CN102190795B - Method for preparing poly(p-phenylene terephthalamide) - Google Patents
Method for preparing poly(p-phenylene terephthalamide) Download PDFInfo
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- CN102190795B CN102190795B CN201010118445.1A CN201010118445A CN102190795B CN 102190795 B CN102190795 B CN 102190795B CN 201010118445 A CN201010118445 A CN 201010118445A CN 102190795 B CN102190795 B CN 102190795B
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- 238000000034 method Methods 0.000 title claims abstract description 48
- -1 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 9
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 238000009834 vaporization Methods 0.000 claims abstract description 6
- 230000008016 vaporization Effects 0.000 claims abstract description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 239000007863 gel particle Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000001294 propane Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000001307 helium Substances 0.000 claims description 12
- 229910052734 helium Inorganic materials 0.000 claims description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 12
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000012535 impurity Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 230000004907 flux Effects 0.000 description 11
- 150000003222 pyridines Chemical class 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 4
- 229920006231 aramid fiber Polymers 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000001273 butane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 (is also called Fanglun l414, the English PPTA that is called for short) be a kind of liquid crystal state polymkeric substance by the long molecular composition of rigidity, by du pont company's 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 and have extremely strong interchain force along its length, its intensity is greater than 28 grams/dawn, is 5～6 times of high-quality steel, and modulus is steel or glass fibre 2～3 times, and toughness is 2 times of steel, and weight is only 1/5 of steel.Use temperature scope is extremely wide continuously, within the scope of-196 ℃ to 204 ℃, can normally move for a long time.Shrinking percentage at 150 ℃ is 0, under the high temperature of 560 ℃, does not decompose and does not melt, and has good insulativity and erosion resistance, and life cycle is very long, thereby wins the good reputation of " synthetic steel wire ".Be widely used in the fields such as defence and military, space flight and aviation, electromechanics, building, automobile, marine fishery, sports goods, world's annual requirement is over 500,000 tons.
At present, the preparation method of Fanglun l414 is mainly low-temperature solution polycondensation.First for example, for example, acid absorber (pyridine) and solubilizing agent (CaCl
2and LiCl) be dissolved in N-Methyl pyrrolidone (NMP), after all dissolving, add a certain amount of Ursol D, after it dissolves completely, with be cooled to-15-5 ℃ of ice-brine bath, add equimolar amount or slightly many p-phthaloyl chlorides (TPC), be adjusted to corresponding stirring velocity, carry out polycondensation, to reaction system generation gelation, then that gelinite is broken by certain mode, and water is washed residual solvent, solubilizing agent, hydrochloric acid and acid absorber off, finally the product after washing is dried, obtain pulverous Fanglun l414.
In this process, current prior art is all bathed as the type of cooling with cryosel, carrys out the temperature of control process.But when the scale of polymerization is larger, the area of simple reactor jacket heat exchange mode is limited, can not extraordinary control temperature, (reaction raw materials instantaneous time rapid polymerization becomes many short chain polymers to make reaction process exist implode, being accompanied by system viscosity increases with process and emits a large amount of heat rapidly, 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 effectively increase heat interchanging area principle, carries out temperature control.But because product is finally wanted gelation, not only can be bonded on stirring rake, also can be bonded on heat transfer tube, cause the heat-transfer capability of heat transfer tube to decline, also can exist the phenomenon of controlling temperature difficulty.Meanwhile, if a large amount of polymkeric substance is bonded on heat transfer tube, be equivalent to fix polymer gel, also increased the stirring rake needed power of cracking gel again.In addition, if once there is implode phenomenon, can form a large solid mass in whole reactor, not only affect the homogeneity of product, it is taken out to reactor also very difficult.Cause continuous production poor.If twin screw device is combined in polymerization process, the bulk solid block that can the be effective broken polymerization reaction late stage of its huge shearing force forms, but the reactant of this individual system (Ursol D and p-phthaloyl chloride) is responsive to water or oxygen, not only require raw material not moisture and isolated with oxygen, and high for the sealing requirements of device.And twin screw device is owing to existing mechanical rotation device, be difficult for sealing together with other equipment, or sealing difficulty is very big.It is very difficult that the reason of these engineerings causes the amplification of Fanglun l414 to be produced, and cost is huge, still there is no ripe amplification production technology at present.Even if produce relatively easy aramid fiber 1313 (a position aramid fiber, production process viscosity is low, relatively easy to control), its single cover reaction unit can not be too large, and production efficiency is lower, cannot effectively meet huge military and commercial market.
For 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 of preparing PPTA, wherein in reaction system, have the alkane with 3-12 carbon atom, utilize the latent heat of vaporization of described alkane to carry out the Heat of Formation of shift reaction, thereby control temperature of reaction.
Method of the present invention comprises the following steps:
A. in the container stirring, add polar solvent, acid absorber, Ursol D, solubility promoter and there is the alkane of 3-12 carbon atom
B. making the pressure in container is 0.001-1MPa, adds and accounts for the p-phthaloyl chloride that Ursol D mole number is 50%-110%.
C. add in addition p-phthaloyl chloride, making the total mole number of added p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.1, and reaction forms gel.
Embodiment
The inventive method is characterised in that in synthetic system, by certain operating method or under rare gas element existence condition, by the latent heat of vaporization of alkane, control the heat of moving of reaction, and the emulsification with polymeric solution phase by this alkane, the gel granularity generating due to formed emulsion droplet is less than 5mm, thereby guarantees that in polymerization process, overall viscosity increases few, in reactor, conduct heat so good, power of agitator changes little, makes polymerization process temperature steady, and scaling-up is easy.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, the method also comprises to passing into rare gas element in reaction system or having the alkane of 1-3 carbon atom.Preferably described rare gas element is selected from helium, argon gas, nitrogen and their mixture, described in there is 1-3 carbon atom alkane be selected from methane, ethane, propane and their mixture.
In one embodiment, described temperature regulates by one or more in following three kinds of modes and realizes: (1) is carried the alkane with 3-12 carbon atom with rare gas element or the alkane with 1-3 carbon atom and volatilized; (2) pressurized operation makes to have the alkane liquefaction of 3-12 carbon atom; (3) decompression operation makes to have the alkane gasification of 3-12 carbon atom.
In one embodiment, described temperature of reaction is-25-5 ℃.
In one embodiment, add in reaction system described alkane is disposable.
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 comprises the following steps:
A. in the container stirring, add polar solvent, acid absorber, Ursol D, solubility promoter and there is the alkane of 3-12 carbon atom
B. making the pressure in container is 0.001-1MPa, adds and accounts for the p-phthaloyl chloride that Ursol D mole number is 50%-110%.
C. add in addition p-phthaloyl chloride, making the total mole number of added p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.1, and reaction forms gel.
In one embodiment, p-phthaloyl chloride adds with powder type, or adds with the liquid form of solution or molten state.
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 all with 3-12 carbon atom.
In a preferred embodiment, the inventive method is further comprising the steps of:
J. broken gel particle is filtered, washed.
In one embodiment, described polar solvent is selected from 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-methylpyridine, beta-picoline, γ-picoline, 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 Ursol D mole number is 50%-80%, more preferably add and account for the p-phthaloyl chloride that Ursol D mole number is 50%-70%, most preferably add and account for the p-phthaloyl chloride that Ursol D mole number is 50%-60%.
In one embodiment, the pressure in step b in container is 0.001-0.1MPa, more preferably 0.001-0.05MPa.
In one embodiment, in step c, adding the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number is 1: 1 to 1: 1.006.
In the application, the relative molecular weight of resulting polymers characterizes by intrinsic viscosity.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 solvent, concentration C=0.5 Grams Per Minute liter, 30 degrees Celsius of probe temperatures.
Compare with the technology of existing production Fanglun l414, technology tool provided by the invention has the following advantages.
1) utilize the phase transformation evaporation and heat-exchange of liquid alkane to control temperature, do not need to use the cryosel that power consumption is large to bathe the type of cooling, complicated heat transfer tube need to be set in polymerization reactor, can significantly reduce production costs and device fabrication cost and maintenance cost so yet.
2) utilize liquid alkane emulsion polymerization reaction system, generated polymer poly granule footpath can be controlled at below 5mm, avoided the rod climbing phenomenon of polymkeric substance on stirring rake completely, can control the smooth discharging of polymkeric substance, carry out successive reaction, and can effectively reduce used power of motor, save power consumption.Do not need the polymerization reactor that uses dual-screw-stem machine or there are a plurality of stirring rakes, greatly reduce equipment sealing difficulty.
3) mode of utilizing liquid stable hydrocarbon and rare gas element jointly to add, effectively the heat exchange of modulation process and emulsification need, operate very easy, because polymer poly granule footpath is little, remaining reactant TPC and Ursol D are easily diffused into agglomerate inside, contact with each other, and the mole of polymerized such as carry out. and the polymerization effect than traditional technology (generating centimetre-sized bulk) is good, time is short, quality product high (the approximately high 2-3 of intrinsic viscosity).
4) mode of utilizing liquid stable hydrocarbon and rare gas element jointly to add, effectively the 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 affect the last handling process of Fanglun l414.
5) method of utilizing above-mentioned liquid stable hydrocarbon and rare gas element jointly to add is carried out the technology of the heat exchange of modulation polymerization process and emulsification needs, can allow to produce the Fanglun l414 that intrinsic viscosity reaches 7-10, only use conventional art to produce the corresponding motor of product and stirring rake mode that intrinsic viscosity is 2-5, can make equipment manufacturing cost reduce by 50%.
6) method of utilizing above-mentioned liquid stable hydrocarbon and rare gas element jointly to add is carried out the technology of the heat exchange of modulation process and emulsification needs, goes for single device and reaches ten thousand tons/year of Fanglun l414 production lines, can make the production cost of Fanglun l414 reduce 15-30%.
Following examples are used for further illustrating the present invention, but protection scope of the present invention are not had to 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 the stainless steel stirring tank of 1 liter, adds 100 milliliters of NMP, and 20 milliliters of pyridines and 80 milliliters of Skellysolve As, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.2mol/L (with the volumeter of NMP), CaCl
2massfraction be 3%, LiCl massfraction is that 0.5%. nitrogen flow is 1.32L/min,, reacting kettle inner pressure is controlled as 0.1MPa (absolute pressure).When solution temperature is-2 ℃, the Powdered TPC that adds Ursol D total mole number 50.06%, temperature of reaction rises to 4 ℃, nitrogen flow is increased to 6L/min and solution temperature is reduced to-6 ℃, then the Powdered TPC that adds Ursol D total mole number 50%, reaction rises to 1.2 ℃.After 2 minutes, form gel, the particle size range of gel is 1-3mm, median size 2.8mm.Strengthen power of agitator 30%, gel is broken, then strengthen nitrogen flow to 13.2L/min, Skellysolve As all in system is taken out of.Gained gel particle is filtered, and washing, removes after all impurity, and the intrinsic viscosity that obtains product is 7.5.
Embodiment 2
Using a volume is the stainless steel stirring tank of 100 liters, adds 30 liters of NMP, 3 liters of pyridines, and 20 liters of Skellysolve As and 25 liters of normal hexanes, then add Ursol D, CaCl
2and LiCl, the concentration of controlling Ursol D is 0.8mol/L (with the volumeter of NMP), CaCl
2massfraction be 2%, LiCl massfraction is 1%, argon flow amount is 0.5m
3/ min, reacting kettle inner pressure is controlled as 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 ℃, then adds the Powdered TPC of Ursol D total mole number 50%, and reaction rises to 1.2 ℃, after 6 minutes, forms gel, and the particle size range of polymkeric substance agglomerate is 1-3mm, median size 2.3mm.Strengthen power of agitator 30%, gel is broken.Then strengthen argon flow amount to 4.8m
3/ min, takes Skellysolve As all in system and normal hexane out of.Gained gel particle is filtered, and washing, removes after all impurity, and the intrinsic viscosity that obtains product is 8.5.
Embodiment 3
Using a volume is the stainless steel stirring tank of 10 liters, adds 4 liters of NMP, 0.5 liter of pyridine, and 0.6 liter of iso-pentane and 1 liter of neohexane, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.1mol/L (with the volumeter of NMP), CaCl
2massfraction be 1%, LiCl massfraction is 0.4%, helium gas flow is 36L/min, reacting kettle inner pressure is controlled as 0.1MPa (absolute pressure).When solution temperature is-15 ℃, in 4 minutes, add the TPC (concentration is 0.1mol/L) in NMP that is 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 ℃.After 5 minutes, form gel, the particle size range of gel is 0.5-3.5mm, all particle diameter 1.8mm.Strengthen power of agitator 20%, gel is broken.Then strengthen helium gas flow to 0.2m
3/ min, takes iso-pentane all in system and neohexane out of. and gained gel particle is filtered, and washing, removes after all impurity, and the intrinsic viscosity that obtains product is 7.8.
Embodiment 4
Using a volume is the stainless steel stirring tank of 1 liter, adds 100 milliliters of NMP, 10 milliliters of pyridines, and 200 ml n-hexanes and 150 milliliter 2,3-dimethylbutane, then adds Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.2mol/L (with the volumeter of NMP), CaCl
2massfraction be 3%, LiCl massfraction 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 as 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 ℃, then the Powdered TPC that adds Ursol D total mole number 20%, reaction rises to 2 ℃.After 3 minutes, form gel, the particle size range of gel is 1-4mm, median size 1.5mm.Strengthen power of agitator 10%, gel is broken.Then strengthen the total flux of methane and nitrogen to 26L/min, normal hexanes all in system and 2,3-dimethylbutane are taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 7.3 of product.
Embodiment 5
Using a volume is the glass stirring tank of 1 liter, adds 200 milliliters of NMP, 30 milliliters of pyridines, and 200 milliliters of isohexanes and 100 milliliters of neohexanes, then add Ursol D and CaCl
2, the concentration of controlling 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 as 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 and solution temperature is reduced to-2 ℃, then the Powdered TPC that adds Ursol D total mole number 50%, reaction rises to 3.5 ℃.After 6 minutes, form gel, the particle size range of gel is 1-4.5mm, median size 2.8mm.Strengthen power of agitator 10%, gel is broken.Then strengthen the total flux of ethane and propane to 10L/min, neohexanes all in system and isohexane are taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 10 of product.
Embodiment 6
Using a volume is the stainless steel stirring tank of 500 liters, adds 100 liters of NMP, 14 liters of pyridines, and 100 liters of iso-pentane and 50 liters of Skellysolve As, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.24mol/L (with the volumeter of NMP), CaCl
2massfraction be 3%, LiCl massfraction is 1%, methane flow is 1.6m
3/ min, reacting kettle inner pressure is controlled as 0.1MPa (absolute pressure).When solution temperature is-10 ℃, in 10 minutes, add the TPC (concentration is 0.24mol/L) in NMP that is 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 ℃.After 8 minutes, form gel, the particle size range of gel is 0.5-5mm, median size 3mm.Strengthen power of agitator 30%, gel is broken, then keep methane flow, iso-pentane all in system and Skellysolve A are taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 7.5. of product
Embodiment 7
Using a volume is the stainless steel stirring tank of 500 liters, adds 150 liters of NMP, and 20 liters of pyridines and 200 liters of normal hexanes, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.3mol/L (with the volumeter of NMP), CaCl
2massfraction be 3.8%, LiCl massfraction is 0.8%, methane, the flow of ethane and propane is 3m
3/ min (volume ratio of methane and ethane and propane is 2: 1: 1), reacting kettle inner pressure is controlled as 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 by methane, the total flux of ethane and propane is increased to 20m
3/ min is reduced to solution temperature-4 ℃, then adds the Powdered TPC of Ursol D total mole number 50%, and reaction rises to 3 ℃.After 5 minutes, form gel, the particle size range of gel is 1-4mm, median size 2.8mm.Strengthen power of agitator 30%, gel is broken.Then keep methane, the total flux of ethane and propane, reduces system pressure gradually to 0.1MPa (absolute pressure), and normal hexanes all in system is taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 7 of product.
Embodiment 8
Using a volume is the stainless steel stirring tank of 500 liters, adds 180 liters of NMP, and 30 liters of pyridines and 130 liters of Skellysolve As, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2massfraction be 3.6%, LiCl massfraction 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 as 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 ℃.After 4 minutes, form gel, the particle size range of gel is 1-5mm, median size 2.0mm.Strengthen power of agitator 25%, gel is broken.Keeping the total flux of methane and helium is 14m
3/ min, takes Skellysolve As all in system out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 7.6 of product.
Embodiment 9
Using a volume is the stainless steel stirring tank of 500 liters, adds 180 liters of NMP, then adds Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2massfraction be 3.6%, LiCl massfraction is 0.2%, reacting kettle inner pressure is controlled as 1MPa (absolute pressure), adds 30 liters, 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 ℃, the Powdered TPC that adds Ursol D total mole number 70%, temperature of reaction rises to 2 ℃, and propane spontaneous evaporation is reduced to solution temperature-5 ℃, then the Powdered TPC that adds Ursol D total mole number 30%, reaction rises to 2.5 ℃.After 4 minutes, form gel, the particle size range of gel is 1-5mm, median size 2.3mm.Strengthen power of agitator 25%, gel is broken.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 system.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 8.4 of product.
Embodiment 10
Using a volume is the stainless steel stirring tank of 500 liters, adds 180 liters of NMP, then adds Ursol D and CaCl
2, the concentration of controlling Ursol D is 0.28mol/L (with the volumeter of NMP), CaCl
2massfraction be 3.6%, reacting kettle inner pressure is controlled as 0.1MPa (absolute pressure), add 220 liters of butane, when solution temperature is 0 ℃, the molten TPC that adds Ursol D total mole number 80%, temperature of reaction rises to 5 ℃, and butane spontaneous evaporation is reduced to 0 ℃ by solution temperature, then the molten TPC that adds Ursol D total mole number 20%, reaction rises to 4.5 ℃.After 7 minutes, form gel, the particle size range of gel is 1-5mm, median size 3.0mm.Strengthen power of agitator 28%, gel is broken.Slowly reduce system pressure, make butane vaporization effusion reactors all in system.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 8.6 of product.
Embodiment 11
Using a volume is the stainless steel stirring tank of 500 liters, adds 180 liters of NMP, then adds Ursol D and CaCl
2, LiCl, the concentration of controlling 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 as 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 ℃, hexane spontaneous evaporation is reduced to solution temperature-5 ℃, then adds the molten TPC of Ursol D total mole number 20%, and reaction rises to 4.5 ℃.After 7 minutes, form gel, the particle size range of gel is 1-5mm, median size 3.0mm.Strengthen power of agitator 28%, gel is broken.Keeping system pressure, makes hexane steam effusion reactors all in system.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 9.6 of product.
Embodiment 12
Using a volume is the stainless steel stirring tank of 1 liter, adds 100 milliliters of NMP, and 18 milliliters of pyridines and 80 milliliters of normal heptanes and 80 milliliters of octane-iso, then add Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.3mol/L (with the volumeter of NMP), CaCl
2massfraction be 4%, LiCl massfraction is that 1.2%. nitrogen flow is 6L/min,, reacting kettle inner pressure is controlled as 0.001MPa (absolute pressure).When solution temperature is-2 ℃, the Powdered TPC that adds Ursol D total mole number 50.06%, temperature of reaction rises to 5 ℃, nitrogen flow is increased to 12L/min and solution temperature is reduced to-6 ℃, then the Powdered TPC that adds Ursol D total mole number 50%, reaction rises to 1.2 ℃.After 2 minutes, form gel, the particle size range of gel is 1-3mm, median size 2.8mm.Strengthen power of agitator 30%, gel is broken, then strengthen nitrogen flow to 16L/min, alkane all in system is taken out of.Gained gel particle is filtered, and washing, removes after all impurity, and the intrinsic viscosity that obtains product is 7.8.
Embodiment 13
Using a volume is the stainless steel stirring tank of 1 liter, adds 150 milliliters of NMP, 15 milliliters of pyridines, and 80 milliliters of isoheptanes, 20 milliliters of neoheptanes and 50 milliliter 3,3-dimethylpentane, then adds Ursol D and CaCl
2, LiCl, the concentration of controlling Ursol D is 0.24mol/L (with the volumeter of NMP), CaCl
2massfraction is that the massfraction of 3.6%, LiCl is 0.8%, and nitrogen flow is 6L/min, and reacting kettle inner pressure is controlled as 0.05MPa (absolute pressure).When solution temperature is-10 ℃, the Powdered TPC that adds Ursol D total mole number 60.06%, temperature of reaction rises to 5 ℃, nitrogen flow is increased to 12L/min and solution temperature is reduced to-6 ℃, then the Powdered TPC that adds Ursol D total mole number 40%, reaction rises to 5 ℃.After 5 minutes, form gel, the particle size range of polymkeric substance agglomerate is 1-5mm, median size 3.8mm.Strengthen power of agitator 35%, gel is broken, keep nitrogen flow, alkane all in system is taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 6.8 of product.
Embodiment 14
Using a volume is the stainless steel stirring tank of 500 liters, adds 150 liters of NMP, 15 liters of pyridines, and 250 liters of neoheptanes, then add Ursol D and CaCl
2, the concentration of controlling 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 is controlled as 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 ℃, then adds the molten TPC of Ursol D total mole number 40%, and reaction rises to 3 ℃.After 4 minutes, form gel, the particle size range of polymkeric substance agglomerate is 1-5mm, median size 3.5mm.Strengthen power of agitator 35%, gel is broken, keep methane flow and system pressure, neoheptanes all in system is taken out of.Gained gel particle is filtered, and washing, removes after all impurity, obtains the intrinsic viscosity > 7.3 of product.
Claims (23)
1. by p-phthaloyl chloride and Ursol D, prepared a method for PPTA, it comprises the following steps:
A. in the container stirring, add polar solvent, acid absorber, Ursol D, solubility promoter and there is the alkane of 3-12 carbon atom,
B. making the pressure in container is 0.001-1MPa, add and account for the p-phthaloyl chloride that Ursol D mole number is 50%-110%,
C. add in addition p-phthaloyl chloride, making the total mole number of added p-phthaloyl chloride and the ratio of Ursol D mole number is 1:1 to 1:1.1, and reaction forms gel,
Wherein in reaction system, there is the alkane with 3-12 carbon atom, utilize the latent heat of vaporization of described alkane to carry out the Heat of Formation of shift reaction, thereby control temperature of reaction by one or more in following three kinds of modes: (1) carries the alkane volatilization with 3-12 carbon atom with rare gas element or the alkane with 1-3 carbon atom; (2) pressurized operation makes to have the alkane liquefaction of 3-12 carbon atom; (3) decompression operation makes to have the alkane gasification of 3-12 carbon atom.
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 to the alkane that passes into 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. the method for claim 3, the alkane of the wherein said 1-3 of a having carbon atom is selected from methane, ethane, propane and their mixture.
6. claim 1 or 2 method, described temperature of reaction is-25-5 ℃.
7. claim 1 or 2 method, wherein add in reaction system described alkane is disposable.
8. claim 1 or 2 method, wherein, according to the Temperature Feedback of reaction, add described alkane stage by stage in batches.
9. the process of claim 1 wherein that p-phthaloyl chloride adds with powder type, or add with the liquid form of solution or molten state.
10. the method for claim 1, it is further comprising the steps of:
D. formed gel is broken by stirring.
The method of 11. claims 1, it is further comprising the steps of;
E. remove the alkane all with 3-12 carbon atom.
The method of 12. claims 1, it is further comprising the steps of:
J. broken gel particle is filtered, washed.
13. the process of claim 1 wherein that described polar solvent is selected from amides polar solvent.
14. the process of claim 1 wherein that described polar solvent is selected from N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl propylene acid amides, hexamethylphosphoric acid triamide and their mixture.
15. the process of claim 1 wherein that described acid absorber is selected from pyridine, α-methylpyridine, beta-picoline, γ-picoline, 2,6-lutidine, triethylamine, liquefied ammonia and their mixture.
16. the process of claim 1 wherein that described solubility promoter is selected from LiCl, CaCl
2, MgCl
2with their mixture.
17. the process of claim 1 wherein to add in step b and account for the p-phthaloyl chloride that Ursol D mole number is 50%-80%.
18. the process of claim 1 wherein to add in step b and account for the p-phthaloyl chloride that Ursol D mole number is 50%-70%.
19. the process of claim 1 wherein to add in step b and account for the p-phthaloyl chloride that Ursol D mole number is 50%-60%.
20. the process of claim 1 wherein that the pressure in container is 0.001-0.1MPa in step b.
21. the process of claim 1 wherein that the pressure in container is 0.001-0.05MPa in step b.
22. the process of claim 1 wherein that in step c, adding the total mole number of p-phthaloyl chloride and the ratio of Ursol D mole number is 1:1 to 1:1.006.
23. the process of claim 1 wherein that the volume ratio of described acid absorber and polar solvent is 0-0.2.
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|---|---|---|---|---|
| CN85100134A (en) * | 1985-04-01 | 1986-07-09 | 清华大学 | The synthesis technique of PPTA |
| US5789530A (en) * | 1996-12-20 | 1998-08-04 | The Penn State Research Foundation | Catalyzed synthesis of aramid from carbon monoxide, aromatic dichlorides, and diamines |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100134A (en) * | 1985-04-01 | 1986-07-09 | 清华大学 | The synthesis technique of PPTA |
| US5789530A (en) * | 1996-12-20 | 1998-08-04 | The Penn State Research Foundation | Catalyzed synthesis of aramid from carbon monoxide, aromatic dichlorides, and diamines |
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| Title |
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| "NMP-CaCl2体系中低温缩聚合成PPTA研究";冀国龙等;《合成技术及应用》;20081231;第23卷(第4期);第1-4页 * |
| 冀国龙等."NMP-CaCl2体系中低温缩聚合成PPTA研究".《合成技术及应用》.2008,第23卷(第4期),第1-4页. |
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