CN103214604A - 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 dispersion agent of the inorganic-organic hybrid 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, and monomer is dispersed into to the polyreaction that countless small dropletss suspends in water and caused.The dispersion of monomer and cohesion are reversing processes; for stoping monomer droplet no longer to condense when colliding; must add dispersion agent; form layer protecting film or be adsorbed on the monomer liquid bead surface around the monomer liquid pearl; thereby play the cohesion that buffer action stops or delay the monomer liquid pearl; and reach the particle motion balance, can obtain high-quality polymerisate thus.
Generally, a kind of dispersion agent that is 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 the product polymer epigranular; (2) make the polymer beads porous, be easy to processing, can reduce the generation of flake in product; (3) form and aspect of product do not produced to adverse influence, and can not cause polywater solution gonorrhoea; (4) in the aqueous solution, foaminess is low, reduces to prevent the aggregation container effective volume, thereby reduces productive rate etc.
In suspension polymerization at present, 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, commonly used have a gelatin; The cellulose ethers macromole, as methylcellulose gum, carboxymethyl cellulose, ethyl cellulose, Natvosol and hydroxypropylcellulose; And polyvinyl alcohol etc.This kind of dispersion system is in suspension polymerization, to be used at most, Chinese patent CN101928357A selects the polyvinyl alcohol that the molecule side group is hydroxyl, its mean polymerisation degree at least 600, and alcoholysis degree is 60 ~ 80 mol%, can obtain the narrow polymkeric substance of particle size distribution, wherein coarse particles is few.The polyvinyl alcohol auxiliary dispersants polymerization degree that Chinese patent CN102311516A produces is 200 ~ 400, alcoholysis degree is 33 ~ 55 mol%, has solved the problem that the low alcoholysis level auxiliary dispersants not exclusively is dissolved in water.But adopt this water-soluble high-molecular substance, often make particle surface be surrounded by the epithelium that one deck graft copolymer forms, in the obstruction polymer beads, monomer removes, and the plasticizing that is unfavorable for the polymkeric substance later stage is processed, and when polymerization temperature is higher, the dispersion effect of polyvinyl alcohol obviously reduces, and sticky still is serious.
2, inorganic dispersant, once attempted comprising numerous inorganicss of natural mineral in scientific research and industrial practice, what final reservation was used is magnesium hydroxide and calcium phosphate powder, and different due to its preparation method and mineralising time of these two kinds of dispersion agents, can cause its performance that very large difference is arranged, thereby make its dispersion effect in suspension polymerization also different, wherein magnesium hydroxide is because of its unstable properties, need fresh preparation, usually the fresh preparation process that polymer industry has comprised magnesium hydroxide in producing, the preparation of calcium phosphate powder and activity keeping are extremely complicated processes, so that China at present can't the production performance excellence product, the calcium phosphate powder used in industrial production at present need be 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 used separately 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 the use, particle is inhomogeneous and uneconomical, so general and organic dispersion agent is used jointly.
3, organic and inorganic composite dispersing agent, owing to using separately a certain class dispersion agent, often dispersion effect is undesirable, so force people to have to use the dispersion agent of compound system, usually, a kind of way is to use inorganic and organic dispersing agent in using the suspension polymerization process simultaneously, using method is unified standard not, and the method for use and the dispersant of use also are not quite similar; Another kind method is that inorganic dispersant is re-used in advance after organically-modified or special processing, as used Sodium dodecylbenzene sulfonate in the calcium phosphate powder preparation process, it is carried out to hydrophobically modified, in order to make, it is easy and the oil phase reaction solution is affine.This is a product syntheti c route with high content of technology, that course of industrialization is complicated, with high costs.Chinese patent CN101633709A makes inorganic main dispersant with the calcium phosphate or the magnesiumcarbonate that are slightly soluble in water, anhydrous sodium sulphate or sodium pyrosulfate are made inorganic auxiliary dispersants, 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 is used the composite dispersing agent of polyvinyl alcohol and calcium triphosphate to prepare polystyrene/expanded graphite composite foaming material.But this dispersion system is that main dispersant is therefore particle surface still can be coated with the epithelium that graft copolymer forms owing to still adopting polyvinyl alcohol, and in inorganic components as magnesium hydroxide and calcium phosphate powder working conditions harshness and cost high, all be unfavorable for the post-production of polymer industry in producing.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization for the deficiency of above-mentioned prior art existence, prevent the adhesion of oil phase reaction drop in the polymer suspension polymerization, improve the dispersiveness of polymer beads, prevent the sticky still of the sticky bar of polymer product.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 % form described host.
Press such scheme, the particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μ m.
Press such scheme, described diatomite powder and calcined kaolin powder are through super-dry, and drying temperature is 80 ℃, and the time is 6 hours.
Press such scheme, described polyvinyl alcohol is polyvinyl alcohol 1788.
Diatomite of the present invention is piled up and is formed by the remains of unicellular low diatom such as waterplant such as grade, and its chemical composition is with unformed SiO
2be main, a small amount of Al is arranged
2o
3, Fe
2o
3, CaO, MgO etc.Diatomite is non-crystal structure, is overlapped the random network structure formed to the three-dimensional space development by bridging oxygen by silicon-oxy tetrahedron, wherein exists the plasma polymkeric substance.
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 dissolve, 20 ℃ almost completely water-soluble, photostabilization is good, is not subject to 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 soak-swelling-infinite swelling-dissolving.
The application method of the dispersion agent of the inorganic-organic hybrid for suspension polymerization of the present invention, its step is as follows:
(1) according to the mass percent meter, take diatomite powder 70～90%, calcined kaolin powder 10～30% forms the inorganic mineral powder, as host;
(2) account for 10 ~ 30% weighing polyvinyl alcohol of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is standby that it is configured to the polyvinyl alcohol solution that mass fraction is 2.0 ~ 3.0 %;
(3) standby polyvinyl alcohol solution is scattered in the water of 40 ~ 60 ℃, obtain aqueous dispersion liquid, to be dissolved fully after, by the 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%, thereby obtains the dispersant solution for suspension polymerization;
(4) raw material of suspension polymerization is mixed with the described dispersant solution for suspension polymerization of step (3), can obtain good dispersity, cross-linking products bead that circularity is high after reaction.
In step (3), account for aqueous dispersion liquid quality 0.6～2.3% according to the quality of inorganic mineral powder, can calculate the quality of aqueous dispersion liquid; Then the quality of inorganic dispersion liquid is deducted to the quality of polyvinyl alcohol solution, can draw the quality of water in step (3).
The suspension polymerization that suspension polymerization of the present invention is vinylbenzene and multipolymer, esters of acrylic acid and comonomer thereof, as suspension polymerization of vinylbenzene homopolymerization (linear or crosslinked), vinylbenzene-stearyl methacrylate copolymerization (linear or crosslinked), vinylbenzene-butyl methacrylate copolymerization (linear or crosslinked), vinylbenzene-methyl methacrylate copolymer (linear or crosslinked), methyl methacrylate homopolymerization and copolymerization thereof etc.
It is main dispersant that the present invention utilizes natural mineral diatomite and kaolinic compound, being equipped with macromolcular dispersant is auxiliary agent, can take full advantage of on the basis of polymer to good guarantor's glue effect of polymer beads like this, and the mechanical isolation effect of increase inorganic nano mineral pair hanging drop, thereby reduce the epithelium that polymer produces at particle surface, make monomer in particle be easy to remove, be conducive to later stage plasticizing processing, and so collocation is used and can be reached good dispersion effect, make that uniform particles, circularity are good, narrow diameter distribution, and good circulation ratio is arranged.Dispersion agent excellent in stability of the present invention, meet the desired performance index of 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 the polymer suspension polyreaction, dispersion agent of the present invention can obviously improve the dispersiveness of oil phase reaction drop and the circularity of polymer beads, prevent that the oil phase reaction solution from dropping in adhesion and the assembly on agitator arm and stirring blade, do not occur the sticky still phenomenon of sticky bar in actual the 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 thereof, esters of acrylic acid and comonomer thereof, as suspension polymerization of vinylbenzene homopolymerization (linear or crosslinked), vinylbenzene-stearyl methacrylate copolymerization (linear or crosslinked), vinylbenzene-butyl methacrylate copolymerization (linear or crosslinked), vinylbenzene-methyl methacrylate copolymer (linear or crosslinked), methyl methacrylate homopolymerization and copolymerization thereof etc.
(3) preparation technology is simple, with low cost, and the inorganic mineral that raw material sources are natural is nontoxic, does not produce environmental pollution.
The accompanying drawing explanation
The SEM shape appearance figure that Fig. 1 is diatomite original ore.
Fig. 2 is calcined kaolin SEM shape appearance figure.
The bead of the cross-linked styrene homopolymerization that Fig. 3 is embodiment 1 preparation.
The bead of the cross-linked styrene that Fig. 4 is embodiment 2 preparations-stearyl methacrylate copolymerization.
The bead of the linear methyl methacrylate homopolymerization that Fig. 5 is embodiment 3 preparations.
The bead of the cross-linked styrene that Fig. 6 is embodiment 4 preparations-butyl methacrylate copolymerization oil-absorbing resin.
The cross-linked styrene that Fig. 7 is embodiment 5 preparations-vinyl acetate copolymerized bead.
Embodiment
For understanding better and utilizing the present invention, this specification sheets is further illustrated content of the present invention in conjunction with the embodiments, but content of the present invention not only is confined to described case study on implementation.
Diatomite of the present invention is taken from rich still area, Lincang City, Yunnan Province, belongs to clayey diatom soil.Impurity is mainly clay, quartzy etc., and clay is mingled with organic parcel mutually, 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 the diatom shell structure, by scanning electron microscope Fig. 1, can be seen, mainly contains round shape, fan-shaped etc., and the 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, arrange in order, illustrate that it has highly porous, bigger serface and the good characteristics such as absorption property.Be filled with some clay mineral fragment and organic matter between diatom test and in shell, these compositions and diatom shell mutually are mingled with, wrap up, and obstruction partly appears in diatomaceous pore structure, diatomaceous specific surface area thereby decrease.Due to diatomite, in the present invention as the obstruct particle of oil phase reaction drop, the clay wherein contained is also effective ingredient, thus in the present invention to diatomite only do desanding, except after organic the processing, no longer carry out other purification.
Calcined kaolin of the present invention is from the calcined kaolin of pool, Tangshan uncommon kaolin company, product type is white snow 90 types, this calcined kaolin is the product of kaolin original soil through 950 ℃ of calcinings, there is higher chemically reactive and oleophylic performance performance, the present invention mainly utilizes its this performance, the sample chemical composition is as shown in table 2, and its microscopic appearance as shown in Figure 2.
embodiment 1:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 μ m, and described diatomite powder and calcined kaolin powder be through super-dry, and drying temperature is 80 ℃, and the time is 6 hours.
Dispersion agent of the present invention is as the suspension polymerization of cross-linked styrene homopolymerization, and its step is as follows:
(1) according to the mass percent meter, take diatomite powder 70%, calcined kaolin powder 30% forms inorganic mineral powder 1.746kg, standby as host;
(2) account for 30% weighing polyvinyl alcohol 0.524kg of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is configured to the polyvinyl alcohol solution that massfraction is 2.4%, volume is 21.83 standby;
(3) add 65.48 L water in the suspension polymerization still, be warming up to 60 ℃, standby polyvinyl alcohol solution is scattered in this reactor, obtain aqueous dispersion liquid, stir 3～5 minutes, to be dissolved fully after, standby inorganic mineral powder is dropped into to aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 2.0%), thereby obtains the dispersant solution for suspension polymerization;
(4) according to water and oil-phase solution volume ratio, be the 6:1 meter, take the styrene monomer solution of 12kg, add the linking agent Vinylstyrene 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 ℃, insulation reaction 4h, be warming up to 95 ℃, slaking 1h, be cooled to 40～50 ℃, the feeding suction filtration, washed product for several times, suction filtration, to dry, is dried 5h for 60 ℃ 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 ℃ of oven dry, weigh, then slowly be poured on the glass upper end of 10 ° of tilting, allow resin dispersion ground Free-rolling downwards, the resin rolled is weighed again, and the percentage ratio of the latter and the former ratio is rate of small round spheres.The rate of small round spheres that the present embodiment obtains the bead of polystyrene homopolymerization is 96.2 %, also can find out the bead good dispersity of the polystyrene homopolymerization that gained is crosslinked from Fig. 3, and circularity is high, and recording particle size distribution range with vernier callipers is 0.60 ~ 2.12 mm.
embodiment 2:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 μ m.
Dispersion agent of the present invention is as the suspension polymerization of cross-linked styrene-stearyl methacrylate copolymerization, and its step is as follows:
(1) according to the mass percent meter, take diatomite powder 75%, calcined kaolin powder 25% forms inorganic mineral powder 1.410 kg, standby as host;
(2) account for 25% weighing polyvinyl alcohol 0.353kg of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is configured to the polyvinyl alcohol solution that massfraction is 2.0 %, volume is that 17.625L is standby;
(3) add 70.495L water in the suspension polymerization still, be warming up to 60 ℃, standby polyvinyl alcohol solution is scattered in this reactor, obtain aqueous dispersion liquid, stir 3～5 minutes, to be dissolved fully after, standby inorganic mineral powder is dropped into to aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.6 %), thereby obtains the dispersant solution for suspension polymerization;
(4) according to water and oil-phase solution volume ratio, be the 6:1 meter, take the styrene monomer solution of 9.5 kg, add the linking agent Vinylstyrene 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 ℃, insulation reaction 4 h, be warming up to 95 ℃, slaking 1 h, be cooled to 40～50 ℃, the feeding suction filtration, washed product for several times, suction filtration, to dry, is dried 5 h for 60 ℃ in baking oven, obtains the bead of good dispersity, crosslinked polystyrene-Sipacril 2739OF that circularity is high.
The rate of small round spheres that the present embodiment obtains vinylbenzene-stearyl methacrylate copolymerization bead is 98.7%, and recording particle size distribution range with vernier callipers is 0.54 ~ 2.08 mm.
embodiment 3:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 μ m.
Dispersion agent of the present invention is as the suspension polymerization of linear methyl methacrylate homopolymerization, and its step is as follows:
(1) according to the mass percent meter, take diatomite powder 80%, calcined kaolin powder 20% forms inorganic mineral powder 1.017 kg, standby as host;
(2) account for 20% weighing polyvinyl alcohol 0.203 kg of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is configured to the polyvinyl alcohol solution that massfraction is 2.6 %, volume is that 7.823 L are standby;
(3) add 76.927 L water in the suspension polymerization still, be warming up to 60 ℃, standby polyvinyl alcohol solution is scattered in this reactor, obtain aqueous dispersion liquid, stir 3～5 minutes, to be dissolved fully after, standby inorganic mineral powder is dropped into to aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.2%), thereby obtains the dispersant solution for suspension polymerization;
(4) be the 8:1 meter according to water and oil-phase solution volume ratio, take the monomer solution of 10 kg methyl methacrylates, add the initiator benzoyl peroxide of 0.14 kg, dissolve, mix in rear input aforesaid reaction vessel, be warming up to 85～90 ℃, insulation reaction 4 h, be warming up to 95 ℃, slaking 1 h, be cooled to 40～50 ℃, the feeding suction filtration, washed product for several times, suction filtration, to dry, is dried 5 h for 60 ℃ 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:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 as the suspension polymerization of cross-linked styrene-butyl methacrylate copolymerization oil-absorbing resin, and its step is as follows:
(1) according to the mass percent meter, take diatomite powder 85%, calcined kaolin powder 15% forms inorganic mineral powder 0.993 kg, standby as host;
(2) account for 15% weighing polyvinyl alcohol 0.149kg of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is configured to the polyvinyl alcohol solution that massfraction is 2.8 %, volume is that 5.321 L are standby;
(3) add 93.979 L water in the suspension polymerization still, be warming up to 60 ℃, standby polyvinyl alcohol solution is scattered in this reactor, obtain aqueous dispersion liquid, stir 3～5 minutes, to be dissolved fully after, standby inorganic mineral powder is dropped into to aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 1.0 %), thereby obtains the dispersant solution for suspension polymerization;
(4) according to water and oil-phase solution volume ratio, be the 8:1 meter, take the monomer mixture solution of 5 kg vinylbenzene and 5 kg butyl methacrylate, add the linking agent Vinylstyrene of 1.2 kg and the initiator benzoyl peroxide of 0.15 kg, dissolve, mix in rear input aforesaid reaction vessel, be warming up to 85～90 ℃, insulation reaction 4 h, be warming up to 95 ℃, slaking 1 h, be cooled to 40～50 ℃, the feeding suction filtration, washed product for several times, suction filtration is to dry, dry 5 h for 60 ℃ in baking oven, obtain good dispersity, the multipolymer beadlet of polystyrene-butyl methacrylate that the flexibility that circularity is high is crosslinked, can be used as oil-absorbing resin.
The rate of small round spheres that the present embodiment obtains vinylbenzene-butyl methacrylate copolymerization bead is 96.8%, and recording particle size distribution range with vernier callipers is 0.84 ~ 1.82 mm.
embodiment 5:
A kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization, take the inorganic mineral powder as host, and 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 μ m, and described diatomite powder and calcined kaolin powder be through super-dry, and drying temperature is 80 ℃, and the time is 6 hours.
Dispersion agent of the present invention is as cross-linked styrene-vinyl acetate copolymerized suspension polymerization, and its step is as follows:
(1) according to the mass percent meter, take diatomite powder 30%, calcined kaolin powder 70% forms inorganic mineral powder 0.976 kg, standby as host;
(2) account for 15% weighing polyvinyl alcohol 0.146 kg of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is configured to the polyvinyl alcohol solution that massfraction is 3.0 %, volume is that 4.880 L are standby;
(3) add 117.140 L water in the suspension polymerization still, be warming up to 60 ℃, standby polyvinyl alcohol solution is scattered in this reactor, obtain aqueous dispersion liquid, stir 3～5 minutes, to be dissolved fully after, standby inorganic mineral powder is dropped into to aqueous dispersion liquid (wherein the quality of inorganic mineral powder accounts for aqueous dispersion liquid quality 0.8 %), thereby obtains the dispersant solution for suspension polymerization;
(4) according to water and oil-phase solution volume ratio, be the 8:1 meter, take the monomer mixture solution of 5 kg vinylbenzene and 5 kg vinyl acetates, add the linking agent Vinylstyrene of 1.2 kg and the initiator benzoyl peroxide of 0.15 kg, dissolve, mix in rear input aforesaid reaction vessel, be warming up to 85～90 ℃, insulation reaction 4 h, be warming up to 95 ℃, slaking 1 h, be cooled to 40～50 ℃, the feeding suction filtration, washed product for several times, suction filtration is to dry, dry 5 h for 60 ℃ 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 (5)
1. the dispersion agent of the inorganic-organic hybrid for suspension polymerization, is characterized in that it take the inorganic mineral powder as host, and 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 % form described host.
2. a kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization according to claim 1, is characterized in that the particle diameter of described diatomite powder and calcined kaolin powder is less than 75 μ m.
3. a kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization according to claim 1, is characterized in that described diatomite powder and calcined kaolin powder are through super-dry, and drying temperature is 80 ℃, and the time is 6 hours.
4. a kind of dispersion agent of the inorganic-organic hybrid for suspension polymerization according to claim 1, is characterized in that described polyvinyl alcohol is polyvinyl alcohol 1788.
5. the application method of the dispersion agent of the inorganic-organic hybrid for suspension polymerization claimed in claim 1, is characterized in that it comprises the steps:
(1) according to the mass percent meter, take diatomite powder 70～90%, calcined kaolin powder 10～30 % form the inorganic mineral powder, as host;
(2) account for 10 ~ 30% weighing polyvinyl alcohol of inorganic mineral powder quality according to the polyvinyl alcohol quality, as assistant agent, and it is standby that it is configured to the polyvinyl alcohol solution that mass fraction is 2.0 ~ 3.0 %;
(3) standby polyvinyl alcohol solution is scattered in the water of 40 ~ 60 ℃, obtain aqueous dispersion liquid, to be dissolved fully after, by the 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%, thereby obtains the dispersant solution for suspension polymerization;
(4) raw material of suspension polymerization is mixed with the described dispersant solution for suspension polymerization of step (3), can obtain good dispersity, cross-linking products bead that circularity is high after reaction.
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| US10766983B2 (en) | 2015-03-05 | 2020-09-08 | Sekisui Specialty Chemicals America, Llc | PVOH dispersant for VCM polymerization |
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