CN103665214B - The manufacture method of polymkeric substance and the washing unit of polymkeric substance - Google Patents
The manufacture method of polymkeric substance and the washing unit of polymkeric substance Download PDFInfo
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Abstract
The invention provides a kind of manufacture method of polymkeric substance.In order to remove the impurity contained by the polymkeric substance after suspension polymerization efficiently, polymkeric substance is obtained with high harvest yield, in the manufacture method of polymkeric substance of the present invention, comprise: make the polymer suspension after suspension polymerization in water and left standstill, by the first operation that the water layer after being separated polymkeric substance does not remove with not using filter material; Make the polymer suspension obtained by the first operation in water, use filter material to carry out second operation of filtering; With make the polymer suspension obtained by the second operation in water, use filter material to carry out the 3rd operation of filtering; The same washing unit (100) that utilization possesses filter material (10) carries out all operations.
Description
Technical field
The present invention relates to the manufacture method of polymkeric substance and the washing unit of polymkeric substance.
Background technology
In the manufacture method of vinylidene fluoride polymer, the partial fluorine ethylene polymer obtained by suspension polymerization, after polymerization terminates, carries out the washing step utilizing pure water etc. to be cleaned repeatedly, will be attached to the impurity removings such as the organism of polymkeric substance.Then, through dehydration procedure utilization water extracter to carry out and the drying process utilizing drying machine to carry out, reclaimed by as powder.
As the clean method of the polymkeric substance obtained by suspension polymerization, Patent Document 1 discloses the reaction mixture sat that one (a) will be obtained by suspension polymerization, removing aqueous phase, obtain the filter cake of Porous polymer particle, b () is by this filter cake size degradation, left standstill after Porous polymer particle is suspended in water, removing aqueous phase, the c filter cake size degradation of Porous polymer particle that () will obtain, Porous polymer particle is suspended in water, filter material is utilized to filter this Porous polymer particle, the d filter cake size degradation of Porous polymer particle that () will obtain, Porous polymer particle is made to be suspended in organic solvent, filter material is utilized to filter, thus obtain the method for Porous polymer particle.
In patent documentation 2, disclose a kind of filter material as using in the filtration unit for being removed by the impurity in the various fluids such as molten polymer, there is metal and become the stacked and metal net layer laminated sinter of sintering of netted wire netting for fibrous steel fiber and by more than at least two panels by metal wireform, at the surface back side configuration metal net layer laminated sinter of steel fiber and the strainer of one sintering.As mentioned above, as the clean method of the polymkeric substance after suspension polymerization, the method for impurity removing is carried out in the filtration be known to by employing strainer.
Patent documentation 1: Japanese Laid-Open Patent Publication " JP 2009-280760 publication (on December 3rd, 2009 is open) ".
Patent documentation 2: Japanese Laid-Open Patent Publication " JP 2010-75832 publication (on April 8th, 2010 is open) ".
Comprise in the liquid (hereinafter referred to as polymer syrup) of the partial fluorine ethylene polymer after the polymerization obtained by suspension polymerization and contain the residual component such as polymerization starter and auxiliary as impurity.If impurity is directly taken in goods, then can impact the quality characteristic of tone and leachable etc.Therefore, in the manufacture of polymkeric substance, comprise removing the washing step adding pure water etc. for the purpose of impurity and carry out cleaning.Owing to repeatedly repeatedly carrying out water-filling in this washing step, clean and dewater, so spended time.In addition, the loss of polymkeric substance can be produced when dewatering.In addition, if the polymerization starter contained by polymer syrup is active state, then owing to becoming the important factor that impurity generates in slurry, so need to heat-treat for polymer syrup, polymerization starter is made to lose activation.In addition, in the clean method described in patent documentation 1, do not use filter material to remove the operation of water layer and to use filter material to remove the operation of water layer, so waste time and energy owing to adopting different devices respectively.
Summary of the invention
The present invention proposes in view of above-mentioned problem, the object of the invention is to the loss of the polymkeric substance reduced in the matting of polymkeric substance, obtains the polymkeric substance of removing impurity with the short period of time.
The manufacture method of the polymkeric substance that the present invention relates to is for solving above-mentioned problem, it is the manufacture method of the polymkeric substance by suspension polymerization, comprise: make the polymer syrup of the polymkeric substance after containing suspension polymerization suspend in water and be left standstill, with not using filter material by be separated after this polymkeric substance water layer removing the first operation; Make the polymer suspension obtained by above-mentioned first operation in water, use filter material to carry out second operation of filtering; With make the polymer suspension obtained by above-mentioned second operation in water, use filter material to carry out the 3rd operation of filtering; The manufacture method of this polymkeric substance has utilization and possesses the same washing unit of above-mentioned filter material to carry out the formation of the above-mentioned all process steps of the first ~ three.
The present invention plays and shorten the washing step time in the manufacture of polymkeric substance, and reduces this effect of goods recovery loss.
Accompanying drawing explanation
Fig. 1 is the figure of the schematic configuration of the washing unit of the partial fluorine ethylene polymer represented in an embodiment of the invention.
Fig. 2 is the vertical view of the filter material in an embodiment of the invention.
Fig. 3 is the vertical view of the pedestal in an embodiment of the invention.
Fig. 4 is the vertical view of the pressing plate in an embodiment of the invention.
Embodiment
Below, be described in detail for the manufacture method of the polymkeric substance that the present invention relates to and an embodiment of washing unit.Wherein, in the following embodiments, the manufacture method of partial fluorine ethylene polymer and washing unit are described, but the manufacture method of the polymkeric substance that the present invention relates to and washing unit are not limited thereto.In addition, the washing unit of the polymkeric substance that the present invention relates to preferably is applied to the manufacture method of the polymkeric substance that the present invention relates to, but the purposes of washing unit is not limited thereto.
First, the washing unit for the partial fluorine ethylene polymer that can preferably be applied in the embodiment of the manufacture method of partial fluorine ethylene polymer described later is described.
(1. the washing unit of partial fluorine ethylene polymer)
Fig. 1 is the figure of the schematic configuration of the washing unit of the polymkeric substance represented in present embodiment.As shown in Figure 1, the washing unit 100 in present embodiment possesses: rinse bath 50, filter house 20, water shoot 21, filtrate pipe 22, draining pipe valve 23 and filtrate pipe valve 24.
(rinse bath 50)
Rinse bath 50 is the grooves carrying out cleaning that suspended in water by the polymer syrup containing the partial fluorine ethylene polymer after suspension polymerization.The volume of rinse bath 50 is suitably selected according to the amount of the polymer syrup as cleaning object thing.The whipping appts for stirred suspension is provided with in rinse bath 50.Be not particularly limited as whipping appts, such as, the whipping appts possessing propeller blade, blade (paddle) blade, anchor formula (anchor) blade and turbine blade etc. can be used.
Heating unit for heating the solution in rinse bath 50 is provided with to rinse bath 50.As long as the device that can heat the solution in rinse bath 50, the kind of heating unit is not particularly limited, and can use known heating unit.
(filter house 20)
Filter house 20 is the parts for filtering the suspension in rinse bath 50, is arranged on the bottom of rinse bath 50.Filter house 20 is configured to comprise pressing plate 3, filter material 10 and pedestal 4 in order from upper.
［ filter material 10 ］
Filter material 10 is to the actual cancellous parts filtered of the suspension in rinse bath 50.By using filter material 10 pairs of suspension to filter, the polymkeric substance caught in suspension is stayed in rinse bath 50, on the other hand, is discharged by the water containing impurity etc. as filtrate.
Fig. 2 is the vertical view of filter material 10.As shown in Figure 2, communicating pores 5 is provided with in the central portion to filter material 10.By arranging communicating pores 5 to filter material 10, filtration ground can not carried out to the liquid composition in rinse bath 50 yet, be not namely discharged to the outside of washing unit 100 from the mesh portion of filter material 10 with passing through.As long as the aperture of communicating pores 5 suitably determines according to the scale of device.
Filter material 10 in present embodiment is stacked multiple wire nettings, and the sintered compact it being sintered and obtains.
Although do not limit stacked metal netting index, preferably stacked more than 3 layers wire nettings, more preferably stacked more than 7 layers.By having such lit-par-lit structure, enough carrying capacitys can be obtained relative to pressure when filtering.In addition, compared with being formed the situation of fibrous steel fiber with use metal, the cleaning of the filter material 10 after can easily using.Therefore, can repeatedly Reusability.
As the kind of the metal of each wire netting, be not particularly limited, such as, can enumerate stainless steel.In addition, stacked wire netting can mesh size mutually different.When using the wire netting of different mesh size, preferably by metal mesh arrangement thinner for mesh to inside.In addition, the mesh size of each wire netting suitably can be selected according to the particle diameter of the polymkeric substance becoming cleaning object.Such as, when the median diameter of particle is 50 μm ~ 300 μm, preferably in the sintered compact that multiple layer metal net is laminated, the structure of at least 1 use 100 mesh ~ 400 mesh in wire netting, more preferably be the structure of 100 mesh ~ 400 meshes as the wire netting (when stacked even number sheet wire netting, being at least 1 of the two panels being arranged in inner side) of the layer being positioned at inner side.In addition, as the wire netting of layer in addition, preferably use the structure of 10 mesh ~ 400 meshes.
By using such sintered compact as filter material 10, the filtration resistance of suspension can be reduced, shortening filtration time.
In addition, in the present embodiment, filter material 10 also possesses porous plate (not shown) at the lower surface of the sintered compact of above-mentioned wire netting.Porous plate is provided with to the communicating pores of equal size in the position identical with communicating pores 5, is also provided with the multiple communicating poress (little communicating pores) less than communicating pores 5 in the position different from communicating pores 5.By arranging porous plate, filter material 10 can be protected further not by the impact of pressure when filtering, the wearing quality of filter material 10 can be improved.In addition, little communicating pores is provided with more than 100.Therefore, filter pressure can not rise because of the existence of porous plate.
In addition, as described later, pedestal 4 is provided with projection 8.Therefore, if filter material 10 directly contacts with pedestal 4, then filter material 10 can produce distortion because of pressure when filtering and this projection, makes filter material 10 easily damaged.Therefore, by arranging porous plate, filter material 10 can be prevented to be out of shape, to can further improve wearing quality.
The size of the little communicating pores of porous plate is such as 5mm ~ 15mm.
［ pedestal 4 ］
Pedestal 4 is the parts for loading filter material 10, is located at the bottom of filter material 10.The size of preferred pedestal 4 and the equal and opposite in direction of filter material 10.
Fig. 3 is the vertical view of pedestal 4.The central part of the position, the i.e. pedestal 4 that overlap with the communicating pores 5 of filter material 10 in pedestal 4, is provided with the water vent (first row water hole) 7 of being discharged by the liquid composition in rinse bath 50.The aperture of the water vent 7 of pedestal 4 is equal with the aperture of the communicating pores 5 of filter material 10.In addition, in the position do not overlapped with the communicating pores 5 of filter material 10, multiple filtrate hole (second row water hole) 6 of the filtrate after being filtered by filter material 10 being discharged are to be located at equal intervals on the same circle centered by water vent 7.Wherein, in the present embodiment, filtrate hole 6 is provided with four around water vent 7, but is not limited thereto.In addition, when having two or more filtrate hole 6, in order to balancedly filtrate can be discharged from filter material 10 entirety, preferably by the position of filtrate hole 6 the entirety in the face of filter material 10 unbiased be distributed.
Water vent 7 is connected with the water shoot 21 for the draining from water vent 7 being discharged to the outside of rinse bath 50.In addition, water shoot 21 possesses opening and closing water discharge valve 23 freely.In addition, filtrate hole 6 is connected with the filtrate pipe 22 for the filtrate from filtrate hole 6 being discharged to the outside of rinse bath 50.Filtrate pipe 22 possesses opening and closing filtrate valve 24 freely.
By the opening and closing operations of water discharge valve 23 and filtrate valve 24, the draining in adjustable drain pipe 21 and filtrate pipe 22.When discharging the liquid composition in rinse bath 50, by making water discharge valve 23 "ON", making filtrate valve 24 " closing " and only carrying out draining from water vent 7.That is, liquid composition can not be discharged from the mesh portion of filter material 10 with passing through.On the other hand, by making water discharge valve 23 " closing ", making filtrate valve 24 "ON", only can carry out draining from filtrate hole 6.The liquid composition of the mesh portion that have passed filter material 10 can be only made to arrive filtrate hole 6.Based on above explanation, when not needing to filter, by making water discharge valve 23 "ON", make filtrate valve 24 " closing ", filtration ground directly liquid effluent composition can not be carried out, when filtering, by making water discharge valve 23 " closing ", make filtrate valve 24 "ON", the filtration utilizing filter material 10 to carry out can be implemented.
In addition, be positioned at the center of the bottom of rinse bath 50, draining is easily concentrated by the communicating pores 5 of filter material 10 and the water vent 7 of pedestal 4, drainage efficiency rises.In addition, when the layer of polymkeric substance suspension being separated into water layer in rinse bath 50 and formed on the top of water layer, when discharging water layer from rinse bath 50, carry out draining from the layer position farthest of distance polymkeric substance.Therefore, it is possible to prevent polymkeric substance be rolled into the current of the water layer of discharge and together flow out with water layer.Thus, the loss of polymkeric substance can be restricted to inferior limit.
The projection 8 of multiple wire of the stream for the formation of water is formed at the upper surface (face of mounting filter material 10) of pedestal 4.Thus, between pedestal 4 and filter material 10, space is formed.In addition, projection 8 is formed on the concentric(al) circles centered by water vent 7, and by the structure interrupted at equal intervals.Such as, on the line two filtrate hole 6 being positioned at symmetric position centered by water vent 7 connected, the projection 8 of wire is interrupted.Thus, water arrives to filtrate hole 6 and becomes smooth and easy.
［ pressing plate 3 ］
Pressing plate 3 is parts of that be provided in the top of filter material 10, fixing filter material 10.By possessing pressing plate 3, filter material 10 can be protected not by the pressure influence produced during communicating pores 5 draining when filtering and via filter material 10.Thus, the wearing quality of filter material 10 can be improved.In addition, to situation about reducing pressure in rinse bath 50, or water is provided in the lower side direction rinse bath 50 of filter material 10, with the direction contrary with when filtering, pressure is applied to filter material 10 upward.By pressing plate 3 being located at the top of filter material 10, filter material can be protected also not affect by such applied pressure upward.As such pressure, can imagine ± the pressure of about 0.1MPa, by arranging pressing plate 3, filter material 10 possesses resistance to pressure for such pressure.
Fig. 4 is the vertical view of pressing plate 3.As shown in Figure 4, pressing plate 3 is metal sheets 9 by with the shape of radial configuration.Wherein, metal sheet 9 is tabular, combines with the state being erected into dull and stereotyped long limit level.The centre portions that metal sheet 9 does not arrive pressing plate 3, the partly formation opening namely overlapped with the communicating pores 5 of filter material 10 and the water vent 7 of pedestal 4.By having such shape, the weight lightness of pressing plate 3 and easy handling can be made, and can with the entirety of uniform pressure pressing filter material 10.Never hinder this viewpoint of filtration employing filter material 10 to set out, the area preferably connected with filter material 10 is little.
To rinse bath 50 be provided with than the top side of filter house 20 in rinse bath 50 for feedwater admission port, top (the second water supply unit) (not shown), this admission port, top is connected with water service pipe (not shown).In addition, be provided with on the lower than filter house 20 for by filter material 10 in rinse bath 50 for feedwater admission port, bottom (the first water supply unit) (not shown), this admission port, bottom is connected with water service pipe 25.The quantity of admission port, top and admission port, bottom is not particularly limited.
As mentioned above; if the filter house 20 of the washing unit of partial fluorine ethylene polymer 100 contains pressing plate 3 on the top of the sintered compact of wire netting as described above; the formation of porous plate is contained in bottom; then due to filter material 10 can be protected not by the pressure influence of positive and negative two sides, so filter material 10 is difficult to impaired.As a result, when Reusability filter material 10, the number of times of Reusability can increase, therefore, it is possible to reduce the replacing number of times of filter material 10, reduce the expense and time labour changed.Thus, can improve in the manufacture of partial fluorine ethylene polymer and manufacture efficiency.
In addition, owing to there is communicating pores 5 on filter material 10 and on pedestal 4, there is water vent 7, and positions different from water vent 7 on pedestal 4 also has filtrate hole 6, so the operation of filter material ground draining can not used continuously and use filter material to carry out the operation of filtering in a device.
(2. the manufacture method of partial fluorine ethylene polymer)
The manufacture method of the polymkeric substance in present embodiment is the manufacture method of the partial fluorine ethylene polymer undertaken by suspension polymerization, comprise and the polymer syrup containing the polymkeric substance after suspension polymerization suspended in water and is left standstill, the first operation of water layer removing will be separated after this polymkeric substance with using filter material; By the polymer suspension that obtained by the first operation in water, filter material is used to carry out second operation of filtering; With the polymer suspension will obtained by the second operation in water, filter material is used to carry out the 3rd operation of filtering; Being for all process steps by adopting the same washing unit possessing above-mentioned filter material to carry out the above first ~ three, by the impurity removing contained by the partial fluorine ethylene polymer after suspension polymerization, obtaining the manufacture method of partial fluorine ethylene polymer.
(polymerization process)
In the present embodiment, carried out the independent polymerization of vinylidene by suspension polymerization, or can with the copolymerization of the monomer of vinylidene copolymerization and vinylidene.
In suspension polymerization, utilize suspension agent make vinylidene separately or with can the monomer of copolymerization together be distributed in aqueous medium, be polymerized under the existence of the polymerization starter in the drop dissolving in generated monomer.In addition, also the molecular weight of telomerized polymer can be carried out for usage chain transfer agent.
As polymerization starter, as long as partial fluorine ethylene polymer can the polymerization starter of suspension polymerization, be not particularly limited, the peroxy dicarbonates such as di-isopropyl peroxydicarbonate and peroxy dicarbonate di-n-propyl ester can be enumerated.
As suspension agent, as long as partial fluorine ethylene polymer can the suspension agent of suspension polymerization, be not particularly limited, the cellulose compound such as methylcellulose gum and Natvosol can be enumerated.
In polymerization process, for the object regulated the molecular weight of the polymkeric substance obtained, also known chain-transfer agent can be used.As chain-transfer agent, such as, vinyl acetic monomer and propyl acetate etc. can be enumerated.
As aqueous medium during polyreaction, pure water etc. can be enumerated.
The condition such as usage quantity, temperature of reaction of the monomer in the polyreaction of partial fluorine ethylene polymer of the present invention, polymerization starter, suspension agent, chain-transfer agent and other auxiliarys is not particularly limited, as long as suitably determine.
In addition, the median diameter of the partial fluorine ethylene polymer particle used in preferred the present invention is more than 50 μm less than 300 μm, is more preferably more than 70 μm less than 250 μm.
(the first operation (front matting))
In this operation, by adding water and stir in the polymer syrup containing the partial fluorine ethylene polymer after suspension polymerization, the suspension agent being attached to polymkeric substance is contacted with added water.Because the proportion of the polymkeric substance after suspension polymerization is less than water, so left standstill after stirring in water, can be separated into layer and the water layer of polymkeric substance, the layer of the polymkeric substance of vinylidene floats on water layer.The suspension agent that polymerization uses and other impurity are in the state being contained in water layer.In this operation, the water layer removing will be so separated after polymkeric substance with using filter material.By the water layer removing after layer that polymkeric substance will be separated, the suspension agent and other impurity that contain in polymer syrup can be removed.
If the suspension agent such as methylcellulose gum and methyl hydroxyethylcellulose being adapted at using in the manufacture of the partial fluorine ethylene polymer undertaken by suspension polymerization is stirred in the water more than 60 DEG C, then easily bubble.Therefore, in this operation, preferably use the water of less than 60 DEG C to stir and clean.Be more preferably the water of more than 20 DEG C less than 60 DEG C, be preferably the water of more than 30 DEG C less than 60 DEG C further.By using the water of less than 60 DEG C, suspension agent can being suppressed to bubble, can preventing because being steeped that the polymkeric substance that is involved in is attached to the top plate portion of rinse bath that cleaning reduces.In addition, the water added to polymer syrup can add after being heated to desired temperature in advance, also can at interpolation post-heating to desired temperature.
The water added to polymer syrup can enumerate deionized water, pure water and distilled water etc., industrial from the view point of cost and obtain difficulty or ease, is particularly preferably deionized water.
As the added water yield, be preferably 1 ~ 5 times of the weight of the polymkeric substance in polymer syrup, be more preferably about 3 times.In addition, speed and the time of repose of stirring are not particularly limited, as long as determine according to the suitable scale manufactured.
This operation can repeatedly be implemented repeatedly before entering into subsequent processing.By repeatedly carrying out, the polymkeric substance that the less purity of impurity is higher can be manufactured.
(the second operation (heat treatment step))
This operation is added water to the polymkeric substance obtained in the first operation and stirs, and makes polymer suspension in water, then after having carried out thermal treatment, uses filter material to carry out the operation of filtering.On the polymkeric substance obtained by the first operation, the polymerization starter that the polymerization being attached with vinylidene uses.Therefore, in this operation, heat-treated before filtering.Thereby, it is possible to make the polymerization starter being attached to polymkeric substance lose activation.Losing the polymerization starter after activation to depart from from polymkeric substance, can be removed in the lump with filtrate by filtering.
In order to heat-treat, the water being heated to desired temperature in advance can be added, or also can be heated to desired temperature after with the addition of water.As long as lose the heat treated temperature of activation for making polymerization starter and the hold-time suitably determines according to the kind of used polymerization starter.Such as, the peroxy dicarbonate di-n-propyl ester of the polymerization starter preferably used in the suspension polymerization of partial fluorine ethylene polymer is known as by losing activation with 80 DEG C of process more than 60 minutes.
From the view point of the heating efficiency in thermal treatment, the temperature of the water preferably added in this operation is more than 70 DEG C, is more preferably more than 90 DEG C, more preferably more than 95 DEG C.In addition, the special upper limit is not had, as long as be less than 100 DEG C.
Deionized water, pure water and distilled water etc. can be enumerated to the water that polymkeric substance adds in this operation, industrial from the view point of cost and obtain ease, be particularly preferably deionized water.
The speed stirred is not particularly limited, as long as determine according to the suitable scale manufactured.
After heat treatment, filter before, also can add water further.The temperature of preferred water is now less than 80 DEG C, is more preferably less than 60 DEG C, most preferably is less than 30 DEG C.By after heat treatment, carry out the interpolation water that takes a step forward that filters, more can be cooled fast to the temperature in subsequent processing.
Then, filter material is used to filter.
This operation repeatedly can be implemented repeatedly before entering subsequent processing.By repeatedly carrying out, the polymkeric substance that the less purity of impurity is higher can be manufactured.
(the 3rd operation (washing step))
This operation is added water to the polymkeric substance obtained by the second operation and stirs, and makes polymer suspension in water, then, uses filter material to carry out the operation of filtering.In this operation, by further cleaning, the impurity cleaning removing residual by not being removed to the second operation.
The water added to polymkeric substance in this operation can enumerate deionized water, pure water, distilled water etc., industrial from the view point of cost or obtain ease, is particularly preferably deionized water.
This viewpoint of the easier stripping of impurity containing organic solvent from aqueous phase, the water preferably added to polymkeric substance in this operation is more than 30 DEG C, is more preferably more than 60 DEG C.In addition, by using the water of more than 60 DEG C, can prevent microorganism and algae etc. from breeding in the device implementing this operation, thus preventing the pollution because microorganism and algae etc. cause.
In this operation, from the downside of filter material, namely the opposition side, side that is captured with polymkeric substance supply water through filter material.Thus, the inverse cleaning of filter material can be carried out, the eyelet blocking of filter material can be eliminated.Therefore, when using identical filter material again to filter, can filter efficiently.
The speed stirred and time of repose are not particularly limited, as long as determine according to the suitable scale manufactured.
Then, filter material is used to filter in the same manner as when the second operation.
This operation can repeatedly be implemented repeatedly before entering subsequent processing.By repeatedly carrying out, the polymkeric substance that the less purity of impurity is higher can be manufactured.
Use same washing unit to implement the first ~ three above-mentioned operation.Such as, can be implemented with same washing unit by using the washing unit 100 of above-mentioned partial fluorine ethylene polymer.In this situation, in the first operation, make draining pipe valve 23 "ON", make filtrate pipe valve 24 " closing ", without filter material 10 mesh portion remove water layer via the communicating pores 5 of filter material 10 and the water vent 7 of pedestal 4.In addition, in the second operation and the 3rd operation, by making draining pipe valve 23 " closing ", making filtrate pipe valve 24 "ON", the filtrate after being filtered being discharged from filtrate hole 6, filter by the mesh portion of filter material 10.Thereby, it is possible to utilize the same rinse bath of same washing unit to implement the first ~ three operation.
After implementing the 3rd operation, by carrying out processed and drying treatment for partial fluorine ethylene polymer, the powder of partial fluorine ethylene polymer can be obtained.
In sum, the manufacture method of the polymkeric substance that the present invention relates to is the manufacture method of the polymkeric substance undertaken by suspension polymerization, comprise: make the polymer syrup of the polymkeric substance after containing suspension polymerization suspend in water and be left standstill, by the first operation that the water layer after being separated this polymkeric substance does not remove with not using filter material; Make the polymer suspension obtained by above-mentioned first operation in water, use filter material to carry out second operation of filtering; With make the polymer suspension obtained by above-mentioned second operation in water, use filter material to carry out the 3rd operation of filtering; Have and use the same washing unit possessing above-mentioned filter material to carry out the formation of the above-mentioned all process steps of the first ~ three.
According to above-mentioned formation, in the first operation, the impurity contained by polymer syrup is contained in water layer mostly, and water is together discharged.In addition, second and the 3rd in operation, due to by filtering impurity contained in water removing, so the time that cleaning spends can be shortened.In addition, owing to removing more impurity in the first operation, so can prevent from eyelet blocking occurs in the filtration after the second operation.And, owing to using same washing unit to carry out all operations, so do not need to shift polymkeric substance in each operation, can clean more rapidly, more easily.
As a mode more specifically of the manufacture method of the polymkeric substance that the present invention relates to, following method can be enumerated: above-mentioned washing unit possesses the pedestal for loading above-mentioned filter material in the bottom of above-mentioned filter material, above-mentioned filter material has for not carrying out make above-mentioned water layer pass through communicating pores with filtering, above-mentioned pedestal has the first row water hole arranged in the position overlapped with above-mentioned communicating pores, with the second row water hole arranged in the position do not overlapped with above-mentioned communicating pores, in above-mentioned first operation, above-mentioned water layer is removed via above-mentioned communicating pores and above-mentioned first row water hole, in above-mentioned second operation and above-mentioned 3rd operation, filtrate after being filtered by above-mentioned filter material is discharged from above-mentioned second row water hole.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, preferably in above-mentioned 3rd operation, from the face water of position supply for making above-mentioned polymer suspension on the lower of the discharge filtrate than above-mentioned filter material.
According to above-mentioned formation, by the downside from filter material for feedwater, the inverse cleaning of filter material can be carried out, eliminate the eyelet blocking of filter material.Therefore, when using identical filter material again to filter, can filter efficiently.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, preferred above-mentioned filter material is laminated multi-layer wire netting and the sintered compact of the wire netting carrying out sintering and obtain.
According to above-mentioned formation, the dispersion of liquid being filtered appropriateness, can filter uniformly.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, the water preferably in above-mentioned first operation is less than 60 DEG C.
According to above-mentioned formation, suspension can be suppressed to bubble.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, preferably in above-mentioned second operation, heat-treat before filtration.
According to above-mentioned formation, the polymerization starter being attached to polymkeric substance can be made to lose activation, dissociate from polymkeric substance.Therefore, can by polymerization starter contained in polymer syrup removing.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, the water preferably in above-mentioned 3rd operation is more than 30 DEG C.
According to above-mentioned formation, the impurity containing organic solvent in aqueous phase can be made to be easier to stripping.
In addition, in the manufacture method of the polymkeric substance that the present invention relates to, preferably at least one operation in above-mentioned first operation, above-mentioned second operation and above-mentioned 3rd operation is carried out repeatedly continuously repeatedly.
According to above-mentioned formation, the polymkeric substance that the less purity of impurity is higher can be manufactured.
The washing unit that the present invention relates to possesses rinse bath, filter material, the washing unit of polymkeric substance of the pedestal for loading above-mentioned filter material that arranges in the bottom of above-mentioned filter material, wherein, above-mentioned filter material has the communicating pores for not carrying out making with filtering the liquid composition of cleaned material to pass through, and above-mentioned pedestal has the first row water hole arranged in the position overlapped with above-mentioned communicating pores and the second row water hole arranged in the position do not overlapped with above-mentioned communicating pores.
According to above-mentioned formation, when not filtering, can via the first row water hole liquid effluent composition of the communicating pores of filter material from pedestal, when filtering, can through the second row water hole liquid effluent composition of filter material from pedestal.Therefore, it is possible to realize filtration treatment and do not carry out filtering the drainage sunk well of ground draining in same rinse bath.
In addition, the washing unit that preferably the present invention relates to also possesses: from the side being provided with above-mentioned pedestal of above-mentioned filter material via above-mentioned filter material in said washing groove for the first water supply unit of feedwater and from above-mentioned filter material with the opposition side, side being provided with above-mentioned pedestal in said washing groove for the second water supply unit fed water.
According to above-mentioned formation, not only from the top of rinse bath, also can feed water from the bottom of rinse bath.Therefore, after having carried out filtration treatment, supplied feedwater from the downside of filter material, the inverse cleaning of filter material can have been carried out.Thus, the eyelet blocking of filter material can be eliminated.Thus, when using identical filter material again to filter, can filter efficiently.
In addition, the washing unit that preferably the present invention relates to also possesses the pressing plate for pressing above-mentioned filter material on the top of above-mentioned filter material.
According to above-mentioned formation, filter material can be protected by the impact on filter material and down applied pressure upward.
In addition, in the washing unit that the present invention relates to, preferred above-mentioned pressing plate is metal sheet by with the shape of radial configuration.
According to above-mentioned formation, the weight of pressing plate and easy handling can be alleviated, and with the entirety of uniform pressure pressing filter material.
In addition, in the washing unit that the present invention relates to, preferred above-mentioned filter material is laminated multi-layer wire netting and carries out the sintered compact of the wire netting sintered.
According to above-mentioned formation, the dispersion of liquid being filtered appropriateness, can filter uniformly.
In addition, in the washing unit that the present invention relates to, preferred above-mentioned filter material is stacked more than 3 layers wire nettings and carries out the sintered compact of the wire netting sintered.
According to above-mentioned formation, enough carrying capacitys can be obtained relative to pressure when filtering.In addition, the cleaning of the filter material after can easily using.Therefore, can repeatedly Reusability.
In addition, in the washing unit that the present invention relates to, preferred above-mentioned filter material also possesses at the lower surface of the sintered compact of above-mentioned wire netting the porous plate being formed with multiple hole.
According to above-mentioned formation, filter material can be prevented to be out of shape, improve the wearing quality of filter material further.
In addition, in the washing unit that the present invention relates to, preferred above-mentioned communicating pores and above-mentioned first row water hole are positioned at the center of the bottom of said washing groove.
According to above-mentioned formation, draining can be made to be easy to concentrated, improve drainage efficiency.
In addition, the washing unit that the present invention relates to preferably also possesses for the heating unit heated in said washing groove.
According to above-mentioned formation, when needing to implement heat treated to the solution in rinse bath, the solution in rinse bath can be heated to desired temperature.
Below show embodiment, embodiments of the present invention are illustrated in greater detail.Certainly, the present invention is not limited to following embodiment, certainly can adopt in various manners for discreet portions.Further, the present invention is not limited to above-mentioned embodiment, the scope represented by claim can carry out various change, suitably combines and the embodiment obtained is also contained in technical scope of the present invention about technique means disclosed in each.In addition, the document recorded in this specification sheets is all quoted as reference.
[embodiment]
(embodiment 1)
To internal volume 10m
3polymerization tank load 6,091kg water, 100kg methylated cellulose aqueous solution (methyl cellulose concentration 1.43 quality %), 2,850kg vinylidene, 17.2kg peroxy dicarbonate di-n-propyl ester, 35.1kg vinyl acetic monomer, carried out the suspension polymerization of 11 hours with 25 DEG C.The cleaning of the partial fluorine ethylene polymer after polymerization uses to be had the same washing unit formed to carry out with the washing unit 100 represented by above-mentioned embodiment.Therefore, corresponding parts are added suitable unit number to illustrate.
(filter material)
Employ from top the sintered compact of the stainless steel wire netting of the SUS304/SUS316L being 20,30,60,200,30 and 20 meshes in order.Wherein, porous plate is equipped with in the bottom of filter material.
First, after polymerization terminates, polymer syrup is transplanted on the rinse bath 50 of washing unit.Then, the first ~ three operation shown below is carried out.
(the first operation)
Stir polymer syrup, and with the addition of 10, the 610kg water of 30 DEG C.After interpolation, stop stirring and leaving standstill 50 minutes, be separated into the layer of water layer and polymkeric substance.Next, filter material 10 ground is not used to discharge water layer through water vent 7 and the water shoot 21 that is connected with water vent 7 from the bottom of rinse bath 50.
(the second operation)
The polymkeric substance remained in rinse bath 50 after first operation is stirred, and with the addition of 3, the 821kg water of 60 DEG C.Then, the suspension in rinse bath 50 be warmed up to 98 DEG C further and keep 90 minutes.Then, with the addition of 11, the 734kg water of 30 DEG C.After interpolation, stir, and use filter material 10 pairs of polymkeric substance to filter, fluid apertures 6 and the filtrate pipe 22 that is connected with filtrate hole 6 discharge filtrate from the bottom of rinse bath 50 after filtration.
(the 3rd operation)
Stirred by the polymkeric substance remained in rinse bath 50 that filter material 10 catches in the second operation, and, with the addition of 14, the 433kg water of 60 DEG C from the bottom of rinse bath 50.Stir after interpolation, and use filter material 10 pairs of polymkeric substance to filter, fluid apertures 6 and the filtrate pipe 22 that is connected with filtrate hole 6 discharge filtrate from the bottom of rinse bath 50 after filtration.
(dehydrating operation)
Utilize centrifuge to dewater to the water contained by the polymkeric substance obtained after having carried out the 3rd operation, and with 80 DEG C of dryings 1.4 hours, obtain 2,613kg partial fluorine ethylene polymer.The logarithmic viscosity number (making the log viscosities of the solution of 4g polymer dissolution in 1 liter of DMF at 30 DEG C) of the partial fluorine ethylene polymer obtained is 1.1dl/g.In addition, the median diameter of the particle of the partial fluorine ethylene polymer obtained is 160 μm.
(embodiment 2)
Except repeatedly carrying out three the first operations continuously in embodiment 1, after then carrying out the second operation, repeatedly carry out continuously, beyond two order three operations, having carried out operation similarly to Example 1.As a result, 2,353kg partial fluorine ethylene polymer is obtained.In addition, the result measured aberration (b value) is b value is+1.89.Wherein, b value is by by dried partial fluorine ethylene polymer powder, with 240 DEG C of heating and meltings 10 minutes, the compressing tablet of the 50mm × 50mm that is shaped × 3mm measured.The mensuration of b value is by being put into the opening portion of colour-difference meter (Japanese electric look industry (strain) ZE2000 processed) and measuring tone to carry out by the center of compressing tablet.Wherein, the b value used in the present embodiment is the b value in L*a*b* color specification system.
(comparative example 1)
Attempt replacing in the first operation of embodiment 1 discharging water layer from water vent 7 and using filter material 10 pairs of polymkeric substance to filter in the same manner as the second operation, discharged filtrate from filtrate hole 6.As a result, can not filter completely, after the second operation cannot be entered into due to the mesh of polymer plugging filter material 10.
(comparative example 2)
Except in the 3rd operation of embodiment 1, replace and use filter material 10 pairs of polymkeric substance to filter, filtrate is discharged from filtrate hole 6, and leave standstill for some time afterwards in suspension, be separated into the layer of water layer and polymkeric substance in the same manner as the first operation, do not carry out discharging beyond water layer from water vent 7 with filtering, carried out operation similarly to Example 1.As a result, 2,290kg partial fluorine ethylene polymer is obtained.In addition, be b value to the result of b pH-value determination pH be+2.99.
(comparative example 3)
Except in the second operation of embodiment 1, replace and use filter material 10 pairs of polymkeric substance to filter, filtrate is discharged from filtrate hole 6, and leave standstill for some time afterwards in suspension, be separated into the layer of water layer and polymkeric substance in the same manner as the first operation, do not carry out discharging beyond water layer from water vent 7 with filtering, carried out operation similarly to Example 1.As a result, 2,333kg partial fluorine ethylene polymer is obtained.
Above result is generalized into table 1.
[table 1]
Industrial utilizability
The present invention can utilize in the manufacture of the partial fluorine ethylene polymer by suspension polymerization.
Description of reference numerals
3-pressing plate; 4-pedestal; 5-communicating pores; 6-filtrate hole; 7-water vent; 8-projection; 9-metal sheet; 10-filter material; 20-filter house; 21-water shoot; 22-filtrate pipe; 23-draining pipe valve; 24-filtrate pipe valve; 25-water service pipe; 50-rinse bath; 100-washing unit.
Claims (16)
1. a manufacture method for polymkeric substance, is the manufacture method of the polymkeric substance by suspension polymerization, it is characterized in that, comprising:
Make the polymer syrup of the polymkeric substance after containing suspension polymerization suspend in water and be left standstill, with not using filter material by be separated after this polymkeric substance water layer removing the first operation;
Make the polymer suspension obtained by above-mentioned first operation in water, use filter material to carry out second operation of filtering; With
Make the polymer suspension obtained by above-mentioned second operation in water, use filter material to carry out the 3rd operation of filtering;
Utilize the same washing unit possessing above-mentioned filter material to carry out the above-mentioned all process steps of the first ~ three;
Above-mentioned washing unit possesses the pedestal for loading above-mentioned filter material in the bottom of above-mentioned filter material,
Above-mentioned filter material has for not carrying out make above-mentioned water layer pass through communicating pores with filtering,
Above-mentioned pedestal has the first row water hole arranged in the position overlapped with above-mentioned communicating pores and the second row water hole arranged in the position do not overlapped with above-mentioned communicating pores,
In above-mentioned first operation, remove above-mentioned water layer via above-mentioned communicating pores and above-mentioned first row water hole,
In above-mentioned second operation and above-mentioned 3rd operation, the filtrate after being filtered by above-mentioned filter material is discharged from above-mentioned second row water hole.
2. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
In above-mentioned 3rd operation, from the face water of position supply for making above-mentioned polymer suspension on the lower of the discharge filtrate than above-mentioned filter material.
3. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
Above-mentioned filter material is laminated multi-layer wire netting and carries out the sintered compact of the wire netting sintered.
4. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
Water in above-mentioned first operation is less than 60 DEG C.
5. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
In above-mentioned second operation, heat-treat before filtration.
6. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
Water in above-mentioned 3rd operation is more than 30 DEG C.
7. the manufacture method of polymkeric substance according to claim 1, is characterized in that,
At least one operation in above-mentioned first operation, above-mentioned second operation and above-mentioned 3rd operation is carried out repeatedly continuously repeatedly.
8. a washing unit for polymkeric substance, being possess rinse bath, filter material, the washing unit of polymkeric substance of the pedestal for loading above-mentioned filter material that arranges in the bottom of above-mentioned filter material, it is characterized in that,
Above-mentioned filter material has the communicating pores for not carrying out making with filtering the liquid composition of cleaned material to pass through,
Above-mentioned pedestal has the first row water hole arranged in the position overlapped with above-mentioned communicating pores and the second row water hole arranged in the position do not overlapped with above-mentioned communicating pores.
9. the washing unit of polymkeric substance according to claim 8, is characterized in that,
Also possess: from the side being provided with above-mentioned pedestal of above-mentioned filter material via above-mentioned filter material in said washing groove for the first water supply unit of feedwater and from above-mentioned filter material with the opposition side, side being provided with above-mentioned pedestal in said washing groove for the second water supply unit fed water.
10. the washing unit of polymkeric substance according to claim 8, is characterized in that,
The pressing plate for pressing above-mentioned filter material is also possessed on the top of above-mentioned filter material.
The washing unit of 11. polymkeric substance according to claim 10, is characterized in that,
Above-mentioned pressing plate is metal sheet by with the shape of radial configuration.
The washing unit of 12. polymkeric substance according to claim 8, is characterized in that,
Above-mentioned filter material is laminated multi-layer wire netting and carries out the sintered compact of the wire netting sintered.
The washing unit of 13. polymkeric substance according to claim 8, is characterized in that,
Above-mentioned filter material is stacked more than three layers wire nettings and carries out the sintered compact of the wire netting sintered.
The washing unit of 14. polymkeric substance according to claim 12 or 13, is characterized in that,
Above-mentioned filter material also possesses at the lower surface of the sintered compact of above-mentioned wire netting the porous plate being formed with multiple hole.
The washing unit of 15. polymkeric substance according to claim 8, is characterized in that,
Above-mentioned communicating pores and above-mentioned first row water hole are positioned at the center of the bottom of said washing groove.
The washing unit of 16. polymkeric substance according to claim 8, is characterized in that,
Also possess for the heating unit heated in said washing groove.
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| JP2012196660 | 2012-09-06 | ||
| JP2012-196660 | 2012-09-06 | ||
| JP2013117331A JP2014065888A (en) | 2012-09-06 | 2013-06-03 | Production method of polymer and washing equipment of polymer |
| JP2013-117331 | 2013-06-03 |
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| CN1972968A (en) * | 2004-06-23 | 2007-05-30 | 埃克森美孚化学专利公司 | Methods for separating slurry components |
| CN101018595A (en) * | 2004-09-15 | 2007-08-15 | 株式会社钟化 | Process for production of suspensions, solution, or dispersions |
| CN101624432A (en) * | 2009-08-05 | 2010-01-13 | 上海三爱富新材料股份有限公司 | Method for reducing impurity content in fluorine-containing polymer |
| CN203419865U (en) * | 2012-09-06 | 2014-02-05 | 株式会社吴羽 | Polymer cleaning device |
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| CN1972968A (en) * | 2004-06-23 | 2007-05-30 | 埃克森美孚化学专利公司 | Methods for separating slurry components |
| CN101018595A (en) * | 2004-09-15 | 2007-08-15 | 株式会社钟化 | Process for production of suspensions, solution, or dispersions |
| CN101624432A (en) * | 2009-08-05 | 2010-01-13 | 上海三爱富新材料股份有限公司 | Method for reducing impurity content in fluorine-containing polymer |
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