect of dispersion agent, becomes countless small dropletss to suspend in water monomer dispersion and carries out the polyreaction that causes.The dispersion of monomer and cohesion are reversing processes; do not re-unite when colliding for stoping monomer droplet; dispersion agent must be added; around monomer liquid pearl, form layer protecting film or be adsorbed on monomer liquid bead surface; play buffer action thus stop or delay the cohesion of monomer liquid pearl; and reach particle motion balance, high-quality polymerisate can be obtained thus.
Generally, a kind of dispersion agent being applicable to the excellent performance of suspension polymerization, need meet following four requirements: (1) has good colloid protection ability to monomer and polymer beads, and makes product polymer epigranular; (2) make polymer beads porous, be easy to processing, the generation of flake in product can be reduced; (3) adverse influence is not produced to the form and aspect of product, and polywater solution gonorrhoea can not be caused; (4) foaminess is low in aqueous, to prevent aggregation container effective volume from reducing, thus reduces productive rate etc.
In current suspension polymerization, three kinds of technological lines are followed in the use of dispersion agent:
1, adopt macromolecule dispersing agent, comprise derivative, the modified product of synthetic polymer and natural polymer and natural polymer, conventional has gelatin; Cellulose ethers macromole, as methylcellulose gum, carboxymethyl cellulose, ethyl cellulose, Natvosol and hydroxypropylcellulose; And polyvinyl alcohol etc.This kind of dispersion system is used at most in suspension polymerization, Chinese patent CN101928357A selects molecule side base to be the polyvinyl alcohol of hydroxyl, its mean polymerisation degree at least 600, and alcoholysis degree is 60 ~ 80 mol%, can obtain the polymkeric substance that particle size distribution is narrow, wherein coarse particles is few.The polyvinyl alcohol auxiliary dispersants polymerization degree that Chinese patent CN102311516A produces is 200 ~ 400, and alcoholysis degree is 33 ~ 55 mol%, solves low alcoholysis level auxiliary dispersants and is not exclusively dissolved in water problem.But adopt this water-soluble high-molecular substance, particle surface is often made to be surrounded by the epithelium of one deck graft copolymer formation, in obstruction polymer beads, monomer removes, and be unfavorable for the plasticizing processing in polymkeric substance later stage, and when polymerization temperature is higher, the dispersion effect of polyvinyl alcohol obviously reduces, and sticky still is serious.
2, inorganic dispersant, once the numerous inorganicss comprising natural mineral were attempted in scientific research and industrial practice, final reservation uses magnesium hydroxide and calcium phosphate powder, and different due to its preparation method and mineralising time of these two kinds of dispersion agents, its performance can be caused to have very large difference, thus make its dispersion effect in suspension polymerization also different, wherein magnesium hydroxide is because of its unstable properties, need fresh preparation, usual polymer industry contains the fresh preparation process of magnesium hydroxide in producing, the preparation of calcium phosphate powder and active maintenance are then extremely complicated processes, so that China at present can't the product of production performance excellence, the calcium phosphate powder used in current industrial production need from Japanese import.This kind of system, its mechanism of action is the surface that particles of inorganic material is adsorbed on drop, plays a part mechanical isolation, and the dispersion effect be used alone is unsatisfactory, and a small amount of use can not make particle keep dispersed, and sticky still phenomenon is serious; During a large amount of use, particle is uneven and uneconomical, so general and organic dispersion agent uses jointly.
3, organic and inorganic composite dispersing agent, owing to being used alone a certain class dispersion agent, often dispersion effect is undesirable, so force people to have to use the dispersion agent of compound system, usually, simultaneously a kind of way uses inorganic and organic dispersing agent in use suspension polymerization, using method is not sought unity of standard, and the method for use and the dispersant of use are also not quite similar; Another kind method is re-used after organically-modified or special processing in advance by inorganic dispersant, as used Sodium dodecylbenzene sulfonate to carry out hydrophobically modified to it in calcium phosphate powder preparation process so that make its easily and oil phase reaction solution affine.This be one with high content of technology, the product syntheti c route that course of industrialization is complicated, with high costs.The Chinese patent CN101633709A calcium phosphate or magnesiumcarbonate being slightly soluble in water makes inorganic main dispersant, inorganic auxiliary dispersants made by anhydrous sodium sulphate or sodium pyrosulfate, carry out in-situ suspension polymerization with polyvinyl alcohol or carboxymethyl cellulose as organic dispersing agent, utilize this compound dispersing agent to obtain the polymkeric substance of uniform particle diameter.Chinese patent CN101891852A uses the composite dispersing agent of polyvinyl alcohol and calcium triphosphate to prepare polystyrene/expanded graphite composite foaming material.But this dispersion system is the epithelium that main dispersant event particle surface still can be coated with graft copolymer formation owing to still adopting polyvinyl alcohol, and as magnesium hydroxide and calcium phosphate powder working conditions are harsh and cost is high in inorganic components, be all unfavorable for polymer industry produce in post-production.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of inorganic-organic hybrid dispersion agent for suspension polymerization, the adhesion of oil phase reaction drop in preventing polymer suspension to be polymerized, improve the dispersiveness of polymer beads, prevent polymer product from gluing bar and glue still.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 10 ~ 30% of host quality; By mass percentage, by diatomite powder 70 ~ 90%, calcined kaolin powder 10 ~ 30 % forms described host.
By such scheme, the particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μm.
By such scheme, described diatomite powder and calcined kaolin powder are through super-dry, and drying temperature is 80 DEG C, and the time is 6 hours.
By such scheme, described polyvinyl alcohol is polyvinyl alcohol 1788.
Diatomite of the present invention is piled up by the remains of unicellular low diatom such as waterplant such as grade and is formed, and its chemical composition is with unformed SiO
2be main, have a small amount of Al
2o
3, Fe
2o
3, CaO, MgO etc.Diatomite is non-crystal structure, is overlapped and forms the random network structure to three-dimensional space development, wherein there is plasma polymkeric substance by silicon-oxy tetrahedron by bridging oxygen.
The alcoholysis degree of polyvinyl alcohol 1788 of the present invention is 80 ~ 88 %, and its remaining acetate is 12%, is partial alcoholysis, can comparatively fast dissolves, almost completely water-soluble at 20 DEG C, photostabilization is good, not by illumination effect, and the viscosity stability of its aqueous solution is good, nonpoisonous and tasteless, pollution-free.The dissolution process of polyvinyl alcohol carries out stage by stage, that is: affine wetting-swelling-infinite swelling-dissolving.
The application method of the inorganic-organic hybrid dispersion agent for suspension polymerization of the present invention, its step is as follows:
(1) according to mass percent, take diatomite powder 70 ~ 90%, calcined kaolin powder 10 ~ 30% forms inorganic mineral powder, as host;
(2) account for 10 ~ 30% weighing polyvinyl alcohol of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and to be configured to mass fraction be that the polyvinyl alcohol solution of 2.0 ~ 3.0 % is for subsequent use;
(3) polyvinyl alcohol solution for subsequent use is scattered in the water of 40 ~ 60 DEG C, obtain aqueous dispersion liquid, to be dissolved completely after, by inorganic mineral powder, drop into aqueous dispersion liquid, wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 0.6 ~ 2.3%, thus obtains the dispersant solution for suspension polymerization;
(4) raw material of suspension polymerization is mixed with the dispersant solution for suspension polymerization step (3) Suo Shu, good dispersity, cross-linking products bead that circularity is high after reaction, can be obtained.
In step (3), account for aqueous dispersion liquid quality 0.6 ~ 2.3% according to the quality of inorganic mineral powder, the quality of aqueous dispersion liquid can be calculated; Then the quality of inorganic dispersion liquid is deducted the quality of polyvinyl alcohol solution, the quality of water in step (3) can be drawn.
Suspension polymerization of the present invention is the suspension polymerization of vinylbenzene and multipolymer, esters of acrylic acid and comonomer thereof, as the suspension polymerization etc. of vinylbenzene homopolymerization (linear or crosslinked), styrene-t octadecyl ester copolymerization (linear or crosslinked), styrene-t butyl ester copolymerization (linear or crosslinked), styrene methyl methacrylate copolymerization (linear or crosslinked), methyl methacrylate homopolymerization and copolymerization thereof.
The present invention utilizes natural mineral diatomite and kaolinic compound to be main dispersant, being equipped with macromolcular dispersant is auxiliary agent, can polymer made full use of on the basis of excellent guarantor's glue effect of polymer beads like this, and increase the mechanical isolation effect of inorganic nano mineral pair hanging drop, thus the epithelium that minimizing polymer produces at particle surface, monomer in particle is made to be easy to remove, be conducive to later stage plasticizing processing, and so collocation use can reach good dispersion effect, make that uniform particles, circularity are good, narrow diameter distribution, and have good circulation ratio.Dispersion agent excellent in stability of the present invention, meet the performance index required by dispersant for suspension polymerization, and cost is low, non-environmental-pollution, has novelty and practicality.
Compared with prior art, the effect that the present invention is useful is:
(1) in polymer suspension polyreaction, dispersion agent of the present invention can significantly improve the oil phase reaction dispersiveness of drop and the circularity of polymer beads, prevent oil phase reaction solution from dropping in adhesion on agitator arm and stirring blade and assembly, do not occur that sticky bar glues still phenomenon in actual use, the rate of small round spheres of gained cross-linking products bead reaches more than 96%
.
(2) applied widely, can be used for the suspension polymerization of vinylbenzene and multipolymer, esters of acrylic acid and comonomer thereof, as the suspension polymerization etc. of vinylbenzene homopolymerization (linear or crosslinked), styrene-t octadecyl ester copolymerization (linear or crosslinked), styrene-t butyl ester copolymerization (linear or crosslinked), styrene methyl methacrylate copolymerization (linear or crosslinked), methyl methacrylate homopolymerization and copolymerization thereof.
(3) preparation technology is simple, with low cost, the inorganic mineral that raw material sources are natural, nontoxic, does not produce environmental pollution.
Accompanying drawing explanation
Fig. 1 is the SEM shape appearance figure of diatomite original ore.
Fig. 2 is calcined kaolin SEM shape appearance figure.
Fig. 3 is the bead of cross-linked styrene homopolymerization prepared by embodiment 1.
Fig. 4 is the bead of cross-linked styrene-stearyl methacrylate copolymerization prepared by embodiment 2.
Fig. 5 is the bead of linear methyl methyl acrylate homopolymerization prepared by embodiment 3.
Fig. 6 is the bead of cross-linked styrene-butyl methacrylate copolymerization oil-absorbing resin prepared by embodiment 4.
Fig. 7 is the bead of cross-linked styrene-vinyl acetate copolymerized prepared by embodiment 5.
Embodiment
For understanding better and utilizing the present invention, this specification sheets illustrates content of the present invention in conjunction with the embodiments further, but content of the present invention is not only confined to described case study on implementation.
Diatomite of the present invention takes from rich still area, Lincang City of Yunnan Province, belongs to clayey diatomite.Impurity is mainly clay, and quartz etc., clay and organic matter mutually wrap up and being mingled with, and its main chemical compositions is Al
2o
3, Fe
2o
3, MgO, CaO etc., wherein Al
2o
3, Fe
2o
3content more.Table 1 is described diatomaceous compositional data.
Described diatomite has diatom shell structure, can be seen by scanning electron microscope Fig. 1, and mainly contain round shape, fan-shaped etc., diatom size is between a few to tens of microns; Diatomaceous main bore dia is 100 ~ 500 nm.Can see that from figure diatomaceous hole is obvious, arrangement in order, illustrates that it has the characteristics such as highly porous, bigger serface and good absorption property.Be filled with some clay mineral fragment and organic matter between diatom test and in shell, these compositions and diatom shell are mingled with mutually, wrap up, there is blocking in diatomaceous pore structure part, thus diatomaceous specific surface area decreases.Because diatomite is used as the obstruct particle of oil phase reaction drop in the present invention, the clay wherein contained also is effective ingredient, thus in the present invention, diatomite is only done to desanding, except after organic process, is no longer carried out other and purify.
Calcined kaolin of the present invention is from the calcined kaolin of Tangshan Ze Xi kaolin company, product type is white snow 90 types, this calcined kaolin is the product of kaolin original soil through 950 DEG C of calcinings, there is higher chemically reactive and oleophylic performance performance, the present invention mainly utilizes its this performance, sample chemical composition is as shown in table 2, and its microscopic appearance as shown in Figure 2.
embodiment 1:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 30% of host quality; By mass percentage, by diatomite powder 70%, calcined kaolin powder 30% forms described host; The particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μm, and described diatomite powder and calcined kaolin powder are through super-dry, and drying temperature is 80 DEG C, and the time is 6 hours.
Dispersion agent of the present invention is used as the suspension polymerization of cross-linked styrene homopolymerization, and its step is as follows:
(1) according to mass percent, take diatomite powder 70%, calcined kaolin powder 30% forms inorganic mineral powder 1.746kg, for subsequent use as host;
(2) account for 30% weighing polyvinyl alcohol 0.524kg of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and be configured to the polyvinyl alcohol solution that massfraction is 2.4%, volume is 21.83 for subsequent use;
(3) in suspension polymerization still, 65.48 L water are added, be warming up to 60 DEG C, polyvinyl alcohol solution for subsequent use is scattered in this reactor, obtain aqueous dispersion liquid, stir 3 ~ 5 minutes, to be dissolved completely after, inorganic mineral powder for subsequent use is dropped into aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 2.0%), thus obtains the dispersant solution for suspension polymerization;
(4) according to aqueous phase and oil-phase solution volume ratio be 6:1 meter, take the styrene monomer solution of 12kg, add the cross-linker divinylbenzene of 1.2kg and the initiator benzoyl peroxide of 0.16kg, dissolve, mix in rear input aforesaid reaction vessel, be warming up to 85 ~ 90 DEG C, insulation reaction 4h, be warming up to 95 DEG C, slaking 1h, is cooled to 40 ~ 50 DEG C, feeding suction filtration, washed product for several times, suction filtration, to dry, dries 5h for 60 DEG C in baking oven, obtains the bead of good dispersity, crosslinked polystyrene homopolymerization that circularity is high.
The measuring method of resin rate of small round spheres, be first by resin 60 DEG C of oven dry, weigh, be then slowly poured on the glass upper end of inclination 10 °, allow resin dispersion ground Free-rolling downwards, weighed by the resin rolled, the percentage ratio of the latter and the former ratio is rate of small round spheres again.The rate of small round spheres that the present embodiment obtains the bead of polystyrene homopolymerization is 96.2 %, and also can find out the bead good dispersity of the polystyrene homopolymerization that gained is cross-linked from Fig. 3, circularity is high, and recording particle size distribution range with vernier callipers is 0.60 ~ 2.12 mm.
embodiment 2:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 25% of host quality; By mass percentage, by diatomite powder 75%, calcined kaolin powder 25% forms described host; The particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μm.
Dispersion agent of the present invention is used as the suspension polymerization of cross-linked styrene-stearyl methacrylate copolymerization, and its step is as follows:
(1) according to mass percent, take diatomite powder 75%, calcined kaolin powder 25% forms inorganic mineral powder 1.410 kg, for subsequent use as host;
(2) account for 25% weighing polyvinyl alcohol 0.353kg of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and be configured to the polyvinyl alcohol solution that massfraction is 2.0 %, volume is that 17.625L is for subsequent use;
(3) in suspension polymerization still, 70.495L water is added, be warming up to 60 DEG C, polyvinyl alcohol solution for subsequent use is scattered in this reactor, obtain aqueous dispersion liquid, stir 3 ~ 5 minutes, to be dissolved completely after, inorganic mineral powder for subsequent use is dropped into aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.6 %), thus obtains the dispersant solution for suspension polymerization;
(4) according to aqueous phase and oil-phase solution volume ratio be 6:1 meter, take the styrene monomer solution of 9.5 kg, add the cross-linker divinylbenzene of 1.2 kg and the initiator benzoyl peroxide of 0.18 kg, dissolve, mix in rear input aforesaid reaction vessel, be warming up to 85 ~ 90 DEG C, insulation reaction 4 h, be warming up to 95 DEG C, slaking 1 h, is cooled to 40 ~ 50 DEG C, feeding suction filtration, washed product for several times, suction filtration, to dry, dries 5 h for 60 DEG C in baking oven, obtains the bead of good dispersity, crosslinked polystyrene-methacrylic acid multipolymer that circularity is high.
The rate of small round spheres that the present embodiment obtains styrene-t octadecyl ester copolymerization bead is 98.7%, and recording particle size distribution range with vernier callipers is 0.54 ~ 2.08 mm.
embodiment 3:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 20% of host quality; By mass percentage, by diatomite powder 80%, calcined kaolin powder 20% forms described host; The particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μm.
Dispersion agent of the present invention is used as the suspension polymerization of linear methyl methyl acrylate homopolymerization, and its step is as follows:
(1) according to mass percent, take diatomite powder 80%, calcined kaolin powder 20% forms inorganic mineral powder 1.017 kg, for subsequent use as host;
(2) account for 20% weighing polyvinyl alcohol 0.203 kg of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and be configured to the polyvinyl alcohol solution that massfraction is 2.6 %, volume is that 7.823 L are for subsequent use;
(3) in suspension polymerization still, 76.927 L water are added, be warming up to 60 DEG C, polyvinyl alcohol solution for subsequent use is scattered in this reactor, obtain aqueous dispersion liquid, stir 3 ~ 5 minutes, to be dissolved completely after, inorganic mineral powder for subsequent use is dropped into aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.2%), thus obtains the dispersant solution for suspension polymerization;
(4) according to aqueous phase and oil-phase solution volume ratio be 8:1 meter, take the monomer solution of 10 kg methyl methacrylates, add the initiator benzoyl peroxide of 0.14 kg, dissolve, mix rear input in aforesaid reaction vessel, be warming up to 85 ~ 90 DEG C, insulation reaction 4 h, be warming up to 95 DEG C, slaking 1 h, is cooled to 40 ~ 50 DEG C, feeding suction filtration, washed product for several times, suction filtration, to dry, dries 5 h for 60 DEG C in baking oven, obtains the bead of good dispersity, linear polymethylmethacrylate homopolymerization that circularity is high.
The rate of small round spheres that the present embodiment obtains methyl methacrylate homopolymerization bead is 97.5%, and recording particle size distribution range with vernier callipers is 0.66 ~ 2.14 mm.
embodiment 4:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 15% of host quality; By mass percentage, by diatomite powder 85%, calcined kaolin powder 15% forms described host.
Dispersion agent of the present invention is used as the suspension polymerization of cross-linked styrene-butyl methacrylate copolymerization oil-absorbing resin, and its step is as follows:
(1) according to mass percent, take diatomite powder 85%, calcined kaolin powder 15% forms inorganic mineral powder 0.993 kg, for subsequent use as host;
(2) account for 15% weighing polyvinyl alcohol 0.149kg of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and be configured to the polyvinyl alcohol solution that massfraction is 2.8 %, volume is that 5.321 L are for subsequent use;
(3) in suspension polymerization still, 93.979 L water are added, be warming up to 60 DEG C, polyvinyl alcohol solution for subsequent use is scattered in this reactor, obtain aqueous dispersion liquid, stir 3 ~ 5 minutes, to be dissolved completely after, inorganic mineral powder for subsequent use is dropped into aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.0 %), thus obtains the dispersant solution for suspension polymerization;
(4) according to aqueous phase and oil-phase solution volume ratio be 8:1 meter, take the monomer mixture solution of 5 kg vinylbenzene and 5 kg butyl methacrylate, add the cross-linker divinylbenzene of 1.2 kg and the initiator benzoyl peroxide of 0.15 kg, dissolve, drop into after mixing in aforesaid reaction vessel, be warming up to 85 ~ 90 DEG C, insulation reaction 4 h, be warming up to 95 DEG C, slaking 1 h, be cooled to 40 ~ 50 DEG C, feeding suction filtration, washed product for several times, suction filtration is to dry, 5 h are dried for 60 DEG C in baking oven, obtain good dispersity, the multipolymer beadlet of the polystyrene-methacrylic acid butyl ester that the flexibility that circularity is high is cross-linked, can be used as oil-absorbing resin.
The rate of small round spheres that the present embodiment obtains styrene-t butyl ester copolymerization bead is 96.8%, and recording particle size distribution range with vernier callipers is 0.84 ~ 1.82 mm.
embodiment 5:
For an inorganic-organic hybrid dispersion agent for suspension polymerization, with inorganic mineral powder for host, polyvinyl alcohol is assistant agent, and the quality of assistant agent accounts for 25% of host quality; By mass percentage, by diatomite powder 30%, calcined kaolin powder 70% forms described host; The particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μm, and described diatomite powder and calcined kaolin powder are through super-dry, and drying temperature is 80 DEG C, and the time is 6 hours.
Dispersion agent of the present invention is used as the suspension polymerization of cross-linked styrene-vinyl acetate copolymerized, and its step is as follows:
(1) according to mass percent, take diatomite powder 30%, calcined kaolin powder 70% forms inorganic mineral powder 0.976 kg, for subsequent use as host;
(2) account for 15% weighing polyvinyl alcohol 0.146 kg of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and be configured to the polyvinyl alcohol solution that massfraction is 3.0 %, volume is that 4.880 L are for subsequent use;
(3) in suspension polymerization still, 117.140 L water are added, be warming up to 60 DEG C, polyvinyl alcohol solution for subsequent use is scattered in this reactor, obtain aqueous dispersion liquid, stir 3 ~ 5 minutes, to be dissolved completely after, inorganic mineral powder for subsequent use is dropped into aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 0.8 %), thus obtains the dispersant solution for suspension polymerization;
(4) according to aqueous phase and oil-phase solution volume ratio be 8:1 meter, take the monomer mixture solution of 5 kg vinylbenzene and 5 kg vinyl acetates, add the cross-linker divinylbenzene of 1.2 kg and the initiator benzoyl peroxide of 0.15 kg, dissolve, drop into after mixing in aforesaid reaction vessel, be warming up to 85 ~ 90 DEG C, insulation reaction 4 h, be warming up to 95 DEG C, slaking 1 h, be cooled to 40 ~ 50 DEG C, feeding suction filtration, washed product for several times, suction filtration is to dry, 5 h are dried for 60 DEG C in baking oven, obtain good dispersity, the multipolymer beadlet of crosslinked polystyrene-vinyl acetate that circularity is high.
The rate of small round spheres that the present embodiment obtains vinylbenzene-vinyl acetate copolymerized bead is 98.4 %, and recording particle size distribution range with vernier callipers is 0.68 ~ 1.78 mm.
Claims (1)
1., for an application method for the inorganic-organic hybrid dispersion agent of suspension polymerization, it is characterized in that it comprises the steps:
(1) according to mass percent, take diatomite powder 70 ~ 90%, calcined kaolin powder 10 ~ 30 % forms inorganic mineral powder, as host;
(2) account for 10 ~ 30% weighing polyvinyl alcohol of inorganic mineral powder quality according to polyvinyl alcohol quality, as assistant agent, and to be configured to mass fraction be that the polyvinyl alcohol solution of 2.0 ~ 3.0 % is for subsequent use;
(3) polyvinyl alcohol solution for subsequent use is scattered in the water of 40 ~ 60 DEG C, obtain aqueous dispersion liquid, to be dissolved completely after, by inorganic mineral powder, drop into aqueous dispersion liquid, wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 0.6 ~ 2.3%, thus obtains the dispersant solution for suspension polymerization;
(4) raw material of suspension polymerization is mixed with the dispersant solution for suspension polymerization step (3) Suo Shu, good dispersity, cross-linking products bead that circularity is high after reaction, can be obtained.
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