CN102190795A - Method for preparing poly(p-phenylene terephthalamide) - Google Patents
Method for preparing poly(p-phenylene terephthalamide) Download PDFInfo
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Abstract
The invention discloses a method for preparing poly(p-phenylene terephthalamide). Alkanes with 3-12 carbon atoms exist in the reaction system, and the latent heat of vaporization of the alkanes is utilized to transfer heat generated by the reaction, thereby controlling the reaction temperature. The method solves the key project problem of heat management in the amplification process of a low-temperature liquid phase polymerization reactor, simplifies the structure of large-up equipment, effectively controls the product quality, is simple to operate, can easily implement continuity and scale-up, and has the advantages of low energy consumption, lower manufacturing cost of equipment, and the like.
Description
Technical field
The present invention relates to prepare the method for PPTA.
Background technology
PPTA (also is called Fanglun l414, the English PPTA that is called for short) be a kind of liquid crystal state polymkeric substance that constitutes by the long molecule of rigidity, by du pont company a kind of high-performance synthon that late nineteen seventies is developed in last century six, outward appearance is flavous tinsel.Because its molecular chain is height-oriented along its length and have extremely strong interchain force, its intensity is 5～6 times of high-quality steel greater than 28 gram/dawn, and modulus is steel or glass fibre 2～3 times, and toughness is 2 times of steel, and weight only is 1/5 of steel.The use temperature scope is extremely wide continuously, can normally move for a long time in-196 ℃ to 204 ℃ scopes.Shrinking percentage under 150 ℃ is 0, does not decompose under 560 ℃ high temperature and does not melt, and has good insulation performance and erosion resistance, and life cycle is very long, thereby wins the good reputation of " synthetic steel wire ".Be widely used in fields such as defence and military, space flight and aviation, electromechanics, building, automobile, marine fishery, sports goods, world's annual requirement is above 500,000 tons.
At present, the preparation method of Fanglun l414 is mainly low-temperature solution polycondensation.Promptly earlier acid absorber (for example pyridine) and solubilizing agent (CaCl for example
2And LiCl) is dissolved in the N-Methyl pyrrolidone (NMP), all after the dissolving, add a certain amount of Ursol D, after treating that it dissolves fully, be cooled to-15-5 ℃ with ice-brine bath, add equimolar amount or slightly many p-phthaloyl chlorides (TPC), transfer to corresponding stirring velocity, carry out polycondensation, to reaction system generation gelation, then with gelinite with certain mode fragmentation, and water is washed residual solvent, solubilizing agent, hydrochloric acid and acid absorber off, product oven dry after will washing at last obtains pulverous Fanglun l414.
In this process, present prior art is all bathed as the type of cooling with cryosel, comes the temperature of control process.But when the polymeric scale is bigger, the area of simple reactor jacket heat exchange mode is limited, can not extraordinary controlled temperature, (reaction raw materials instantaneous time rapid polymerization becomes many short chain polymers to make reaction process exist implode, be accompanied by rapid increase of system viscosity and emit a large amount of heat with process, and the thermally sensitive raw material of part is decomposed, produce unnecessary impurity) danger.The mode that heat transfer tube is set in polymerization reactor can increase heat interchanging area effectively on principle, carry out temperature control.But because product is finally wanted gelation, not only can be bonded on the stirring rake, also can be bonded on the heat transfer tube, cause the heat-transfer capability of heat transfer tube to descend, also can exist the phenomenon of controlled temperature difficulty.Simultaneously,, be equivalent to fix polymer gel, also increased the stirring rake desired power of cracking gel once more if a large amount of polymkeric substance is bonded on the heat transfer tube.In a single day in addition, if the implode phenomenon takes place, can form a big solid mass in the whole reactor, not only influence the homogeneity of product, it is also very difficult that it is taken out reactor.Cause the production poor continuity.If the twin screw device is combined in the polymerization process, the bulk solid block that can the be effective broken polymerization reaction late stage of its great shear forces forms, but the reactant of this individual system (Ursol D and p-phthaloyl chloride) is to water or oxygen sensitivity, not only require raw material not moisture and isolated with oxygen, and high for the sealing requirements of device.And the twin screw device is difficult for sealing with other equipment owing to exist mechanical rotation device, or sealing difficulty is very big.The reason of these engineerings causes the amplification of Fanglun l414 to produce very difficulty, and cost is huge, does not still have sophisticated amplification production technology at present.Even produce relatively easy aramid fiber 1313 (a position aramid fiber, production process viscosity is low, and is easy to control relatively), its single cover reaction unit can not be too big, and production efficiency is lower, can't effectively satisfy huge military and commercial market.
At the deficiency of above aramid fiber production process, be desirable to provide a kind of serialization that is easy to, maximize and produce the method for aramid fiber.
Summary of the invention
The invention provides a kind of method for preparing PPTA, wherein in reaction system, have alkane, utilize the latent heat of vaporization of described alkane to come the generation heat of shift reaction with 3-12 carbon atom, thus control reaction temperature.
Method of the present invention may further comprise the steps:
A. in the container that stirs, add polar solvent, acid absorber, Ursol D, solubility promoter and have the alkane of 3-12 carbon atom
B. making the pressure in the container is 0.001-1MPa, adds to account for the p-phthaloyl chloride that the Ursol D mole number is 50%-110%.
C. add p-phthaloyl chloride in addition, make that institute adds the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.1, react the formation gel.
Embodiment
The inventive method is characterised in that in synthetic system, by certain operating method or under the rare gas element existence condition, control the heat of moving of reaction with the latent heat of vaporization of alkane, and by this alkane and polymeric solution emulsification mutually,, thereby guarantee that overall viscosity increases seldom in the polymerization process because the gel granularity that formed emulsion droplet generates is less than 5mm, it is good to conduct heat in the reactor like this, power of agitator changes little, makes the polymerization process temperature steady, and reactor amplifies easily.After reaction finishes, reclaim alkane, recycle.
In one embodiment, described alkane is selected from propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, isohexane, 2,2-dimethylbutane, normal heptane, isoheptane, neoheptane, 3,3-dimethylpentane, octane-iso, nonane, decane, undecane, dodecane and their mixture.
In one embodiment, this method also comprises the alkane that feeds rare gas element or have 1-3 carbon atom in reaction system.Preferably described rare gas element is selected from helium, argon gas, nitrogen and their mixture, and the alkane of the described 1-3 of a having carbon atom is selected from methane, ethane, propane and their mixture.
In one embodiment, described temperature regulation realizes by in following three kinds of modes one or more: (1) carries the alkane volatilization with 3-12 carbon atom with rare gas element or alkane with 1-3 carbon atom; (2) pressurized operation makes the alkane liquefaction with 3-12 carbon atom; (3) decompression operation makes the alkane gasification with 3-12 carbon atom.
In one embodiment, described temperature of reaction is-25-5 ℃.
In one embodiment, with in the disposable adding reaction system of described alkane.
In one embodiment, the Temperature Feedback according to reaction adds described alkane stage by stage in batches.
In one embodiment, method of the present invention may further comprise the steps:
A. in the container that stirs, add polar solvent, acid absorber, Ursol D, solubility promoter and have the alkane of 3-12 carbon atom
B. making the pressure in the container is 0.001-1MPa, adds to account for the p-phthaloyl chloride that the Ursol D mole number is 50%-110%.
C. add p-phthaloyl chloride in addition, make that institute adds the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.1, react the formation gel.
In one embodiment, p-phthaloyl chloride adds with powder type, and perhaps the liquid form with solution or molten state adds.
In one embodiment, the inventive method is further comprising the steps of:
D. formed gel is broken by stirring.
In one embodiment, the inventive method is further comprising the steps of:
E. remove the alkane that all has 3-12 carbon atom.
In a preferred embodiment, the inventive method is further comprising the steps of:
J. the gel particle with fragmentation filters, washs.
In one embodiment, described polar solvent is selected from the amides polar solvent, and is preferably selected from N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethylformamide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl propylene acid amides, hexamethylphosphoric acid triamide and their mixture.
In one embodiment, described acid absorber is selected from pyridine, α-Jia Jibiding, beta-picoline, γ-picoline, and 2,6-lutidine, triethylamine, liquefied ammonia and their mixture.The volume ratio of this acid absorber and polar solvent is 0-0.2.
In one embodiment, described solubility promoter is selected from LiCl, CaCl
2, MgCl
2With their mixture.
In one embodiment, in step b, add and account for the p-phthaloyl chloride that the Ursol D mole number is 50%-80%, more preferably adding accounts for the p-phthaloyl chloride that the Ursol D mole number is 50%-70%, most preferably adds to account for the p-phthaloyl chloride that the Ursol D mole number is 50%-60%.
In one embodiment, the pressure in step b in the container is 0.001-0.1MPa, more preferably 0.001-0.05MPa.
In one embodiment, adding the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number in step c is 1: 1 to 1: 1.006.
The relative molecular weight of resulting polymers characterizes by intrinsic viscosity among the application.The intrinsic viscosity testing method is to use the general viscosity test method in this area, and particularly test condition is to use Ubbelohde viscometer, and 98% vitriol oil is a solvent, concentration C=0.5 Grams Per Minute liter, 30 degrees centigrade of probe temperatures.
Compare with the technology of existing production Fanglun l414, technology provided by the invention has following advantage.
1) utilizes the phase transformation evaporation and heat-exchange controlled temperature of liquid alkane, do not need to use the big cryosel of power consumption to bathe the type of cooling, complicated heat transfer tube need be set in polymerization reactor yet, can reduce production costs significantly and device fabrication cost and maintenance cost like this.
2) utilize liquid alkane emulsion polymerization reaction system, can directly be controlled at the polymer poly granule that is generated below the 5mm, avoided the rod climbing phenomenon of polymkeric substance on stirring rake fully, smooth discharging that can controlling polymers, carry out successive reaction, and can effectively reduce employed power of motor, save power consumption.Do not need the polymerization reactor that uses dual-screw-stem machine or have a plurality of stirring rakes, reduce the equipment sealing difficulty greatly.
3) utilize the common mode that adds of liquid stable hydrocarbon and rare gas element, effectively heat exchange of modulation process and emulsification need, operate very easy, because polymer poly granule footpath is little, it is inner that remaining reactants TPC and Ursol D easily are diffused into poly-group, contacts with each other, and mole of polymerized such as carries out. and the polymerization effect than traditional technology (generating the centimetre-sized bulk) is good, time is short, quality product height (the high approximately 2-3 of intrinsic viscosity).
4) utilize the common mode that adds of liquid stable hydrocarbon and rare gas element, effectively heat exchange of modulation process and emulsification need, and operates very easyly, and are reacting at the end, can utilize rare gas element that all liquid stable hydrocarbon are taken away, not influence the last handling process of Fanglun l414.
5) technology of utilizing the common method that adds of above-mentioned liquid stable hydrocarbon and rare gas element to come heat exchange of modulation polymerization process and emulsification to need, can allow to produce the Fanglun l414 that intrinsic viscosity reaches 7-10, only use conventional art to produce intrinsic viscosity and be pairing motor of the product of 2-5 and stirring rake mode, can make equipment manufacturing cost reduce by 50%.
6) technology of utilizing the common method that adds of above-mentioned liquid stable hydrocarbon and rare gas element to come heat exchange of modulation process and emulsification to need goes for single device and reaches ten thousand tons of/year Fanglun l414 production lines, can make the production cost of Fanglun l414 reduce 15-30%.
Following examples are used to further specify the present invention, but protection scope of the present invention are not had any restriction.It will be understood by those skilled in the art that protection scope of the present invention is limited by claims.
Embodiment 1
Using a volume is 1 liter stainless steel stirring tank, adds 100 milliliters of NMP, and 20 milliliters of pyridines and 80 milliliters of Skellysolve As add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.2mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3%, the massfraction of LiCl is 1.32L/min for the 0.5%. nitrogen flow,, reacting kettle inner pressure is controlled to be 0.1MPa (absolute pressure).When solution temperature is-2 ℃, add the Powdered TPC of Ursol D total mole number 50.06%, temperature of reaction rises to 4 ℃, nitrogen flow is increased to 6L/min solution temperature is reduced to-6 ℃, the Powdered TPC that adds Ursol D total mole number 50% then, reaction rises to 1.2 ℃.Form gel after 2 minutes, the particle size range of gel is 1-3mm, median size 2.8mm.Strengthen power of agitator 30%,, strengthen nitrogen flow then, Skellysolve As all in the system is taken out of to 13.2L/min with the gel fragmentation.The gained gel particle is filtered, the washing, remove all impurity after, the intrinsic viscosity that obtains product is 7.5.
Embodiment 2
Using a volume is 100 liters stainless steel stirring tank, adds 30 liters of NMP, 3 liters of pyridines, and 20 liters of Skellysolve As and 25 liters of normal hexanes add Ursol D, CaCl then
2And LiCl, the concentration of control Ursol D is 0.8mol/L (with the volumeter of NMP), CaCl
2Massfraction be 2%, the massfraction of LiCl is 1%, argon flow amount is 0.5m
3/ min, reacting kettle inner pressure are controlled to be 0.1MPa (absolute pressure).When solution temperature is-4 ℃, add the Powdered TPC of Ursol D total mole number 50%, temperature of reaction rises to 4.5 ℃, and argon flow amount is increased to 3m
3/ min is reduced to solution temperature-2 ℃, adds the Powdered TPC of Ursol D total mole number 50% then, and reaction rises to 1.2 ℃, forms gel after 6 minutes, and the particle size range of polymer poly group is 1-3mm, median size 2.3mm.Strengthen power of agitator 30%, with the gel fragmentation.Strengthen argon flow amount then to 4.8m
3/ min takes Skellysolve As all in the system and normal hexane out of.The gained gel particle is filtered, the washing, remove all impurity after, the intrinsic viscosity that obtains product is 8.5.
Embodiment 3
Using a volume is 10 liters stainless steel stirring tank, adds 4 liters of NMP, 0.5 liter of pyridine, and 0.6 liter of iso-pentane and 1 liter of neohexane add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.1mol/L (with the volumeter of NMP), CaCl
2Massfraction be 1%, the massfraction of LiCl is 0.4%, helium gas flow is 36L/min, reacting kettle inner pressure is controlled to be 0.1MPa (absolute pressure).When solution temperature is-15 ℃, in 4 minutes, add the TPC (concentration is 0.1mol/L) among the NMP of being dissolved in mole numbers such as Ursol D, temperature of reaction rises to 4.5 ℃, and helium gas flow is increased to 0.1m
3/ min is reduced to solution temperature-5 ℃.Form gel after 5 minutes, the particle size range of gel is 0.5-3.5mm, all particle diameter 1.8mm.Strengthen power of agitator 20%, with the gel fragmentation.Strengthen helium gas flow then to 0.2m
3/ min takes iso-pentane all in the system and neohexane out of. the gained gel particle is filtered, the washing, remove all impurity after, the intrinsic viscosity that obtains product is 7.8.
Embodiment 4
Using a volume is 1 liter stainless steel stirring tank, adds 100 milliliters of NMP, 10 milliliters of pyridines, and 200 ml n-hexanes and 150 milliliter 2, the 3-dimethylbutane adds Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.2mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3%, the massfraction of LiCl is 0.6%, methane and nitrogen total flux are 2L/min (methane and nitrogen volume ratio are 1: 2), reacting kettle inner pressure is controlled to be 0.1MPa (absolute pressure).When solution temperature is-25 ℃, the Powdered TPC that adds Ursol D total mole number 80%, temperature of reaction rises to 3 ℃, the total flux of methane and nitrogen is increased to 7.6L/min, solution temperature is reduced to-2 ℃, the Powdered TPC that adds Ursol D total mole number 20% then, reaction rises to 2 ℃.Form gel after 3 minutes, the particle size range of gel is 1-4mm, median size 1.5mm.Strengthen power of agitator 10%, with the gel fragmentation.The total flux that strengthens methane and nitrogen then is to 26L/min, and with normal hexanes all in the system and 2, the 3-dimethylbutane is taken out of.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞7.3 of product.
Embodiment 5
Using a volume is 1 liter glass stirring tank, adds 200 milliliters of NMP, 30 milliliters of pyridines, and 200 milliliters of isohexanes and 100 milliliters of neohexanes add Ursol D and CaCl then
2, the concentration of control Ursol D is 0.36mol/L (with the volumeter of NMP), CaCl
2Massfraction be 5%, the total flux of ethane and propane is 3.8L/min (volume ratio of ethane and propane is 1: 3), reacting kettle inner pressure is controlled to be 0.2MPa (absolute pressure).When solution temperature is-12 ℃, the Powdered TPC that adds Ursol D total mole number 50.03%, temperature of reaction rises to 3 ℃, the total flux of ethane and propane is increased to 7L/min solution temperature is reduced to-2 ℃, the Powdered TPC that adds Ursol D total mole number 50% then, reaction rises to 3.5 ℃.Form gel after 6 minutes, the particle size range of gel is 1-4.5mm, median size 2.8mm.Strengthen power of agitator 10%, with the gel fragmentation.The total flux that strengthens ethane and propane is then taken neohexanes all in the system and isohexane out of to 10L/min.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞10 of product.
Embodiment 6
Using a volume is 500 liters stainless steel stirring tank, adds 100 liters of NMP, 14 liters of pyridines, and 100 liters of iso-pentane and 50 liters of Skellysolve As add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.24mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3%, the massfraction of LiCl is 1%, methane flow is 1.6m
3/ min, reacting kettle inner pressure are controlled to be 0.1MPa (absolute pressure).When solution temperature is-10 ℃, in 10 minutes, add the TPC (concentration is 0.24mol/L) among the NMP of being dissolved in mole numbers such as Ursol D, temperature of reaction rises to 2.5 ℃, and methane flow is increased to 4m
3/ min is reduced to solution temperature-5 ℃.Form gel after 8 minutes, the particle size range of gel is 0.5-5mm, median size 3mm.Strengthen power of agitator 30%,, keep methane flow then, iso-pentane all in the system and Skellysolve A are taken out of the gel fragmentation.The gained gel particle is filtered, washing, remove all impurity after, obtain the intrinsic viscosity＞7.5. of product
Embodiment 7
Using a volume is 500 liters stainless steel stirring tank, adds 150 liters of NMP, and 20 liters of pyridines and 200 liters of normal hexanes add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.3mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3.8%, the massfraction of LiCl is 0.8%, methane, the flow of ethane and propane are 3m
3/ min (volume ratio of methane and ethane and propane is 2: 1: 1), reacting kettle inner pressure is controlled to be 0.3MPa (absolute pressure).When solution temperature is-5 ℃, add the Powdered TPC of Ursol D total mole number 50%, temperature of reaction rises to 4 ℃, and with methane, the total flux of ethane and propane is increased to 20m
3/ min is reduced to solution temperature-4 ℃, adds the Powdered TPC of Ursol D total mole number 50% then, and reaction rises to 3 ℃.Form gel after 5 minutes, the particle size range of gel is 1-4mm, median size 2.8mm.Strengthen power of agitator 30%, with the gel fragmentation.Keep methane then, the total flux of ethane and propane reduces system pressure gradually to 0.1MPa (absolute pressure), and normal hexanes all in the system is taken out of.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞7 of product.
Embodiment 8
Using a volume is 500 liters stainless steel stirring tank, adds 180 liters of NMP, and 30 liters of pyridines and 130 liters of Skellysolve As add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3.6%, the massfraction of LiCl is 0.3%, methane and helium gas flow are 3m
3/ min (volume ratio of methane and helium is 1: 1), reacting kettle inner pressure is controlled to be 0.1MPa (absolute pressure).When solution temperature is-9 ℃, add the Powdered TPC of Ursol D total mole number 70%, temperature of reaction rises to 2 ℃, and the total flux of methane and helium is increased to 6m
3/ min is reduced to solution temperature-5 ℃, and then adds the Powdered TPC of 50 liters of Skellysolve As and Ursol D total mole number 30%, and reaction rises to 2.5 ℃.Form gel after 4 minutes, the particle size range of gel is 1-5mm, median size 2.0mm.Strengthen power of agitator 25%, with the gel fragmentation.Keeping the total flux of methane and helium is 14m
3/ min takes Skellysolve As all in the system out of.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞7.6 of product.
Embodiment 9
Using a volume is 500 liters stainless steel stirring tank, adds 180 liters of NMP, adds Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3.6%, the massfraction of LiCl is 0.2%, reacting kettle inner pressure is controlled to be 1MPa (absolute pressure), adds 30 liters in propane, rare gas element is methane and helium, its flow is 3m
3/ min (volume ratio of methane and helium is 1: 1).When solution temperature is-9 ℃, add the Powdered TPC of Ursol D total mole number 70%, temperature of reaction rises to 2 ℃, and the propane spontaneous evaporation is reduced to solution temperature-5 ℃, the Powdered TPC that adds Ursol D total mole number 30% then, reaction rises to 2.5 ℃.Form gel after 4 minutes, the particle size range of gel is 1-5mm, median size 2.3mm.Strengthen power of agitator 25%, with the gel fragmentation.Keeping the total flux of methane and helium is 14m
3/ min slowly reduces system pressure to 0.1MPa (absolute pressure), makes propane vaporization effusion reactors all in the system.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞8.4 of product.
Embodiment 10
Using a volume is 500 liters stainless steel stirring tank, adds 180 liters of NMP, adds Ursol D and CaCl then
2, the concentration of control Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3.6%, reacting kettle inner pressure is controlled to be 0.1MPa (absolute pressure), add 220 liters of butane, when solution temperature is 0 ℃, add the molten TPC of Ursol D total mole number 80%, temperature of reaction rises to 5 ℃, and the butane spontaneous evaporation is reduced to 0 ℃ with solution temperature, the molten TPC that adds Ursol D total mole number 20% then, reaction rises to 4.5 ℃.Form gel after 7 minutes, the particle size range of gel is 1-5mm, median size 3.0mm.Strengthen power of agitator 28%, with the gel fragmentation.Slowly reduce system pressure, make butane vaporization effusion reactors all in the system.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞8.6 of product.
Embodiment 11
Using a volume is 500 liters stainless steel stirring tank, adds 180 liters of NMP, adds Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.26mol/L (with the volumeter of NMP), CaCl
2Massfraction be 3.4%, the massfraction of LiCl is 0.9%, reacting kettle inner pressure is controlled to be 0.01MPa (absolute pressure), add 260 liters of hexanes, when solution temperature is-15 ℃, add the molten TPC of Ursol D total mole number 80%, temperature of reaction rises to 2 ℃, the hexane spontaneous evaporation is reduced to solution temperature-5 ℃, adds the molten TPC of Ursol D total mole number 20% then, and reaction rises to 4.5 ℃.Form gel after 7 minutes, the particle size range of gel is 1-5mm, median size 3.0mm.Strengthen power of agitator 28%, with the gel fragmentation.Keep system pressure, make hexane steam effusion reactors all in the system.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞9.6 of product.
Embodiment 12
Using a volume is 1 liter stainless steel stirring tank, adds 100 milliliters of NMP, and 18 milliliters of pyridines and 80 milliliters of normal heptanes and 80 milliliters of octane-iso add Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.3mol/L (with the volumeter of NMP), CaCl
2Massfraction be 4%, the massfraction of LiCl is 6L/min for the 1.2%. nitrogen flow,, reacting kettle inner pressure is controlled to be 0.001MPa (absolute pressure).When solution temperature is-2 ℃, add the Powdered TPC of Ursol D total mole number 50.06%, temperature of reaction rises to 5 ℃, nitrogen flow is increased to 12L/min solution temperature is reduced to-6 ℃, the Powdered TPC that adds Ursol D total mole number 50% then, reaction rises to 1.2 ℃.Form gel after 2 minutes, the particle size range of gel is 1-3mm, median size 2.8mm.Strengthen power of agitator 30%,, strengthen nitrogen flow then, alkane all in the system is taken out of to 16L/min with the gel fragmentation.The gained gel particle is filtered, the washing, remove all impurity after, the intrinsic viscosity that obtains product is 7.8.
Embodiment 13
Using a volume is 1 liter stainless steel stirring tank, adds 150 milliliters of NMP, 15 milliliters of pyridines, and 80 milliliters of isoheptanes, 20 milliliters of neoheptanes and 50 milliliter 3, the 3-dimethylpentane adds Ursol D and CaCl then
2, LiCl, the concentration of control Ursol D is 0.24mol/L (with the volumeter of NMP), CaCl
2Massfraction is 3.6%, and the massfraction of LiCl is 0.8%, and nitrogen flow is 6L/min, and reacting kettle inner pressure is controlled to be 0.05MPa (absolute pressure).When solution temperature is-10 ℃, add the Powdered TPC of Ursol D total mole number 60.06%, temperature of reaction rises to 5 ℃, nitrogen flow is increased to 12L/min solution temperature is reduced to-6 ℃, the Powdered TPC that adds Ursol D total mole number 40% then, reaction rises to 5 ℃.Form gel after 5 minutes, the particle size range of polymer poly group is 1-5mm, median size 3.8mm.Strengthen power of agitator 35%,, keep nitrogen flow, alkane all in the system is taken out of the gel fragmentation.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞6.8 of product.
Embodiment 14
Using a volume is 500 liters stainless steel stirring tank, adds 150 liters of NMP, 15 liters of pyridines, and 250 liters of neoheptanes add Ursol D and CaCl then
2, the concentration of control Ursol D is 0.8mol/L (with the volumeter of NMP), CaCl
2Massfraction be 5%, methane flow is 2m
3/ min, reacting kettle inner pressure are controlled to be 0.05MPa (absolute pressure).When solution temperature is-12 ℃, add the molten TPC of Ursol D total mole number 60.06%, temperature of reaction rises to 4 ℃, and nitrogen flow is increased to 4m
3/ min is reduced to solution temperature-6 ℃, adds the molten TPC of Ursol D total mole number 40% then, and reaction rises to 3 ℃.Form gel after 4 minutes, the particle size range of polymer poly group is 1-5mm, median size 3.5mm.Strengthen power of agitator 35%,, keep methane flow and system pressure, neoheptanes all in the system is taken out of the gel fragmentation.The gained gel particle is filtered, washing, remove all impurity after, obtain intrinsic viscosity＞7.3 of product.
Claims (25)
1. wherein there is the alkane with 3-12 carbon atom in method for preparing PPTA in reaction system, utilize the latent heat of vaporization of described alkane to come the generation heat of shift reaction, thus control reaction temperature.
2. the method for claim 1, wherein said alkane is selected from propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, isohexane, 2,2-dimethylbutane, normal heptane, isoheptane, neoheptane, 3,3-dimethylpentane, octane-iso, nonane, decane, undecane, dodecane and their mixture.
3. claim 1 or 2 method, it also comprises the alkane that feeds rare gas element or have 1-3 carbon atom in reaction system.
4. the method for claim 3, wherein said rare gas element is selected from helium, argon gas, nitrogen and their mixture.
5. claim 3 or 4 method, the alkane of the wherein said 1-3 of a having carbon atom is selected from methane, ethane, propane and their mixture.
6. the method for one of claim 1-5, wherein said temperature regulation realizes by in following three kinds of modes one or more: (1) carries the alkane volatilization with 3-12 carbon atom with rare gas element or alkane with 1-3 carbon atom; (2) pressurized operation makes the alkane liquefaction with 3-12 carbon atom; (3) decompression operation makes the alkane gasification with 3-12 carbon atom.
7. the method for one of claim 1-6, described temperature of reaction be-25-5 ℃.
8. the method for one of claim 1-7 is wherein with in the disposable adding reaction system of described alkane.
9. the method for one of claim 1-8 wherein according to the Temperature Feedback of reaction, adds described alkane stage by stage in batches.
10. the method for one of claim 1-9, it may further comprise the steps:
A. in the container that stirs, add polar solvent, acid absorber, Ursol D, solubility promoter and have the alkane of 3-12 carbon atom,
B. making the pressure in the container is 0.001-1MPa, add to account for the p-phthaloyl chloride that the Ursol D mole number is 50%-110%,
C. add p-phthaloyl chloride in addition, make that institute adds the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.1, react the formation gel.
11. the method for claim 10, wherein p-phthaloyl chloride adds with powder type, and perhaps the liquid form with solution or molten state adds.
12. the method for claim 10 or 11, it is further comprising the steps of:
D. formed gel is broken by stirring.
13. the method for one of claim 10-12, it is further comprising the steps of:
E. remove the alkane that all has 3-12 carbon atom.
14. the method for one of claim 10-13, it is further comprising the steps of:
J. the gel particle with fragmentation filters, washs.
15. the method for one of claim 10-14, wherein said polar solvent is selected from the amides polar solvent.
16. the method for one of claim 10-15, wherein said polar solvent are selected from N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl propylene acid amides, hexamethylphosphoric acid triamide and their mixture.
17. the method for one of claim 10-16, wherein said acid absorber are selected from pyridine, α-Jia Jibiding, beta-picoline, γ-picoline, 2,6-lutidine, triethylamine, liquefied ammonia and their mixture.
18. the method for one of claim 10-17, wherein said solubility promoter is selected from LiCl, CaCl
2, MgCl
2With their mixture.
19. the method for one of claim 10-18, wherein adding accounts for the p-phthaloyl chloride that the Ursol D mole number is 50%-80% in step b.
20. the method for one of claim 10-19, wherein adding accounts for the p-phthaloyl chloride that the Ursol D mole number is 50%-70% in step b.
21. the method for one of claim 10-20, wherein adding accounts for the p-phthaloyl chloride that the Ursol D mole number is 50%-60% in step b.
22. the method for one of claim 10-21, wherein the pressure in the container is 0.001-0.1MPa in step b.
23. the method for one of claim 10-22, wherein the pressure in the container is 0.001-0.05MPa in step b.
24. the method for one of claim 10-23, wherein adding the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number in step c is 1: 1 to 1: 1.006.
25. the method for one of claim 10-24, the volume ratio of wherein said acid absorber and polar solvent are 0-0.2.
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| CN102558548A (en) * | 2011-12-15 | 2012-07-11 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN102838744A (en) * | 2012-10-03 | 2012-12-26 | 上海会博新材料科技有限公司 | Continuous production device for poly-p-phenylene terephthamide resin |
| CN114230786A (en) * | 2021-11-23 | 2022-03-25 | 烟台泰普龙先进制造技术有限公司 | Preparation method and application of superfine poly (p-phenylene terephthalamide) powder |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558548A (en) * | 2011-12-15 | 2012-07-11 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN102558548B (en) * | 2011-12-15 | 2014-01-29 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN102838744A (en) * | 2012-10-03 | 2012-12-26 | 上海会博新材料科技有限公司 | Continuous production device for poly-p-phenylene terephthamide resin |
| CN102838744B (en) * | 2012-10-03 | 2014-08-13 | 上海会博新材料科技有限公司 | Continuous production device for poly-p-phenylene terephthamide resin |
| CN114230786A (en) * | 2021-11-23 | 2022-03-25 | 烟台泰普龙先进制造技术有限公司 | Preparation method and application of superfine poly (p-phenylene terephthalamide) powder |
| CN114230786B (en) * | 2021-11-23 | 2023-09-22 | 烟台泰和兴材料科技股份有限公司 | Preparation method and application of superfine poly-p-phenylene terephthamide powder |
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