CN204779450U - A production facility for preparing polyamide 5X's device and polyamide 5X - Google Patents
A production facility for preparing polyamide 5X's device and polyamide 5X Download PDFInfo
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- CN204779450U CN204779450U CN201520303256.XU CN201520303256U CN204779450U CN 204779450 U CN204779450 U CN 204779450U CN 201520303256 U CN201520303256 U CN 201520303256U CN 204779450 U CN204779450 U CN 204779450U
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Abstract
The utility model provides a preparation polyamide 5X's device, the device is separator, separator includes: the cauldron body, the extrusion jar, with the cauldron body links to each other, screw conveyor, set up in the extrusion jar, and the gate type agitator, set up in the cauldron body, and with screw conveyor links to each other, wherein, the gate type agitator including the stirring frame and with the spiral shell area that the stirring frame links to each other. The utility model discloses a be used for preparing polyamide 5X's device, through setting up through -hole on the stirring frame lateral wall cauldron wall of constantly swiping, reduced the formation of gel, material accessible through -hole flows in the inside and outside both sides of stirring frame simultaneously, has strengthened stirring effect for the separation effect is better. The utility model discloses a polyamide 5X's production facility is further provided.
Description
Technical field
The utility model relates to a kind of device for the preparation of polymeric amide, is specially the production unit of a kind of device for the preparation of polymeric amide 5X and polymeric amide 5X.
Background technology
In prior art, the polymerization process of polymeric amide generally can be divided into and add thermal polycondensation or interface polycondensation.Such as: (BaconKe, A.W.Sisko, Differentialthermalanalysisofhighpolymers.III.Polyamides, JournalofPolymerScience the 50th volume the 153rd phase, 87-98 page, in March, 1961) describe and add thermal polycondensation process, but, according to report, add thermal polycondensation process compared to interface polycondensation, obtained polymeric amide fusing point low and thermotolerance deterioration (J.Polym.Sci.50,87,1961; Macromolecules, 30,8540,1998).And interface polycondensation operation is very complicated, be difficult to industrially be suitable for.Above-mentioned technique is all short distance polymerization technique, no matter all there is certain defect in which kind of technique, and obtained polymeric amide, particularly the polymeric amide 5X polymerization degree is not high, and industrial application is very restricted.
Along with the development of polymerization technique, continuous polymerization technique arises at the historic moment, and compensate for the defect of short distance polymerization to a certain extent.Existing continuous polymerization technique specifically mainly comprises following link: concentrated → high pressure precondensation → flash distillation → normal pressure or vacuum polycondensation.E.I.Du Pont Company, as polymeric amide manufacturer well-known in world wide, improves the continuous polymerization technique of polyamide 66, and the continuous polymerization technique of its uniqueness mainly comprises following link: high pressure concentrates precondensation → flash distillation → normal pressure polycondensation.
Above-mentioned each technique all removes the moisture in reaction system, to drive the carrying out of polyreaction by flash distillation.But flash distillation mainly by the moisture vaporization in reaction system, obtains the blister polymkeric substance of gas-liquid mixed, not obvious to the removal effect of moisture.
Utility model content
For solving the problems of the technologies described above, the utility model provides a kind of device for the preparation of polymeric amide 5X, and described device is tripping device, comprising: kettle; Squeeze cylinder, is connected with described kettle; Conveying screw rod, is arranged at described squeeze cylinder; And grid agitator, be arranged at described kettle, and be connected with described conveying screw rod; Wherein, described grid agitator comprises the ribbon stirring frame and be connected with described stirring frame.
According to an embodiment of the present utility model, wherein said stirring frame comprises the cylinder of both ends open, and the side of described cylinder offers at least one through hole.
According to another embodiment of the present utility model, the side of wherein said cylinder is reticulated structure.
According to another embodiment of the present utility model, wherein said cylinder comprises the first annulus, the second annulus and at least two connecting strips, described first annulus is connected by described at least two connecting strips with the second annulus, described ribbon one end connects described first annulus, and the other end connects described conveying screw rod.
According to another embodiment of the present utility model, wherein in the region that described first annulus, described connecting strip and described second annulus surround, be formed with multiple grid.
According to another embodiment of the present utility model, wherein said first annulus is preferably parallel to described second annulus; Described connecting strip is preferably perpendicular to described first annulus, the second annulus.
According to another embodiment of the present utility model, wherein said grid agitator also comprises the 3rd annulus, and described 3rd annulus is connected with described second annulus; Preferably, described at least two connecting strips connect described first annulus, the second annulus and the 3rd annulus simultaneously.
According to another embodiment of the present utility model, the stirring frame of wherein said grid agitator and the distance≤13mm of described kettle wall.
According to another embodiment of the present utility model, wherein said kettle is formed by a cylinder and the inverted cone that is connected with described cylinder, and the height of described cylinder is 1 ~ 2 times of described inverted cone height; Preferably, described tripping device also comprises material inlet, venting port and material outlet, and described material inlet is arranged at the top of described kettle, and described material outlet is arranged at the bottom of described squeeze cylinder; In described kettle, be preferably provided with material conduit, the upper port of described material conduit connects described material inlet.
The utility model additionally provides a kind of separation method for the preparation of polymeric amide 5X, comprises and gas-liquid mixture is carried out gas-liquid separation by above-mentioned device.
The utility model further provides the production unit of a kind of polymeric amide 5X, comprises the concentrating unit, pre-polymerization device, reliever, above-mentioned tripping device and the whole poly-device that connect successively.
The utility model further provides the production method of a kind of polymeric amide 5X, comprise: by base polyamide salts solution after enrichment step, prepolymerization reaction step, depressurization steps, separating step and whole poly-reactions steps process, obtained described polymeric amide, wherein said separating step carries out in above-mentioned tripping device.
According to an embodiment of the present utility model, the temperature of gathering reactions steps wherein said end is 250 ~ 320 DEG C, is preferably 250 ~ 300 DEG C; And/or gather reactions steps described end and carry out under normal pressure or vacuum condition, carry out under normal pressure adopting protection of inert gas when gathering end, when carrying out under vacuum condition gathering end, pressure is 0 ~ 760mmHgA, preferably 150 ~ 250mmHgA.
According to another embodiment of the present utility model, the concentration of wherein said base polyamide salts solution is more than 50wt%, preferred 50wt% ~ 65wt%.
According to another embodiment of the present utility model, wherein said enrichment step adopts shell-and-tube concentrating unit to carry out evaporation concentration, and tube side pressure is 0.005 ~ 0.35MPa, preferably 0.05 ~ 0.35MPa, and tube side temperature is 60 ~ 200 DEG C, preferably 80 ~ 160 DEG C; And/or shell side pressure is 0 ~ 2.0MPa, uneven shell-side temperature is less than 250 DEG C, preferably less than 212 DEG C; And/or the mass percent concentration of the polyamide salt aqueous solution after concentrated is 50 ~ 80%, be preferably 70 ~ 80%.
According to another embodiment of the present utility model, the polymer quality degree that wherein said prepolymerization reaction step terminates rear gained is 80 ~ 100%, preferably 85 ~ 95%; The temperature of described prepolymerization reaction is 200 ~ 300 DEG C, preferably 220 ~ 280 DEG C, preferably 230 ~ 260 DEG C further; And/or the pressure of described prepolymerization reaction is below 3.0MPa, preferred below 2.0MPa, preferred 1.0 ~ 1.8MPa further.
According to another embodiment of the present utility model, the reliever in wherein said depressurization steps is flasher, and the temperature of described depressurization steps is the temperature of more than the fusing point of described polymeric amide 5X, is preferably 200 ~ 300 DEG C, more preferably 230 ~ 260 DEG C; The temperature of described separating step is preferably 250 ~ 320 DEG C.
Device for the preparation of polymeric amide 5X of the present utility model, constantly to swipe still wall by being arranged at the through hole stirred on frame sidewall, decreasing the formation of gel; Material is by through hole both sides flowing inside and outside stirring frame simultaneously, enhances mixing effect, makes separating effect better.
The production unit of polymeric amide 5X of the present utility model is applicable to continuous polymerization technique and the batch polymerization processes of polymeric amide, is particularly useful for the continuous polymerization technique of polymeric amide.
Accompanying drawing explanation
Fig. 1 is the structural representation of the production unit of the polymeric amide 5X of the utility model one embodiment;
Fig. 2 is the structural representation of tripping device in Fig. 1;
Fig. 3 is the structural representation of the stirring frame of the utility model one embodiment.
Embodiment
The exemplary embodiment embodying the utility model feature & benefits will describe in detail in the following description.Be understood that the utility model can have various changes on different embodiments, it neither departs from scope of the present utility model, and explanation wherein and to be shown in be use when explain in essence, and be not used to limit the utility model.
As shown in Figure 1, the production unit of the polymeric amide 5X of the utility model one embodiment, comprises the concentrating unit 1, pre-polymerization device 2, reliever 3, tripping device 4 and the whole poly-device 5 that connect successively.
During operation, after being concentrated further in concentrating unit 1 by base polyamide salts solution, enter pre-polymerization device 2; In pre-polymerization device 2, polyamide salt generation prepolymerization reaction, product is the prepolymer and water that the polymerization degree is lower, and above-mentioned product is after flash distillation plant 3, tripping device 4, and most of water is separated with prepolymer; Subsequently, prepolymer enters poly-device 5 eventually and carries out polycondensation, generates final product polymeric amide; Finally by the process of pelletizing, modification or straight spinning equipment, required polyamide product can be obtained.
Wherein, the product generated in pre-polymerization device 2 heats up after decompression through reliever 3, and the moisture vaporization in material, obtains the blister polymkeric substance of gas-liquid mixed.Water vapour in gas-liquid mixture is separated through tripping device 4, and removes by the exhaust system be connected with tripping device 4.
As shown in Figure 2, the tripping device 4 of the utility model one embodiment comprises, kettle 41 and the squeeze cylinder 42 be connected with kettle 41.Conveying screw rod 421 is provided with in squeeze cylinder 42; In kettle 41, be provided with grid agitator, grid agitator is connected with conveying screw rod 421.
Kettle 41 can be made up of superposed cylinder and the inverted cone being positioned at bottom, cylinder one end open, and by this opening and inverted cone seamless link or one-body molded, kettle 41 hollow, is formed with the cavity identical with its outer shape therein.Wherein, the height of cylinder is more than or equal to the height of inverted cone, and preferably, the height of cylinder is 1 ~ 2 times of inverted cone height.
Tripping device 4 also can comprise the material inlet 413 being opened in kettle 41 cylinder upper bottom surface, the venting port 414 being arranged at cylinder side wall and be positioned at the material outlet 422 of squeeze cylinder 42 bottom.In kettle 41, also can arrange a material conduit 415, the upper port of material conduit 415 connects material inlet 413, can avoid the splash of material when material inlet 413 enters kettle 41.
Grid agitator comprises stirring frame 411 and ribbon 412, stir the cylinder that frame 411 can comprise both ends open, the sidewall of cylinder can arrange at least one through hole, through hole scraping still wall so both can have been utilized to prevent gel from assembling, material can be made again by through hole both sides flowing inside and outside cylinder, enhance mixing effect, be beneficial to the separation of gas-liquid.
Stir the cylinder of frame 411 can be formed in one, such as directly on the sidewall of cylinder, offer multiple through hole; Also can be sidewall be the reticulated structure that mesh lines is staggered to form; Can also be connected and composed by multiple parts, as shown in Figure 3, stir frame 411 cylinder can by be positioned at lower port the first annulus 411a, be positioned at upper port the second annulus 411b and connect the first annulus 411a, the second annulus 411b reticulated structure form, this reticulated structure for the multiple grids be staggered to form by many mesh lines, can utilize grid structure scraping still wall in whipping process.The material of the utility model to the shape of grid, size and mesh lines does not limit.Further preferably, the circumference side of cylinder is made up of grid completely.
As shown in Figure 2, in another embodiment of the present utility model, the cylinder stirring frame 411 can comprise the first annulus 411a, the second annulus 411b and at least two connecting strip 411c, wherein, first annulus 411a is connected by connecting strip 411c with the second annulus 411b, the number of the utility model to connecting strip 411c does not limit, such as, can be four.First annulus 411a and the second annulus 411b is preferably the upper bottom surface keeping parallelism with kettle 41 cylinder, connecting strip 411c can be arranged perpendicular to the first annulus 411a, the second annulus 411b, also tiltable is arranged, and is namely acute angle with the angle of the first annulus 411a or the second annulus 411b.Preferably, in the side of cylinder, in the region surrounded by the first annulus 411a, connecting strip 411c and the second annulus 411b, be formed with multiple grid (not shown).
Further preferably, stir frame 411 and also can comprise the 3rd annulus 411d, it is connected with the second annulus 411b by connecting strip 411c, preferably, first annulus 411a, the second annulus 411b and the 3rd annulus 411d are connected by identical connecting strip 411c, connecting strip 411c can be arranged perpendicular to above-mentioned three annulus, and also tiltable is arranged.First annulus 411a, the second annulus 411b and the 3rd annulus 411d are preferably the upper bottom surface keeping parallelism with kettle 41 cylinder.Preferably, in the side of cylinder, in the region surrounded by the first annulus 411a, connecting strip 411c, the second annulus 411b and the 3rd annulus 411d, be formed with multiple grid (not shown).
Ribbon 412 can be positioned at the inverted cone of kettle 41, stirs the cylinder that frame 411 is positioned at kettle 41.The upper end of ribbon 412 can connect the first annulus 411a, lower end connects conveying screw rod 421, grid agitator can be stirred under the drive of squeeze cylinder 42, full-bodied material is made to be thoroughly mixed evenly, reducing gel to generate, simultaneously by stirring the still wall of the scraping agitator present position, side of frame 411, preventing gel from assembling, the distance of agitator and still wall is preferably≤13mm, and this distance refers to the distance between outer rim and kettle 41 still wall stirring frame 411.Meanwhile, ribbon 412 also contributes to downward convey materials, is convenient to material and discharges from the material outlet 422 being positioned at squeeze cylinder 42 bottom.
The material of the utility model to each parts of grid agitator does not limit, and such as the first annulus 411a, the second annulus 411b, the 3rd annulus 411d can be steel ring, and connecting strip 411c can be steel bar.
Below, be further described for the operation carried out in the tripping device of the production unit of polymeric amide 5X and other device and condition, the application does not limit involved concentrating unit, pre-polymerization device, reliever and tripping device, and existing said apparatus all can be used for the production unit of polymeric amide 5X of the present utility model.
First, passed in concentrating unit 1 by base polyamide salts solution and concentrate, the concentrating unit 1 that can be used for the production unit of polymeric amide 5X of the present utility model can be a concentration kettle, heating concentration kettle, moisture in base polyamide salts solution is subject to thermal evaporation, until reach desired concn.Heating source can adopt conventional external steam source, and also can adopt the overheated process steam thermal source that in pre-polymerization device 2, tubular reactor is discharged, vapor temperature can be 220 ~ 280 DEG C.Preferably, concentrating unit 1 can also comprise a primary heater unit, can be heated by the material solution before concentrated, and then carry out evaporation concentration in primary heater unit.Further preferably, concentrating unit 1 can also comprise a condensing tower, and from process steam recoverable heat energy after condensation that concentration kettle produces, the raw material carried secretly in steam such as diamines etc. also can be back in concentration kettle after condensation, to reduce the loss of raw material.
In order to ensure the stability of producing, the heating steam of concentration kettle also the external temperature from general facilities can be no more than the steam of 230 DEG C, to use when the process steam of tubular reactor occurs abnormal.The tube side pressure of concentrating unit 1 can be 0.005 ~ 0.35MPa, and be preferably 0.05 ~ 0.35MPa, tube side temperature can be 60 ~ 200 DEG C, is preferably 80 ~ 160 DEG C; Shell side pressure can be 0 ~ 2.0MPa, and uneven shell-side temperature can be less than 250 DEG C, preferably less than 212 DEG C; The concentration of base polyamide salts solution is preferably more than 50%, and more preferably 50 ~ 65%; The concentration of the polyamide salt solution after concentrated is 50 ~ 80%, is preferably 70 ~ 80%; Described per-cent is the mass percent that polymeric amide accounts for polyamide salt solution.
Polyamide salt solution after concentrated enters pre-polymerization device 2 and carries out prepolymerization reaction, the pre-polymerization device 2 that can be used for the production unit of polymeric amide 5X of the present utility model can be a tubular reactor, such as body is serpentine arrangement, comprises some straight sections and the bent portion of connection.Polyamide salt solution is transferred in body, heat, and polycondensation occurs generates prepolymer and water.Pre-polymerization device 2 may further include at least one, preferably the heating jacket of more than three, is used for heated Tube reactor.Pre-polymerization device 2 further can also comprise one or more heating agent vaporizer, is used for providing heating agent to heating jacket.The heating agent that heating pre-polymerization device 2 uses can be organic heating agent, the overheated liquid phase of organic heating agent is adopted to carry the gas phase heating medium for heating mode of evaporating on the spot, use gas phase heating medium for heating tubular reactor, the heating agent lime set after using can be sent heating agent vaporizer circulating-heating back to and be utilized after reclaiming.
Prepolymerization reaction preferably carries out under high pressure or condition of normal pressure, and pre-polymerization device 2 is tubular reactor, more preferably vertical and/or Horizontal tubular reactor preferably.The temperature of prepolymerization reaction can be 200 ~ 300 DEG C, preferably 220 ~ 280 DEG C, preferably 230 ~ 260 DEG C further; The pressure of prepolymerization reaction can be below 3.0MPa, is preferably below 2.0MPa, more preferably 1.0 ~ 1.8MPa; In the material (being mainly prepolymer and water) that pre-polymerization device 2 exports, polymer content can reach 80 ~ 100%, is preferably 85 ~ 95%.
The material exported from pre-polymerization device 2 enters reliever 3 after the pressurization of reliever supply pump, the reliever 3 that can be used for the production unit of polymeric amide 5X of the present utility model can be a horizontal flasher, comprise a kettle, be provided with snakelike material coil pipe in kettle, the internal diameter of material coil pipe increases successively by entrance.At material disc tube inlet place, pressurization (is generally 20 ~ 25kg/cm to the material of discharging from pre-polymerization device 2
2), material flows in coils, because internal diameter becomes large gradually, add that the drag effect rubbed occurs for material and coil pipe tube wall, pressure reduces rapidly, be down to exit close to normal pressure, moisture in material because of pressure reduce and at high temperature undergoes rapid expansion be vaporizated into water vapour, liquid material is in coil pipe inwall film flow at high speed in the form of a ring, water vapour is then entreated in coils and is flow through, polymkeric substance in coil outlet liquid material can reach 99%, and pressure energy is kinetic energy simultaneously, makes the mixture of liquid material and water enter follow-up Moisture separation device 4 at a high speed.
Reliever 3 can adopt heating medium for heating, the overheated liquid phase heating agent heating out from hot Media Oven is transported under pressure the on-the-spot flasher of heating and carries out vacuum flashing, the gas phase heating agent flashed off also can be used for the tubular reactor heating pre-polymerization device 2, heating agent lime set after each section of tubular reactor chuck uses is received by matchmaker's phlegma withdrawing can by liquid trap, then sends heating medium for heating stove circulating-heating back to heat medium circulation pump.Reliever 3 is flasher preferably, and the temperature and pressure in flasher can be any condition of applicable polymeric amide and moisture flash separation, and the temperature of flash distillation can be the temperature of more than the fusing point of polymeric amide, preferably 200 ~ 300 DEG C, more preferably 230 ~ 260 DEG C.
The tripping device 4 that can be used for the production unit of polymeric amide 5X of the present utility model can be the tripping device of the utility model one embodiment shown in Fig. 2.The prepolymer being entrained with a large amount of water vapour can enter in tripping device 4 by material conduit 415 from material inlet 413, the setting of material conduit 415, splash when preventing material to enter kettle 41.For preventing the generation of gel, in kettle 41, the liquid level of material is preferably higher than grid agitator 411 top 5 ~ 20cm, and because the viscosity of material in kettle 41 is comparatively large, Level Detection can adopt the radioactive source that penetrativity is stronger.Under the drive of conveying screw rod 421, grid agitator 411, by the water surface of evaporation of constantly turning over materials renewal material, makes moisture rapid evaporation be water vapour, and material is fully mixed.Meanwhile, constantly swiping still wall in the side due to grid agitator 411, avoids dead angle, decrease the degraded of prepolymer, makes its viscosity keep homogeneous.
The water vapour be vaporized with after material flash distillation discharges kettle 41 by venting port 414, in order to the water vapour be vaporized with after discharging material flash distillation as early as possible, an exhaust system can be established on venting port 414 side of kettle, water vapour can be discharged by exhaust system from venting port 414.Also containing micro-oligopolymer and 1,5-pentamethylene diamine in the steam of discharging, stick to prevent oligopolymer on the vapor pipe be connected with venting port 414, heating agent jacket heat-preservation taked by vapor pipe, and in exhaust system, pass into spray water, to remove oligopolymer, to absorb 1,5-pentamethylene diamine.For preventing oligopolymer from sticking on vapor pipe further, a movable internal pipe (auxiliary exhaust pipe) also can be set up in vapor pipe.When oligopolymer attachment tube wall blocking pipe, extract auxiliary exhaust pipe, when tripping device normally runs, the blocking of vapor pipe can be got rid of, ensure to produce and normally carry out.In material after steam is separated, the content of prepolymer can reach 99.5%.Temperature in tripping device 4 preferably 250 ~ 320 DEG C, more preferably 250 ~ 300 DEG C.
The kettle 41 of tripping device 4 can adopt the overheated liquid phase of organic heating agent to carry the gas phase heating medium for heating mode of evaporating on the spot.Squeeze cylinder 42 can adopt liquid phase heating medium for heating.
The material that prepolymer content after tripping device 4 processes can reach 99.5% is discharged from the material outlet 422 being positioned at squeeze cylinder 42 bottom, and under the effect gathering unit feeding pump eventually, entering poly-device 5 eventually, prepolymer passes through the whole polymers that polymerization generation molecular weight is larger further in the terminal polymerization kettle of whole poly-device 5.The end that can be used for the production unit of polymeric amide 5X of the present utility model gathers the squeeze cylinder that device 5 can comprise a terminal polymerization kettle and be connected with terminal polymerization kettle, in squeeze cylinder, be provided with conveying screw rod; In terminal polymerization kettle, be provided with grid agitator, grid agitator is connected with conveying screw rod.Grid agitator comprises stirring frame, stir the cylinder that frame can comprise both ends open, the sidewall of cylinder can arrange at least one through hole, so both can utilize through hole scraping still wall, material can be made again by through hole both sides flowing inside and outside cylinder, enhance the mixing effect in polymerization process, the forward being beneficial to poly-reaction eventually carries out.In order to prevent splash and channel, forming desirable polymer flow form, preferably, in the kettle gathering device 5 eventually, immediately below material inlet, a porous feed plate being set.
The kettle of poly-device 5 can adopt the overheated liquid phase of organic heating agent to carry the gas phase heating medium for heating mode of evaporating on the spot eventually.Poly-reaction can be carried out under normal pressure or vacuum condition eventually, and the temperature of poly-reaction is eventually preferably 250 ~ 320 DEG C, more preferably 250 ~ 300 DEG C; Preferably carry out under rare gas element (as nitrogen) condition when carrying out under normal pressure; Rare gas element passes into covering material from polymerization reactor top.When continuing under vacuum to be polymerized, pressure can be 0 ~ 760mmHgA, preferably 150 ~ 250mmHgA.
The polymkeric substance generated in whole poly-device 5 can be transported to end of extruded band via Melt Pump and carry out extruding pelletization, or delivers to screw extrusion press and carry out modification granulation, or delivers to and directly spin.
The utility model additionally provides a kind of polymeric amide 5X obtained by aforesaid device, polymeric amide 5X of the present utility model refers to 1, the polymeric amide that 5-pentamethylene diamine and organic dibasic acid are formed by polycondensation, this organic dibasic acid can be hexanodioic acid or aliphatics long carbochain biatomic acid.
1,5-pentamethylene diamine (is called for short pentamethylene diamine, has another name called 1,5-1,5-DAP), also claiming cadaverine, is a polyamine species, be extensively exist in organism there is bioactive nitrogenous base, for protein corrupt time Methionin under the effect of decarboxylase, there is decarboxylic reaction generate.Industrial pentamethylene diamine also can be obtained by chemical method, such as, after being boiled by the ethanol solution of trimethylene cyanide, adds sodium Metal 99.5 with speed faster, add water after having reacted, steamed by ethanol, remaining reactant superheated vapour distills, acidizing neutralization again, the method for distillation obtains pentamethylene diamine.Discovered in recent years pentamethylene diamine can obtain by the lysine decarboxylase (L-lysinedecarboxylase, EC4.1.1.18) passed through in hafnia alvei (Hafnia.Alvei) biological process that acts on Methionin.1,5-pentamethylene diamine of the present utility model can be formed by Biological preparation, also can be prepared from by chemical method, and can containing the organic carbon of renewable source meeting ASTMD6866 standard.
Aliphatics long carbochain biatomic acid of the present utility model can be sebacic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 and △ 9-1, any one or a few combination in 18-octadecylene diprotic acid, is preferably sebacic acid or SL-AH.Above-mentioned aliphatics long carbochain biatomic acid can be prepared from by biological process or chemical method, and also can containing the bio-based organic carbon meeting ASTMD6866 standard.
The formic acid relative viscosity of polymeric amide 5X of the present utility model is preferably 45 ~ 100; Terminal amino group content is preferably 10 ~ 100mol/ton, more preferably 20 ~ 60mol/ton, and the Amino End Group of too high amount at high temperature easily side reaction occurs again.
Polymeric amide 5X narrow molecular weight distribution of the present utility model, represents Mw/Mn, the preferred < 2.5 of Mw/Mn with the polydispersity coefficient d of conventional molecular weight distribution; Mw representative take weight as the average weight-molecular mass of statistical weight:
Mn representative take quantity as the equal relative molecular mass of number of statistical weight:
The utility model further provides a kind of polymeric amide 5X resin, comprises other polymkeric substance beyond above-mentioned polymeric amide 5X, polymeric amide 5X and/or additive, and wherein, the amount of polymeric amide 5X accounts for more than the 80wt% of the amount of polymeric amide 5X resin.
Wherein, additive can be any one or a few the combination in oxidation inhibitor, heat-resisting stabilizing agent, weather resisting agent, pigment, gloss enhancer, dyestuff, crystal nucleating agent, matting agent, softening agent, static inhibitor, fire retardant, metal and metal-salt.
Heat-resisting stabilizing agent includes but not limited to the compound based on hindered phenol, the compound based on quinhydrones, the compound based on thiazole, the compound based on phosphorus (as phenyl-phosphonic acid), based on compound (as 2-mercaptobenzimidazole) and substitution product, copper halide and the iodine compound etc. of imidazoles.
Weather resisting agent include but not limited to Resorcinol, salicylate, benzotriazole, benzophenone and hindered amine etc.Pigment includes but not limited to Cadmium Sulfide, phthalocyanine and carbon black etc.Gloss enhancer includes but not limited to titanium oxide and calcium carbonate etc.Dyestuff includes but not limited to Ni Gehei and nigrosine etc.Crystal nucleating agent includes but not limited to talcum, silicon-dioxide, kaolin and clay etc.Softening agent includes but not limited to oxybenzoic acid monooctyl ester and N-butylbenzenesulfonamide etc.
Static inhibitor includes but not limited to alkyl sulphate type anionic antioxidant, quaternary ammonium salt cationic type static inhibitor, non-ionic antistatic agent (as Tween-60) and the both sexes static inhibitor etc. based on trimethyl-glycine.
Fire retardant includes but not limited to melamine cyanurate, oxyhydroxide (as magnesium hydroxide or aluminium hydroxide), ammonium polyphosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin, the combination etc. that is made up of any fire retardant based on bromine and antimonous oxide.
Other composition polymkeric substance is other compound outside 1,5-pentamethylene diamine and aliphatics long carbochain biatomic acid.
(1) other composition polymkeric substance can contain the structural unit derived from following component: aliphatic carboxylic acid is (as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, pimelic acid, suberic acid, nonane diacid etc.), alicyclic dicarboxylic acid (as cyclohexyl dicarboxylic acid etc.) or aromatic dicarboxylic acid are (as terephthalic acid, m-phthalic acid, naphthalic acid, diphenyldicarboxylic acid, anthracene dicarboxylic acid, luxuriant and rich with fragrance dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylethane dicarboxylic acid, 1, 4-cyclohexyl dicarboxylic acid, 5-sodiosulfoisophthalic acid, 5-4-butyl-phosphonium m-phthalic acid etc.).
(2) other composition polymkeric substance can contain the structural unit derived from following component: aliphatie diamine is (as quadrol, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 11-diamino undecane, 1, 12-diamino dodecane, 1, 13-diamino tridecane, 1, the 14-diamino tetradecane, 1, 15-diamino pentadecane, 1, 16-diamino n-Hexadecane, 1, 17-diamino heptadecane, 1, 18-diamino octadecane, 1, 19-diamino nonadecane, 1, 20-diamino eicosane or 2-methyl isophthalic acid, 5-pentamethylene diamine), alicyclic diamine (as cyclohexanediamine or two-(4-Aminohexyl) methane) or aromatic diamine (as benzene dimethylamine).
(3) other composition polymkeric substance can contain the structural unit derived from following component: aromatic series, aliphatics or alicyclic diol compound are (as ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, quinhydrones, Resorcinol, dihydroxybiphenyl, naphthalene glycol, anthracene glycol, luxuriant and rich with fragrance glycol, 2, two (4-hydroxy phenyl) propane, 4 of 2-, 4 '-dihydroxydiphenyl ether or bisphenol S).
(4) other composition polymkeric substance can contain the structural unit derived from following component: have the aromatics of hydroxyl and carboxylic acid, fatty compounds or cycloaliphatic hydroxyl group carboxylic acid cpd.Wherein, cycloaliphatic hydroxyl group carboxylic acid includes but not limited to lactic acid, 3-hydroxy propionate, 3-hydroxybutyrate ester, 3-hydroxybutyrate ester-valerate, hydroxy-benzoic acid, hydroxyl naphthalene monocarboxylic acid, hydroxyl anthracene carboxylic acid, hydroxyl phenanthrene carboxylic acid, (hydroxy phenyl) vinyl carboxylic acid.
(5) other composition polymkeric substance can contain the structural unit derived from following component: amino acid (as 6-aminocaprolc acid, 11-amino undecanoic acid, 12 amino dodecanoic acid or PAMBA) or lactan (as ε-caprolactam or ε-laurolactam).
(6) other composition polymkeric substance can be can with the comonomer of 1,5-pentamethylene diamine and the copolymerization of aliphatics long carbochain biatomic acid.This comonomer includes but not limited to amino acid, lactan, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic diol, aliphatic diol, alicyclic diol, aromatic diamine, aliphatie diamine, alicyclic diamine, aromatic hydroxy-carboxylic, aliphatic hydroxyl carboxylic acid, cycloaliphatic hydroxyl group carboxylic acid, and above-mentioned comonomer derivative separately.Wherein, above-mentioned comonomer derivative separately comprises the resultant of above-mentioned any two kinds of comonomers reaction, such as, and the product of an amino of a part diamines and a carboxyl reaction salify of a part dicarboxylic acid.
Below, the production method of polymeric amide 5X of the present utility model and equipment are described further.
The preparation of polyamide salt solution
Under the protection of nitrogen, the deionized water of 1,5-pentamethylene diamine degasification of high density is diluted to certain density solution (30% ~ 50%).Aliphatic dibasic acid and 1, the 5-pentamethylene diamine diluted are joined continuously in reactor, water coolant removes reaction heat during neutralization reaction in time simultaneously.The pH value of solution is constantly detected in N-process, make the mol ratio of the diamine/diprotic acid in reactor a little less than 1, after stable, this gained salts solution is transferred to (multiple stage of can connecting in the reactor of connecting below, but be generally no more than 3), the mol ratio of diamine/diprotic acid and the mass concentration of salt is regulated, the flow of Data Control two amine aqueous solution detected with pH with the further fractional neutralization of two amine aqueous solutions.Until finally make the salts solution that mass percent concentration is 50 ~ 65%, leave in salt hold-up vessel stand-by.
Enrichment step
Be that the 5X polyamide salt aqueous solution of 50 ~ 65% is for starting raw material with mass percent concentration, through metre filter, send into scale tank in batches, the common additives (being generally no more than 5% of polyamide salt quality) of a certain amount of different size can be added in scale tank, make polyamide salt mixing solutions, after being uniformly mixed, be admitted to the second medial launder under scale tank.Polyamide salt mixed solution in second medial launder is supplied in concentrating unit by salt strainer, salt preheater continuous print by salt supply pump.In concentrating unit, polyamide salt solution concentration is made to be concentrated to 70 ~ 80% by 50 ~ 65%.
Prepolymerization reaction step
Concentrated solution reactor supply pump in concentrating unit is delivered in pre-polymerization device and carries out prepolymerization reaction.
Prepolymerization reaction flows through continuously with polyamide salt solution and occurs gradually under controllable High Temperature High Pressure in tubular reactor.Period, the pressure of reactor can control automatically, tubular reactor is divided into more than three sections independent heatings, still with simmer down to master in the tubular reactor of first 2/3 section, strength of solution is concentrated to about 90% (being suitable for carrying out the concentration of polyreaction) by 70 ~ 80%, final stage is combined into master to carry out pre-polymerization, and in the material of outlet, the content of prepolymer can reach 85 ~ 95%.
Depressurization steps
Reliever (flasher) given continuously by the prepolymer pressure reducer pump obtained by tubular reactor.Material is rapidly by reliever, and pressure reduces continuously and close to normal atmosphere, the dissolved water in prepolymer gasified rapidly from prepolymer, forms the mixture of material, water vapour.
Pipeline between pressure reducer pump and pressure reducer can also be provided with additive and add entrance, such as, according to kind and addition, the matting agent TiO of the purposes determination additive of PA5X resin
2suspension liquid etc., add entrance by additive, can be injected into continuously and quantitatively in prepolymer in this stage, after being reduced pressure by reliever, finally form the mixture of material, water vapour and additive.
Separating step
The gas-liquid mixture continuous print that the prepolymer aqueous solution obtained through flasher process and water vapor are formed enters in the kettle of tripping device, under the effect of conveying screw rod and grid agitator, water vapour is discharged by the exhaust system be connected with venting port from venting port from tripping device, and pre-polymer solution escapes and enter poly-device eventually from the material outlet being positioned at squeeze cylinder bottom.
Poly-reactions steps eventually
With gathering the supply pump of device eventually sending in the terminal polymerization kettle of poly-device eventually from the isolated prepolymer of tripping device; gathering in device eventually; prepolymer is polymerized to the higher whole polymers of molecular weight further; moisture remaining in polymkeric substance and the further water that produces of polymerization is removed, the high quality polymer obtaining applicable granulation or modification or directly spin under condition of negative pressure.In order to prevent material to be oxidized, adopt nitrogen-sealed.
Wherein, embodiment 1 to 3 is all carried out according to above-mentioned steps, concrete raw material and processing parameter as follows.
Embodiment 1
Configuration pH is 56 salts solutions of 65% concentration of 7.95, and be polymerized by the condition of table 1 by the production unit of described polymeric amide 5X, kettle pressure is 210mmHgA, obtains the section that relative viscosity is 68.9, and its terminal amino group content is 40.4.
Embodiment 2
Configuration pH is 56 salts solutions of 65% concentration of 8.05, be polymerized by the condition of enforcement 1 by the production unit of described polymeric amide 5X, but the pressure adjusting of kettle is to 180mmHgA, load improves 20% than embodiment 1, obtain the section that relative viscosity is 69.7, its terminal amino group content is 40.1.
Embodiment 3
Except the pressure change in kettle is 216mmHgA, other condition is identical with embodiment 2, and load is also identical, obtains the section that relative viscosity is 56.1, and its terminal amino group content is 42.6.
Table 1 shows the relevant experimental data of the PA56 (polymeric amide 56) of prepared embodiment 1 to 3:
Table 1
Unless limited otherwise, the utility model term used is the implication that those skilled in the art understand usually.
Embodiment described by the utility model is only for exemplary purpose; and be not used to limit protection domain of the present utility model; those skilled in the art can make other replacements various, changes and improvements in scope of the present utility model; thus; the utility model is not limited to above-mentioned embodiment, and is only defined by the claims.
Claims (10)
1., for the preparation of a device of polymeric amide 5X, described device is tripping device, it is characterized in that, comprising:
Kettle;
Squeeze cylinder, is connected with described kettle;
Conveying screw rod, is arranged at described squeeze cylinder; And
Grid agitator, is arranged at described kettle, and is connected with described conveying screw rod;
Wherein, described grid agitator comprises the ribbon stirring frame and be connected with described stirring frame.
2. device according to claim 1, is characterized in that, described stirring frame comprises the cylinder of both ends open, and the side of described cylinder offers at least one through hole.
3. device according to claim 2, is characterized in that, the side of described cylinder is reticulated structure.
4. device according to claim 2, it is characterized in that, described cylinder comprises the first annulus, the second annulus and at least two connecting strips, described first annulus is connected by described at least two connecting strips with the second annulus, described ribbon one end connects described first annulus, and the other end connects described conveying screw rod.
5. device according to claim 4, is characterized in that, in the region that described first annulus, described connecting strip and described second annulus surround, be formed with multiple grid.
6. device according to claim 4, is characterized in that, described first annulus is preferably parallel to described second annulus; Described connecting strip is preferably perpendicular to described first annulus, the second annulus.
7. device according to claim 4, is characterized in that, described grid agitator also comprises the 3rd annulus, and described 3rd annulus is connected with described second annulus; Preferably, described at least two connecting strips connect described first annulus, the second annulus and the 3rd annulus simultaneously.
8. device according to any one of claim 1 to 7, is characterized in that, the stirring frame of described grid agitator and the distance≤13mm of described kettle wall.
9. device according to claim 8, is characterized in that, described kettle is formed by a cylinder and the inverted cone that is connected with described cylinder, and the height of described cylinder is 1 ~ 2 times of described inverted cone height; Preferably, described tripping device also comprises material inlet, venting port and material outlet, and described material inlet is arranged at the top of described kettle, and described material outlet is arranged at the bottom of described squeeze cylinder; In described kettle, be preferably provided with material conduit, the upper port of described material conduit connects described material inlet.
10. a production unit of polymeric amide 5X, is characterized in that, comprises the concentrating unit, pre-polymerization device, reliever, device according to any one of claim 1 to 9 and the poly-device eventually that connect successively.
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| CN105885041A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Device for preparing polyamide 5X, separation method and production equipment and method of polyamide 5X |
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| CN105885041A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Device for preparing polyamide 5X, separation method and production equipment and method of polyamide 5X |
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