Classifications

• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/18—Stationary reactors having moving elements inside
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/785—Preparation processes characterised by the apparatus used
• • 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
  • C08G69/04—Preparatory processes
• • 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
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • 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
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/0004—Processes in series
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00184—Controlling or regulating processes controlling the weight of reactants in the reactor vessel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00761—Details of the reactor
  • B01J2219/00763—Baffles
  • B01J2219/00765—Baffles attached to the reactor wall
  • B01J2219/00768—Baffles attached to the reactor wall vertical

Definitions

• the invention relates to a process and a device for the continuous preparation of polyphosphonates, polysulfones, polyarylates, polyamides, polyarylene ethers and polyether ketones by melt condensation of a hydroxycarbonyl, dicarboxylic, anhydride, phosphoric, phosphono, phosphonate, phosphino, phosphinate, Carbonyl, carboxyl, sulfonyl, sulfonate, Siioxan- and amino groups carrying monomer each with itself or with at least one of the onomeric diphenol, dialcohol, diamine and carbonate.
• DE-A-10059616 discloses a process for the preparation of polycarbonates by reacting a monomeric carbonate component with at least one diphenol or dialcohol in the presence of a transesterification catalyst, wherein the molten components are stirred with the transesterification catalyst and a transesterification product is produced which is polycondensed.
• the polycarbonates produced should have the narrowest possible molecular weight distribution and low sokettenverzweigonne, be as free of black particles as possible, have a vanishingly small yellowing and only a low gel content. This is achieved by passing the transesterification product through a prereactor, at least one intermediate reactor and a final reactor for polycondensation.
• the series-connected reactors have a substantially horizontally driven shaft with Rrockeleme ⁇ ten attached thereto.
• the temperatures in the prereactor are in a range of 220 to 300 ° C and in Final reactor in a range of 240 to 350 ° C, wherein the pressure in the prereactor is 100 to 800 mbar and in the final reactor 0.1 to 50 mbar.
• the number of intermediate reactors connected in series is usually 1 to 3.
• the formed vapors are removed by suction from each reactor.
• the residence time of the melt in the prereactor and in the " final reactor is in each case 5 to 120 min.
• the invention provides that the molten monomers fed to a stirred reactor and in this at a temperature of 150 to 300 ° C, a pressure of 1 5001 to 150001 mbar and a residence time of 10 to 240 min in the presence of a added or transesterified, the produced a viscosity of 0.1 to 100 Pa -s having Ver or transesterification product for precondensation in fine annular disc reactor at a pressure of 5 to 95% of the pressure prevailing in the stirred reactor, a residence time of 10 to 90 min continuously heated to a relation to the Ei ⁇ storystemperatur by 30 to 120 ° C higher temperature and precondensed, the one Viscosity of 10 to 1000 Pa-s
• the monomers are obtained by fractional condensation or by distillation from the vapors contained in the Ver / transesterification, the precondensation, the polycondensation and the final polycondensation and returned to the process, wherein the molar ratio of fresh and recycled Monomeren ⁇ in the Stirred reactor depending on the vapor pressure of the monomers to each other and of the reaction conditions 1: 10001 to 1: 3.5, preferably 1: 1.1 to 1: 2.5.
• the vapors are sucked off with only slight negative pressure, whereby steam and liquid jet pumps have proven to be particularly reliable.
• the temperature of the precondensation product prior to entry into the polycondensation and / or the Poiykondensations. before entering the final polycondensation, for example by Rohrbegleitsammlungung or a heat exchanger to increase 2 to 50 ° C.
• the temperature of the precondensation product before entry into the polycondensation and / or of the polycondensation product prior to entry into the final polycondensation may be due to shearing stress from reactor elements or a heat exchanger to lower 2 to 30 ° C.
• This adaptation has the advantage that lower temperatures can be set in the precondensation at a relatively low viscosity and in relation to the end polycondensation of a relatively low melting point of the polymer.
• the ratio of length to diameter of the interior is 0.5: 1 to 10: 1, preferably 2: 1 to 5: 1.
• one or more of the annular disk reactors can be conically designed to avoid high flow velocities and the entrainment of small liquid particles.
• the ratio of length to diameter ⁇ 1.1: 1 / preferably 0.5: 1 to 1: 1 can be at the narrowest point.
• the annular disk reactor used to carry out the precondensation consists of a horizontal cylindrical container with a double outer jacket for heating and setting the necessary temperature in the reaction space, in the lower portion of the front of the Ver- / transesterification product occurs horizontally.
• the discharge of the precondensation product takes place at the rear side radially downward and the discharge opposite the vapor withdrawal radially upward or axially to the rear or bottom.
• In the reaction space attached to a continuous shaft on spokes ring disks are arranged individually or in combination depending on the melt viscosity to be processed.
• the annular disks rotate in chambers located in the lower section of the container and separated by sheet metal walls, which prevent the esterification / transesterification product entering the reaction space from mixing up to this end Discharge flows through.
• the sheet metal walls are provided with specially designed openings, which ensure a targeted product exchange from chamber to chamber.
• the annular discs take from the up to about 75% filled chambers on the Ver / Verest réelleseck and pull this on the annular disc with After exceeding the horizontal, the effect of gravity occurs more and more visible and allows the adhesive layer on two ways to get back into the chambers and to be mixed in there again.
• the path along the ring disc leads to a jam, as the run-down has to start against the raised product. This obstruction greatly promotes vertical drainage and dripping from the inner edge of the discs, and over the entire free disc surface, there are thin, high surface area films that flow back into the sump and are remixed there.
• the precondensation product is fed horizontally from the front into the lower section of the reactor and / or the shaft bearing in the cover.
• the vapor withdrawal is at the end of the reaction space at the reactor circumference or in the back.
• a stub shaft with a plurality of spokes attached thereto annular discs and at the end of a short stub shaft with an attached washer . .. arranged.
• These annular disks are connected by transverse elements extending over the length of the reactor vessel, to which further annular disks are fastened in the section between the two stub shafts, so that the stirrer is a kind of self-supporting cage.
• the cross elements have an oblique employment and fulfill Schöpffunktionen.
• the output of the polymer product can be equipped with a special stator or near-wall scraper. Scrapers and washers strike as close as possible to the container wall.
• the exhaust for the vapors is depending on requirements on the container circumference or in the product outlet side of the back of the container.
• the HVS annular disk reactor has a heatable hollow shaft in the reaction chamber, which carries the rotatable annular disks (stirring elements).
• a powdered monomeric phosphate component is fed via line 1 to the feed tank 2 and powdered diphenol via line 3 to the feed tank 4, from these via lines 5 and 6 metering screws 7 and 8 abandoned.
• the discharges of the dosing screws 7, 8 are continuously introduced via lines 9, 10 into the heat exchangers 15, 16 provided with heat exchangers 11, 12 and stirrers 13, 14. From the two accompanying heated melt pumping lines 17, 18, the aliquot mass flows of the molten monomers determined by the stoichiometry of the esterification / transesterification are conveyed via lines 19, 20 into the heatable boiler reactor 23 equipped with a chamber 21 and an agitator 22 Line 24 from the feed tank 25, a mixed catalyst is supplied.
• the Ver / transesterification product produced by the reaction of the two monomers is fed via line 26 into the heatable annular disk reactor 27 for the purpose of precondensation.
• the vapors formed during the Ver / transesterification flow via line 28 to Destiiiationskoiönne 29, in which the entrained fission products are discharged overhead through line 30.
• Via line 31 the vapors are sucked out of the annular disk reactor 27 by means of an unspecified steam or liquid jet system, condensed in the tank 32, fed via line 33 to the collecting tank 34 and fed via line 35 to the distillation column 29.
• the precondensation product leaving the annular disk reactor 27 flows via line 36 via the bearing of the agitator shaft into the LVS annular disk reactor 37, from which the vapors are sucked off via line 38 by means of a vapor or liquid radiator system not described in further detail, condensed in the container 39, via line 40 are fed to the collecting tank 34 and from there via line 35 of the distillation column 29 abandoned.
• the polycondensation product emerging via the line 41 from the LVS annular disk reactor 37 is fed to the HVS annular disk reactor 43 by means of at least one gear pump 42.
• the vapors are sucked off via line 44, condensed in the container 45, fed via line 46 to the collecting tank 47 and from this via line 48 of the distillation column 29.
• the final polycondensation product is discharged via line 49 using a gear pump 50 and fed to further processing.
• the method according to the invention will be explained below by several exemplary embodiments.
• the precondensation is carried out in an annular disc reactor with a reaction volume of 50 l and a length: diameter ratio of 6.
• the polycondensation takes place in an LVS annular disk reactor with a reaction space volume of 48 l and a ratio of length: diameter of 4.
• an HVS annular disk reactor with a reaction space volume of 45 l and a ratio of length: diameter of 2.5 is used ,
• the throughput is based on the amount of end polycondensation product 50 kg / h.
• the average residence time of the products in the individual annular disk reactors is determined by means of tracer marking.
• 1st Exemplary Embodiment Powdered bispheric oil A is continuously introduced from the preliminary container 2 and diphenylmethyl phosphate from the feed tank 4 into the melters 15 and 16, respectively, and the aliquot mass flows of molten monomers determined by the stoichiometry of the reaction are fed into the stirred tank reactor 23.
• a mixed catalyst consisting of an alkali metal salt of bisphenol and zinc acetate, in the stirred tank reactor 23.
• the reaction of the two monomers takes place at a temperature of 240 ° C and a pressure of 800 mbar.
• the resulting released phenols are collected to determine the progress of the reaction and weighed.
• the transesterification product leaving the stirred-tank reactor 23 still has a low melt viscosity and still contains small amounts of unreacted monomers.
• the molecular weight distribution, the residual content of monomers and the average molecular weight are monitored by chromatography.
• the transesterification product is introduced into the annular disk reactor 27 which is operated at a pressure of 200 mbar and in which continuous heating of 240 ° C. to 280 ° C. takes place over the length of the reaction space .
• the transesterification product is condensed by the apertured rotating annular discs in thin films of large surface at a residence time of 30 min to chain lengths of 10 repeating units.
• the resulting cleavage products are filtered off, condensed and fed to the distillation 29 for reprocessing.
• the precondensation product flows into the operated at a pressure of 15 mbar LVS ring disk reactor 37, the Vorkondensatidns slaughter is heated within 20 min to a temperature of 305 ° C over the reaction space length.
• the condensable to a chain length of 20 to 55 repeat units polycondensation product it is necessary to subject the precondensation of shear deformation by appropriately attached shear elements and thereby obtain an intensive mixing.
• the polycondensation product passes into the HVS ring disk reactor 43 in which it is heated continuously at a pressure of 1.5 mbar and a residence time of 20 min over the length of the reactor space to a temperature of 330 ° C while the polycondensation is completed. Since the melt viscosity of the polycondensation product continuously increases over the length of the reaction space, the polymerization product is subject to increased shear deformation.
• the end polycondensation product leaving the HVS ring disk reactor 43 has only a slight yellow discoloration by decomposition products, extremely low proportions of gels and black particles, and a narrow molecular weight distribution.
• the stirred tank reactor 23 is charged with terephthalic acid, isophthalic acid and bisphenol A in a molar ratio of 1: 0.75: 1.75.
• the reaction of the monomers is initiated at a temperature of 280 ° C and a pressure of 800 mbar.
• the water released is collected and weighed to determine the progress of the reaction.
• the esterification product exiting from the boiler reactor 23 is fed to the annular disk reactor 27 and continuously heated in this at a pressure of 250 mbar and a residence time of 45 min over the length of the reactor space from a temperature of 280 ° C to a temperature of 300 ° C and precondensed.
• the resulting cleavage products are filtered off and passed into the distillation column 29.
• the precondensation product flows into the LVS annular disc reactor 37 and is heated continuously in this at a pressure of 25 mbar and a residence time of 20 minutes over the length of the reaction space to a temperature of 320 ° C.
• the polycondensation product leaving the LVS annular disk reactor 37 then passes into the HVS annular disk reactor 43 in which it is continuously heated to a temperature of 330 ° C. at a pressure of 0.5 mbar and a residence time of 25 min over the length of the reaction space and the polycondensation is increased End is led.
• the end polycondensation product discharged from the HVS ring disk reactor 43 shows only a slight yellowing by decomposition products, extremely low proportions of gels and black particles, and a narrow molecular weight distribution.
• the same result is achieved when the mixture of terephthalic acid, isophthalic acid and bisphenol A as a catalyst nor an alkali salt of bisphenol is added, is ...
• the stirred tank reactor 23 is fed with terephthalic acid, isophthalic acid, p-phenylenediamine and o-phenylenediamine in a molar ratio of 1: 1: 1.03: 1.
• the addition of a catalyst takes place in the form of an organo-organic compound.
• the reaction of the monomers takes place at a temperature of 80.degree. C. and a pressure of 1000 mbar.
• the water released is collected and weighed to determine the progress of the reaction.
• From the stirred tank reactor 23 passes the esterification product in the annular disk reactor 27, in which the precondensation at a pressure of 500 mbar, a residence time of 25 min and a continuous Aufgenesisu ⁇ g of a temperature of 180 ° C to a temperature of 250 ° C over the length of Reaction space is performed.
• the resulting spaite products are sucked off and fed to the distillation column 29.
• the precondensation product flows out of the annular disk reactor 27 into the LVS annular disk reactor 37 in which a pressure of 25 mbar prevails.
• the precondensation product is heated continuously over the length of the reactor space to a temperature of 270 ° C and thereby polycondensed.
• the polycondensation product is conveyed into the HVS ring disk reactor 43, in which at a pressure of 0.5 mbar and a residence time of 15 min, the polycondensation in a continuous heating over the length of the reaction chamber to a temperature of 300 ° C the Polycondensation is completed.
• the final polycondensation product has the same advantageous properties as those of the final polycondensation products of the previous embodiments.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyesters Or Polycarbonates (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

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• 2003
  • 2003-08-07 DE DE10336164A patent/DE10336164B4/de not_active Expired - Lifetime
• 2004
  • 2004-05-26 WO PCT/EP2004/005653 patent/WO2005023905A1/de active Application Filing
  • 2004-05-26 EA EA200600195A patent/EA009105B1/ru not_active IP Right Cessation
  • 2004-05-26 KR KR1020067002416A patent/KR20060128819A/ko not_active Application Discontinuation
  • 2004-05-26 EP EP04734836A patent/EP1654303A1/de not_active Withdrawn
  • 2004-05-26 CN CNA2004800226252A patent/CN1867616A/zh active Pending
  • 2004-05-26 US US10/569,846 patent/US20070112173A1/en not_active Abandoned
  • 2004-05-26 JP JP2006522242A patent/JP2007533769A/ja not_active Withdrawn
• 2006
  • 2006-01-18 IL IL173217A patent/IL173217A0/en unknown

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