CN109553769A - A kind of p-aramid fiber resin continuous polymerization system and its method - Google Patents
A kind of p-aramid fiber resin continuous polymerization system and its method Download PDFInfo
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- CN109553769A CN109553769A CN201811433341.2A CN201811433341A CN109553769A CN 109553769 A CN109553769 A CN 109553769A CN 201811433341 A CN201811433341 A CN 201811433341A CN 109553769 A CN109553769 A CN 109553769A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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Abstract
The present invention relates to a kind of p-aramid fiber resin continuous polymerization system and its methods, belong to macromolecule synthesising technology field.Present system includes a double screw extruder and a reaction kettle, it is equipped with inlet port and outlet port, monomer solution is conveyed by the feed inlet of double screw extruder, the discharge port of double screw extruder is connected with the feed inlet of reaction kettle, and p-aramid fiber resin is discharged by the discharge port of the reaction kettle.The present invention is by the pre-polymerization in double screw extruder and then carries out subsequent solid phase polycondensation in a kettle and is crushed, it not only ensure that the stability of polymerization reaction, but also the advantage of the big volume of reaction kettle can well solve polymerization later period polymerizate Volumetric expansion.The combination of reaction kettle and twin-screw can not only greatly improve the efficiency of single device polymerization, but also equipment cost can be greatly reduced.
Description
Technical field
The present invention relates to a kind of p-aramid fiber resin continuous polymerization system and its methods, belong to macromolecule synthesising technology neck
Domain.
Background technique
Para-aramid fiber is a kind of high score with numerous excellent properties such as high-strength and high-modulus, high temperature resistant, resistant to chemical etching
Sub- material has important application value in national defence, aerospace and numerous civil fields.High-volume continuous and stable production contraposition virtue
Synthetic fibre resin poly(p-phenylene terephthalamide) (PPTA) is to realize the precondition of para-aramid fiber batch production.Utilize low temperature
It has been well-known technique that solution polycondensation, which synthesizes PPTA resin, i.e., by monomer paraphthaloyl chloride (TPC) and p-phenylenediamine (PPD)
Low-temperature polycondensation is carried out in solvent N-methyl pyrilidone (NMP) and cosolvent calcium chloride compound system, is washed out dry
To pure PPTA resin.In order to guarantee the stability of PPTA resin quality, it is all made of continuous polymerization production PPTA at present.PPTA
Polymerization be a complicated phase transition process, from low-viscosity (mobile) liquid to gel until reaction the later period become solid.In addition, PPTA is poly-
Conjunction thermal discharge is big, and entire polymerization process needs to keep stirring polymerization system, TPC and PPD end group is on the one hand made to have the chance of reaction,
On the other hand it is exactly that can remove reaction heat in time, prevents local implode.Therefore suitable PPTA polymerization reaction dress is designed
Setting is a key.
Double screw extruder (or kneader) is the main reactor pattern of current PPTA continuous polymerization.For theoretically,
The combination of different function element can make twin-screw meet in PPTA polymerization process the requirement for mixing, shearing, be crushed and conveying, still
How to design twin-screw reaction system and still remains many problems.Such as in order to guarantee that polymerization system can in PPTA polymerization process
Sufficient hybrid reaction is obtained, interface is updated by shear agitation and removes reaction heat, guarantees do not have dead angle in aggregation container, utilizes
It is optimal that single-order twin-screw, which carries out polymerization,.But single-order twin-screw cannot improve PPTA difference polymerization rank by adjusting the speed respectively
The reaction condition of section.In addition, volume expansion after PPTA polymerization later period material is broken, easily causes blocking or material reflux, single-order
Twin-screw is difficult to solve this problem.PPTA polymerization reaction is carried out using multistage (mostly using two ranks) twin-screw system, although tool
Have the advantages that adjust the speed respectively to better conform to PPTA difference polymerization stage difference and require, but high equipment cost, connect between screw rod
Connect complexity.Other than the design challenges of above-mentioned twin-screw polymer reactor, there are one very for multistage double-screw reactor
Big disadvantage: the polymerization efficiency of second-order double-screw reactor is lower, and cost effectiveness is higher in other words.It can be produced in PPTA polymerization process
Raw byproduct hydrogen chloride, under the conditions of polymerizeing higher temperature and strong friction, hydrogen chloride is to common metal screw element and cylinder
It will cause serious corrosion.Serious corrosion will lead between screw element and gap increases between element and cylinder, cause
Polymer residue and polymerization time extend, and polymerize quality decline.If manufacturing double-screw reactor, a side using special alloy
Face can be such that equipment manufacturing cost greatly improves, and production cost is substantially improved, and special alloy manufacture major diameter twin-screw system is adding
Work is technically also faced with lot of challenges.
Self-cleaning reactor is another PPTA polymer reactor, is invented earliest by LIST company, Switzerland.Automatically cleaning is anti-
It answers device that screw rod and tradition stirring are integrated into an equipment, not only with the self-cleaning function of screw rod, but also biography can be retained
The advantages of system stirring.But structure is complicated for self-cleaning reactor, the speed of service is lower, for the broken and delivery ratio in PPTA later period
It is more difficult.Reaction kettle is the reactor of PPTA batchwise polymerization.Reaction kettle has many advantages, such as that structure simple operation is high-efficient, but one
A reaction kettle is difficult to meet the requirement of all phase transition process in PPTA polymerization process simultaneously, does not also have quantity-produced condition.
Therefore new PPTA polymerization reaction system is designed to have great importance for high-efficiency stable continuous polymerization PPTA.
Summary of the invention
The purpose of the present invention is to propose to a kind of p-aramid fiber resin efficient stable continuous polymerization method and its systems, by PPTA
Polymerization completed in two different reactors in two stages: the polymerization before PPTA gel be placed in double screw extruder into
Row carries out the solid phase polycondensation in PPTA later period and broken put in a kettle.Using double-screw structure advantage, can effectively solve
Strong mixing, conveying and the reaction that PPTA polymerization initial stage needs move heat, and reaction kettle can satisfy the broken expansion of PPTA polymerization later period
And need the process of long period completion solid phase polycondensation.By double screw extruder and reaction kettle in conjunction with continuous to complete PPTA
Polymerization reaction, not only single device production capacity can be substantially improved, and equipment cost can decline to a great extent, and can guarantee that PPTA is poly-
The continuous-stable of conjunction.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of p-aramid fiber resin continuous polymerization system proposed by the present invention, which is characterized in that squeezed including a twin-screw
Machine and a reaction kettle out, are equipped with inlet port and outlet port, and it is molten to convey monomer by the feed inlet of the double screw extruder
Liquid, the discharge port of the double screw extruder are connected with the feed inlet of the reaction kettle, are arranged by the discharge port of the reaction kettle
P-aramid fiber resin out.
Further, the reaction kettle includes autoclave body, drive system and two refrigeration systems;Stirring is equipped in the autoclave body
Crusher members, including main shaft and with main shaft rotation and spaced multilayer stirs broken paddle, adjacent two layers stirring is broken
Paddle is arranged in the angle of 180/N, and N is the number of plies for stirring broken paddle, and each layer stirs broken paddle by being fixed on the main shaft
Cross bar is formed with evenly arranged multiple blades on the cross bar are fixed on, and blade is in small point of the big centre in both ends on corresponding cross bar
Cloth;One end of the main shaft protrude from the outer wall of the autoclave body and by the drive system drive rotate, the main shaft it is another
End is fixedly connected with bearing;The outer wall of the autoclave body be equipped with it is jacket structured, two refrigeration systems by this it is jacket structured will
Temperature in the reaction kettle is controlled at 50~70 DEG C;Further respectively had on the outer wall of the autoclave body feed inlet, nitrogen inlet and
Discharge port, the discharge outlet are equipped with the outlet valve for controlling discharging speed.
Further, polymer material stops 10~20min in the reaction kettle, and the volume of the reaction kettle is described
2~4 times of the monomer solution volume conveyed in twin-screw extrusion machine inlet 15min.
Further, the reaction kettle uses vertical structure, and the autoclave body top is cylindrical, lower part is vertebral body structure,
And the bearing is located inside vertebral body structure, the discharge port is located at vertebral body structure bottom.
Further, the reaction kettle uses horizontal type structure;The autoclave body is integrally cylindrical, and described stir is crushed paddle
Blade has 3~5 ° of deflection angle relative to the main shaft 21;The bearing is located at outside the autoclave body.
The present invention also proposes a kind of side that p-aramid fiber resin is prepared using above-mentioned p-aramid fiber resin continuous polymerization system
Method, which is characterized in that method includes the following steps:
(1) under nitrogen protection prepare p-phenylenediamine/salt/N-Methyl pyrrolidone solution, wherein salt p-phenylenediamine/
Molar concentration in salt/N-Methyl pyrrolidone solution is 0.4-0.8mol/L, and p-phenylenediamine is in p-phenylenediamine/salt/N- methyl
Molar concentration in pyrrolidone solution is 0.2-0.5mol/L, water content in p-phenylenediamine/salt/N-Methyl pyrrolidone solution
In 50-150ppm, fluctuation range is ± 10ppm for control;Then p-phenylenediamine/salt/N-Methyl pyrrolidone solution is cooled to-
5~5 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and the first solution is made;Another polymerized monomer is weighed to benzene
Dimethyl chloride is maintained at 90-105 DEG C, and temperature fluctuation is no more than ± 0.5 DEG C;
(2) when polymerization starts, by pipeline the first solution and paraphthaloyl chloride are respectively delivered to metering pump described in
It is mixed in the monomer mixer of double screw extruder, and leads to nitrogen protection in monomer mixer, obtain the second solution, the
It is (1.01~1) to the molar ratio of paraphthaloyl chloride and p-phenylenediamine in two solution: 1, mixed second solution flows automatically to
Prepolymerization reaction is carried out in the double-screw reactor and obtains prepolymer product, wherein screw speed control is in 100-300rpm, reaction
Temperature is controlled at 30~70 DEG C, and the viscosity of the polymer material of the double screw extruder discharge outlet is maintained at ten thousand cp.s of 5-20;
(3) prepolymer product made from step (2) is pipelined in the reaction kettle and is carried out under nitrogen protection
Solid phase polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 300-
1000rpm controls polymerization temperature at 50-70 DEG C;
(4) polymerizate made from step (3) is washed, it is then 8-15 hours dry at 80-150 DEG C, it obtains
Poly(p-phenylene terephthalamide) toner.
A kind of p-aramid fiber resin continuous polymerization system proposed by the present invention and its method, its advantage is that:
The method of the present invention improves the polymerization methods of p-aramid fiber resin PPTA, and continuously gathers for high-efficiency stable
Conjunction method specially devises the composite reaction device that a twin-screw adds reaction kettle, to ensure high efficiency, the stabilization of PPTA polymerization
Property and continuity.Demand as mixed uniformly as possible is needed early period for PPTA polymerization, is mixed with twin-screw completion monomer and pre-
Collecting process;Aiming at the problem that polymerizeing the later period and needing strength to be crushed condensate and condensate volume to significantly increase, with reaction kettle come
Complete PPTA later period solid phase polycondensation and shattering process.In addition, double screw extruder is difficult to because being limited by processing method
Significant volume, single machine production capacity are limited.And reaction kettle is then without volumetric constraint, therefore after completing polymerization with reaction kettle substitution twin-screw
The function of phase, not only continuous production and stability are more preferable, but also can break through twin-screw single machine production capacity, and reaction kettle cost
Far below double screw extruder, equipment cost can also be greatly reduced.
Detailed description of the invention
Fig. 1 is vertical reaction kettle structural representation in p-aramid fiber resin efficient stable continuous polymerization system proposed by the present invention
Figure.
Fig. 2 is horizontal reacting kettle structural representation in p-aramid fiber resin efficient stable continuous polymerization system proposed by the present invention
Figure.
Specific embodiment
With reference to the accompanying drawings and embodiments to a kind of p-aramid fiber resin continuous polymerization system proposed by the present invention and its side
Detailed description are as follows for method:
It is a kind of overall structure diagram of p-aramid fiber resin continuous polymerization system of the embodiment of the present invention referring to Fig. 1,
The continuous polymerization system includes a double screw extruder and a reaction kettle, is equipped with inlet port and outlet port, passes through double spiral shells
The feed inlet conveying monomer paraphthaloyl chloride and p-phenylenediamine/N-Methyl pyrrolidone/salting liquid of bar extruder, twin-screw squeeze
The discharge port of machine is connected with the feed inlet of reaction kettle out, and p-aramid fiber resin is discharged by the discharge port of reaction kettle.
Double screw extruder is conventional single-order double screw extruder, the reaction for the polymerization reaction before PPTA gel
Device, including drive system 11, monomer mixer 12, double-screw reactor 13 and two refrigeration systems (15,16);Wherein, monomer
The discharge port of mixer 12 is connected with the feed inlet of double-screw reactor 13 by pipeline, and single order is equipped in double-screw reactor 13
Screw element 14, the screw element drive rotating Vortex by drive system 11, and single order screw element 14 is by hybrid element and conveying
Element (each element in the present embodiment single order twin-screw element is commercial product) composition, screw slenderness ratio are designed as 10-20,
Screw speed is controlled in 100-300rpm;Monomer p-phenylene diamine and paraphthaloyl chloride are completed uniformly mixed in double screw extruder
It closes, and spontaneous is polymerize.Double-screw reactor 13 is respectively equipped with refrigerating fluid import on the side wall of inlet port and outlet port
It is exported with refrigerating fluid, which connect with the liquid outlet of refrigeration system and liquid return hole respectively, refrigeration system
(15,16) for the heat of polymerization of PPTA in double-screw reactor 13 to be continuously removed, it is ensured that PPTA, which polymerize continuous-stable, to carry out.It is logical
Cross the automatic control of refrigeration system, it is ensured that PPTA polymerization temperature is controlled at 30~70 DEG C.
Vertical structure, including autoclave body 1, drive system 3 and two refrigeration systems (4,5) can be used in reaction kettle.It is set in autoclave body 1
There are stirring crusher members 2, which uses high strength steel or stainless steel material, it is ensured that will not be broken in operation.Stirring
Crusher members 2 include main shaft 21 and are crushed paddle 22 with main shaft rotation and the stirring of spaced multilayer, and two adjacent stirrings are broken
Paddle spacing is not less than high 1.5 times of maximum stirrer paddle, and 3 times high no more than maximum stirrer paddle.Adjacent two layers stir
It mixes broken paddle 22 to be arranged in the angle of 180/N, N is the number of plies for stirring broken paddle 22, and each layer stirs broken paddle 22 by being fixed on master
The cross bar 221 of axis 21 and be fixed on evenly arranged multiple blades 222 composition on the cross bar (in Fig. 1 for illustrate label 21,
22,221,222, it is detailed in Fig. 2), and blade 222 is in the small distribution in the big centre in both ends on corresponding cross bar 221, for ensuring own
PPTA gel group can be stirred paddle Stirring and arrive, thus by being strongly crushed, and this no dead angle of design, it is ensured that PPTA
Gel group can be crushed in time, and local implode will not occur.The present embodiment, which sets to have three layers, stirs broken paddle, and adjacent two stirring is broken
Angle between broken paddle 22 is 60 °;In Fig. 1, due to being laid at an angle between the adjacent broken paddle of two stirrings, show in sectional view
The length of cross bar, which shows, in the broken paddle of stirring anticipated out from top to bottom successively becomes larger and blade is in the state of upper tightly lower sparse, respectively
The laying that layer stirs 221 size of cross bar and blade 222 in broken paddle can be (each according to industrial design standard setting according to torque
The size of the broken slurry of layer stirring can be identical or different);One end of main shaft 21 protrudes from 1 outer wall of autoclave body and by drive system 3
Driving rotation, so that the revolving speed of the broken slurry 22 of stirring is in 300-1000rpm, the other end of main shaft 21 is fixedly connected with bearing 6, should
Bearing 6 is used for fixed main shaft 21, it is ensured that stable when stirring system runs at high speed.The top of the present embodiment autoclave body 1 is in circle
Tubular, and the external wall of upper portion of autoclave body 1 is equipped with jacket structured (using carbon steel or stainless steel material), two refrigeration systems (4,5) are logical
It is jacket structured by PPTA reaction heat in reaction kettle and the frictional heats such as broken remove to cross this, it is ensured that temperature control is 50 in reaction kettle
~70 DEG C.Feed inlet 10, which is further respectively had, at the top of the outer wall of autoclave body 1 (passes through pipeline for the discharge port with double screw extruder
Connection) and two nitrogen inlets (8,9, it, can for the nitrogen protection of from the offer high-purity such as 99.99-99.999% to autoclave body 1
Reduce the influence of moisture in air and oxygen to polymerization), the outer wall bottom of autoclave body 1 is vertebral body structure and is equipped with discharge port, is convenient for
The discharge of polymerizate, bearing 6 are located in vertebral body structure, and discharge outlet is equipped with the outlet valve 7 for controlling discharging speed.This is
When system operation, driving device 3 drives the broken slurry 22 of stirring to be quickly stirred by main shaft 21 or to be crushed double screw extruder defeated
The gel masses sent, make to be aggregated under solid state shape and continue, and by quickly mix it is broken polymerization reaction heat is taken out of,
Reaction heat is removed by refrigeration system (4,5).Polymer material stops 10-20min in a kettle, and reactor volume squeezes for twin-screw
2~4 times of p-phenylenediamine/calcium chloride/N-Methyl pyrrolidone liquor capacity in machine inlet 15min out.
Horizontal type structure also can be used in reaction kettle, referring to fig. 2, the structure of horizontal reacting kettle and vertical response kettle shown in Fig. 1
It is most of identical, the difference is that:
(1) the generally wholecircle column of autoclave body 1, can be improved the service efficiency of reaction kettle;
(2) for the ease of driving and be discharged polymer material, stir the blade 222 of broken paddle 2 with respect to main shaft 21 have one 3~
5 ° of deflection angles (i.e. blade is about the asymmetric setting of main shaft), the angle may insure to stir broken slurry 2 when rotating at high speed not only
Broken polymer material can be stirred, and polymer material can be conveyed to discharge outlet;
(3) bearing 6 is set to outside autoclave body 1, on the one hand can reduce the hydrogen chloride of PPTA polymerization by-product in this way to bearing 6
Corrosion, on the other hand, outboard bearing be fixedly mounted it is relatively easy.
Remaining is identical as vertical response kettle, and details are not described herein again.
Two kinds of reaction kettles provided in an embodiment of the present invention have the characteristics that respective, wherein horizontal reacting kettle is stable, axis
Hold external, internal structure is simple;Without considering discharging problem, material moves down vertical response kettle automatically by gravity.
The present invention substitutes the high-order double screw extruder in multistage double screw extruder using reaction kettle, has following excellent
Gesture:
1, reaction kettle can be with high-speed stirred.And screw rod is difficult to realize the revolving speed of 400m/min or more, especially major diameter
Screw rod, because screw rod cooperation is close, the restriction of screw speed is more obvious;
2, large volume can be used in reaction kettle, it is easy to solve the problems, such as that PPTA polymerize later period volume expansion.Twin-screw mesh
Preceding maximum gauge can only accomplish diameter 200mm or so, the especially twin-screw of special alloy material;
3, single machine production capacity can be greatly improved with twin-screw+mixer design, and full twin-screw combination is wanted to improve production capacity
It is more difficult;
4, reaction kettle structure is simple, and manufacture is easy, and equipment cost is well below twin-screw.
The present invention also proposes a kind of method for preparing p-aramid fiber using above-mentioned p-aramid fiber continuous polymerization system, the party
Method includes following steps:
(1) it will first be dehydrated salt CaCl under nitrogen protection2, LiCl or CaCl2N- methyl is dissolved into the mixture of LiCl
In pyrrolidones (NMP), quantitative p-phenylenediamine (PPD) is added after solution obtained is then cooled to 10-20 DEG C, makes PPD
Dissolution wherein obtains phenylenediamine/salt/N-Methyl pyrrolidone (PPD/ salt/NMP) solution, salt rubbing in PPD/ salt/nmp solution
Your concentration is 0.4-0.8mol/L, and molar concentration of the p-phenylenediamine in PPD/ salt/nmp solution is 0.2-0.5mol/L, PPD/
In 50-150ppm, fluctuation range is ± 10ppm for water content control in salt/nmp solution;Then PPD/ salt/nmp solution is cooled down
To -5~5 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and the first solution is made;Weigh another polymerized monomer pair
Phthalyl chloride (TPC) places it in and keeps the temperature 90-105 DEG C in storage tank, and temperature fluctuation is no more than ± 0.5 DEG C.
(2) when polymerization starts, the first solution and TPC are respectively delivered to by double screw extruder by pipeline with metering pump
It is quickly mixed in monomer mixer, and leads to nitrogen protection in monomer mixer, obtain the second solution, it is right in the second solution
The molar ratio of TPC and PPD are as follows: TPC:PPD=(1.01~1): 1, mixed second solution quickly flows automatically to twin-screw reaction
Prepolymerization reaction is carried out in device, obtains prepolymer product.Wherein, screw speed control, will be anti-by refrigeration system in 100-300rpm
Answer temperature control at 30~70 DEG C;By adjusting polymerization temperature and screw speed, make the polymerization of double screw extruder discharge outlet
Material is maintained at low-viscosity gel state, and viscosity is in ten thousand cp.s of 5-20;
(3) prepolymer product made from step (2) is pipelined in reaction kettle and carries out solid phase under nitrogen protection
Polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 300-
1000rpm controls 50-70 DEG C of polymerization temperature;
(4) polymerizate made from step (3) is washed, it is then 8-15 hours dry at 80-150 DEG C, it obtains
Poly(p-phenylene terephthalamide) (PPTA) toner.
The embodiment of the method for the present invention introduced below:
Embodiment 1
(1) PPD/CaCl is intermittently or serially prepared with reference first to ZL201210485817.3 or CN201610239874.12/
Nmp solution, the specific steps are as follows: under nitrogen protection by chloride dehydrate calcium (CaCl2) it is dissolved into N-Methyl pyrrolidone (NMP)
In, then the solution is cooled to after 15 DEG C, quantitative p-phenylenediamine (PPD) stirring and dissolving is added, obtains PPD/CaCl2/NMP
Solution;Wherein, calcium chloride is in PPD/CaCl2Molar concentration in/nmp solution is 0.6mol/L, and p-phenylenediamine is in PPD/CaCl2/
Molar concentration in nmp solution is 0.4mol/L, PPD/CaCl2Water content in/nmp solution is 100 ± 5ppm.Then will
PPD/CaCl2/ nmp solution cools to 0 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and the first solution is made.Claim
Another polymerized monomer paraphthaloyl chloride (TPC) is taken, it is kept the temperature to 100 DEG C in storage tank, temperature fluctuation is no more than ± 0.5
℃。
(2) when polymerization starts, the first solution and TPC are respectively delivered to by twin (double) screw extruder by pipeline with metering pump
Monomer mixer is quickly mixed, and leads to nitrogen protection in monomer mixer, obtains the second solution.Wherein paraphenylene terephthalamide
The molar ratio of chlorine and p-phenylenediamine are as follows: paraphthaloyl chloride: p-phenylenediamine=1.0007:1, mixed second solution are quick
It flows automatically to and carries out prepolymerization reaction in the double-screw reactor of twin (double) screw extruder;Screw speed control exists in double screw extruder
200rpm, by refrigeration system by reaction temperature control 30-70 DEG C (since screw rod difference zone temperatures can be different, just into
The temperature of screw rod can be lower, higher in the backward, therefore reaction temperature control is in a section.Temperature of reaction kettle section reason
It is identical), obtain prepolymer product;By adjusting polymerization temperature and screw speed, make the polymer material in double screw extruder exit
It is maintained at low-viscosity gel state, viscosity is about in 100,000 cp.s.
(3) prepolymer product is pipelined in reaction kettle and carries out solid phase polycondensation under nitrogen protection and is finally broken
It is broken into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring controls polymerization temperature and exists in 500rpm
50-70℃。
(4) crumbs shape polymerizate obtained is first washed with massive laundering, then filters out polymer and is done at 110 DEG C
Dry 12 hours, obtain poly(p-phenylene terephthalamide) (PPTA) toner.
The logarithmic viscosity number of the present embodiment PPTA toner is tested with Ubbelohde viscometer, takes 5 at random in production process
A sample surveys its viscosity, calculates its data deviation with normalized form.Determination of ubbelohde viscometer logarithmic specific concentration viscosity is 6.3 ± 0.2.
Embodiment 2
(1) PPD/CaCl is intermittently or serially prepared with reference first to ZL201210485817.3 or CN201610239874.12/
Nmp solution, the specific steps are as follows: under nitrogen protection by chloride dehydrate calcium (CaCl2) it is dissolved into N-Methyl pyrrolidone (NMP)
In, then the solution is cooled to after 20 DEG C, quantitative p-phenylenediamine (PPD) stirring and dissolving is added, obtains PPD/CaCl2/NMP
Solution;Wherein, calcium chloride is in PPD/CaCl2Molar concentration in/nmp solution is 0.7mol/L, and p-phenylenediamine is in PPD/CaCl2/
Molar concentration in nmp solution is 0.5mol/L, PPD/CaCl2Water content is 80 ± 5ppm in/nmp solution.Then by PPD/
CaCl2/ nmp solution cools to 0 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and the first solution is made.It weighs another
It is kept the temperature 100 DEG C by one polymerized monomer paraphthaloyl chloride (TPC) in storage tank, and temperature fluctuation is no more than ± 0.5 DEG C.
(2) when polymerization starts, the first solution and TPC are respectively delivered to by twin (double) screw extruder by pipeline with metering pump
Monomer mixer is quickly mixed, and leads to nitrogen protection in monomer mixer, obtains the second solution.Wherein paraphenylene terephthalamide
The molar ratio of chlorine and p-phenylenediamine are as follows: paraphthaloyl chloride: p-phenylenediamine=1.0006:1, mixed second solution are quick
It flows automatically to and carries out prepolymerization reaction in the double-screw reactor of twin (double) screw extruder;The screw speed control of twin (double) screw extruder exists
Reaction temperature is controlled at 30-70 DEG C by refrigeration system, obtains prepolymer product by 300rpm;By adjusting polymerization temperature and spiral shell
Bar revolving speed makes the polymer material in double screw extruder exit be maintained at low-viscosity gel state, and viscosity is about in 200,000 cp.s.
(3) prepolymer product made from step (2) is pipelined in reaction kettle and carries out solid phase under nitrogen protection
Polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 300rpm, control
Polymerization temperature processed is at 50-70 DEG C.
(4) crumbs shape polymerizate made from step (3) is first washed with massive laundering, then filters out polymer and exists
It is 12 hours dry under the conditions of 100 DEG C, obtain the PPTA powder of water content 1.8% or so.
It is 6.10 ± 0.2 with the logarithmic specific concentration viscosity of determination of ubbelohde viscometer PPTA powder manufactured in the present embodiment.
Embodiment 3
(1) PPD/CaCl is intermittently or serially prepared with reference first to ZL201210485817.3 or CN201610239874.12/
Nmp solution, the specific steps are as follows: under nitrogen protection by chloride dehydrate calcium (CaCl2) it is dissolved into N-Methyl pyrrolidone (NMP)
In, then the solution is cooled to after 10 DEG C, quantitative p-phenylenediamine (PPD) stirring and dissolving is added, obtains PPD/CaCl2/NMP
Solution;Wherein, calcium chloride is in PPD/CaCl2Molar concentration in/nmp solution is 0.5mol/L, and p-phenylenediamine is in PPD/CaCl2/
Molar concentration in nmp solution is 0.3mol/L, PPD/CaCl2Water content is 130 ± 10ppm in/nmp solution.Then will
PPD/CaCl2/ nmp solution cools to 0 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, obtains the first solution.Claim
Another polymerized monomer paraphthaloyl chloride (TPC) is taken, it is kept the temperature to 100 DEG C in storage tank, temperature fluctuation is no more than ± 0.5
℃。
(2) when polymerization starts, the first solution and TPC are respectively delivered to by twin (double) screw extruder by pipeline with metering pump
Monomer mixer is quickly mixed, and leads to nitrogen protection in monomer mixer, obtains the second solution.Wherein paraphenylene terephthalamide
The molar ratio of chlorine and p-phenylenediamine are as follows: paraphthaloyl chloride: p-phenylenediamine=1.0008:1, mixed second solution are quick
It flows automatically to and carries out prepolymerization reaction in the double-screw reactor of twin (double) screw extruder;Wherein, the screw speed control of twin (double) screw extruder
System controls reaction temperature at 30-70 DEG C in 100rpm, by refrigeration system, obtains prepolymer product;By adjusting polymerization temperature
And screw speed, so that the polymer material in double screw extruder exit is maintained at low-viscosity gel state, viscosity is about 150,000
cp.s。
(3) prepolymer product made from step (2) is pipelined in reaction kettle and carries out solid phase under nitrogen protection
Polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 800rpm, control
Polymerization temperature processed is at 50-70 DEG C;
(4) crumbs shape polymerizate made from step (3) is first washed with massive laundering, then filters out polymer and exists
It is 12 hours dry under the conditions of 100 DEG C, obtain 1.5% or so PPTA powder of water content.
It is 6.30 ± 0.2 with the logarithmic specific concentration viscosity of determination of ubbelohde viscometer PPTA powder manufactured in the present embodiment.
Embodiment 4
(1) PPD/CaCl is intermittently or serially prepared with reference first to ZL201210485817.3 or CN201610239874.12/
Nmp solution, the specific steps are as follows: under nitrogen protection by chloride dehydrate calcium (CaCl2) it is dissolved into N-Methyl pyrrolidone (NMP)
In, then the solution is cooled to after 15 DEG C, quantitative p-phenylenediamine (PPD) stirring and dissolving is added, obtains PPD/CaCl2/NMP
Solution;Wherein, calcium chloride is in PPD/CaCl2Molality in/nmp solution is 0.8mol/L, and p-phenylenediamine is in PPD/
CaCl2Molar concentration in/nmp solution is 0.4mol/L, PPD/CaCl2Water content is 120 ± 10ppm or so in/nmp solution.
Then by PPD/CaCl2/ nmp solution cools to 0 DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and it is molten to be made first
Liquid.Another polymerized monomer paraphthaloyl chloride (TPC) is weighed, it keeps the temperature to 100 DEG C in storage tank, temperature fluctuation is no more than ±
0.5℃。
(2) when polymerization starts, the first solution and TPC are respectively delivered to by twin (double) screw extruder by pipeline with metering pump
Monomer mixer is quickly mixed, and leads to nitrogen protection in monomer mixer, obtains the second solution.Wherein paraphenylene terephthalamide
The molar ratio of chlorine and p-phenylenediamine are as follows: paraphthaloyl chloride: p-phenylenediamine=1.0005:1, mixed second solution are quick
It flows automatically to and carries out prepolymerization reaction in the double-screw reactor of twin (double) screw extruder;Wherein, the screw speed control of twin (double) screw extruder
System controls reaction temperature at 30-70 DEG C in 200rpm, by refrigeration system, obtains prepolymer product;By adjusting polymerization temperature
And screw speed, so that the polymer material in double screw extruder exit is maintained at low-viscosity gel state, viscosity is about 60,000
cp.s。
(3) prepolymer product made from step (2) is pipelined in reaction kettle and carries out solid phase under nitrogen protection
Polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 800rpm, control
Polymerization temperature processed is at 50-70 DEG C;
(4) crumbs shape polymerizate made from step (3) is first washed with massive laundering, then filters out polymer and exists
It is 8 hours dry under the conditions of 150 DEG C, obtain 0.5% or so PPTA powder of water content.
It is 6.50 ± 0.2 with the logarithmic specific concentration viscosity of determination of ubbelohde viscometer PPTA powder manufactured in the present embodiment.
Claims (8)
1. a kind of p-aramid fiber resin continuous polymerization system, which is characterized in that reacted including a double screw extruder and one
Kettle is equipped with inlet port and outlet port, conveys monomer solution by the feed inlet of the double screw extruder, the twin-screw squeezes
The discharge port of machine is connected with the feed inlet of the reaction kettle out, and p-aramid fiber resin is discharged by the discharge port of the reaction kettle.
2. p-aramid fiber resin continuous polymerization system as described in claim 1, which is characterized in that the reaction kettle includes kettle
Body, drive system and two refrigeration systems;It is equipped with stirring crusher members in the autoclave body, including main shaft and is rotated with the main shaft
And spaced multilayer stirs broken paddle, adjacent two layers stir broken paddle and are arranged in the angle of 180/N, and N is that the stirring is broken
The number of plies of broken paddle, each layer stir broken paddle by being fixed on the cross bar of the main shaft and being fixed on evenly arranged multiple on the cross bar
Blade composition, and blade is in the small distribution in the big centre in both ends on corresponding cross bar;One end of the main shaft protrudes from the autoclave body
Outer wall and being driven by the drive system rotates, and the other end of the main shaft is fixedly connected with bearing;The outer wall of the autoclave body is set
Have jacket structured, two refrigeration systems are controlled by the jacket structured temperature by the reaction kettle at 50~70 DEG C;
Feed inlet, nitrogen inlet and discharge port are further respectively had on the outer wall of the autoclave body, the discharge outlet is equipped with for controlling out
Expect the outlet valve of speed.
3. p-aramid fiber resin continuous polymerization system as claimed in claim 2, which is characterized in that between the adjacent broken paddle of two stirrings
Away from 1.5~3 times controlled in the maximum blade height.
4. p-aramid fiber resin continuous polymerization system as claimed in claim 2, which is characterized in that the broken slurry of stirring turns
Speed control is in 300-1000rpm.
5. p-aramid fiber resin continuous polymerization system as claimed in claim 2, which is characterized in that polymer material is in the reaction
10~20min is stopped in kettle, and the volume of the reaction kettle is by the interior list conveyed of the twin-screw extrusion machine inlet 15min
2~4 times of liquid solution volume.
6. p-aramid fiber resin continuous polymerization system as claimed in claim 2, which is characterized in that the reaction kettle is using vertical
Structure, the autoclave body top is cylindrical, lower part is vertebral body structure, and the bearing is located inside vertebral body structure, the discharging
Mouth is located at vertebral body structure bottom.
7. p-aramid fiber resin continuous polymerization system as claimed in claim 2, which is characterized in that the reaction kettle is using horizontal
Structure;The autoclave body is integrally cylindrical, and the blade for stirring broken paddle has 3~5 ° of deflection relative to the main shaft 21
Angle;The bearing is located at outside the autoclave body.
8. a kind of utilize the p-aramid fiber resin continuous polymerization system preparation contraposition virtue as described in any one of claim 1~7
The method of synthetic fibre resin, which is characterized in that method includes the following steps:
(1) p-phenylenediamine/salt/N-Methyl pyrrolidone solution is prepared under nitrogen protection, wherein salt is in p-phenylenediamine/salt/N-
Molar concentration in methylpyrrolidone solution is 0.4-0.8mol/L, and p-phenylenediamine is in p-phenylenediamine/salt/N- crassitude
Molar concentration in ketone solution is 0.2-0.5mol/L, and water content control exists in p-phenylenediamine/salt/N-Methyl pyrrolidone solution
50-150ppm, fluctuation range are ± 10ppm;Then p-phenylenediamine/salt/N-Methyl pyrrolidone solution is cooled to -5~5
DEG C, and constant temperature makes temperature fluctuation error be no more than ± 0.5 DEG C, and the first solution is made;Weigh another polymerized monomer terephthaldehyde
Acyl chlorides is maintained at 90-105 DEG C, and temperature fluctuation is no more than ± 0.5 DEG C;
(2) when polymerization starts, the first solution and paraphthaloyl chloride are respectively delivered to by double spiral shells by pipeline with metering pump
It is mixed in the monomer mixer of bar extruder, and leads to nitrogen protection in monomer mixer, obtain the second solution, second is molten
It is (1.01~1) to the molar ratio of paraphthaloyl chloride and p-phenylenediamine in liquid: 1, mixed second solution flows automatically to described
Prepolymerization reaction is carried out in double-screw reactor and obtains prepolymer product, wherein screw speed is controlled in 100-300rpm, reaction temperature
At 30~70 DEG C, the viscosity of the polymer material of the double screw extruder discharge outlet is maintained at ten thousand cp.s of 5-20 for control;
(3) prepolymer product made from step (2) is pipelined in the reaction kettle and carries out solid phase under nitrogen protection
Polycondensation is simultaneously finally fractured into crumbs shape polymerizate;Wherein, the revolving speed of the broken slurry of reaction kettle control stirring is in 300-
1000rpm controls polymerization temperature at 50-70 DEG C;
(4) polymerizate made from step (3) is washed, it is then 8-15 hours dry at 80-150 DEG C, obtain poly- pair
Phenylene terepthalamide's toner.
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CN110605079A (en) * | 2019-10-12 | 2019-12-24 | 惠生(中国)投资有限公司 | Ultrasonic atomization micromixer, microchannel reactor, prepolymerization system, and para-aramid resin continuous polymerization reaction system and method |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101215376A (en) * | 2007-12-29 | 2008-07-09 | 中蓝晨光化工研究院有限公司 | Material mixer used for high temperature difference quick reaction |
CN101220148A (en) * | 2007-01-08 | 2008-07-16 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
CN102153745A (en) * | 2011-03-04 | 2011-08-17 | 清华大学 | Method for synthesizing high-viscosity polyphenylene terephthalamide |
CN202030686U (en) * | 2011-04-28 | 2011-11-09 | 上海舟汉纤维材料科技有限公司 | Device for continuously preparing poly-p-phenylene terephthamide polymer |
CN104119526A (en) * | 2013-04-24 | 2014-10-29 | 中国石油化工股份有限公司 | Method for continuously preparing poly-p-phenylene terephthalamide resin |
CN104667846A (en) * | 2015-02-13 | 2015-06-03 | 清华大学 | Micro-reaction system and micro-reaction method for preparing para/meta-aramid |
CN105696104A (en) * | 2016-04-21 | 2016-06-22 | 山东万圣博科技股份有限公司 | Method for preparing black para-aramid fibers |
CN106046364A (en) * | 2016-08-12 | 2016-10-26 | 上海会博新材料科技有限公司 | Method for continuously preparing highly-pure poly(m-phenylene isophthalamide) resin solution |
CN106076232A (en) * | 2016-08-12 | 2016-11-09 | 上海会博新材料科技有限公司 | Prepare the device of high-purity poly(isophthaloyl metaphenylene diamine) resin solution continuously |
CN206168411U (en) * | 2016-10-02 | 2017-05-17 | 上海会博新材料科技有限公司 | High viscosity polymerization cauldron for experiments |
CN108236910A (en) * | 2018-01-31 | 2018-07-03 | 浙江大学 | A kind of agitating device and a kind of horizontal-type biaxial self-cleaning reactor |
CN108479667A (en) * | 2018-05-02 | 2018-09-04 | 江苏广盛源科技发展有限公司 | A kind of reaction kettle being used to prepare Fanglun slurry cake |
-
2018
- 2018-11-28 CN CN201811433341.2A patent/CN109553769B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101220148A (en) * | 2007-01-08 | 2008-07-16 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
CN101215376A (en) * | 2007-12-29 | 2008-07-09 | 中蓝晨光化工研究院有限公司 | Material mixer used for high temperature difference quick reaction |
CN102153745A (en) * | 2011-03-04 | 2011-08-17 | 清华大学 | Method for synthesizing high-viscosity polyphenylene terephthalamide |
CN202030686U (en) * | 2011-04-28 | 2011-11-09 | 上海舟汉纤维材料科技有限公司 | Device for continuously preparing poly-p-phenylene terephthamide polymer |
CN104119526A (en) * | 2013-04-24 | 2014-10-29 | 中国石油化工股份有限公司 | Method for continuously preparing poly-p-phenylene terephthalamide resin |
CN104667846A (en) * | 2015-02-13 | 2015-06-03 | 清华大学 | Micro-reaction system and micro-reaction method for preparing para/meta-aramid |
CN105696104A (en) * | 2016-04-21 | 2016-06-22 | 山东万圣博科技股份有限公司 | Method for preparing black para-aramid fibers |
CN106046364A (en) * | 2016-08-12 | 2016-10-26 | 上海会博新材料科技有限公司 | Method for continuously preparing highly-pure poly(m-phenylene isophthalamide) resin solution |
CN106076232A (en) * | 2016-08-12 | 2016-11-09 | 上海会博新材料科技有限公司 | Prepare the device of high-purity poly(isophthaloyl metaphenylene diamine) resin solution continuously |
CN206168411U (en) * | 2016-10-02 | 2017-05-17 | 上海会博新材料科技有限公司 | High viscosity polymerization cauldron for experiments |
CN108236910A (en) * | 2018-01-31 | 2018-07-03 | 浙江大学 | A kind of agitating device and a kind of horizontal-type biaxial self-cleaning reactor |
CN108479667A (en) * | 2018-05-02 | 2018-09-04 | 江苏广盛源科技发展有限公司 | A kind of reaction kettle being used to prepare Fanglun slurry cake |
Non-Patent Citations (5)
Title |
---|
中国化工协会研究组主编: "《油漆的生产、加工使用技术标准与质量检测检验 上》", 31 January 2004, 中国科学技术出版社 * |
全国勘察设计注册工程师环保专业管理委员会,中国环境保护产业协会编: "《注册环保工程师专业考试复习教材 固体废弃物处理处置工程技术与实践 上 第4版》", 31 March 2017, 中国环境出版社 * |
成都科技大学,四川轻化工学院编: "《化工轻工设备机械基础》", 31 May 1988, 成都科技大学出版社 * |
王学生著: "《化工设备设计 第2版》", 30 September 2017, 华东理工大学出版社 * |
赵临五,王春鹏编著: "《脲醛树脂胶黏剂 制备、配方、分析与应用》", 30 September 2005, 化学工业出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110605079A (en) * | 2019-10-12 | 2019-12-24 | 惠生(中国)投资有限公司 | Ultrasonic atomization micromixer, microchannel reactor, prepolymerization system, and para-aramid resin continuous polymerization reaction system and method |
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