CN1318426A - Stirring arm, stirrer and method of preparing polymer using the stirrer - Google Patents
Stirring arm, stirrer and method of preparing polymer using the stirrer Download PDFInfo
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- CN1318426A CN1318426A CN00137661A CN00137661A CN1318426A CN 1318426 A CN1318426 A CN 1318426A CN 00137661 A CN00137661 A CN 00137661A CN 00137661 A CN00137661 A CN 00137661A CN 1318426 A CN1318426 A CN 1318426A
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- paddle
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- tank diameter
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- dirt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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Abstract
The present invention provided a stirring blade or a stirring unit which is improved in a mixing performance while corresponding to a widespread stirring conditions and, in particular, to provide a unit capable of suppressing the scale generation and being adapted even to emulsion polymerization in various cases. This stirring unit is constituted in such a manner that a sheet- like bottom paddle blade and a sheet-like upper paddle blade which has a crossing angle &alpha of 30-90 deg. with respect to the bottom paddle blade at the position upper than the bottom paddle blade are attached to a stirring shaft, therein, the bottom plate paddle blade has a sweepback angle &beta of 0-60 deg. and the upper paddle blade has a sweepback angle &gamma of 5-60 deg.
Description
The present invention relates to a kind of agitating device (paddle and container), in more detail, relate to more effectively and mixing, dissolving, partial crystallization, reaction, emulsification, the agitating device of stirring operations such as mark.
The application is to serve as that make on the basis to Japanese publication (special hope flat 11-361938 number), and the record content of this Japanese publication is documented in the application's the specification as the part of present specification.
Agitating device uses various paddles according to different purposes.For example, use swept-back flap leaf-propeller blade, use the double helix leaf as the high viscosity leaf as the low viscosity leaf.
Yet, when using swept-back flap leaf-propeller blade,, need bigger stirring power, and mixed characteristic is very poor though, the polylith barrier plate is set on the tank diameter wall for promoting the generation of circular flow.And the double helix leaf is invalid to low viscosity liquid.
On the other hand, be High Level and variation to the agitating device performance demands, and seek for and obtain to adapt to the wider agitating device of stirring condition.Especially, in even mixing, conduct heat, solid-liquid stirs, and aspects such as liquid liquid dispersion need improve performance with batch process.
For example, for carrying out the polymerisation in solution of stirring operation, suspension polymerisation, the polymerisation of emulsion polymerisation etc. can realize the raising of polymer yield rate, the minimizing of polymer agglutinator, the raising of polymer quality, agitating device, the stirring condition of performances such as raising heat-removal capability.
Wherein, especially for the emulsion polymerization process, use when possessing the agitating device of above-mentioned swept-back flap leaf and propeller blade, in polymerization process, can produce the polymer agglutinator, promptly so-called dirt, wall in the polymerization tank, paddle can adhere to these dirts on the barrier plate etc.When producing dirt, not only can cause the polymer yield rate to descend, and, cause quality of item to descend owing to can in normal polymer, sneak into dirt.And, when not removing these dirts and then carry out the polymerization of next batch, with the thermal conductivity in the polymerization tank is descended, the problem that production efficiency descends can appear.Therefore, in emulsion polymerisation, for preventing the shearing aggegation of latex particle under the high shear occasion, and suppress because of mixing certain paddle shape and the stirring condition of bad generation dirt needs.
Herein, a day disclosure special permission communique (A) has disclosed the scheme of using special paddle flat 6-16708 number, and this paddle is that 2 sections tabular blades are up and down combined.Day disclosure special permission (A) flat 9-143231 communique and 9-143206 communique have disclosed a kind of method, and this method is by rotating the dirt that produces when this paddle is cut down emulsion polymerisation in polymerization tank with specified rotation number.
By the paddle that in the emulsion polymerisation system, uses these communiques to put down in writing,, can cut down a certain amount of dirt with existing swept-back flap leaf-compare with the turbine leaf.
Yet, require in recent years under the high performance present situation of goods, require to use special material to carry out special emulsion polymerisation process and because require great attention to productivity ratio and environment aspect, and further require to reduce the generation of dirt, to avoid especially attached in the tank diameter and the dirt on the paddle remove operation.
Especially, under the occasion of 2 sections paddles about the use of being put down in writing as above-mentioned special permission communique, operate for emulsion polymerization, the problem that exists is the situation above (1) exposes liquid level in the paddle upper end, (2) in polymerization, the drip situation of monomer from liquid level top, (3) along with dripping, situation of level change etc. is adhered to dirt easily in the polymerization near liquid level.
The present invention proposes in order to address the above problem, the stirring condition that provides a kind of correspondence wider is provided its purpose, all can improve the agitating device of mixed characteristic, particularly, even the emulsion polymerisation under the corresponding various situation can both suitably suppress the device that dirt takes place.
In view of the above problems, the present invention is to be example with the emulsion polymerisation, and according to the situation that dirt in the detailed analysis tank diameter takes place, the result has confirmed at the monomer that drips above liquid level mixed process dirt to take place near liquid level.This is to cause what instabilityization caused because of the existence of stirring shearing force and unreacted monomer, and draw such conclusion: near being suppressed at this liquid level, produce dirt, by reducing near the shearing the liquid level, and use and possess that can to promote unreacted monomer to disperse the agitating device of the paddle of (mixing) be very effective.
Paddle of the present invention is that tabular bottom paddle and the plate-shaped upper portion paddle that has a 30-90 degree angle of the crossing (α) with respect to this bottom paddle that is positioned at above the paddle of this bottom are installed on the shaft,
The bottom paddle has the angle of sweep (β) of 0-60, and the top paddle has the angle of sweep (γ) of 5-60 degree.
The top paddle is preferably in the tabular wing that formation is stretched on its leading section downwards.
The top paddle upwards diminishes in order to rotate diameter, preferably reduced from bottom to top.
Agitating device feature of the present invention is the device that possesses above-mentioned paddle.That is, have tank diameter, be arranged on barrier plate on this tank diameter internal face and central part vertically is provided with in tank diameter shaft,
Tabular bottom paddle is installed on the shaft and is positioned at and have the plate-shaped upper portion paddle of the 30-90 degree angle of the crossing (α) with respect to this bottom paddle above the paddle of this bottom, wherein
The bottom paddle has the angle of sweep (β) of 0-60, and the top paddle has the angle of sweep (γ) of 5-60 degree.
The top paddle is preferably in the tabular wing that formation is stretched on its leading section downwards.
The top paddle upwards diminishes in order to rotate diameter, preferably reduced from bottom to top.
The manufacture method of polymer of the present invention, particularly emulsion polymer latexes, feature are to use above-mentioned agitating device, carry out polymerisation.
Fig. 1 is the routine sectional drawing that agitating device of the present invention is shown.
Fig. 2 is the paddle plane at explanation angle of sweep.
Fig. 3 is the paddle plane at explanation angle of sweep.
Fig. 4 is the paddle plane of the explanation angle of the crossing.
Fig. 5 is the paddle plane of the explanation angle of the crossing.
Fig. 6 illustrates the agitating device sectional drawing that uses in the comparative example.
Fig. 7 is the summary pie graph of the latex manufacturing installation of use in embodiment 4.
Below, describe the present invention in detail.The invention is not restricted to use in the emulsion polymerisation system, in order to specify, is that example describes with the emulsion polymerisation.
Agitating device of the present invention is for example shown in Figure 1, has tank diameter 11, vertically is located at shaft 12 centre, can drive rotation outside groove in the tank diameter 11.
The shape of tank diameter is not particularly limited, and comparatively it is desirable to possess the cylindrical shape tank diameter of cap, and the ratio (degree of depth/internal diameter) of the degree of depth of tank diameter and tank diameter internal diameter is preferably in the scope between the 0.8-2.5.In addition, the capacity of tank diameter can be from supplying laboratory 0.05-0.1m
3Scale up to 10-100m
3The large-scale industrial production scale, its capacity is not done special restriction.On the tank diameter outside, the thermal medium path is set, so that the thermal medium of predetermined temperature is flow through, so that the temperature of control tank diameter in this path.
Adorning bottom paddle 13 and top paddle 14 on this shaft 12.
These bottom paddles 13 and top paddle 14 are made the shape with angle of sweep.The shape of bottom paddle 13 is that angle of sweep (β) is the 0-60 degree, and the shape of top paddle 14 is that angle of sweep (γ) is the 5-60 degree.
Here, so-called angle of sweep is the angle with respect to the rotation direction sweepback, and the shape of each paddle as long as can satisfy this important document, has all being suitable for of flat or curved shape of bend.That is to say, as shown in Figure 2, can design the angle of sweep like this, flat paddle is formed bend 18 in bending back, centre form the angle of sweep, perhaps as shown in Figure 3, tabular paddle is curved circular-arc back form the angle of sweep.
Tabular paddle bending back is being formed under the situation at angle of sweep, and the position of this bend 18 is preferably in from the position at the center forward distolateral (foreign side) of shaft 12 and paddle front end 20.
Crooked forming after the so-called angle of sweep bending paddle as shown in Figure 2, means by the straight line of bend that connects paddle when a plurality of (, outermost) 18 and front end 20 and is connected the angle of the straight line formation of shaft 12 and paddle front end 20.For the angle of sweep of curved shape, as shown in Figure 3, mean the angle that forms by tangent line on the paddle front end 20 and the straight line that is connected shaft 12 and paddle front end 20.
About bottom paddle 13, though can not need angle of sweep (β),, can reduce the shear rate of blade front end by forming the angle of sweep, when the polymerisation of emulsion polymerisation etc., can prevent the shearing aggegation of latex particle.But if greater than 60 degree,, must improve revolution,, when emulsion polymerisation etc., can increase the generation of dirt though consequently increased the shear rate of paddle fore-end then in order to obtain well-mixed state.
Therefore, the angle of sweep of bottom paddle is preferably between the 15-45 degree.
If it is the angle of sweep (γ) of top paddle 14 is less than 5 degree, then bad because can not suppress fully as near the shear rate the liquid level of the object of the invention.If surpass 60 degree, then the same with above-mentioned bottom paddle, must be improved revolution in order to mix fully, though consequently increased the shear rate of paddle fore-end, the dirt amount when having increased emulsion polymerisation.
The angle of sweep of top paddle is preferably between the 15-45 degree.
In addition, bottom paddle 13 and top paddle 14 should be installed on the shaft 12 as follows, and promptly the angle of the crossing (α) that forms between the two guarantees that top paddle 14 is gone ahead of the rest and formation 30-90 degree on rotation direction.
Therefore, as the angle of the crossing (α),,, be the angle of bottom paddle 13 and 14 formation of top paddle about connecting the straight line of shaft 12 and bend 18 by behind the mode warpage as shown in Figure 4 during the design angle of sweep.In addition, as shown in Figure 5, when after bending, designing the angle of sweep,, be the angle of bottom paddle 13 and 14 formation of top paddle about the tangent line of the circular arc on the shaft 12.
If the angle of the crossing (α) less than 30 degree, the feature of this agitating device of reason then can appear, and promptly flowing of taking place of 2 part paddles is not smooth up and down, and can not improve mixing efficiency fully.
As shown in Figure 1, it is desirable on the blade front end of top paddle 14, form the tabular wing 15 that extends downwards.
The tabular barrier plate 16 substantially parallel with shaft 12 is set on the tank diameter interior sidewall surface of agitating device used in the present invention.
The quantity of barrier plate is not done special restriction, but the most handy usually 1-4 piece, and separates with appropriate intervals.Barrier plate has makes content be changed to the effect of axial flow from circumferencial direction, from the side wall surface to top, is formed by a continuous flat board.The plate width of cloth of barrier plate should be designed to not contact with paddle when paddle is rotated, and the plate width of cloth should be according to the suitably decision of works such as quantity of tank diameter internal diameter and handicapping baffle plate.The fixing means of barrier plate can adopt the side on the side wall surface that directly is fixed to tank diameter to wash or be fixed to method on the cap of tank diameter.In addition, the thermal medium of predetermined temperature is flow through in the barrier plate, carry out temperature control.Can also use bar-shaped baffle plate, finger-type baffle plate or D type baffle plate etc. replace barrier plate.
When using the cylindrical shape tank diameter, the ratio (L1/D) of the internal diameter (D) of span of bottom paddle 13 (L1) and tank diameter is preferably between 0.4-0.8.If less than 0.4, then in order to reach well-mixed state, just must improve rotating speed, the result is the shear rate that will increase the paddle fore-end, can increase dirt when emulsion polymerisation.If surpass at 0.8 o'clock, and the interval between the barrier plate can be too small, increases partial cut speed, and the possibility that increases dirt when emulsion polymerisation is also arranged.
About the bottom span (L2) of top paddle 14, preferably the bottom paddle span (L1) 70%-100%.If excessive, paddle forms independent flow region up and down.Mixing delays, and is too small, when then liquid viscosity improves, can reduce mixed performance and dispersive property.
About the axial length of bottom paddle 13 and top paddle 14, preferably much more as far as possible to satisfy following 4 important documents.
(ⅰ) be decided to be from the length between the upper end of lower end to the top paddle 14 of bottom paddle 13 maximum liquid dark more than 50%.
(ⅱ) for the blade leading section, the upper end of bottom paddle 13 is positioned at the top, lower end of the tabular wing 15 of top paddle 14.
(ⅲ) for the blade leading section, the length of the above-below direction of top paddle 14 is in 0.8 times to 2.5 times scope of the above-below direction length of bottom paddle 13.
(ⅳ) the above-below direction length on the blade leading section of bottom paddle 13 is below 1.5 times of leaf span (L1).
Above-mentioned each condition all is the conditions of well mixing for realizing, its effect is the revolution that can either suppress paddle, has realized that again necessary mixing disperses, and has suppressed to produce dirt because of shearing simultaneously.
For agitating device of the present invention, when paddle was rotated, the bottom content of tank diameter was radially discharged and is impacted on the side wall surface by court, and can not adhere on the diapire face of tank diameter under the effect of bottom paddle 13.The content on tank diameter top is radially discharged and is impacted on the side wall surface by court under the effect of top paddle 14.Content its flow direction under the effect of barrier plate 16 that impacts is changed into axially from circumferencial direction, both moves to central side from side wall surface, moves down near top paddle 14 again, turns back to again near the bottom paddle 13 of tank diameter 11 bottoms.The sectionalization of the content of convection current is carried out simultaneously with the circulative convection that flows through in the whole groove near paddle the bigger space, finishes mixing at short notice.Thereby, when using such agitating device,, can not give the excessive shearing force of content in the tank diameter, fully the mixed content thing even increase rotation number when stirring yet.
Thereby, owing to can suppress near the shear rate of the paddle front end the liquid level, and content is mixed fully, therefore comparatively suitable to polymerisations such as emulsion polymerisations, and cause the generation of dirt and mix bad dirt generation can suppress because of excessive shearing the time.
Thereby, do not need removing operation that tank diameter is adhered to dirt as frequent clean, do not need coating yet and add antifouling compound, thereby can improve the frequency of utilization of tank diameter, enhance productivity.In addition, also improved the rate of recovery of product of polymerization, dirt can not sneaked in the goods, also can improve Products Quality.
Moreover, upwards reduce gradually for the ease of rotating diameter, preferably top paddle 14 upwards is contraction-like from the bottom at paddle two ends.
If such shape, then mixing efficiency can be higher.
Make whole its of such top paddle rotate diameter upwards reduce from the paddle bottom when top is tapered, the ratio (L3/L2) of the upper end span (L3) of top paddle and the bottom span (L2) of top paddle is preferably in more than 0.6.During less than 0.6, the undercompounding on content top for example, when emulsion polymerisation, causes incorporation time to prolong and because of mixing the bad adverse consequences such as dirt increase that causes.(L3/L2) better scope is 0.7-0.95.
The capacity that drops into the content in the tank diameter is not particularly limited, for example when emulsion polymerisation is used, and the volume V of content and the internal volume V of tank diameter during the polymerization end
oRatio (V/V
o) 0.5-0.95 preferably.
At this moment, when polymerization finished, the upper end of top paddle 14 preferably was immersed in the state of content liquid level below, the difference in height of the upper end of top paddle 14 and content liquid level preferably the tank diameter inside diameter D 30%.If top paddle 14 upper ends and content liquid level difference surpass 30% of tank diameter internal diameter, content is mixed fully, polymerization time can occur and prolong, or the bad situation that causes that dirt increases of contents mixed.
In the present invention, when using agitating device in the emulsion polymerisation system, during to the contents stirred of tank diameter, mixer stirs preferably 0.02-2.0kw/m of needed power to per unit volume
3If not enough 0.02kw/m
3, then mixed content thing fully polymerization time can occur and prolong, or the bad situation that causes that dirt increases of contents mixed.If surpass 2.0kw/m
3, then shearing force increases, and produces dirt.
As mixer per unit volume being stirred needed power, is exactly that the interior content of tank diameter is stirred the net energy of per unit volume.That is, under the state when having adorned content in the state of polymerization tank sky and the tank diameter in the polymerization, it is poor that the rotating drive of variable-speed motor, reductor and mixer self is loaded.
As measuring the method that mixer stirs the power of wanting, the method for the difference that the rotating drive of variable-speed motor, reductor and the mixer self when trying to achieve the state of having adorned content in the state of sky tank diameter and the tank diameter by the current value of drive unit is loaded and the method that the mounting torque meter is tried to achieve on drive unit.
Be set at 0.02-2.0kw/m stirring the power of wanting
3, then according to the capacity of tank diameter and content, suitably established to stir and rotated number, no matter use the tank diameter of much capacity, all can reduce the generation of dirt.The purposes of agitating device of the present invention is not limited to afore mentioned rules and uses in needs carry out any purposes of stir process.Need to carry out the polymerisation in solution of stir process especially, suspension polymerisation when using in the polymerisations such as emulsion polymerisation, improves because of mixed characteristic improves the polymer properties that causes, and all there is good effect aspects such as polymer yield raising.In above-mentioned several performances improve, in emulsion polymerisation, use especially, can reduce the dirt that produces in the tank diameter better.
When using agitating device of the present invention in polymerisation, do not limit that raw material is placed method in the agitating device, add together, add continuously, add in batches, the multistage adds etc. and all can adopt, and also these above-mentioned methods can be combined.
Especially, among the present invention, produce effect for the interpolation of raw materials such as polymerizable monomer in polymeric applications or situation about changing along with following dropping liquid face.
In polymerisation, use when of the present invention, usually the raw material that can in polymerisation, use (initator, agent, other auxiliary agent are adjusted in polymerization for polymerizable monomer (monomer), emulsifying agent).
As polymerizable monomer, the dienes monomer is arranged for instance, vinyl cyanide class monomer, vinyl unsaturated carboxylic acid class monomer, unsaturated carbon dialkylaminobenzoic acid esters monomer, ethylene halide class monomer contains the type siloxane monomer of functional group and succinimide class monomer etc.
As the dienes monomer, 1,3 butadiene, 1,4 butadiene, isoprene, chlorobutadienes etc. can be with the use that combines more than a kind or 2 kinds.
As aromatic vinyl class monomer, be not particularly limited, but can styrene be arranged for instance, AMS, vinyltoluene, divinylbenzenes etc. can be with the use that combines more than a kind or 2 kinds.
As vinyl cyanide class monomer, be not particularly limited, acrylonitrile is arranged for instance, methacrylonitrile, α-Lv Bingxijing, and α-ethyl acrylonitrile can be with a kind or the 2 kinds uses that combines.
As vinyl unsaturated carboxylic acid class monomer, acrylic acid, methacrylic acid, maleic acid, single, the dicarboxylic acids of itaconic acids etc. can be with a kind or the 2 kinds uses that combines.
As the unsaturated carboxylic acid alkyl ester monomer, be not particularly limited, methacrylate is arranged for example, the ethyl propylene acid esters, butylacrylic acid ester, propyl group acrylate, the 2-ethylhexyl acrylate, pi-allyl acrylate, glycidyl acrylate, methyl methacrylate, EMA, butyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, allyl methyl acrylate, glycidyl methacrylate, a kind or the 2 kinds use that combines.
Type siloxane monomer as containing the functional group has tetraethoxysilane for example.γ metering system oxygen propyl group dimethoxy methyl-monosilane, octamethylcy-clotetrasiloxane etc. also can be with a kind or the 2 kinds use that combines.
As ethylene halide class monomer, be not particularly limited, vinyl chloride is arranged for example, vinylidene chloride etc., a kind or the 2 kinds use that combines.
As succinimide class monomer, be not particularly limited, succinimide is arranged for example, N-phenyl succinimide, N-cyclohexyl succinimide, N-citraconic acid imines etc. can be with a kind or the 2 kinds use that combines.
The monomer that uses in the polymerisations such as the ethene beyond above-mentioned monomer, propylene, vinyl acetate, vinylpyridine all can use.
In addition, also can with divinylbenzene, 1,3-butylene dimethylacrylate, the allyl methyl acrylate, the crosslinking agent of glycidyl methacrylate etc., thio-alcohol, the chain-transferring agent of terebene class uses simultaneously.
Polymerization initiator also is not particularly limited, uses water-soluble or oil-soluble peracetic dithionite, peroxide, azo-compound etc.For example, can use potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, the diisopropyl benzene hydroperoxides are to alkane hydroperoxides in the Meng, cumene hydroperoxide, tert-butyl hydroperoxide, the methylcyclohexyl hydroperoxides, 1,1,3,3-tetramethyl butyl hydroperoxides, 1,1,3,3-tetramethyl butyl peroxide-2-Ethylhexyl Alcohol, t-butyl peroxy 3,5,5-trimethyl hexanol, benzoyl peroxide, 2,2-azodiisobutyronitrile etc.In addition, also can use the so-called reducing agent that has cooperated reducing agents such as rongalite as initator.
Emulsifying agent when carrying out emulsion polymerisation is not done special restriction, and the alkali metal salt of sulfonic acid such as the alkali metal salt of senior aliphatic acid such as homogenizing roseolic acid, oleic acid, stearic acid, DBSA will not be used in combination more than a kind or 2 kinds.
Adjust agent as polymerization, be not particularly limited, can use NaOH, potassium hydroxide, the pH of sodium acid carbonate etc. adjusts the chelating agent of agent or ethylene diamin(e) four sodium acetates etc., electrolyte etc.
The present invention is especially with emulsion polymerisation manufactured butadiene rubber, SBR styrene butadiene rubbers, when carrying out glycerol polymerization with emulsion polymerization when acrylic rubber, the rubber-like polymer of silica type rubber etc. and in the presence of above-mentioned rubber-like polymer etc., dirt reduces the effect highly significant.
Embodiment
Below, specify the present invention with reference to embodiment.
In addition, said " total dirt generating capacity " is to use the polymer total amount is represented attached to tank diameter internal face, paddle, dirt on the barrier plate and the value of not passing through the total dry weight of polymer agglutinator of 140 orders (aperture 106 μ m).So-called " near the dirt amount of adhering to the liquid level " is to use the polymer total amount is represented the total amount value of adhering to dirt on paddle, the tank diameter internal face in final liquid level ± 20cm scope.Mixer stirs required power to per unit volume among the embodiment, tries to achieve by the current value of drive unit.
<ABS?BLX>
Embodiment 1
On as shown in Figure 1, that have shaft 12 and paddle, side wall surface in tank diameter 11, set in the stainless steel tank diameter 11 of 2 barrier plates 16, deionized water 150 weight portions of packing into, roseolic acid potassium 1 weight portion, potassium oleate 1 weight portion, formaldehyde sodium sulfoxylate 2 water and thing 0.4 weight portion, sodium sulphate 0.1 weight portion, uncle-lauryl mercaptan 0.3 weight portion, hydroperoxides diisopropyl benzene 0.5 weight portion, 1,3-butadiene 26.2 weight portions, and styrene 1.4 weight portions begin to stir and be warmed up to 57 ℃.At this moment, the upper end of top paddle 14 is positioned on the liquid level.
Then, in the temperature-rise period, add sodium pyrophosphate 0.2 weight portion, ferrous sulfate 7 water salt 0.003 weight portion, the beginning polymerization, be warming up to 57 ℃ of polymerization temperatures after, drip the monomer that forms by 1,3-butadiene 68.8 weight portions and styrene 3.6 weight portions continuously.Then, reach at 40% o'clock, add n-octyl mercaptan 0.3 weight portion, afterwards, kept 8 hours, in tank diameter, take out at polymerisation conversion.In polymerization at the end, the upper end of top paddle is immersed under the liquid level.
Stirring revolution in the polymerization is set in conjunction with stirring required drive shown in the table 1, carries out according to 3 conditions respectively.Table 1 illustrates the relation that mixer under each condition stirs required drive and dirt generating capacity.
The each several part value that Fig. 1 illustrates the stainless steel agitating device is as follows:
Tank diameter internal diameter (D): 350mm
The paddle angle of the crossing (α) up and down: 60 degree
Bottom paddle span (L1): 210mm
Paddle angle of sweep (β), bottom: 28 degree
Top paddle span (L2): 190mm
Top paddle span (L3): 170mm
Paddle angle of sweep, top (γ): 28 degree
[comparative example 1]
As shown in Figure 6, except the angle of sweep (γ) with top paddle 24 is made as 0 degree (not establishing the angle of sweep), top paddle span (L3) is beyond the 190mm, and other is identical with embodiment 1.
Stirring revolution in the polymerization is set in conjunction with stirring required drive shown in the table 1, carries out according to 3 conditions respectively.Table 1 illustrates the relation that mixer under each condition stirs required drive and dirt generating capacity.
Table 1
| Stir required drive (kw/m 3) | Revolution (rpm) | Total dirt generating capacity (ph) | Attached near the dirt amount (phr) the liquid level | ||
| Embodiment 1 | Condition 1 | ?0.10 | ?75 | ?0.10 | ?0.02 |
| Condition 2 | ?0.40 | ?101 | ?0.08 | ?0.02 | |
| Condition 3 | ?0.80 | ?160 | ?0.12 | ?0.03 | |
| Comparative example 1 | Condition 1 | ?0.10 | ?75 | ?0.15 | ?0.09 |
| Condition 2 | ?0.40 | ?100 | ?0.13 | ?0.07 | |
| Condition 3 | ?0.80 | ?157 | ?0.19 | ?0.12 | |
＜ABS grafting 〉
[embodiment 2]
Agitating device is identical with the stainless steel agitating device of use among the embodiment 1, rubber-like polymer latex 250 weight portions that in embodiment 1, are made into (in rubber-like polymer, 100 weight portions), water 150 weight portions, glucose 0.6 weight portion, sodium pyrophosphate 0.1 weight portion, ferrous sulfate 7 water salt 0.01 weight portion are packed in the above-mentioned agitating device, and begin to stir.At this moment, the upper end of top paddle is positioned on the liquid level.
Then, after carrying out nitrogen replacement, be warming up to 60 ℃, in 200 minutes, drip the monomer mixture that forms by fine 30 weight portions of propylene, styrene 70 weight portions, uncle-dodecyl mercaptans 1.2 weight portions and cumene hydroperoxide 0.3 weight portion, during this, interior temperature control is added cumene hydroperoxide 0.12 weight portion again after 65 ℃ of droppings finish, after keeping 1 hour under 70 ℃, in tank diameter, take out again.When polymerization finishes, under the upper end immersed in liquid level of top paddle.
Stirring revolution in the polymerization is set in conjunction with stirring required drive shown in the table 2, carries out according to 4 conditions respectively.Table 2 illustrates the relation that mixer under each condition stirs required drive and dirt generating capacity.
[comparative example 2]
Except using the stainless steel agitating device identical, carry out the research identical with embodiment 2 with use in the comparative example 1.
Stirring revolution in the polymerization is set in conjunction with stirring required drive shown in the table 2, carries out according to 4 conditions respectively.Table 2 illustrates the relation that mixer under each condition stirs required drive and dirt generating capacity.
Table 2
| Stir required drive (kw/m 3) | Revolution (rpm) | Total dirt generating capacity (phr) | Attached near the dirt amount (phr) the liquid level | ||
| Embodiment 2 | Condition 1 | ?0.05 | ?65 | ?0.18 | ?0.04 |
| Condition 2 | ?0.20 | ?90 | ?0.10 | ?0.03 | |
| Condition 3 | ?0.40 | ?110 | ?0.18 | ?0.05 | |
| Condition 4 | ?0.80 | ?162 | ?0.60 | ?0.16 | |
| Comparative example 2 | Condition 1 | ?0.05 | ?63 | ?0.24 | ?0.14 |
| Condition 2 | ?0.20 | ?89 | ?0.12 | ?0.08 | |
| Condition 3 | ?0.40 | ?109 | ?0.21 | ?0.12 | |
| Condition 4 | ?0.80 | ?159 | ?0.70 | ?0.40 | |
<methablene?S>
Embodiment 3
With tetraethoxysilane 2 weight portions, γ methacryloxypropyl dimethoxy methyl-monosilane 0.5 weight portion and octamethylcy-clotetrasiloxane 97.5 weight portions mix, and obtain mixture of siloxanes 100 weight portions.In deionized water 200 weight portions that dissolved each 1 weight portion of neopelex and DBSA, add above-mentioned hybrid silicone mixture 100 weight portions, after stirring in advance with 10000rpm with homogenizer, with homogenizer emulsification under the pressure of 30Mpa, dispersion, obtain organosiloxane latex.This mixed liquor is packed in the tank diameter, begin to stir.80 ℃ down keep 5 hours after, placed 48 hours down at 20 ℃, with sodium hydrate aqueous solution the pH value of this latex is neutralized 7.4, the end polymerization is taken out polysiloxane rubber-like polymer latex in tank diameter.
Polymer emulsion 33 weight portions of the polysiloxane rubber that obtains (in rubber-like polymer, 10 weight portions) put in the stainless steel agitating device identical with use among the embodiment 1, add polyoxyethylene alkylphenyl ether sulfate salt (flower king's (strain) society's system " Emal NC-35 " 1.4 weight portions again, deionized water 271 weight portions, carry out being warmed up to 50 ℃ behind the nitrogen replacement, adding is by n-butyl acrylate 78.4 weight portions, the mixed liquor that allyl methyl acrylate 1.6 weight portions and tert-butyl hydroperoxide 0.40 weight portion form stirred 30 minutes.Then, add by ferrous sulfate 0.002 weight portion, Calcium Disodium Versenate 0.006 weight portion, the mixed liquor of rongalite 0.26 weight portion and deionized water 5 weight portions, beginning radical polymerization afterwards, kept 2 hours down for 70 ℃ in interior temperature.Then, the mixed liquor that makes tert-butyl hydroperoxide 0.05 weight portion and methyl methacrylate 10 weight portions afterwards, after keeping 4 hours under 70 ℃, takes out from reactor in dripping in 15 minutes under 70 ℃.When polymerization finished, the upper end of top paddle was immersed under the liquid level.
Stirring in the polymerization is rotated and is stirred the required drive setting shown in the number associative list 3, carries out according to 3 conditions respectively.The relation of mixer stirring required drive and dirt generating capacity is shown in Table 3 under each condition.
Comparative example 3
Except that using the stainless steel agitating device identical with use in the comparative example 1,, carry out the research identical with embodiment 3.
Stir required drive shown in the stirring revolution associative list 3 in the polymerization and set, be shown in Table 3 according to 3 conditions relation that under each condition mixer stirs required drive and dirt generating capacity of advancing to record respectively.
Table 3
| Stir required drive (kw/m 3) | Revolution (rpm) | Total dirt generating capacity (phr) | Attached near the dirt amount (phr) the liquid level | ||
| Embodiment 3 | Condition 1 | ?0.05 | ?52 | ?0.33 | ?0.14 |
| Condition 2 | ?0.25 | ?100 | ?0.09 | ?0.03 | |
| Condition 3 | ?0.90 | ?170 | ?0.15 | ?0.05 | |
| Comparative example 3 | Condition 1 | ?0.05 | ?50 | ?0.60 | ?0.36 |
| Condition 2 | ?0.25 | ?98 | ?0.10 | ?0.07 | |
| Condition 3 | ?0.90 | ?170 | ?0.19 | ?0.11 | |
When using agitating device shown in Figure 1 to carry out polymerisation, the agitating device of comparison diagram 6 even under the stirring condition of wide region, also can suppress the generation of dirt, and near the tank diameter wall liquid level and the adhesion amount of shaft significantly reduce especially.
Embodiment 4
Use latex manufacturing installation shown in Figure 7, that on agitating device, connect pre-dispersed machine 24 and this dispersion machine 26.
At first, deionized water 150 weight portions that are dissolved with each 1 weight portion of neopelex and DBSA are packed in the tank diameter 11, begin to stir.The temperature of this aqueous solution is 30 ℃.Supply with down by 2 weight portion tetrem oxosilanes from tank diameter 11 tops at 30 ℃, 0.5 weight portion γ methacryloxypropyl dimethoxy-methyl silane and 97.5 weight portions are by hexamethyl cyclotrisiloxane 3%, octamethylcy-clotetrasiloxane 66%, the annular siloxane mixture that decamethylcyclopentaandoxane 30% and other ring-type dimethyl siloxane 1% are formed, formed mixture of siloxanes 100 weight portions.Stir continuously on the limit, the limit is carried out outer loop by pump 22 with mixed liquor, at first, only make pre-dispersed machine (special machine chemical industry society system, the line style mixer) 24 work are 20 minutes, after the pre-emulsification, pre-dispersed machine 24 and this dispersion machine (go-リ Application society system, pressure type homogenizer) 26 are worked simultaneously carried out emulsification in 1 hour.When pre-dispersed machine 24 and this dispersion machine 26 were started working back 30 minutes simultaneously, in the chuck of tank diameter 11, feed 95 ℃ of hot water, begin to heat up, when the temperature of mixed liquor reaches 80 ℃, the temperature of hot water is become 80 ℃.The temperature of mixed liquor becomes 25 ℃ with the hot water temperature in the chuck after keeping 5 hours under 80 ℃.After 1 hour, stop to stir, latex was placed 48 hours.Stir this latex with agitating device once more, add the aqueous solution 2.6 weight portions of 5% NaOH simultaneously from tank diameter 11 tops, in and DBSA, make the pH value of latex be about 7, polymerization finishes, and makes polysiloxane rubber-like polymer latex.
Do not observe the generation of cullet or dirt.
Comparative example 4
In embodiment 4, except the agitating device that uses Fig. 6 formation, other operation is identical with embodiment 4.Observing the emulsion or the latex that return from tank diameter top in the externally circulation disperses on mixed liquor.And on the inwall of tank diameter gas phase portion, generate the agglutinator shape dirt of polysiloxane rubber.
If use paddle of the present invention or agitating device, for various uses, all can improve mixed characteristic, boost productivity quality and security.
Especially, when in emulsion polymerization, using, owing to can suppress near the liquid level shearing, and abundant mixed content thing, therefore, can suppress to produce dirt and because of mixing the bad generation that causes dirt because of excessive shearing.
Therefore, can avoid continually tank diameter being made washing and cleaning operation, in addition, also not need because of preventing the dirt painting compound, or add other compound for removing dirt.Can improve the frequency of utilization of tank diameter, enhance productivity.Moreover, can improve the rate of recovery of products such as polymer, and, also improve quality of item because there is not dirt.
The present invention can also implement by other various forms under the prerequisite that does not break away from its spirit or principal character.Therefore, the foregoing description is the example that make on the basis with the each point only, can not be as limited explanation.Scope of the present invention is limited by claims.Do not impose any restrictions in this manual.In addition, belong to interior similar distortion of claim scope or change all within the scope of the present invention.
Claims (7)
1. paddle, this paddle have tabular bottom paddle and are positioned at the plate-shaped upper portion paddle of paddle top, said bottom, and both are installed on the shaft with the 30-90 degree angle of the crossing (α),
The bottom paddle has the angle of sweep (β) of 0-60 degree,
The top paddle has the angle of sweep (γ) of 5-60 degree.
2. paddle according to claim 1 is characterized in that above-mentioned top paddle forms the tabular wing that extends downwards on its leading section.
3. paddle according to claim 1 and 2 is characterized in that above-mentioned top paddle reduced from bottom to top, thereby its rotation diameter reduces from bottom to up.
4. agitating device, this agitating device possesses tank diameter, is arranged on barrier plate on this tank diameter internal face and central part vertically is provided with in tank diameter shaft,
Tabular bottom paddle is installed on the shaft and is positioned at and have the plate-shaped upper portion paddle of the 30-90 degree angle of the crossing (α) with respect to this bottom paddle above the paddle of this bottom, wherein
The bottom paddle has the angle of sweep (β) of 0-60,
The top paddle has the angle of sweep (γ) of 5-60 degree, and, form the tabular wing that extends downwards in paddle end, top.
5. agitating device according to claim 4 is characterized in that above-mentioned top paddle reduced from bottom to top, thereby its rotation diameter reduces from bottom to up.
6. the manufacture method of a polymer is characterised in that, uses the agitating device of claim 4 or 5 records to carry out polymerisation.
7. the manufacture method of an emulsion polymer latexes is characterised in that, uses the agitating device of claim 4 or 5 records to carry out emulsion polymerisation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36193899A JP3533407B2 (en) | 1999-12-20 | 1999-12-20 | Stirrer, stirrer, and method for producing polymer using same |
| JP361938/1999 | 1999-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1318426A true CN1318426A (en) | 2001-10-24 |
| CN1201856C CN1201856C (en) | 2005-05-18 |
Family
ID=18475361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001376616A Expired - Lifetime CN1201856C (en) | 1999-12-20 | 2000-12-20 | Stirring arm, stirrer and method of preparing polymer using the stirrer |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3533407B2 (en) |
| KR (1) | KR100638631B1 (en) |
| CN (1) | CN1201856C (en) |
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|---|---|---|---|---|
| JPH0616708A (en) * | 1992-04-28 | 1994-01-25 | Sumitomo Dow Ltd | Production of polymer latex |
| JPH07292002A (en) * | 1994-04-27 | 1995-11-07 | Asahi Chem Ind Co Ltd | Production of polymer latex |
-
1999
- 1999-12-20 JP JP36193899A patent/JP3533407B2/en not_active Expired - Lifetime
-
2000
- 2000-12-09 KR KR1020000075011A patent/KR100638631B1/en active IP Right Grant
- 2000-12-20 CN CNB001376616A patent/CN1201856C/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2001170467A (en) | 2001-06-26 |
| JP3533407B2 (en) | 2004-05-31 |
| KR20010062314A (en) | 2001-07-07 |
| CN1201856C (en) | 2005-05-18 |
| KR100638631B1 (en) | 2006-10-26 |
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Address after: Tokyo, Japan Co-patentee after: Kobelco Eco Solutions Co., Ltd. Patentee after: Mitsubishi Kasei Corporation Address before: Tokyo, Japan Co-patentee before: Kobelco Eco Solutions Co., Ltd. Patentee before: Mitsubishi Reiyon Co., Ltd. |
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Granted publication date: 20050518 |