The material mixer that is used for high temperature difference quick reaction
Technical field
The utility model relates to a kind of material mixer of high temperature difference quick reaction, is specially adapted to NMP-CaCl
2Blender when producing the reaction of PPTA resin initial mixing continuously for solvent.
Background technology
Nineteen thirty-five, du pont company scientist Carothers utility model fatty polyamide fiber (be polyhexamethylene adipamide<nylon 66〉fiber), from then on, for being applied to industrial circle, Fypro opened up new world, wherein delivered compelling high-performance Fanglun 1414 in 1966 with E.I.Du Pont Company, its formal commodity are by name
(China is called for short p-aramid fiber, Fanglun l414 and aramid fiber II).Because of it has high strength, high-modulus and characteristic such as resistant to elevated temperatures, be widely used in tire cord, high strength rigging, high-pressure bottle shell, automobile wearing piece at present, build geotechnological material, replace the various reinforced composites, conveyer belt, extraordinary canvas of iron and steel etc.At military aspect as making flak jackets, the helmet, tub, armour plate, radar installations outer cover etc.Because its purposes is very extensive, once is called as " all-round fibre ", existing at present 170 multiple uses.
From E.I.Du Pont Company in 1971 finish trial production equipment (100~200t/a) produce since, through repeatedly expanding production and joint, E.I.Du Pont Company at present
Production capacity has surpassed 30,000 t/a.Japan Supreme Being people company has just begun to produce high-intensity copolymerization para-aramid fiber in Guia Hill factory, at the Twaron fiber of the Dutch Aksu of purchase company with after repeatedly expanding production, has reached 2.5 ten thousand t/a at present.This two company has occupied 98% of para-aramid fiber output in the world.
Research and develop some other fiber company that also has of contraposition aromatic polyamide the same period, do not high, dissolving aspect and can not select difficulty such as qualified solvent and stopped research because produce high molecular relative molecular weight continuously mostly.
Obtain the resin of high inherent viscosity, HMW, two monomers of the product p-aramid fiber resin of will seeking survival instantaneous time at low temperatures are that proportioning mixes with the precise chemical structure stoichiometric coefficient, just relate to the blender that mixes two monomers and will address this problem.Though China since the eighties in 20th century also the research of para-aramid fiber, aspect resin polymerization, obtained certain progress at that time, but in solvent and cosolvent, be to enter into polymer reactor after the mixing of proportioning continous-stable just with the precise chemical structure stoichiometric coefficient because never find two monomers that suitable mixing apparatus makes reaction, thereby cause the resin properties viscosity of producing inhomogeneous, make the fracture strength coefficient of dispersion of fiber very big, can not reach instructions for use.
The rational blender of project organization is difficulty relatively, mainly contains following reason.The one, make two monomers is that proportioning is mixed with the stoichiometric coefficient, just require two monomers be liquid or one for liquid another for molten state so that accurate measurement mixes to guarantee the balance of stoichiometric coefficient, so just to be beneficial at short notice.At present because the PPTA resin with NMP-CaCl
2To solvent, but discover paraphthaloyl chloride and NMP-CaCl
2Solvent can react at a certain temperature, though such reaction trace also can cause final molecular resin amount not high, can only be that p-phenylenediamine (PPD) is dissolved in NMP-CaCl therefore
2Exist with liquid form in the system, and paraphthaloyl chloride exists with the molten state form; Two is to undergo phase transition in the fast especially and course of reaction of two monomer reaction speed (promptly to become gel state very soon from liquid state, react again become after a period of time solid-state), so require two monomers to mix and in time remove within a short period of time, otherwise the overstand polymer will exist with gel form and be difficult to flow, though also have material time of staying in blender short but resin still has small amount of polymer exists with little gel form, so just be easy to be bonded on the mixer wall, make reaction can carry out continuously and stably blowing and sending to reactor off and further react with regard to needing in time will to stick on material on the mixer wall; The 3rd, carry out at low temperatures during for two monomer initial mixing reactions of rate request of the resin that obtains HMW and the reaction of control initial mixing, so not only require NMP-CaCl
2Prepolymer system such as p-phenylenediamine (PPD) enter in the blender with very low temperature, and preferably keep low-temperature condition in the blender, but paraphthaloyl chloride is with molten state and enters the little a lot of mode of the relative prepolymer system of flow and enter into blender, make paraphthaloyl chloride solidify out so the charging aperture of paraphthaloyl chloride may be subjected to the influence of low temperature system in the blender and blockedly fall, continuous mixing can not be carried out smoothly.
In a word, because of the problem of blender makes the industrialization continuously and stably of PPTA production of resins, but because the Fanglun 1414 is of many uses, the potential demand amount is very big in China, and at present the para-aramid fiber that uses of China all by import, import price also increased crazily in recent years (8 years internal expanding 15 times).So realize that China's para-aramid fiber produces industrialization and just seems particularly important.
The utility model content
It is to enter into polymer reactor after the mixing of proportioning continous-stable with the precise chemical structure stoichiometric coefficient in solvent and cosolvent that the utility model is intended at two monomers that do not have suitable mixing apparatus to make reaction for above-mentioned reasons at present, so that the present situation that can not produce the resin of HMW continuously and stably, a kind of material mixer that is used for high temperature difference quick reaction is provided, hybrid reaction is carried out smoothly.And the utility model is applied to during aramid fiber produces, realize PPTA resin continuous stabilization ground industrial production.
The material mixer that is used for high temperature difference quick reaction, be applicable to the continuous mixing of rapid-action component in blender of high temperature difference, comprise mixing bunker, two fluid passages of leading to mixing bunker and the charging aperture in housing, the housing, the discharging opening of mixing bunker lower end, it is characterized in that: mixing bunker is positioned at the lower end of charging aperture, a piston storehouse isometrical with it is arranged in the upper end of mixing bunker, establish a hollow piston in it, there is vertical guide groove the two side of piston; In the upper end of charging aperture a horizontal slotting Fixed latches is arranged, pass the guide groove of piston both sides; Piston cavity is settled a scrapper, is connected as a single entity with Fixed latches; Described two charging apertures are corresponding with the position of piston guide groove when piston moves downward.
Described piston storehouse can be changed.
Described two charging apertures one place at least are provided with needle valve.
There is the chuck that cools off or add thermal material the described two fluid passages outer setting of one at least.
The outer setting of described mixing bunker has cooling or adds the chuck of thermal material.
Described two charging apertures forward positioned opposite on the mixing bunker inwall.
Below the operation principle of structure of the present utility model and each parts is set forth:
This patent is the fast reaction component continuous mixing in blender that is used for high temperature difference, and mixer shafts to each cross section component to form all be homogeneous, discharging opening is exactly top said blender end.The place that forward is relative on mixer inner walls has two charging apertures, and two strands of materials spray from charging aperture respectively and enter into mixing bunker and centre position collision mixing in mixing bunker, have also avoided fluid directly to flow to the bottom of mixing bunker simultaneously.A hollow piston is housed above charging aperture, when piston moves downward, its effect is to be used for wiping off mixing the material on the bulkhead and this material being pushed in the reactor of back, and the effect of two guide grooves opening on the direction of charging aperture relatively on the piston is can enter into mixing bunker continuously and stably by this guide groove from the jet component flow of coming in when piston moves downward.
A strigil is housed in the above-mentioned hollow piston of mentioning in this patent, this strigil passes the piston guide groove by a latch and is fixed on the blender, strigil and mixing bunker are actionless when piston moves, and the effect of strigil is to be used for wiping off the material that enters into mixing bunker from guide groove.
Have chuck near the feed pipe of this blender and the jet in the utility model, thereby logical heating or cooling medium is separated out blocking pipe to guarantee that material can not solidify or precipitate before entering mixing bunker in the chuck.
Mixing bunker also is to have chuck in this patent, can heat or cools off to guarantee that blending ingredients mixes under suitable temperature according to the process conditions needs.
Adopt polymerization process of the present utility model to be:
This equipment can be used for producing the process of PPTA resin continuous polymerization.Promptly be meant and contain 4.5%~8% p-phenylenediamine (PPD), NMP-CaCl
2Enter into blender continuously with two kinds of reactive components of paraphthaloyl chloride of the remaining molten state of the pre-polymer solution of part paraphthaloyl chloride preparation and another part and to generate a kind of diamines and acyl chlorides mixed solution that is as the criterion with stoichiometric coefficient behind the high velocity impact.Enter into first order polymer reactor and carry out fierce stirring so that component spreads out after in blender, stopping for 1 second at this, cool off this mixture simultaneously, after this stays for some time, mixture is advanced in the polymer reactor of the second level, enough shearing force must be provided second level polymer reactor so that solation (shear rate is not less than 100sec-1), also control mixture temperature simultaneously and be not higher than 80 ℃, become crumbs shape product to enter subsequent purification behind reaction 5~30min and handle workshop section.
The utility model beneficial effect shows:
Therefore the material temperature difference that is used to mix can differ greatly, and material just can enter in the blender with the liquid form that is beneficial to metering of liquid state or molten state, and can satisfy with the stoichiometric coefficient is continuous mixing between the component of proportioning; Mixed temperature of charge controlled range is very big, because of the strap clamp cover of blender own can cool off mixture or heat according to actual needs; Can satisfy and mix the mixing of materials that becomes thickness even become solid to be precipitated out after the mixing of materials of back, thickness or solid are precipitated out the material that is attached on the mixer wall and can blow in the follow-up workshop section by the motion of piston, thereby avoid the obstruction of blender.
Description of drawings
Fig. 1 comprises the simple and easy schematic diagram of the polymerization process of the utility model blender.
The master of Fig. 2 the utility model blender looks cross-sectional view
The left view of piston among the above-mentioned Fig. 2 of Fig. 3
The cross-sectional view of 5-5 position among the above-mentioned Fig. 3 of Fig. 4
The specific embodiment
Fig. 1 is the concise and to the point description in the polymerization process.Two solution (one is pre-polymer solution A, and another is molten state material B) enter into blender 1 rapid mixing in this process.Mixture enters into first order polymer reactor 2 apace afterwards.First order polymer reactor 2 provides mixture fierce mixing before reaction becomes gel, and cools off this mixture, makes mixture be controlled at our needed temperature.The mixture that comes out from first order polymer reactor enters into second level reactor 3, and second level reactor provides high shear forces power to mixture and cools off reaction mass with the control reaction temperature.If necessary, first order polymer reactor 2 and second level reactor 3 may be incorporated in a polymer reactor.
Fig. 2 is the detailed structure schematic diagram of blender 1 among Fig. 1.It has a movably needle valve 20, is used for regulating the back and enters into the pressure that passage 19 enters into the liquid of spray-hole 11 again by passage 18.Chuck 17,21 provides the mode of a kind of heating or cooling liquid according to actual needs.Second kind of fluid enters into spray-hole 12 after by passage 13 again, and passage 13 also can be installed chuck according to the actual conditions needs and cool off or heat.Two guide grooves that latch 8 passes on the piston 4 are fixed on the blender shell.The cross section of mixing bunker 14 is preferably circular, and other shape also is available.Spray-hole 11 and 12 size are preferably to provide the fluid velocity of a proper operation, promptly the mass velocity of two strands of materials (equaling fluid density * linear speed) is about equally, so just just with the collision (in two spray-hole centre positions apart) in the middle of mixing bunker.When may being used for regulating the pressure drop (and energy loss) of material before entering each hole, valve control 20 uses.
Mixing bunker 14 also has chuck 15, can cool off according to actual conditions to add thermal material, and the length of mixing bunker 14 should be 6~12 times (best multiple is 8~10 times) of mixing bunker diameter.
What Fig. 3 and 4 described is to be with the hollow piston 4 of guide groove 6 to slide up and down at Fixed latches 8.Removable housing 5 provides the effect of a similar packed-piston 4.When piston moves downward 16 places, exit position (referring to Fig. 2, purpose is to mix residual material on the bulkhead in order to wipe off), two strands of materials continue to flow down to 9 places, center by two guide grooves 6 on the piston.With the latch 8 joining curettes 10 of examining are polymer and the gels that are used for when piston is mentioned, cleaning out 9 places, and latch 8 is to be used for wiping polymer and gel in the guide groove off when what piston was mentioned.Scrape and examine device 10 and may be a bar-shaped shape and closely paste mutually, and be fixed on the upstream position of mixing bunker inner fluid charging aperture with hollow piston.
This blender preferably vertically uses, and exit position 16 directly is connected with first order polymer reactor 2.
Embodiment 1
This example is meant at solvent NMP-CaCl
2Middle process of producing the PPTA resin, two polymer reactors of this process are double-screw reactor simultaneously.
Be dissolved in NMP-CaCl
2In contain 4.5%~8% p-phenylenediamine (PPD), be cooled to the temperature of needs, add the prepolymer A solution that part paraphthaloyl chloride (account for total amount 20%~50%) reaction generates, with this prepolymer be cooled to 0 ℃~15 ℃ stand-by, while heating and melting B material paraphthaloyl chloride, temperature is controlled at 85 ℃~120 ℃, treat that after the preparation be well that the proportioning injection enters in the blender with the stoichiometric coefficient with two strands of materials, collide mixing fiercely in the mixing bunker centre position, the mixture that generates rarer (viscosity is in the 100cp) enters into first polymer reactor (the blender piston is with the motion frequency scraper of 2~5 times/min) approximately stopped for 1 second in blender after.The material that enters into first order polymer reactor is fiercely mixed there, (temperature is controlled at and is not higher than 60 ℃) simultaneously is cooled, (viscosity of the material that this moment is partially polymerized probably is 10~100p) after first order polymer reactor the inside material stopped for 4~60 seconds, mixture is fed to and continues in the polymer reactor of the second level to be mixed by high shear rate (being not less than 100Ssec-1), simultaneous temperature is controlled at and is not higher than 70 ℃, discharging behind reaction 1~15min, final products are a kind of crumbs dry powder solid matters, sample analysis.
Analytical test result such as following table: test result all meets the demands, and shows that such blender is suitable for the continous-stable polymerization of aramid fiber II very much.
Table 1 resin test result