CN101215376A - Material mixer used for high temperature difference quick reaction - Google Patents
Material mixer used for high temperature difference quick reaction Download PDFInfo
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- CN101215376A CN101215376A CNA2007100510555A CN200710051055A CN101215376A CN 101215376 A CN101215376 A CN 101215376A CN A2007100510555 A CNA2007100510555 A CN A2007100510555A CN 200710051055 A CN200710051055 A CN 200710051055A CN 101215376 A CN101215376 A CN 101215376A
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Abstract
The invention discloses a material mixer for fast reaction of high temperature difference, which leads mixing reaction to go on smoothly, and the invention is applied in the production of aramid fiber, the continuous and stable industrial production of poly-para-phenylene two formyl to phenylene-diamine resin is achieved. The mixer comprises a casing body, a mixing bin n the casing body, two fluid channels which lead to the mixing bin and a feed inlet, the upper end of the mixing bin is a piston bin, both lateral walls of a piston are provided with vertical guiding grooves, the upper portion of the feed inlet is provided with a bolt which penetrates the guiding grooves on both sides of the piston. Two monomers which are reacted can get into a polymerization reactor after continuously and stably mixing with accurate stoichiometry coefficient to be proportioning in dissolvent and cosolvent by adopting the invention, resin with high molecular weight can be continuously and stably produced.
Description
Technical field
The present invention relates to a kind of material mixer of high temperature difference quick reaction, be specially adapted to NMP-CaCl
2Mixing tank when reacting for solvent continuous production PPTA resin initial mixing.
Background technology
Nineteen thirty-five, du pont company scientist Carothers has invented fatty polyamide fiber (be polyhexamethylene adipamide＜nylon 66〉fiber), from then on, for being applied to industrial circle, tynex opened up new world, wherein delivered compelling high-performance Fanglun 1414 in 1966 with E.I.Du Pont Company, its formal commodity are called Kevlar (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 vessel shell, automobile wearing piece at present, build geotechnological material, replace the various reinforced composites, conveying belt, extraordinary canvas of iron and steel etc.At military aspect as making flak jackets, the helmet, tub, armor plate, radar set outer cover etc.Because its purposes is very extensive, once is called as " all-round fibre ", existing at present 170 multiple uses.
(since 100～200t/a) productions, through repeatedly expanding production with joint, the Kevlar throughput of E.I.Du Pont Company has surpassed 30,000 t/a at present to finish trial production equipment from E.I.Du Pont Company in 1971.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 turnout in the world.
Research and develop some other fiber company that also has of contraposition aromatic polyamide the same period, can not select difficulty such as qualified solvent and stopped research because the high molecular relative molecular weight of continuous production is done not high, dissolving aspect mostly.
Obtain high inherent viscosity, high-molecular weight resin, 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, mix two monomeric mixing tanks and will address this problem just to relate to.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 solubility promoter, be to enter into polymerization reactor after the mixing of proportioning continous-stable just with the precise chemical structure stoichiometric coefficient because never find two monomers that suitable mixing equipment makes reaction, thereby cause the resin properties viscosity of producing inhomogeneous, make the breaking tenacity coefficient of dispersion of fiber very big, can not reach service requirements.
The rational mixing tank 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 p-phthaloyl 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 Ursol D is dissolved in NMP-CaCl therefore
2Exist with liquid form in the system, and p-phthaloyl chloride exists with the molten state form; Two is to undergo phase transition in the fast especially and reaction process of two monomer reaction speed (promptly to become gel state very soon from liquid state, react again become after for some time solid-state), so require two monomers to mix and in time remove within a short period of time, otherwise the overstand polymkeric substance will exist with gel form and be difficult to flow, though also have material residence time in mixing tank 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 when reacting, so not only require NMP-CaCl for two the monomer initial mixing of rate request that obtain high-molecular weight resin and the reaction of control initial mixing
2Prepolymer system such as Ursol D enter in the mixing tank with very low temperature, and preferably keep low-temperature condition in the mixing tank, but p-phthaloyl chloride is with molten state and enters the little a lot of mode of the relative prepolymer system of flow and enter into mixing tank, make p-phthaloyl chloride solidify out so the opening for feed of p-phthaloyl chloride may be subjected to the influence of low temperature system in the mixing tank and blockedly fall, continuous mixing can not be carried out smoothly.
In a word, because of the problem of mixing tank 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.
Summary of the invention
It is to enter into polymerization reactor after the mixing of proportioning continous-stable with the precise chemical structure stoichiometric coefficient in solvent and solubility promoter that the present invention is intended at two monomers that do not have suitable mixing equipment to make reaction for above-mentioned reasons at present, so that the present situation that can not produce the high-molecular weight resin 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 present invention is applied to during aramid fiber produces, realize PPTA resin continuous stabilization ground industrial production.
A kind of material mixer that is used for high temperature difference quick reaction, be applicable to the continuous mixing of quick response component in mixing tank of high temperature difference, the discharge port that comprises housing, the intravital mixing bunker of shell, two fluid channels of leading to mixing bunker and opening for feed, mixing bunker lower end, it is characterized in that: mixing bunker is positioned at the lower end of opening for feed, 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 opening for feed 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 opening for feeds are corresponding with the position of piston guide groove when piston moves downward.
Described piston storehouse can be changed.
Described two opening for feeds one place at least are provided with needle type valve.
There is the chuck that cools off or add thermal material the described two fluid channels outer setting of one at least.
The outer setting of described mixing bunker has cooling or adds the chuck of thermal material.
Described two opening for feeds forward positioned opposite on the mixing bunker inwall.
Below the principle of work of structure of the present invention and each parts is set forth:
This patent is that the rapid reaction component successive in mixing tank that is used for high temperature difference mixes, and mixer shafts to each square section component to form all be homogeneous, discharge port is exactly top said mixing tank end.The place that forward is relative on mixer inner walls has two opening for feeds, and two strands of materials spray from opening for feed respectively and enter into mixing bunker and mid-way 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 opening for feed, 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 opening for feed relatively on the piston is can enter into mixing bunker continuously and stably by this guide groove from the jet orifice 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 mixing tank, strigil and mixing bunker are actionless when piston motion, 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 mixing tank and the jet orifice among the present invention, 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 processing condition needs.
Adopt polymerization process of the present invention to be:
This equipment can be used for the process of production PPTA resin successive polymerization.Promptly be meant and contain 4.5%～8% Ursol D, NMP-CaCl
2Enter into mixing tank continuously with two kinds of reactive components of p-phthaloyl chloride of the remaining molten state of the pre-polymer solution of part p-phthaloyl chloride preparation and another part and to generate a kind of diamines and acyl chlorides mixing solutions that is as the criterion with stoichiometric coefficient behind the high velocity impact.Enter into first step polymerization reactor and carry out fierce stirring so that component spreads out after in mixing tank, stopping for 1 second at this, cool off this mixture simultaneously, after this stays for some time, mixture is advanced in the polymerization reactor of the second stage, enough shearing force must be provided second stage polymerization reactor so that solation (shearing rate is not less than 100sec-1), also control mixture temperature simultaneously and be not higher than 80 ℃, become crumb shape product to enter subsequent purification behind reaction 5～30min and handle workshop section.
Beneficial effect of the present invention shows:
Therefore being used for the blended material temperature difference can differ greatly, and material just can enter in the mixing tank 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 mixing tank 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 precipitation to come out after the mixing of materials of back, the material that thickness or solid precipitation come out to be attached on the mixer wall can blow in the follow-up workshop section by the motion of piston, thereby avoids the obstruction of mixing tank.
Description of drawings
Fig. 1 comprises the simple and easy synoptic diagram of the polymerization process of mixing tank of the present invention.
The master of Fig. 2 mixing tank of the present invention 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
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 mixing tank 1 short mix in this process.Mixture enters into first step polymerization reactor 2 apace afterwards.First step polymerization 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 step polymerization reactor enters into second stage reactor 3, and second stage reactor provides high shear forces power and cools off reaction mass with control reaction temperature mixture.If necessary, first step polymerization reactor 2 and second stage reactor 3 may be incorporated in a polymerization reactor.
Fig. 2 is the detailed structure synoptic diagram of mixing tank 1 among Fig. 1.It has a movably needle type valve 20, is used for regulating the back and enters into the pressure that passage 19 enters into the liquid of jet hole 11 again by passage 18.Chuck 17,21 provides the mode of a kind of heating or cooling liqs according to actual needs.Second kind of fluid enters into jet hole 12 after by passage 13 again, and passage 13 also can be installed chuck according to the practical situation needs and cool off or heat.Two guide grooves that latch 8 passes on the piston 4 are fixed on the mixing tank shell.The square section of mixing bunker 14 is preferably circular, and other shape also is available.Jet 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 to collide (in two jet hole mid-ways apart) at the mixing bunker intermediary.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 practical situation 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, outlet 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, central position by two guide grooves 6 on the piston.With the latch 8 joining curettes 10 of examining are polymkeric substance and the gels that are used for when piston is mentioned, cleaning out 9 places, and latch 8 is to be used for wiping polymkeric substance 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 opening for feed with hollow piston.
This mixing tank preferably vertically uses, and outlet position 16 directly is connected with first step polymerization reactor 2.
This example is meant at solvent NMP-CaCl
2The process of middle production PPTA resin, two polymerization reactors of this process are double-screw reactor simultaneously.
Be dissolved in NMP-CaCl
2In contain 4.5%～8% Ursol D, be cooled to the temperature of needs, add the prepolymer A solution that part p-phthaloyl 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 p-phthaloyl chloride, temperature is controlled at 85 ℃～120 ℃, treat that after the preparation work be well that the proportioning injection enters in the mixing tank with the stoichiometric coefficient with two strands of materials, collide mixing fiercely in the mixing bunker mid-way, the mixture that generates rarer (viscosity is in the 100cp) enters into first polymerization reactor (the mixing tank piston is with the motion frequency scraper of 2～5 times/min) approximately stopped for 1 second in mixing tank after.The material that enters into first step polymerization 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 step polymerization reactor the inside material stopped for 4～60 seconds, mixture is fed to and continues in the polymerization reactor of the second stage 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, the finished product are a kind of crumb dry powder solid matters, sampling analysis.
Analytical test result such as following table: test result all meets the demands, and shows that such mixing tank is suitable for the continous-stable polymerization of aramid fiber II very much.
Table 1 resin test result
| Sample time/h | |
| 1 2 4 8 24 36 | 6.3 6.5 6.7 6.5 6.4 6.8 |
| 48 | 6.4 |
Claims (4)
1. material mixer that is used for high temperature difference quick reaction, be applicable to the continuous mixing of quick response component in mixing tank of high temperature difference, the discharge port that comprises housing, the intravital mixing bunker of shell, two fluid channels of leading to mixing bunker and opening for feed, mixing bunker lower end, it is characterized in that: mixing bunker is positioned at the lower end of opening for feed, 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 opening for feed 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 opening for feeds are corresponding with the position of piston guide groove when piston moves downward.
2. according to the described a kind of material mixer that is used for high temperature difference quick reaction of claim 1, it is characterized in that: there is the chuck that cools off or add thermal material the described two fluid channels outer setting of one at least.
3. according to claim 1 or 2 described a kind of material mixers that are used for high temperature difference quick reaction, it is characterized in that: the outer setting of described mixing bunker has cooling or adds the chuck of thermal material.
4. according to the described a kind of material mixer that is used for high temperature difference quick reaction of claim 1, it is characterized in that: described two opening for feeds forward positioned opposite on the mixing bunker inwall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100510555A CN101215376A (en) | 2007-12-29 | 2007-12-29 | Material mixer used for high temperature difference quick reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100510555A CN101215376A (en) | 2007-12-29 | 2007-12-29 | Material mixer used for high temperature difference quick reaction |
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| CN101215376A true CN101215376A (en) | 2008-07-09 |
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| CNA2007100510555A Pending CN101215376A (en) | 2007-12-29 | 2007-12-29 | Material mixer used for high temperature difference quick reaction |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040733A (en) * | 2010-11-12 | 2011-05-04 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN106190769A (en) * | 2015-04-30 | 2016-12-07 | 余家昌 | A kind of material divides deposits formula mixing arrangement |
| CN109553769A (en) * | 2018-11-28 | 2019-04-02 | 清华大学 | A kind of p-aramid fiber resin continuous polymerization system and its method |
-
2007
- 2007-12-29 CN CNA2007100510555A patent/CN101215376A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040733A (en) * | 2010-11-12 | 2011-05-04 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN102040733B (en) * | 2010-11-12 | 2012-07-18 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN106190769A (en) * | 2015-04-30 | 2016-12-07 | 余家昌 | A kind of material divides deposits formula mixing arrangement |
| CN106190769B (en) * | 2015-04-30 | 2018-08-31 | 奥然生物科技（上海）有限公司 | A kind of material point deposits formula mixing arrangement |
| CN109553769A (en) * | 2018-11-28 | 2019-04-02 | 清华大学 | A kind of p-aramid fiber resin continuous polymerization system and its method |
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Open date: 20080709 |