CN102911305A - Preparation method and apparatus of resin particles - Google Patents
Preparation method and apparatus of resin particles Download PDFInfo
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- CN102911305A CN102911305A CN2011102175308A CN201110217530A CN102911305A CN 102911305 A CN102911305 A CN 102911305A CN 2011102175308 A CN2011102175308 A CN 2011102175308A CN 201110217530 A CN201110217530 A CN 201110217530A CN 102911305 A CN102911305 A CN 102911305A
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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 the 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 is used for electronic industry, can make the electronic component of trace impurity content; Ion exchange resin is used for pharmaceutical industry, can make high-purity medicine; Aspect environment protection, in the separation of industrial sewage and scavenging process, also played certain effect.
The ion exchange resin matrix is to generate vinylbenzene-divinylbenzene pearl body by vinylbenzene-divinylbenzene by suspension polymerization, then carries out other reaction kinetic on vinylbenzene-divinylbenzene pearl body again, obtains the ion exchange resin of desired properties.In industrial application, the particle diameter of ion exchange resin all must and require control within the specific limits according to working conditions, require in 0.3 mm～1.25mm scope for some common application process particle diameters, under some special conditionss, require particle diameter even, 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 such as some.
In the existing suspension polymerization process, after vinylbenzene and divinylbenzene required to determine fully to mix after the proportioning according to resin's crosslinkage, add initiator and form oil phase, the proportioning of oil phase raw material is technology contents well known to those skilled in the art.In addition a certain amount of dispersion agent, stopper are added to the water the formation water, the proportioning of water raw material is technology contents well known to those skilled in the art.With the 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 that stirs, oil phase is dispersed in the aqueous phase that contains dispersion agent, stopper and forms a certain size oil droplet, with the rising of temperature, in the oil phase under the polymerization starter effect polymerization reaction take place generate polymer beads.Because the agitator edge is different with middle linear velocity, formed bead not of uniform size, carry out in the process in reaction, bead is constantly broken and also poly-, so that the polymeric articles of copolymerization has certain size-grade distribution, its size-grade distribution depends primarily on dispersion and and the poly-probability of drop in the polymerization process.Polymerization process is the 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 bead in the control size of bead and the reaction process break and and collecting process can control the size of polymer particles and distribute.Yet, affect the factor very complex of bead size, the structure, shape, the rotating speed that comprise agitator, the sizes and shape of reactor, the proportioning of material and the viscosity of water, the kind of dispersion agent and concentration etc., in fact being 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, obtained obvious effect, for example, used the reactor (being tall and thin shaped reaction still of 3 etc. such as ring-like reactor, length-to-diameter ratio) of special processing and adopt oblique slurry formula or grid agitator etc.; And for example, have strong surface-active stablizer or be insoluble in the inorganic powder of water such as the size-grade distribution that silica gel, magnesiumcarbonate etc. also can improve the pearl body by adding, but this improvement is very limited, and polymerization also wants the residual powder in flush away pearl surface after finishing, and has increased the complicacy of technique.
In order further to improve the balling-up yield of polyreaction, CN1389478A discloses and a kind of oil mixture has been passed feed mechanism from the polymerization reactor bottom, and constant speed enters aqueous phase and carries out polyreaction.The polymerization technology condition is: 40 ℃～50 ℃ of the oil phase temperature during charging; Mixing speed 100r/ min～200r/ min; Oil phase feed rate 200ml/min～1000ml/min; 78 ℃～82 ℃/reaction times of temperature 3h～5h; 90 ℃～95 ℃/reaction times 3h～5h; The multipolymer pearl body that obtains 20 orders～30 order sizes after conventional washing, drying, the screening 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 the 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 in advance polymerization of oil phase 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 the 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) forms water according to ordinary method preparation deionized water, dispersion agent and stopper, add again initiator according to the index request preparation vinylbenzene of resin's crosslinkage and divinylbenzene and form oil phase;
(2) oil phase is carried out prepolymerization, the prepolymerization temperature is 40～100 ℃, and the reaction times is 20～250min;
(3) prepolymerized oil phase is distributed to aqueous phase by the oil phase divider, and the mixture of oil phase and water enters the curing reaction still by upcast;
(4) temperature of reaction of curing reaction still is 90 ℃～100 ℃, reaction times 3h～15h;
(5) obtain resin particle through the material behind the curing reaction through washing, drying.
Among the 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 the step (2), tubular reactor is adopted in the oil phase prepolymerization, and 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 ℃～100 ℃, most preferably is 70 ℃～85 ℃, and the preferred reaction times is 30min～150 min, most preferably is 30min～50 min.
Among the resin particle preparation method of the present invention, after oil phase is distributed to aqueous phase in the step (3), enters upcast and overflow in the curing reaction still.Proceed reaction in upcast, the upcast temperature of reaction is 60～90 ℃, is preferably 80 ℃～90 ℃, and the upcast reaction times is 5～30min, is preferably 10min～20min.
Among the resin particle preparation method of the present invention, the curing reaction still in the step (4) is the conventional enamel still of being furnished with grid agitator.Curing reaction temperature is preferably 90～95 ℃, and the time is preferably 3h～8h, most preferably is 3～5h.
Other condition among the resin particle preparation method of the present invention such as mass transport, product washing, drying etc. are contents well known to those skilled in the art.
Resin particle Preparation equipment of the present invention comprises: tubular type pre-polymerization reactor, oil phase divider, upcast and curing reaction still.The oil phase pipeline communicates with tubular type pre-polymerization reactor entrance, the pre-polymerization reactor outlet communicates with oil phase divider entrance, the oil phase divider communicates with the water entrance simultaneously, and the 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, the oil phase divider is double-layer separate matching board structure, the upper strata is the water distribution plate, lower floor is the oil phase distribution plate, be provided with the water feed-pipe between the double-layer separate matching board, the outlet of water feed-pipe is provided with the water divider, at lower floor's oil phase distribution plate at least one oil phase distribution piping is set, and upper strata water distribution plate is passed in oil phase distribution piping upper end; A water dispensing orifice also is set on the water distribution plate of upper strata at least, around the water distribution plate that preferably each oil phase distribution piping is corresponding the water dispensing orifice is set, the oil phase distribution piping passes the water dispensing orifice and enters in the upcast.The oil phase divider is arranged on the bottom of upcast.The oil phase divider most preferably is removably the bottom of putting at upcast is installed, in order to change the isoparametric oil phase divider of different oil phase distribution piping internal diameters, makes things convenient for the production requirement of variable grain degree resin.
Be fixing seal between described oil phase distribution piping and the lower floor's distribution plate, oil phase distribution piping height is advisable can pass upper strata water distribution plate, and the distribution piping internal diameter is 0.05mm～1.5mm, is preferably 0.1mm～1.0mm, most preferably is 0.1mm～0.5mm.When establishing a plurality of distribution piping, distribution piping is arranged for equilateral triangle at 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.
Be spherical structure above the described water feed-pipe outlet distributor, the below is sector structure, is provided with at least a through hole on sphere, through-hole diameter 1～3mm, when being provided with a plurality of through hole, through hole is that equilateral triangle is arranged, corresponding the getting final product of oil phase distribution piping on quantity and spacing and the 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 be greater than oil phase distribution piping external diameter 1～3mm, corresponding the getting final product of oil phase distribution piping on quantity and spacing and the 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 the standard enamel still is furnished with the standard grid agitator.The weight ratio of water and oil phase is 1:1～10:1.
Oil phase distribution piping aperture in the 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 oil phase distribution piping outlet bonding, must maintain a certain distance between the oil phase distribution piping, be generally 1mm～25mm, preferred 2 mm～20mm, that override is selected is 2mm～4 mm.
In order to obtain more uniformly spherical polymer pearl body, in the oil phase divider, be provided with the water feed-pipe, the feed-pipe outlet is provided with the water divider, and water divider top is provided with the water distribution plate.Water divider and water distribution plate can make the water uniformly distributing that enters oil phase divider and upcast, so that the oil droplet that forms by the oil phase distribution piping is subject to the axial water buoyancy that evenly makes progress, so that oil droplet evenly and not is 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, the 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 the 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 continuouslys, and control the size of fluoropolymer resin by the parameters such as aperture of regulating the oil phase distribution piping, prepare the fluoropolymer resin of uniform grading size.
Process research is found, because suspension polymerization system is thermodynamic unstable system, needs to keep stable by stirring and dispersion agent.Stirring under the shearing action, the oil phase that is dissolved with initiator is dispersed into little oil droplet, is suspended in the aqueous phase initiated polymerization.Be insoluble to the oil phase of water under the 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 piece again.The present invention is before oil phase is separated into oil droplet, adopted the prepolymerization process, through the oil phase in the prepolymerization process, the oil droplet that forms behind the process oil phase divider again is because oil phase is lighter than water, so the oil droplet that forms rises in upcast, in uphill process, obtain further polymerization, oil droplet after the polymerization uniform dispersion agent in solidifying still, 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.
The dispersion of oil droplet and polymerization probability have determined the distribution of polymerisate granularity in the suspension polymerization process, and its shape, size are decided with the character of stirring intensity and dispersion agent.Therefore, if the size of control oil droplet and distribution before polyreaction, and in reaction process, to keep the original size and shape of oil droplet, along with the carrying out that reacts do not bond, then can synthesize even-grained polymer resin.
Description of drawings
Fig. 1 is that technical process of the present invention and device consist of synoptic 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 synoptic diagram;
Fig. 5 is oil phase distribution plate and oil phase distribution piping structural representation.
Among the figure: 1 batching kettle; 2 oil phase pumps; 3 pre-polymerization reactors; 4 oil phase dividers; 5 upcasts; 6 solidify the still agitator; 7 solidify still; 8 water pumps.
Embodiment
In the inventive method, method and the device of synthetic single-size resin have been designed, in polyreaction, at first prepare deionized water, dispersion agent, stopper according to this area ordinary method and form water, then prepare vinylbenzene and divinylbenzene according to the index request of resin's crosslinkage and add again initiator and form oil phase.Oil phase is pumped into the tubular type pre-polymerization reactor with pump, the prepolymerization suitable time, then entered in the oil phase divider by the oil phase dispenser bottom, the impulse force that in the oil phase divider, makes progress owing to water, so that oil phase forms oil droplet of uniform size, the oil droplet of formation enters the aqueous phase of upcast, simultaneously water is passed in the oil phase divider by the bottom of the upper strata distribution plate of divider and the top of lower floor's distribution plate, oil droplet overflows in the curing reaction still on the top of upcast, finishes polyreaction.
Material proportion, water: oil phase (weight)=4:1
1 ﹞ oil phase forms such as table 1.
Table 1 embodiment 1 oil phase forms.
| 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 such as table 2.
Table 2 embodiment 1 water forms.
| 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 the pre-polymerization reactor aspect ratio, oil phase distribution piping aperture 0.1mm, and distance is 4 mm between the oil phase distribution piping.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 the upcast aspect ratio is 50.
Batching: at first prepare oil phase in the oil phase batching kettle, vinylbenzene and the mixing of 140g divinylbenzene with 850g add the 10g benzoyl peroxide again as initiator, mix; 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: at first oil phase is warmed up to 60 ℃, the upcast water is warmed up to 80 ℃, solidify still and be warmed up to 95 ℃, then oil phase is added in the pre-polymerization reactor continuously, carry out prepolymerization (temperature 60 C), reaction times 30min, then enter in the upcast by the oil phase divider, constantly rise in upcast and continue reaction 10min, overflow enters and solidifies in the still when rising to upcast top, reacts 5h in the curing reaction still.Product passes through filtration, washing, drying, 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 such as table 3.
Table 3 embodiment 2 oil phases form.
| 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 such as table 4.
Table 4 embodiment 2 waters form.
| 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 the pre-polymerization reactor aspect ratio, oil phase distribution piping aperture 0.2mm, and distance is 6 mm between the oil phase distribution piping.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 the upcast aspect ratio is 50.
Batching: at first prepare oil phase in the oil phase batching kettle, vinylbenzene and the mixing of 130g divinylbenzene with 850g add the 20g benzoyl peroxide again as initiator, mix; 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: at first oil phase is warmed up to 55 ℃, the upcast water is warmed up to 85 ℃, solidify still and be warmed up to 90 ℃, then oil phase is added in the pre-polymerization reactor continuously, carry out prepolymerization (55 ℃), behind the reaction 20min, enter in the upcast by the oil phase divider, constantly rise in upcast and continue reaction 20min, overflow enters and solidifies in the still when rising to upcast top, reacts 3h in the curing reaction still.Product passes through filtration, washing, drying, 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 forms: 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 forms: 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 |
| The 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 the oil |
2 | 4 | 6 | 8 | 10 | 12 |
| The upcast aspect ratio | 10 | 30 | 50 | 70 | 90 | 110 |
| Polymeric reaction condition: | ? | ? | ? | ? | ? | ? |
| The prepolymerization temperature/℃ | 50 | 55 | 60 | 50 | 55 | 60 |
| The upcast temperature of reaction/℃ | 60 | 65 | 70 | 75 | 80 | 85 |
| Curing still temperature of reaction/℃ | 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 forms: 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 forms: 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 |
| The 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 the oil |
2 | 4 | 6 | 8 | 10 | 12 |
| The upcast aspect ratio | 130 | 150 | 20 | 40 | 80 | 80 |
| Polymeric reaction condition: | ? | ? | ? | ? | ? | ? |
| The prepolymerization temperature/℃ | 55 | 50 | 65 | 60 | 55 | 65 |
| The upcast temperature of reaction/℃ | 70 | 75 | 70 | 75 | 80 | 80 |
| Curing still temperature of reaction/℃ | 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 are poured oil phase in the reactor into embodiment 1, stir 10min under the speed of 45 ℃ and 110r/min; Then under 80 ℃ and 92 ℃ of conditions, reacted respectively 3 hours.Weigh after product washing, drying, the screening.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; The reactor bottom is provided with base plate, flow deflector, the feed mechanism of flow-guiding channel and control valve; A ring through hole on the base plate, through-hole aperture are 0.5mm; Through-hole spacing 3mm; Agitator is grid agitator, reactor diameter: stirrer diameter=1:0.7.
Polyreaction: under the water temperature 45 C, oil phase is added in the reactor, stirring velocity 110r/min heats up 81 ℃ subsequently, reacts 3 hours; Be warmed up to 92 ℃, continuing reaction 3 hours, weighing after product filtration, washing, drying, the screening, the yield that obtains fluoropolymer resin particle size were 0.6mm～0.9mm is 84.8%.
Claims (13)
1. the preparation method of a resin particle is characterized in that comprising the steps:
(1) forms water according to ordinary method preparation deionized water, dispersion agent and stopper, add again initiator according to the index request preparation vinylbenzene of resin's crosslinkage and divinylbenzene and form oil phase;
(2) oil phase is carried out prepolymerization, the prepolymerization temperature is 40～100 ℃, and the reaction times is 20～250min;
(3) prepolymerized oil phase is distributed to aqueous phase by the oil phase divider, and the mixture of oil phase and water enters the curing reaction still by upcast;
(4) temperature of reaction of curing reaction still is 90 ℃～100 ℃, reaction times 3h～15h;
(5) obtain resin particle through the material behind the curing reaction through washing, drying.
2. in accordance with the method for claim 1, it is characterized in that: in the step (2), tubular reactor is adopted in the oil phase prepolymerization, and 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.
3. according to claim 1 or 2 described methods, it is characterized in that: in the step (2), the prepolymerized temperature of reaction of oil phase is 60 ℃～100 ℃, is preferably 70 ℃～85 ℃, and the reaction times is 30min～150 min, is preferably 30min～50 min.
4. in accordance with the method for claim 1, it is characterized in that: in the step (3), after oil phase is distributed to aqueous phase, enter upcast and overflow in the curing reaction still, proceed reaction in upcast, the upcast temperature of reaction is 60～90 ℃, is preferably 80 ℃～90 ℃, the upcast reaction times is 5～30min, is preferably 10min～20min.
5. in accordance with the method for claim 1, it is characterized in that: in the step (4), the curing reaction still is the enamel still of being furnished with grid agitator, and curing reaction temperature is 90～95 ℃, and the time is 3h～8h, is preferably 3～5h.
6. a resin particle Preparation equipment is characterized in that comprising: tubular type pre-polymerization reactor, oil phase divider, upcast and curing reaction still; The oil phase pipeline communicates with tubular type pre-polymerization reactor entrance, the pre-polymerization reactor outlet communicates with oil phase divider entrance, the oil phase divider communicates with the water entrance simultaneously, and the oil phase divider is arranged on the bottom of upcast, and upcast top is connected with curing reaction still entrance.
7. according to equipment claimed in claim 6, it is characterized in that: the oil phase divider is double-layer separate matching board structure, the upper strata is the water distribution plate, lower floor is the oil phase distribution plate, be provided with the water feed-pipe between the double-layer separate matching board, the outlet of water feed-pipe is provided with the water divider, at lower floor's oil phase distribution plate at least one oil phase distribution piping is set, and upper strata water distribution plate is passed in oil phase distribution piping upper end; A water dispensing orifice is set on the water distribution plate of upper strata at least, around the water distribution plate that preferably each oil phase distribution piping is corresponding the water dispensing orifice is set, the oil phase distribution piping passes the water dispensing orifice and enters in the upcast.
8. according to equipment claimed in claim 7, it is characterized in that: be fixing seal between oil phase distribution piping and the lower floor's distribution plate, oil phase distribution piping height is for can pass upper strata water distribution plate, and the distribution piping internal diameter is 0.05mm～1.5mm, be preferably 0.1mm～1.0mm, most preferably be 0.1mm～0.5mm.
9. according to claim 7 or 8 described equipment, it is characterized in that: a plurality of oil phase distribution pipings are set, and distribution piping is arranged for equilateral triangle at lower floor's distribution plate, and the spacing of adjacent oil phase distribution piping is 1mm～25mm, be preferably 3mm～20mm, most preferably be 5mm～15mm.
10. according to equipment claimed in claim 7, it is characterized in that: be spherical structure above the water feed-pipe outlet distributor, the below is sector structure, on sphere, be provided with at least 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.
11. according to equipment claimed in claim 7, 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 oil phase distribution piping on the lower distribution plate.
12. according to equipment claimed in claim 6, it is characterized in that: the internal diameter of upcast: height ratio is 1:10～1:200, preferred internal diameter: height ratio is 1:50～1:150, most preferably internal diameter: height ratio is 1:100～1:150.
13. according to equipment claimed in claim 6, it is characterized in that: the curing reaction still is the enamel still of being furnished with grid agitator.
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| CN201110217530.8A CN102911305B (en) | 2011-08-01 | 2011-08-01 | Preparation method and apparatus of resin particles |
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| CN201110217530.8A CN102911305B (en) | 2011-08-01 | 2011-08-01 | Preparation method and apparatus of resin particles |
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| 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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| 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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| CN105500552A (en) * | 2016-02-16 | 2016-04-20 | 黄利文 | Chemical device for efficiently preparing resin particles |
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