CN102911305B - Preparation method and apparatus of resin particles - Google Patents
Preparation method and apparatus of resin particles Download PDFInfo
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- CN102911305B CN102911305B CN201110217530.8A CN201110217530A CN102911305B CN 102911305 B CN102911305 B CN 102911305B CN 201110217530 A CN201110217530 A CN 201110217530A CN 102911305 B CN102911305 B CN 102911305B
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Abstract
The invention discloses a preparation method and an apparatus of resin particles. By employing an oil phase prepolymerization before suspension polymerization reaction and changing a feeding mode of an oil-phase material and a water-phase material, the particle size and uniform distribution of polymers in the suspension polymerization reaction can be controlled easily and conveniently; and problems of low bead yield fitting to particle diameter requirements in the suspension polymerization process are solved effectively. The suspension polymerization apparatus for preparing uniform resin particles comprises a tubular type prepolymerization reactor, an oil phase distributor, a lifting pipe and a curing reaction vessel. The apparatus is simple in structure, is easy to control, and is suitable for the production of the resin particles.
Description
Technical field
The invention belongs to the method and apparatus of resin balling-up, the method is particularly useful for the preparation of single-size resin.
Background technology
Resin is widely used in the industrial production such as material purification, water treatment, catalyzed reaction, medicine Separation & Purification and scientific research field.In Chemical Manufacture, ion exchange resin is replacing the treating processess such as some precipitations, solvent extraction and rectifying; Ion exchange resin, for electronic industry, can make the electronic component of trace impurity content; Ion exchange resin, for pharmaceutical industry, can make high-purity medicine; Aspect environment protection, in the separation of industrial sewage and scavenging process, also play certain effect.
Ion exchange resin matrix is to generate vinylbenzene-divinylbenzene pearl body by vinylbenzene-divinylbenzene by suspension polymerization, then on vinylbenzene-divinylbenzene pearl body, carries out other reaction kinetic again, obtains the ion exchange resin of desired properties.In industrial application, the particle diameter of ion exchange resin all must and require according to working conditions to control within the specific limits, require within the scope of 0.3 mm～1.25mm for some common application process particle diameters, under some special conditionss, require particle diameter even, as some cross range request 0.3mm～0.6mm, 0.6 mm～0.9mm or the comparatively even equal ion-exchange resin particles of 0.9 mm～1.25mm equal diameter.
In existing suspension polymerization process, after vinylbenzene and divinylbenzene are required to determine and fully mixed after proportioning according to resin's crosslinkage, add initiator to form oil phase, the proportioning of oil phase raw material is technology contents well known to those skilled in the art.Separately a certain amount of dispersion agent, stopper are added to the water to formation water, the proportioning of water raw material is technology contents well known to those skilled in the art.By water heat temperature raising, and constantly stir, drop into oil phase, regulate mixing speed, control oil droplet size and degree of uniformity.Under the condition stirring, oil phase is dispersed in the oil droplet that forms a certain size in the water that contains dispersion agent, stopper, and with the rising of temperature, in oil phase, under polymerization starter effect, polymerization reaction take place generates polymer beads.Because agitator edge is different with middle linear velocity, form bead not of uniform size, carry out in process in reaction, bead is constantly broken and also poly-, make the polymeric articles of copolymerization have certain size-grade distribution, its size-grade distribution depends primarily on dispersion and and the poly-probability of drop in polymerization process.Polymerization process is thermal initiation free chain reaction, comprises the reactions such as chain initiation, chainpropagation and chain termination.According to this polymerization reaction mechanism, in theory by control bead in the size of bead and reaction process break and and collecting process can control the size of polymer particles and distribute.But, the factor that affects bead size is quite complicated, comprise structure, shape, the rotating speed of agitator, the sizes and shape of reactor, the proportioning of material and the viscosity of water, kind and the concentration etc. of dispersion agent, in fact be difficult to control well all of these factors taken together, therefore, can only be the condition of determining that some are optimized relatively in actual production, and do like this with very strong empirical, be difficult to carry out industry and amplify.
In order to obtain better the amberlite fat prod of qualified size distribution, people have done a large amount of work, obtain obvious effect, for example, applied the reactor (as ring-like reactor, length-to-diameter ratio tall and thin shaped reaction still that is 3 etc.) of special processing and adopt oblique slurry formula or grid agitator etc.; And for example, by adding the inorganic powder that there is strong surface-active stablizer or be insoluble in water also can improve the size-grade distribution of pearl body as silica gel, magnesiumcarbonate etc., but this improvement is very limited, and polymerization also will wash away the residual powder in pearl surface after completing, and increased the complicacy of technique.
In order further to improve the balling-up yield of polyreaction, CN1389478A disclose a kind of by oil mixture from polymerization reactor bottom through feed mechanism, constant speed enters carries out polyreaction in water.Polymerization technology condition is: 40 DEG C～50 DEG C of oil phase temperature when charging; Mixing speed 100r/ min～200r/ min; Oil phase feed rate 200ml/min～1000ml/min; 78 DEG C～82 DEG C/reaction times of temperature 3h～5h; 90 DEG C～95 DEG C/reaction times 3h～5h; Routine obtains 20 order～30 order sizes multipolymer pearl body after washing, be dried, sieve accounts for 84.8%, median size 0.71mm.The method has improved the balling-up yield of polyreaction effectively, but still exists copolymer size skewness, the deficiency that balling-up yield is low.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of preparation method of resin, before suspension polymerization, adopt oil phase polymerization in advance and change the feed way that oil phase adds water, simply and easily control size and the equally distributed method of polymkeric substance particle diameter in suspension polymerization, effectively solved the existing problem of above-mentioned technology.The present invention provides a kind of equipment of realizing above-mentioned resin preparation process simultaneously.
The preparation method of resin particle of the present invention comprises the steps:
(1) form water according to ordinary method preparation deionized water, dispersion agent and stopper, add again initiator to form oil phase according to the index request preparation vinylbenzene of resin's crosslinkage and divinylbenzene;
(2) oil phase is carried out to prepolymerization, prepolymerization temperature is 40～100 DEG C, and the reaction times is 20～250min;
(3) prepolymerized oil phase is distributed in water by oil phase divider, and the mixture of oil phase and water enters curing reaction still by upcast;
(4) temperature of reaction of curing reaction still is 90 DEG C～100 DEG C, reaction times 3h～15h;
(5) material after curing reaction is through washing, the dry resin particle that obtains.
In resin particle preparation method of the present invention, the water of step (1) and oil phase preparation are contents well known to those skilled in the art.In step (2), oil phase prepolymerization adopts tubular reactor, the internal diameter of tubular reactor: Length Ratio is 1:10～1:250, is preferably 1:30～1:200, most preferably is 1:30～1:150.The preferred temperature of reaction of prepolymerization is 60 DEG C～100 DEG C, most preferably is 70 DEG C～85 DEG C, and the preferred reaction times is 30min～150 min, most preferably is 30min～50 min.
In resin particle preparation method of the present invention, after oil phase is distributed in water in step (3), enters upcast and overflow in curing reaction still.In upcast, proceed reaction, upcast temperature of reaction is 60～90 DEG C, is preferably 80 DEG C～90 DEG C, and the upcast reaction times is 5～30min, is preferably 10min～20min.
In resin particle preparation method of the present invention, the curing reaction still in step (4) is the conventional enamel still of being furnished with grid agitator.Curing reaction temperature is preferably 90～95 DEG C, and the time is preferably 3h～8h, most preferably is 3～5h.
Other condition in resin particle preparation method of the present invention as mass transport, product washing, dry etc. be content well known to those skilled in the art.
Resin particle Preparation equipment of the present invention, comprising: tubular type pre-polymerization reactor, oil phase divider, upcast and curing reaction still.Oil phase pipeline communicates with tubular type pre-polymerization reactor entrance, pre-polymerization reactor outlet communicates with oil phase divider entrance, oil phase divider communicates with water entrance simultaneously, and oil phase divider is arranged on the bottom of upcast, and upcast top is connected with curing reaction still entrance.
In aforesaid device of the present invention, oil phase divider is double-layer separate matching board structure, upper strata is water distribution plate, lower floor is oil phase distribution plate, between double-layer separate matching board, be provided with water feed-pipe, the outlet of water feed-pipe is provided with water divider, and at least one oil phase distribution piping is set on lower floor's oil phase distribution plate, and oil phase distribution piping upper end is through upper strata water distribution plate; A water dispensing orifice is also at least set on the water distribution plate of upper strata, and the water distribution plate that preferred each oil phase distribution piping is corresponding arranges water dispensing orifice around, and oil phase distribution piping enters in upcast through water dispensing orifice.Oil phase divider is arranged on the bottom of upcast.Oil phase divider most preferably is removably the bottom of putting at upcast is installed, to change the isoparametric oil phase divider of different oil phase distribution piping internal diameters, facilitates the production requirement of variable grain degree resin.
Between described oil phase distribution piping and lower floor's distribution plate, be fixing seal, oil phase distribution piping height is being advisable through upper strata water distribution plate, and distribution piping internal diameter is 0.05mm～1.5mm, is preferably 0.1mm～1.0mm, most preferably is 0.1mm～0.5mm.In the time establishing multiple distribution piping, distribution piping is arranged for equilateral triangle on lower floor's distribution plate, and the spacing of adjacent oil phase distribution piping is 1mm～25mm, is preferably 3mm～20mm, most preferably is 5mm～15mm.
Above described water feed-pipe outlet distributor, being spherical structure, is sector structure below, is at least provided with a through hole on sphere, through-hole diameter 1～3mm, in the time being provided with multiple through hole, through hole is that equilateral triangle is arranged, and quantity and spacing is corresponding with the oil phase distribution piping on lower distribution plate.Below sector the number of openings and arrangement is corresponding with lower floor oil phase distribution piping, and bore dia is greater than oil phase distribution piping external diameter 0.2～1mm.
Described upper strata water distribution plate, aperture is greater than oil phase distribution piping external diameter 1～3mm, and quantity and spacing is corresponding with the oil phase distribution piping on lower distribution plate.
The internal diameter of described upcast: height ratio is 1:10～1:200, preferentially selects internal diameter: height ratio is 1:50～1:150, and override is selected internal diameter: height ratio is 1:100～1:150.
Described curing reaction still is that standard enamel still is furnished with standard grid agitator.The weight ratio of water and oil phase is 1:1～10:1.
Oil phase distribution piping aperture in oil phase divider be the important factor that determines polymkeric substance particle diameter size, can select suitable aperture according to the particle diameter of desired product, in general, oil phase distribution piping aperture is less by 20%～60% than product cut size.In order to prevent that oil droplet from, in oil phase distribution piping outlet bonding, must maintain a certain distance between oil phase distribution piping, be generally 1mm～25mm, preferably 2 mm～20mm, that override is selected is 2mm～4 mm.
In order to obtain spherical polymer pearl body more uniformly, in oil phase divider, be provided with water feed-pipe, feed-pipe outlet is provided with water divider, and water divider top is provided with water distribution plate.Water divider and water distribution plate can make to enter the water uniformly distributing of oil phase divider and upcast, make the oil droplet forming by oil phase distribution piping be subject to axially even water buoyancy upwards, make oil droplet evenly and not be with conditions of streaking.The size of water feed-pipe outlet distributor through hole, but water can distributed uniform be advisable, be generally through-hole diameter 1～3mm.Upper strata water distribution plate through hole, aperture is greater than oil phase distribution piping external diameter 1～3mm.
Advantage of the present invention is:
Simple to operate, only need to before standard reaction still, increase a tubular type pre-polymerization reactor and oil phase divider, do not need the non-standard reactor of elongated, cylindrical.And can adopt many stills to switch to realize operate continuously, by regulating the parameter such as aperture of oil phase distribution piping to control the size of fluoropolymer resin, prepare the fluoropolymer resin of uniform grading size.
Find through research, because suspension polymerization system is thermodynamic unstable system, need remain stable by stirring and dispersion agent.Stirring under shearing action, the oil phase that is dissolved with initiator is dispersed into little oil droplet, is suspended in initiated polymerization in water.Be insoluble to the oil phase of water under strong stirring effect, become little oil droplet by grinding dispersion, belong to Unstable Systems, along with the carrying out of reaction, the oil droplet of dispersion may condense into again piece.The present invention is before oil phase is separated into oil droplet, adopt prepolymerization process, through the oil phase in prepolymerization process, the oil droplet forming after oil phase divider again, because oil phase is lighter than water, so the oil droplet forming rises in upcast, in uphill process, obtain further polymerization, oil droplet after polymerization is solidifying in still dispersion agent uniformly, and do not bond, thereby can obtain uniform pearl body.Therefore, pre-polymerization reactor is to form oil droplet with the prolongation in reaction times, whether bonding to occur and play decisive role.
In suspension polymerization process, the dispersion of oil droplet and polymerization probability have determined the distribution of polymerisate granularity, and its shape, size are determined with the character of stirring intensity and dispersion agent.Therefore, as long as controlled the size of oil droplet and distribute before polyreaction, and in reaction process, to keep the original size and shape of oil droplet, along with the carrying out of reaction do not bond, can synthesize even-grained polymer resin.
Brief description of the drawings
Fig. 1 is that technical process of the present invention and device form schematic diagram;
Fig. 2 is oil phase divider side enlarged diagram;
Fig. 3 is oil phase divider upper strata water distribution plate structural representation;
Fig. 4 is water dispensing arrangement schematic diagram;
Fig. 5 is oil phase distribution plate and oil phase distribution piping structural representation.
In figure: 1 batching kettle; 2 oil phase pumps; 3 pre-polymerization reactors; 4 oil phase dividers; 5 upcasts; 6 solidify still agitator; 7 solidify still; 8 water pumps.
Embodiment
In the inventive method, method and the device of synthetic single-size resin are designed, in polyreaction, first prepare deionized water, dispersion agent, stopper according to this area ordinary method and form water, then prepare vinylbenzene according to the index request of resin's crosslinkage and divinylbenzene adds initiator to form oil phase again.Oil phase is pumped into tubular type pre-polymerization reactor with pump, prepolymerization suitable time, then entered in oil phase divider by oil phase dispenser bottom, in oil phase divider due to water impulse force upwards, make oil phase form oil droplet of uniform size, the oil droplet of formation enters in the water of upcast, water is passed in oil phase divider by the bottom of the upper strata distribution plate of divider and the top of lower floor's distribution plate simultaneously, oil droplet overflows in curing reaction still on the top of upcast, completes polyreaction.
Material proportion, water: oil phase (weight)=4:1
1 ﹞ oil phase forms as table 1.
Table 1 embodiment 1 oil phase composition.
| Sequence number | Title | Ratio, %(wt) |
| 1 | Vinylbenzene | 85.0 |
| 2 | Divinylbenzene | 14.0 |
| 3 | Benzoyl peroxide | 1.0 |
| 4 | Add up to | 100.0 |
1 ﹞ water forms as table 2.
Table 2 embodiment 1 water composition.
| Sequence number | Title | Ratio, %(wt) |
| 1 | Water | 92.4 |
| 2 | Polyvinyl alcohol | 3.0 |
| 3 | Methylene blue | 0.1 |
| 4 | Calcium chloride | 4.5 |
| 5 | Add up to | 100 |
It is 50 that equipment adopts pre-polymerization reactor aspect ratio, oil phase distribution piping aperture 0.1mm, and between oil phase distribution piping, distance is 4 mm.Water divider through hole is greater than oil phase distribution piping 2mm, and upper strata water distribution plate through hole is greater than oil phase distribution piping external diameter 0.5mm, and upcast aspect ratio is 50.
Batching: first prepare oil phase in oil phase batching kettle, the vinylbenzene of 850g and 140g divinylbenzene are mixed, then add 10g benzoyl peroxide as initiator, be uniformly mixed; Prepare again water, the polyvinyl alcohol of 120g is dissolved in the deionized water of 3696g, add the calcium chloride of 4g methylene blue and 180g.
Polyreaction: first oil phase is warmed up to 60 DEG C, upcast water is warmed up to 80 DEG C, curing still is warmed up to 95 DEG C, then oil phase is added in pre-polymerization reactor continuously, carry out prepolymerization (temperature 60 C), reaction times 30min, then enter in upcast by oil phase divider, in upcast, constantly rise and continue reaction 10min, in the time rising to upcast top, overflow enters and solidifies in still, in curing reaction still, reacts 5h.Product filters, washs, is dried, weighs.Obtaining granularity is the macroporous polymer resin bead body 975.2g of 0.5mm, and product yield is 98.5%(weight).
Material proportion, water: oil phase (weight)=2:1
1 ﹞ oil phase forms as table 3.
Table 3 embodiment 2 oil phase compositions.
| Sequence number | Title | Ratio, %(wt) |
| 1 | Vinylbenzene | 85.0 |
| 2 | Divinylbenzene | 13.0 |
| 3 | Benzoyl peroxide | 2.0 |
| 4 | Add up to | 100.0 |
1) water forms as table 4.
Table 4 embodiment 2 water compositions.
| Sequence number | Title | Ratio, %(wt) |
| 1 | Water | 93.5 |
| 2 | Polyvinyl alcohol | 2.0 |
| 3 | Methylene blue | 0.5 |
| 4 | Calcium chloride | 4.0 |
| 5 | Add up to | 100 |
It is 100 that equipment adopts pre-polymerization reactor aspect ratio, oil phase distribution piping aperture 0.2mm, and between oil phase distribution piping, distance is 6 mm.Water divider through hole is greater than oil phase distribution piping external diameter 2mm, and upper strata water distribution plate through hole is greater than oil phase distribution piping external diameter 0.5mm, and upcast aspect ratio is 50.
Batching: first prepare oil phase in oil phase batching kettle, the vinylbenzene of 850g and 130g divinylbenzene are mixed, then add 20g benzoyl peroxide as initiator, be uniformly mixed; Prepare again water, the polyvinyl alcohol of 40g is dissolved in the deionized water of 1870g, add the calcium chloride of 10g methylene blue and 80g.
Polyreaction: first oil phase is warmed up to 55 DEG C, upcast water is warmed up to 85 DEG C, curing still is warmed up to 90 DEG C, then oil phase is added in pre-polymerization reactor continuously, carry out prepolymerization (55 DEG C), after reaction 20min, enter in upcast by oil phase divider, in upcast, constantly rise and continue reaction 20min, in the time rising to upcast top, overflow enters and solidifies in still, in curing reaction still, reacts 3h.Product filters, washs, is dried, weighs.Obtaining granularity is the fluoropolymer resin pearl body 956.5g of 0.8mm, and product yield is 97.6%(weight).
Table 5 is implemented complete 3～8 experiment conditions and result.
| |
3 | 4 | 5 | 6 | 7 | 8 |
| Water/oil phase weight ratio | 1.5:1 | 2.0:1 | 2.5:1 | 3.0:1 | 4.5:1 | 5.0:1 |
| Oil phase composition: wt% | ? | ? | ? | ? | ? | ? |
| Vinylbenzene | 80.0 | 90.0 | 80.0 | 95.0 | 85.0 | 90.0 |
| Divinylbenzene | 18.0 | 8.5 | 18.0 | 4.0 | 13.5 | 18.0 |
| Benzoyl peroxide | 2.0 | 1.5 | 2.0 | 1.0 | 1.5 | 2.0 |
| Water composition: wt% | ? | ? | ? | ? | ? | ? |
| Water | 90.0 | 91.0 | 92.0 | 93.0 | 90.0 | 91.0 |
| Polyvinyl alcohol | 3.0 | 4.85 | 3.3 | 1.9 | 4.35 | 2.8 |
| Methylene blue | 0.1 | 0.15 | 0.2 | 0.1 | 0.15 | 0.2 |
| Calcium chloride | 3.5 | 4.0 | 4.5 | 5.0 | 5.5 | 6.0 |
| Pre-polymerization reactor aspect ratio | 10 | 30 | 50 | 70 | 90 | 110 |
| Oil phase distribution piping aperture/mm | 0.05 | 0.1 | 0.2 | 0.3 | 0.4 | 0.5 |
| Distance/mm between oil |
2 | 4 | 6 | 8 | 10 | 12 |
| Upcast aspect ratio | 10 | 30 | 50 | 70 | 90 | 110 |
| Polymeric reaction condition: | ? | ? | ? | ? | ? | ? |
| Prepolymerization temperature/DEG C | 50 | 55 | 60 | 50 | 55 | 60 |
| Upcast temperature of reaction/DEG C | 60 | 65 | 70 | 75 | 80 | 85 |
| Curing still temperature of reaction/DEG C | 90 | 91 | 92 | 93 | 94 | 95 |
| Prepolymerization time/h | 30 | 35 | 40 | 45 | 50 | 55 |
| Set time/ |
3 | 4 | 5 | 6 | 7 | 8 |
| Fluoropolymer resin particle diameter/mm | 0.8 | 0.5 | 0.6 | 0.7 | 1.0 | 1.2 |
| Yield, wt% | 90.6 | 92.4 | 98.5 | 91.8 | 94.8 | 98.7 |
Table 6 is implemented complete 9～14 experiment conditions and result.
| Embodiment | 9 | 10 | 11 | 12 | 13 | 14 |
| Water/oil phase weight ratio | 1.5:1 | 2.0:1 | 2.5:1 | 3.0:1 | 4.5:1 | 5.0:1 |
| Oil phase composition: wt% | ? | ? | ? | ? | ? | ? |
| Vinylbenzene | 80.0 | 90.0 | 80.0 | 95.0 | 85.0 | 90.0 |
| Divinylbenzene | 18.0 | 8.5 | 18.0 | 4.0 | 13.5 | 18.0 |
| Benzoyl peroxide | 2.0 | 1.5 | 2.0 | 1.0 | 1.5 | 2.0 |
| Water composition: wt% | ? | ? | ? | ? | ? | ? |
| Water | 90.0 | 91.0 | 92.0 | 93.0 | 90.0 | 91.0 |
| Polyvinyl alcohol | 3.0 | 4.85 | 3.3 | 1.9 | 4.35 | 2.8 |
| Methylene blue | 0.1 | 0.15 | 0.2 | 0.1 | 0.15 | 0.2 |
| Calcium chloride | 3.5 | 4.0 | 4.5 | 5.0 | 5.5 | 6.0 |
| Pre-polymerization reactor aspect ratio | 20 | 60 | 100 | 150 | 200 | 250 |
| Oil phase distribution piping aperture/mm | 0.05 | 0.1 | 0.2 | 0.3 | 0.4 | 0.5 |
| Distance/mm between oil |
2 | 4 | 6 | 8 | 10 | 12 |
| Upcast aspect ratio | 130 | 150 | 20 | 40 | 80 | 80 |
| Polymeric reaction condition: | ? | ? | ? | ? | ? | ? |
| Prepolymerization temperature/DEG C | 55 | 50 | 65 | 60 | 55 | 65 |
| Upcast temperature of reaction/DEG C | 70 | 75 | 70 | 75 | 80 | 80 |
| Curing still temperature of reaction/DEG C | 92 | 94 | 95 | 93 | 94 | 95 |
| Prepolymerization time/h | 30 | 35 | 40 | 35 | 45 | 30 |
| Set time/ |
3 | 5 | 7 | 8 | 6 | 4 |
| Fluoropolymer resin particle diameter/mm | 0.6 | 0.7 | 0.8 | 1.0 | 1.2 | 1.4 |
| Yield, wt% | 89.6 | 97.4 | 97.5 | 98.7 | 94.8 | 91.7 |
Comparative example 1
Material proportion, distribution, with embodiment 1, are poured oil phase in reactor into, under the speed of 45 DEG C and 110r/min, stir 10min; Then under 80 DEG C and 92 DEG C of conditions, react respectively 3 hours.Product is weighed after washing, be dried, sieve.The yield of fluoropolymer resin particle size were 0.6mm～0.9mm is 51.8%.
Comparative example 2
Material proportion, distribution are with embodiment 1.
Appointed condition: reactor aspect ratio 4:1; Reactor bottom is provided with base plate, flow deflector, the feed mechanism of flow-guiding channel and control valve; A ring through hole on base plate, through-hole aperture is 0.5mm; Through-hole spacing 3mm; Agitator is grid agitator, reactor diameter: stirrer diameter=1:0.7.
Polyreaction: under water temperature 45 C, oil phase is added in reactor, stirring velocity 110r/min, heats up 81 DEG C subsequently, reacts 3 hours; Be warmed up to 92 DEG C, continuation reaction 3 hours, product is weighed after filtering, wash, be dried, sieve, and the yield that obtains fluoropolymer resin particle size were 0.6mm～0.9mm is 84.8%.
Claims (25)
1. a preparation method for resin particle, is characterized in that comprising the steps:
(1) form water according to ordinary method preparation deionized water, dispersion agent and stopper, add again initiator to form oil phase according to the index request preparation vinylbenzene of resin's crosslinkage and divinylbenzene;
(2) oil phase is carried out to prepolymerization, prepolymerization temperature is 40～100 DEG C, and the reaction times is 20～250min;
(3) prepolymerized oil phase is distributed in water by oil phase divider, and the mixture of oil phase and water enters curing reaction still by upcast;
(4) temperature of reaction of curing reaction still is 90 DEG C～100 DEG C, reaction times 3h～15h;
(5) material after curing reaction is through washing, the dry resin particle that obtains;
Wherein oil phase divider is double-layer separate matching board structure, upper strata is water distribution plate, lower floor is oil phase distribution plate, between double-layer separate matching board, be provided with water feed-pipe, the outlet of water feed-pipe is provided with water divider, at least one oil phase distribution piping is set on lower floor's oil phase distribution plate, and oil phase distribution piping upper end is through upper strata water distribution plate; A water dispensing orifice is at least set on the water distribution plate of upper strata, and oil phase distribution piping enters in upcast through water dispensing orifice.
2. in accordance with the method for claim 1, it is characterized in that: in step (2), oil phase prepolymerization adopts tubular reactor, the internal diameter of tubular reactor: Length Ratio is 1: 10～1: 250.
3. according to the method described in claim 1 or 2, it is characterized in that: in step (2), the prepolymerized temperature of reaction of oil phase is 60 DEG C～100 DEG C, and the reaction times is 30min～150min.
4. in accordance with the method for claim 1, it is characterized in that: in step (3), after oil phase is distributed in water, enter upcast and overflow in curing reaction still, in upcast, proceed reaction, upcast temperature of reaction is 60～90 DEG C, and the upcast reaction times is 5～30min.
5. in accordance with the method for claim 1, it is characterized in that: in step (4), curing reaction still is the enamel still of being furnished with grid agitator, and curing reaction temperature is 90～95 DEG C, and the time is 3h～8h.
6. it is characterized in that in accordance with the method for claim 2: the internal diameter of tubular reactor: Length Ratio is 1: 30～1: 200.
7. it is characterized in that in accordance with the method for claim 2: the internal diameter of tubular reactor: Length Ratio is 1: 30～1: 150.
8. in accordance with the method for claim 3, it is characterized in that: the prepolymerized temperature of reaction of oil phase is 70 DEG C～85 DEG C, and the reaction times is 30min～50min.
9. in accordance with the method for claim 4, it is characterized in that: upcast temperature of reaction is 80 DEG C～90 DEG C, and the upcast reaction times is 10min～20min.
10. it is characterized in that in accordance with the method for claim 5: the curing reaction time is 3～5h.
11. in accordance with the method for claim 1, it is characterized in that: the water distribution plate that each oil phase distribution piping is corresponding arranges water dispensing orifice around.
12. 1 kinds of resin particle Preparation equipments, is characterized in that comprising: tubular type pre-polymerization reactor, oil phase divider, upcast and curing reaction still; Oil phase pipeline communicates with tubular type pre-polymerization reactor entrance, pre-polymerization reactor outlet communicates with oil phase divider entrance, oil phase divider communicates with water entrance simultaneously, and oil phase divider is arranged on the bottom of upcast, and upcast top is connected with curing reaction still entrance; Wherein oil phase divider is double-layer separate matching board structure, upper strata is water distribution plate, lower floor is oil phase distribution plate, between double-layer separate matching board, be provided with water feed-pipe, the outlet of water feed-pipe is provided with water divider, at least one oil phase distribution piping is set on lower floor's oil phase distribution plate, and oil phase distribution piping upper end is through upper strata water distribution plate; A water dispensing orifice is at least set on the water distribution plate of upper strata, and oil phase distribution piping enters in upcast through water dispensing orifice.
13. according to the equipment described in claim 12, it is characterized in that: between oil phase distribution piping and lower floor's distribution plate, be fixing seal, oil phase distribution piping height is to pass upper strata water distribution plate, and distribution piping internal diameter is 0.05mm～1.5mm.
14. according to the equipment described in claim 12 or 13, it is characterized in that: multiple oil phase distribution pipings are set, and distribution piping is arranged for equilateral triangle on lower floor's distribution plate, and the spacing of adjacent oil phase distribution piping is 1mm～25mm.
15. according to the equipment described in claim 12, it is characterized in that: above water feed-pipe outlet distributor, be spherical structure, be sector structure below, on sphere, be at least provided with a through hole, through-hole diameter 1～3mm, below sector the number of openings and arrangement is corresponding with lower floor oil phase distribution piping, and bore dia is greater than oil phase distribution piping external diameter 0.2～1mm.
16. according to the equipment described in claim 12, it is characterized in that: the aperture of upper strata water distribution plate is greater than oil phase distribution piping external diameter 1～3mm, and quantity and spacing is corresponding with the oil phase distribution piping on lower distribution plate.
17. according to the equipment described in claim 12, it is characterized in that: the internal diameter of upcast: height ratio is 1: 10～1: 200.
18. according to the equipment described in claim 12, it is characterized in that: curing reaction still is the enamel still of being furnished with grid agitator.
19. according to the equipment described in claim 13, it is characterized in that: oil phase distribution piping internal diameter is 0.1mm～1.0mm.
20. according to the equipment described in claim 13, it is characterized in that: oil phase distribution piping internal diameter is 0.1mm～0.5mm.
21. according to the equipment described in claim 14, it is characterized in that: the spacing of adjacent oil phase distribution piping is 3mm～20mm.
22. according to the equipment described in claim 14, it is characterized in that: the spacing of adjacent oil phase distribution piping is 5mm～15mm.
23. according to the equipment described in claim 17, it is characterized in that: the internal diameter of upcast: height ratio is 1: 50～1: 150.
24. according to the equipment described in claim 17, it is characterized in that: the internal diameter of upcast: height ratio is 1: 100～1: 150.
25. according to the equipment described in claim 12, it is characterized in that: the water distribution plate that each oil phase distribution piping is corresponding arranges water dispensing orifice around.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4572905A (en) * | 1982-02-26 | 1986-02-25 | Kureha Kagaku Kogyo Kabushiki Kaisha | Substrate for analyzing hydrophilic substances of low molecular weight |
| CN101691425A (en) * | 2009-09-27 | 2010-04-07 | 上海大学 | Method for preparing adsorptive resin materials by utilizing waste polystyrene |
| CN101864019A (en) * | 2010-05-13 | 2010-10-20 | 上海现代药物制剂工程研究中心有限公司 | Preparation method of sodium polystyrene sulfonate ion exchange resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4572905A (en) * | 1982-02-26 | 1986-02-25 | Kureha Kagaku Kogyo Kabushiki Kaisha | Substrate for analyzing hydrophilic substances of low molecular weight |
| CN101691425A (en) * | 2009-09-27 | 2010-04-07 | 上海大学 | Method for preparing adsorptive resin materials by utilizing waste polystyrene |
| CN101864019A (en) * | 2010-05-13 | 2010-10-20 | 上海现代药物制剂工程研究中心有限公司 | Preparation method of sodium polystyrene sulfonate ion exchange resin |
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