CN101928387A - Aliphatic polycarbonate washing coagulation devolatilization method and specific device thereof - Google Patents
Aliphatic polycarbonate washing coagulation devolatilization method and specific device thereof Download PDFInfo
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Abstract
The invention discloses an aliphatic polycarbonate washing coagulation devolatilization method and a specific device thereof. The device according to the invention comprises: a polymerization kettle (1), a flash glue solution vessel, a coagulation system composed of more than one washing coagulation kettles (3), a solid-liquid separation system (4), a polymer drying system (5), a gear pump (6) and a connecting pipeline, wherein the polymerization kettle is provided with a product outlet at the lower part thereof and a gas outlet at the upper part thereof; the flash glue solution vessel is provided with an inlet and a gas outlet at the upper part thereof and a liquid outlet at the lower part thereof; and the washing coagulation kettle is provided with a washing coagulant inlet at the lower part thereof, a liquid inlet and a liquid outlet at the middle part thereof and a gas outlet at the upper part thereof. The method according to the invention has the advantages of: simple production technology, good suitability for automated control, continuous washing coagulation devolatilization; sufficient use of materials and energies, no gas-phase emptying in the process owing to the use of a closed vessel with pressure, very few solid-liquid wastes, complete ash removal and devolatilization of products, meeting the use demands in related fields, low industrial production cost and green chemistry standard-reaching industrialization process.
Description
Technical field
The present invention relates to a kind of aliphatic polycarbonate washing coagulation devolatilization method and isolated plant thereof.
Background technology
Carbonic acid gas is the main gas that causes Greenhouse effect, also is one of carbon source the abundantest on the earth.The chemical fixation of carbonic acid gas is an important research field of Green Chemistry.Wherein, utilizing a main direction of carbonic acid gas is to be raw material and epoxy alkane copolymerization polycarbonate under the effect of catalyzer with it.Polycarbonate can photodegradation or biological degradation, also has the performance of good blocking oxygen and water simultaneously, can be used as degradable nonpollution material, disposable medicine and packaging material for food, tackiness agent and matrix material etc.
Since Japanese Inous in 1969 finds that carbonic acid gas can be fixed as complete biolytic polymkeric substance, the patent report for preparing polycarbonate about carbonic acid gas and epoxy alkane copolymerization has been arranged both at home and abroad a lot.Adopt zinc alkyl(s)/glycerine/rare-earth salts three-element catalytic system to be used to prepare molecular weight as (CN 98125654.6, CN 00136189.9 and CN 03105023.9) such as Wang Xianhong and be higher than 20000 polycarbonate, alternating structure is greater than 95%; Chen Liban etc. adopt polymkeric substance load bimetal complex (CN 89100701.6) as catalyzer, and catalysis carbonic acid gas and epoxide copolymerization get molecular weight 10
4～10
6Aliphatic polycarbonate resin, adopt polymkeric substance load bimetal complex as catalyzer, obtain carbonate group mass contg molar fraction in the molecule at 0.2～0.5 aliphatic polycarbonate polybasic alcohol (CN 91109459) by regulating polymerization, and be raw material with this polyvalent alcohol, prepare polyurethane foam (CN 02134631) with superperformance; Meng Yue medium (CN 00130811.4) adopts the load binary zine carboxylate to prepare lined polymethyl ethylene carbonate (CN 200510034892.8), poly methyl ethylene cyclo hexamethylene carbonate (CN200510101885.5), lined polymethyl ethylene-ethylene carbonate (CN 200610035032.0) etc.U.S. Pat 3585168, US 3900424 and US 3953383 adopt the bicomponent catalyst based on zinc alkyl(s) to obtain molecular weight to be higher than 20000 polycarbonate, urethane and polyethers; Kuyper etc. (US 4826953) go out carbonate group mass contg (wt%) liquid low sticking polyhydroxy fatty adoption carbonate resin about 3%～7% in the molecule with the small molecules bimetal complex as catalyst carbon dioxide/epoxide copolymerization.Day disclosure laid-open patent JP02142824 and JP 02575199 adopt expensive metalloporphyrin complex catalysis carbonic acid gas and epoxy alkane polycarbonate synthesis; In U.S. Pat 6133402, a kind of highly active single-activity point organic zinc catalyzer has also been described, obtain molecular weight between 20000-40000 and be the poly-propylene carbonate of narrow distribution, but also produce the cyclic carbonate propylene ester by product of 13-25% synchronously.Lv Xiaobing etc. provides the preparation method (CN 200610200053.3, CN 200510046091.3, CN 200510046092.8) of optically active polycarbonate in addition.These methods are fixing and utilize the good approach of carbonic acid gas, when consuming industrial gaseous waste, produce degradable plastics, the alternative use of these plastics or consume after be difficult to reclaim and to the plastics that environment works the mischief, can effectively alleviate carbonic acid gas to the pollution of environment, reduce until " white pollution " avoiding causing by the non-degradable plastics.
Though aliphatic polycarbonate resin is as a kind of novel high polymer material, demonstrate better market prospect, ground such as interior drizzly west, sky, Henan hat, Hainan CNOOC also build up the testing apparatus of certain scale, but its cohesion process for devolatilization is the bottleneck of its development of restriction.Reaction with carbonic acid gas and epoxide synthetic fat adoption carbonate resin is mass polymerization, when reaction finishes, also have the not reaction of epoxide of 40-70% in the polymeric system, if this part raw material is not reclaimed, the cost of product increases greatly; On the other hand, the residual volatile matter in the polymkeric substance all has certain harm to atmosphere and human body, and has influence on the use properties of material.Taixing imperial Green Chemistry company limited of gold and Guangzhou chemical company of the Chinese Academy of Sciences (CN200410044938.X) propose a kind of process for refining of aliphatic polycarbonate resin, by in the polymkeric substance glue, add sequestrant and sorbent material, handle at a certain temperature filter after for some time, desolventizing, removing the metal complex catalyst in the aliphatic polycarbonate resin, though that its relict catalyst removes is more complete, complex process, do not mention removing of fugitive constituent, the industrialization difficulty is big.Cover western new and high technology group and Changchun and should change the desolventizing method that institute (CN200610077582.9) proposes a kind of aliphatic poly Texacar PC, this desolventizing method is that the polymkeric substance that contains the aliphatic poly Texacar PC of unreacted propylene oxide and residual catalyst is put into the still formula container that band stirs, add desolventizing and under whipped state, carry out repeatedly precipitation, to realize to relict catalyst, the extracting and washing of oligopolymer and PC etc., then material is separated, obtain residual ash content after the drying treatment and be lower than 1% aliphatic poly polypropylene carbonate ester polymer, though its technology is simple, but employing standing sedimentation, separate in the gap, efficient is low, and large scale industry is produced and also is difficult to adopt.The aliphatic polycarbonate resin that sky, Henan hat group of enterprises and Zhongshan University (CN 200620031757.8) propose do not have auxiliary agent devolatilization device adopt a band to stir and the container of heating with the elementary devolatilization of polymerization glue after, pump into the further devolatilization of vented extruder by high-viscosity pump, volatile component in the aliphatic polycarbonate resin that effective removal carbonic acid gas and epoxide polymerization generate, its Technology difficulty is big, the equipment requirements height, investment is big, though the use precedent of success is arranged in the production of the transparent high-impact butadiene styrene resin of height, but can't partly remove catalyst residue and oligopolymer in the polymkeric substance, also be difficult to satisfy the industrial production of aliphatic polycarbonate.
Summary of the invention
The purpose of this invention is to provide a kind of aliphatic polycarbonate washing coagulation devolatilization method and isolated plant thereof.
Aliphatic polycarbonate washing coagulation devolatilization device provided by the invention is characterized in that: it comprises polymerization reaction kettle 1, flash glue solution jar 2, by a washing coagulation still or placed in-line washing coagulation still is formed more than two condensed system, solid-liquid separation system 4, polymer dry drying system 5, toothed gear pump 6 and connecting tube;
The bottom of polymerization reaction kettle 1 is provided with product outlet 1-1, and top is provided with pneumatic outlet 1-2;
The top of flash glue solution jar 2 is provided with inlet 2-1 and pneumatic outlet 2-2, and the bottom is provided with liquid exit 2-3;
The bottom of washing coagulation still 3 is provided with washing coagulation agent inlet 3-1, and the middle part is provided with liquid inlet 3-2 and liquid exit 3-3, and top is provided with pneumatic outlet 3-4;
The pipeline 7 that stretches out from the product of polymerization reaction kettle 1 outlet 1-1 extends to the bottom of flash glue solution jar 2 by behind the inlet 2-1 of flash glue solution jar 2; The pipeline 8 that stretches out from the liquid exit 2-3 of flash glue solution jar 2 enters washing coagulation still 3 by the liquid inlet 3-2 of washing coagulation still 3; On the pipeline 8 between the liquid inlet 3-2 of the liquid exit 2-3 of described flash glue solution jar 2 and described washing coagulation still 3, be provided with toothed gear pump 6; One end of pipeline 9 is positioned at washing coagulation still 3 and near pipeline 8, the other end stretches out washing coagulation agent inlet 3-1; The liquid exit 3-3 of washing coagulation still 3 joins by the inlet of pipeline 10 with solid-liquid separation system 4; The outlet of solid-liquid separation system 4 is joined by pipeline and polymer dry drying system 5.
Said apparatus is as aliphatic polycarbonate washing coagulation devolatilization device first.
The pneumatic outlet 1-2 of described polymerization reaction kettle 1 is used for emptying under improper situation.
In order better to realize the volatilization function, described flash glue solution jar 2 can be equipped with whipping appts, and described washing coagulation still 3 also can be equipped with whipping appts.
Described device also can comprise MONOMER RECOVERY jar 11, monomer-flocculation agent withdrawing can 12, water cooler and condenser;
The pneumatic outlet 1-2 of polymerization reaction kettle 1 joins by the inlet of pipeline and water cooler; The pneumatic outlet 2-2 of flash glue solution jar 2 joins by the inlet of pipeline and water cooler; The outlet of water cooler and MONOMER RECOVERY jar 11 join; The pneumatic outlet 3-4 of washing coagulation still 3 joins by the inlet of pipeline and condenser; The outlet of condenser and monomer-flocculation agent withdrawing can 12 joins.
Said apparatus is as aliphatic polycarbonate washing coagulation devolatilization device second.
Described device also can comprise high pressure separating tank 13, low pressure separation pot 14, solvent recovering system 15, water cooler and vaporizer;
The pneumatic outlet 1-2 of polymerization reaction kettle 1 joins by the inlet of pipeline and water cooler; The pneumatic outlet 2-2 of flash glue solution jar 2 joins by the inlet of pipeline and water cooler; High pressure separating tank 13 joins by the outlet of pipeline and water cooler; Low pressure separation pot 14 is joined by the outlet of pipeline and water cooler;
The pneumatic outlet 3-4 of washing coagulation still 3 joins by pipeline and solvent recovering system 15;
Described pipeline 10 is provided with water cooler; Described solid-liquid separation system 4 is provided with the gas recovery mouth; Described gas recovery mouth joins by the inlet of pipeline and vaporizer; The outlet of vaporizer is joined by pipeline and solvent recovering system 15.
Said apparatus is as aliphatic polycarbonate washing coagulation devolatilization device third.
Described device can be applicable to prepare aliphatic polycarbonate.
Described device also can be applicable to the washing coagulation devolatilization of aliphatic polycarbonate.
The present invention also protects a kind of washing coagulation devolatilization method of aliphatic polycarbonate, is with described device the aliphatic polycarbonate glue to be carried out the washing coagulation devolatilization.
When the aliphatic polycarbonate glue being carried out the washing coagulation devolatilization, comprise the steps: with the device first
Aliphatic polycarbonate glue in the polymerization reaction kettle 1 enters flash devolatilization glue jar 2, and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still 3 by described toothed gear pump 6, spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still 3 inlet 3-1, solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system 4, isolates solid polymer; Solid polymer enters polymer dry drying system 5, obtains the aliphatic polycarbonate after the washing coagulation devolatilization.
When the aliphatic polycarbonate glue being carried out the washing coagulation devolatilization, comprise the steps: with device second
Aliphatic polycarbonate glue in the polymerization reaction kettle 1 enters flash devolatilization glue jar 2, and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still 3 by described toothed gear pump 6, spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still 3 inlet 3-1, solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system 4, isolates solid polymer; Solid polymer enters polymer dry drying system 5, obtains the aliphatic polycarbonate after the washing coagulation devolatilization;
Volatilization gas in the flash devolatilization glue jar 2 enters water cooler, enters MONOMER RECOVERY jar 11 after being cooled; Volatilization gas in the washing coagulation still 3 enters condenser, enters monomer-flocculation agent withdrawing can 12 after being condensed.
When carrying out the washing coagulation devolatilization, comprise the steps: with third pair of aliphatic polycarbonate glue of device
Aliphatic polycarbonate glue in the polymerization reaction kettle 1 enters flash devolatilization glue jar 2, and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still 3 by described toothed gear pump 6, spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still 3 inlet 3-1, solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system 4, isolates solid polymer; Solid polymer enters polymer dry drying system 5, obtains the aliphatic polycarbonate after the washing coagulation devolatilization;
Volatilization gas in the flash devolatilization glue jar 2 enters water cooler, enters high pressure separating tank 13 or low pressure separation pot 14 after being cooled; Volatilization gas in the washing coagulation still 3 enters solvent recovering system 15; Liquid in the solid-liquid separation system 4 evaporates into gas through vaporizer, enters solvent recovering system 15.
Aliphatic polycarbonate glue in the polymerization reaction kettle 1 comprises following component: aliphatic polycarbonate, solvent monomer, oligopolymer and catalyzer; Described solvent monomer is the raw material of preparation aliphatic polycarbonate; Described oligopolymer is for preparing one of by product that produces in the aliphatic polycarbonate.
The condition that described washing coagulation agent need be satisfied is as follows: boiling point is higher than the monomeric boiling point that is used to prepare aliphatic polycarbonate, and aliphatic polycarbonate is insoluble to it.Acting as of described washing coagulation agent: make comonomer volatilization, and make polymkeric substance after removing reaction monomers, can become solid particulate, form the clearly demarcated suspension of phase interface with it.At aliphatic polycarbonate, the washing coagulation agent can be organic solvents such as alcohol, benzene, also can be inorganic solvents such as water, and wherein methyl alcohol has low, the easy low temperature of boiling point and removes, relict catalyst, oligopolymer and PC etc. being had advantages such as certain dissolubility, is first-selected washing coagulation agent.
Condensed system:
Can adopt jet flow cohesion or spraying cohesion: the cohesion of (1) jet flow is that glue is injected to heat and mass in the flocculation agent by many tubules; Resulting polymer flow is good, apparent density is big, and its key factor is the regulation and control of the relative velocity of the diameter of tubule and glue and flocculation agent; (2) the spraying cohesion is that glue is sprayed in the tubular knockouts, and flocculation agent sprays into the gas phase form, and two kinds of airflow collisions to together aggregation take place; This processing requirement has bigger boiling-point difference as the monomer and the flocculation agent of solvent, thereby is easy to gasification, and its advantage is polymer yield height, regular, the good fluidity in surface, apparent density height.Can adopt single still cohesion or the cohesion of many stills: (1) production is suitable for adopting single still cohesion for Small Scale Industry; The advantage of single still cohesion is less investment, flow process weak point, easy and simple to handle, and shortcoming is that gel is higher than height, energy consumption, is used for the poly-system of water-setting; (2) then should use the cohesion of many stills differential pressure for large-scale industrial production; The gel of many stills cohesion than low, the flocculation agent consumption lacks, the energy utilization fully, have lower process cost, be the first-selected technology of methyl alcohol condensed system.
In condensed system, the lower boiling epoxy compounds solvent monomer overwhelming majority of the folded band of polymkeric substance glue is blown out by the washing coagulation agent steam of its nozzle below, carry micro-monomeric sticky polymers micelle secretly and fall into the washing coagulation agent liquid phase of below, under whipped state by washing extraction further with remove monomer.The condensed system micro-pressure operation guarantees that the gas-phase epoxidation thing monomer of carrying washing coagulation agent steam secretly that cohesion still top blast goes out can pressured difference enter the solution recovery system.
Solid-liquid separation system:
Can be standing sedimentation solid-liquid separation, centrifugal settling solid-liquid separation, centrifuging solid-liquid separation, extruding devolatilization solid-liquid separation etc. all can be with the device of solid and liquid separation.For large scale industry production, adopt preferentially that centrifugal settling solid-liquid separation, centrifuging solid-liquid separation, extruding devolatilization solid-liquid separation etc. can maximize, the tripping device of serialization.
Dehumidification system:
Can be drying installation or their set composites such as tubular type air stream drying, fluidised bed drying, spouted drying, case/tube/drum-type oar formula/non-oar formula drying, expansion drying, centrifugal liquefaction drying.Preferentially adopt cartridge type oar formula group device dry and the tray drying case to close at the centrifuging solid-liquid separation, preferentially adopt the expansion drying device at extruding devolatilization solid-liquid separation.
Solvent recovering system:
Solvent recovering system is meant reaction monomers, flocculation agent isolating one by one system from other component.In solvent recovering system,, can adopt refining reclaim (x 〉=0) of n+x level at n the component that needs reclaim.For the bicomponent system that only contains washing coagulation agent and cyclosiloxane monomer oxygen compound, the cyclosiloxane monomer oxygen compound steam of carrying washing coagulation agent gas phase secretly that blows out from the washing coagulation still can be directly as the charging on one-level treating tower top or after the condenser condenses of washing coagulation still top, advance recovery system again, but more abundant without the utilization of the direct charging energy of condensation.Contain oligopolymer and catalyzer from the isolated liquid phase mixture of solid-liquid separation system, after passing through flash distillation and separating, enter the bottom of one-level treating tower with the gas phase form.The flash trapping stage tower is provided with top solvent monomer gas phase or liquid phase feeding mouth and lower wash flocculation agent gas phase or liquid phase feeding mouth; The highly purified washing coagulation agent of one-level treating tower bottom extraction liquid is recycled and reused for the washing coagulation system of production, the gas phase fraction that the refining cat head of one-level is discharged refluxes through the condensation rear section, part is as the charging of secondary treating tower, the further refining thick fraction of solvent monomer that obtains containing the washing coagulation agent returns one-level treating tower system as the 3rd charging of one-level treating tower, and another fraction is that the polymerization reaction kettle that highly purified solvent monomer can return production is reused.For reaction monomers is that propylene oxide/epoxy cyclohexane and carbonic acid gas, flocculation agent are the system of methyl alcohol, recovery system can adopt two tower flow processs, system obtains crude monomer and smart flocculation agent at first rectifying tower, second tower system obtains smart monomer, and thick flocculation agent fraction returns the circulation of first rectifying tower system and reclaims.
Method provided by the invention has following advantage: production technique is simple relatively, be suitable for automatization control, able to continuously wash cohesion devolatilization; The material energy utilization is abundant, and the equipment of use is essentially encloses container with pressure, and process does not have the gas phase emptying substantially, and the solid-liquid waste is few; Product ash disposal devolatilization is more complete, can satisfy the service requirements of association area; Industrial production cost is low, and course of industrialization reaches the requirement of Green Chemistry substantially.
Description of drawings
Fig. 1 is the washing coagulation devolatilization device synoptic diagram of embodiment 1 and embodiment 2.
Fig. 2 is the washing coagulation devolatilization device synoptic diagram of embodiment 3 and embodiment 4.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.
The aliphatic polycarbonate devolatilization device of embodiment 1 and embodiment 2 as shown in Figure 1.It comprises polymerization reaction kettle 1, flash glue solution jar 2, washing coagulation still 3, solid-liquid separation system 4, polymer dry drying system 5, toothed gear pump 6, MONOMER RECOVERY jar 11, monomer-flocculation agent withdrawing can 12, water cooler, condenser and connecting tube; The bottom of polymerization reaction kettle 1 is provided with product outlet 1-1, and top is provided with pneumatic outlet 1-2; The top of flash glue solution jar 2 is provided with inlet 2-1 and pneumatic outlet 2-2, and the bottom is provided with liquid exit 2-3; The bottom of washing coagulation still 3 is provided with washing coagulation agent inlet 3-1, and the middle part is provided with liquid inlet 3-2 and liquid exit 3-3, and top is provided with pneumatic outlet 3-4; The pipeline 7 that stretches out from the product of polymerization reaction kettle 1 outlet 1-1 extends to the bottom of flash glue solution jar 2 by behind the inlet 2-1 of flash glue solution jar 2; The pipeline 8 that stretches out from the liquid exit 2-3 of flash glue solution jar 2 enters washing coagulation still 3 by the liquid inlet 3-2 of washing coagulation still 3; On the pipeline 8 between the liquid inlet 3-2 of the liquid exit 2-3 of described flash glue solution jar 2 and described washing coagulation still 3, be provided with toothed gear pump 6; One end of pipeline 9 is positioned at washing coagulation still 3 and near pipeline 8, the other end stretches out washing coagulation agent inlet 3-1; The liquid exit 3-3 of washing coagulation still 3 joins by the inlet of pipeline 10 with solid-liquid separation system 4; The outlet of solid-liquid separation system 4 is joined by pipeline and polymer dry drying system 5.The pneumatic outlet 1-2 of polymerization reaction kettle 1 joins by the inlet of pipeline and water cooler; The pneumatic outlet 2-2 of flash glue solution jar 2 joins by the inlet of pipeline and water cooler; The outlet of water cooler and MONOMER RECOVERY jar 11 join; The pneumatic outlet 3-4 of washing coagulation still 3 joins by the inlet of pipeline and condenser; The outlet of condenser and monomer-flocculation agent withdrawing can 12 joins.Polymerization reaction kettle 1, flash glue solution jar 2, washing coagulation still 3 are equipped with whipping appts.
The aliphatic polycarbonate devolatilization device of embodiment 3 and embodiment 4 as shown in Figure 2.It comprises polymerization reaction kettle 1, flash glue solution jar 2, washing coagulation still 3, solid-liquid separation system 4, polymer dry drying system 5, toothed gear pump 6, high pressure separating tank 13, low pressure separation pot 14, solvent recovering system 15, water cooler, vaporizer and connecting tube; The bottom of polymerization reaction kettle 1 is provided with product outlet 1-1, and top is provided with pneumatic outlet 1-2; The top of flash glue solution jar 2 is provided with inlet 2-1 and pneumatic outlet 2-2, and the bottom is provided with liquid exit 2-3; The bottom of washing coagulation still 3 is provided with washing coagulation agent inlet 3-1, and the middle part is provided with liquid inlet 3-2 and liquid exit 3-3, and top is provided with pneumatic outlet 3-4; The pipeline 7 that stretches out from the product of polymerization reaction kettle 1 outlet 1-1 extends to the bottom of flash glue solution jar 2 by behind the inlet 2-1 of flash glue solution jar 2; The pipeline 8 that stretches out from the liquid exit 2-3 of flash glue solution jar 2 enters washing coagulation still 3 by the liquid inlet 3-2 of washing coagulation still 3; On the pipeline 8 between the liquid inlet 3-2 of the liquid exit 2-3 of described flash glue solution jar 2 and described washing coagulation still 3, be provided with toothed gear pump 6; One end of pipeline 9 is positioned at washing coagulation still 3 and near pipeline 8, the other end stretches out washing coagulation agent inlet 3-1; The liquid exit 3-3 of washing coagulation still 3 joins by the inlet of pipeline 10 with solid-liquid separation system 4; The outlet of solid-liquid separation system 4 is joined by pipeline and polymer dry drying system 5.The pneumatic outlet 1-2 of polymerization reaction kettle 1 joins by the inlet of pipeline and water cooler; The pneumatic outlet 2-2 of flash glue solution jar 2 joins by the inlet of pipeline and water cooler; High pressure separating tank 13 joins by the outlet of pipeline and water cooler; Low pressure separation pot 14 is joined by the outlet of pipeline and water cooler; The pneumatic outlet 3-4 of washing coagulation still 3 joins by pipeline and solvent recovering system 15; Described pipeline 10 is provided with water cooler; Described solid-liquid separation system 4 is provided with the gas recovery mouth; Described gas recovery mouth joins by the inlet of pipeline and vaporizer; The outlet of vaporizer is joined by pipeline and solvent recovering system 15.Polymerization reaction kettle 1, flash glue solution jar 2, washing coagulation still 3 are equipped with whipping appts.Also be provided with the liquid scrubbing flocculation agent inlet (agent of pumping liquid washing coagulation is to increase the washing coagulation effect) of pumping liquid washing coagulation agent on the described washing coagulation still 3.The end that described pipeline 8 and described pipeline 9 are positioned at described washing coagulation still 3 is equipped with four nozzles, is beneficial to glue and fully contacts with washing coagulation agent steam.
The application of embodiment 1, aliphatic polycarbonate devolatilization device
Polymerization reaction kettle (5L); Flash glue solution jar (20L); Washing coagulation still (10L); 7 ℃ of salt solution are housed in the water cooler; Washing coagulation agent (60 ℃ of methyl alcohol).
In the polymerization reaction kettle, adopt the method for Chinese patent 00136189.9 to prepare carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate glue, utilize the pressure of reactor, glue enters in the flash devolatilization glue jar; In the flash devolatilization glue jar, along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue is sprayed in the washing coagulation still continuously by toothed gear pump; In the washing coagulation still, spray into the washing coagulation agent from washing coagulation agent inlet, solvent monomer (propylene oxide), catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system continuously; Treat that material spray finishes, continue to keep about 10 minutes of cohesion washing; In the solid-liquid separation system, the solid-liquid suspension thing is isolated solid polymer through centrifugal, enters the polymer dry drying system, carries out 40 ℃ of vacuum-dryings, obtains the carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate after the washing coagulation devolatilization.Volatilization gas in the flash devolatilization glue jar (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enters MONOMER RECOVERY jar (carbon dioxide recovery utilization) after being cooled.Volatilization gas in the washing coagulation still (propylene oxide and washing coagulation agent) enters condenser, enters monomer-flocculation agent withdrawing can (separating each component of back can reuse) after being condensed.
Carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate after the washing coagulation devolatilization is carried out property testing: ash 0.9%; Fugitive constituent 0.5%; After the methylene dichloride dissolving, there is not muddiness (not having obvious oligopolymer and catalyst residue separates out) during the methanol extraction washing.
The application of embodiment 2, aliphatic polycarbonate devolatilization device
Polymerization reaction kettle (5L); Flash glue solution jar (20L); Washing coagulation still (10L); 7 ℃ of salt solution are housed in the water cooler; Washing coagulation agent (75 ℃ of ethanol).
In the polymerization reaction kettle, adopt the method for Chinese patent 00136189.9 to prepare carbon dioxide-epoxy propane-epoxy hexane terpolymer aliphatic polycarbonate glue, utilize the pressure of polymerization reaction kettle, glue is pressed in the flash devolatilization glue jar; In the flash devolatilization glue jar, along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue is sprayed in the washing coagulation still continuously by toothed gear pump; In the washing coagulation still, spray into the washing coagulation agent from washing coagulation agent inlet, solvent monomer (propylene oxide), catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system continuously; Treat that material spray finishes, continue to keep about 10 minutes of cohesion washing; In the solid-liquid separation system, the solid-liquid suspension thing is isolated solid polymer through centrifugal, enters the polymer dry drying system, carries out 40 ℃ of vacuum-dryings, obtains the carbon dioxide-epoxy propane-epoxy hexane terpolymer aliphatic polycarbonate after the washing coagulation devolatilization.Volatilization gas in the flash devolatilization glue jar (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enters MONOMER RECOVERY jar (carbon dioxide recovery utilization) after being cooled.Volatilization gas in the washing coagulation still (propylene oxide and washing coagulation agent) enters condenser, enters monomer-flocculation agent withdrawing can (separating each component of back can reuse) after being condensed.
Carbon dioxide-epoxy propane after the washing coagulation devolatilization-epoxy hexane terpolymer aliphatic polycarbonate is carried out property testing: ash 0.9%; Fugitive constituent 0.6%; After the methylene dichloride dissolving, there is not muddiness (not having obvious oligopolymer and catalyst residue separates out) during the methanol extraction washing.
The application of embodiment 3, aliphatic polycarbonate devolatilization device
Polymerization reaction kettle (20.0m
3); Flash glue solution jar (100.0m
3); Washing coagulation still (30.0m
3);-5 ℃ of refrigerated waters are housed in the water cooler; Washing coagulation agent (methyl alcohol).
Solvent recovering system comprises one-level treating tower and secondary treating tower.
In the polymerization reaction kettle, adopt the method for Chinese patent 00136189.9 to prepare carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate glue, utilize the pressure of reactor, glue enters in the flash devolatilization glue jar; In the flash devolatilization glue jar, along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; After treating the canned 4-5 still glue of filling out polymerization reaction kettle of flash glue solution, pump into about 1/3 still methyl alcohol and intensification from liquid scrubbing flocculation agent inlet, treat that washing cohesion still is warmed up to more than 40 ℃, methanol steam sprays into the washing coagulation still continuously by four nozzles, the while toothed gear pump pumps glue from the flash glue solution jar and also sprays into continuously the washing coagulation still by corresponding four nozzles, blow out the propylene oxide that sprays in the glue continuously with methanol steam, and as the washing coagulation agent polymkeric substance is carried out heated scrub with 60 ℃ of left and right sides methanol liquid, liquid enters water cooler continuously, enters solid-liquid separation system after being cooled to below 40 ℃; Entered the polymer dry drying system behind the centrifuge dripping and carried out drying, obtained the carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate after the washing coagulation devolatilization.Volatilization gas in the polymerization reaction kettle (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enter high pressure separating tank or low pressure separation pot after being cooled, the preacceleration inflation gas that can be used as polymerization reaction kettle in the isolated carbonic acid gas gas phase of high pressure separating tank uses, and the isolated carbonic acid gas gas phase of low pressure separation pot then is used further to polymerization after overdraft.Volatilization gas in the flash devolatilization glue jar (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enter high pressure separating tank or low pressure separation pot after being cooled, the preacceleration inflation gas that can be used as polymerization reaction kettle in the isolated carbonic acid gas gas phase of high pressure separating tank uses, and the isolated carbonic acid gas gas phase of low pressure separation pot then is used further to polymerization after overdraft.Volatilization gas in the washing coagulation still (propylene oxide and washing coagulation agent) is as the charging on one-level treating tower top.Liquid phase component in the solid-liquid separation system steams methyl alcohol and makes oligopolymer resolve into cyclic carbonate fat through vaporizer; Base of evaporator utmost point heavy-gravity contains the component of catalyst residue on a small quantity and discharges barrelling; The gas phase that vaporizer steams enters one-level treating tower bottom.The highly purified methanol liquid of one-level treating tower bottom extraction is recycled and reused for the washing coagulation system of production, the gas phase fraction that the refining cat head of one-level is discharged refluxes through the condensation rear section, part is as the charging of secondary treating tower, the further refining thick fraction of propylene oxide that obtains containing methyl alcohol returns one-level treating tower system as the 3rd charging of one-level treating tower, and another fraction is that highly purified propylene oxide can return polymerization reaction kettle and reuses.
Carbon dioxide-epoxy propane binary copolymerization aliphatic polycarbonate after the washing coagulation devolatilization is carried out property testing: ash 0.8%, fugitive constituent 0.2%, after polymkeric substance dissolves with methylene dichloride, there is not muddiness (not having obvious oligopolymer and catalyst residue separates out) during the methanol extraction washing.
The application of embodiment 4, aliphatic polycarbonate devolatilization device
Polymerization reaction kettle (20.0m
3); Flash glue solution jar (100.0m
3); Washing coagulation still (30.0m
3);-5 ℃ of refrigerated waters are housed in the water cooler; Washing coagulation agent (ethanol).
Solvent recovering system 15 comprises one-level treating tower and secondary treating tower.
In the polymerization reaction kettle, adopt the method for Chinese patent 00136189.9 to prepare carbon dioxide-epoxy propane-epoxy hexane terpolymer aliphatic polycarbonate glue, utilize the pressure of reactor, glue enters in the flash devolatilization glue jar; In the flash devolatilization glue jar, along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; After treating the canned 4-5 still glue of filling out polymerization reaction kettle of flash glue solution, pump into about 1/3 still ethanol and intensification from liquid scrubbing flocculation agent inlet, treat that washing cohesion still is warmed up to more than 40 ℃, alcohol vapour sprays into the washing coagulation still continuously by four nozzles, the while toothed gear pump pumps glue from the flash glue solution jar and also sprays into continuously the washing coagulation still by corresponding four nozzles, blow out the propylene oxide that sprays in the glue continuously with alcohol vapour, and as the washing coagulation agent polymkeric substance is carried out heated scrub with 60-70 ℃ of left ethanol liquid, liquid enters water cooler continuously, enters solid-liquid separation system after being cooled to below 40 ℃; Entered the polymer dry drying system behind the centrifuge dripping and carried out drying, obtained the carbon dioxide-epoxy propane-epoxy hexane terpolymer aliphatic polycarbonate after the washing coagulation devolatilization.Volatilization gas in the polymerization reaction kettle (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enter high pressure separating tank or low pressure separation pot after being cooled, the preacceleration inflation gas that can be used as polymerization reaction kettle in the isolated carbonic acid gas gas phase of high pressure separating tank uses, and the isolated carbonic acid gas gas phase of low pressure separation pot then is used further to polymerization after overdraft.Volatilization gas in the flash devolatilization glue jar (great amount of carbon dioxide and minor amount of propylene oxide) enters water cooler, enter high pressure separating tank or low pressure separation pot after being cooled, the preacceleration inflation gas that can be used as polymerization reaction kettle in the isolated carbonic acid gas gas phase of high pressure separating tank uses, and the isolated carbonic acid gas gas phase of low pressure separation pot then is used further to polymerization after overdraft.Volatilization gas in the washing coagulation still (propylene oxide and washing coagulation agent) is as the charging on one-level treating tower top.Liquid phase component in the solid-liquid separation system steams ethanol and makes oligopolymer resolve into cyclic carbonate fat through vaporizer; Base of evaporator utmost point heavy-gravity contains the component of catalyst residue on a small quantity and discharges barrelling; The gas phase that vaporizer steams enters one-level treating tower bottom.The highly purified ethanol liquid of one-level treating tower bottom extraction is recycled and reused for the washing coagulation system of production, the gas phase fraction that the refining cat head of one-level is discharged refluxes through the condensation rear section, part is as the charging of secondary treating tower, further refiningly obtain containing the thick fraction of alcoholic acid propylene oxide and return one-level treating tower system as the 3rd charging of one-level treating tower, another fraction is that highly purified propylene oxide can return polymerization reaction kettle and reuses.
Carbon dioxide-epoxy propane after the washing coagulation devolatilization-epoxy hexane terpolymer aliphatic polycarbonate is carried out property testing: test polymer ash 0.8%, fugitive constituent 0.2%, after polymkeric substance dissolves with methylene dichloride, there is not muddiness (not having obvious oligopolymer and catalyst residue separates out) during the methanol extraction washing.
Comparative Examples,
The industrial alcohol of 500L is joined 830Kg to be contained in the reactor that has agitator of aliphatic poly polypropylene carbonate ester polymer of unreacted propylene oxide and residual catalyst and tentatively stirs, stirring after 1 hour sealing enters hermetic rinse bath and carries out the secondary washing precipitation, secondary washing adds industrial alcohol 1200L, churning time 40min, after treating thick polymkeric substance pulverize powder, sedimentation, getting supernatant liquor with pump washs for the third time again, washing for the third time adds industrial alcohol 900L, churning time 30min, get supernatant liquor with pump again and carry out the 4th washing again, the 4th washing adds industrial alcohol 400L, churning time 10min squeezes into the slip header tank by the slag stock pump with slurry and carries out centrifugal, drying obtains solvent and is lower than 0.2% aliphatic poly polypropylene carbonate ester polymer.Propylene oxide in the supernatant liquid and industrial alcohol carry out rectifying separation, recycle.(Chinese patent CN200610077582.9, embodiment 4)
Claims (10)
1. aliphatic polycarbonate washing coagulation devolatilization device is characterized in that: it comprises polymerization reaction kettle (1), flash glue solution jar (2), by a washing coagulation still or placed in-line washing coagulation still is formed more than two condensed system, solid-liquid separation system (4), polymer dry drying system (5), toothed gear pump (6) and connecting tube;
The bottom of polymerization reaction kettle (1) is provided with product outlet (1-1), and top is provided with pneumatic outlet (1-2);
The top of flash glue solution jar (2) is provided with inlet (2-1) and pneumatic outlet (2-2), and the bottom is provided with liquid exit (2-3);
The bottom of washing coagulation still (3) is provided with washing coagulation agent inlet (3-1), and the middle part is provided with liquid inlet (3-2) and liquid exit (3-3), and top is provided with pneumatic outlet (3-4);
The pipeline 7 (7) that stretches out from the product of polymerization reaction kettle (1) outlet (1-1) extends to the bottom of flash glue solution jar (2) by behind the inlet (2-1) of flash glue solution jar (2); Pipeline 8 (8) liquid inlets by washing coagulation still (3) (3-2) of stretching out from the liquid exit (2-3) of flash glue solution jar (2) enter washing coagulation still (3); On the pipeline 8 (8) between the liquid inlet (3-2) of the liquid exit (2-3) of described flash glue solution jar (2) and described washing coagulation still (3), be provided with toothed gear pump (6); One end of pipeline 9 (9) is positioned at washing coagulation still (3) and near pipeline 8 (8), the other end stretches out washing coagulation agent inlet (3-1); The liquid exit (3-3) of washing coagulation still (3) joins by the inlet of pipeline 10 (10) with solid-liquid separation system (4); The outlet of solid-liquid separation system (4) is joined by pipeline and polymer dry drying system (5).
2. aliphatic polycarbonate washing coagulation devolatilization device as claimed in claim 1 is characterized in that: described flash glue solution jar (2) is equipped with whipping appts; Described washing coagulation still (3) is equipped with whipping appts.
3. aliphatic polycarbonate washing coagulation devolatilization device as claimed in claim 2 is characterized in that: described device also comprises MONOMER RECOVERY jar (11), monomer-flocculation agent withdrawing can (12), water cooler and condenser;
The pneumatic outlet (1-2) of polymerization reaction kettle (1) joins by the inlet of pipeline and water cooler; The pneumatic outlet (2-2) of flash glue solution jar (2) joins by the inlet of pipeline and water cooler; The outlet of water cooler and MONOMER RECOVERY jar (11) join; The pneumatic outlet (3-4) of washing coagulation still (3) joins by the inlet of pipeline and condenser; The outlet of condenser and monomer-flocculation agent withdrawing can (12) joins.
4. aliphatic polycarbonate washing coagulation devolatilization device as claimed in claim 2 is characterized in that: described device also comprises high pressure separating tank (13), low pressure separation pot (14), solvent recovering system (15), water cooler and vaporizer;
The pneumatic outlet (1-2) of polymerization reaction kettle (1) joins by the inlet of pipeline and water cooler; The pneumatic outlet (2-2) of flash glue solution jar (2) joins by the inlet of pipeline and water cooler; High pressure separating tank (13) joins by the outlet of pipeline and water cooler; Low pressure separation pot (14) is joined by the outlet of pipeline and water cooler;
The pneumatic outlet (3-4) of washing coagulation still (3) joins by pipeline and solvent recovering system (15);
Described pipeline 10 (10) is provided with water cooler; Described solid-liquid separation system (4) is provided with the gas recovery mouth; Described gas recovery mouth joins by the inlet of pipeline and vaporizer; The outlet of vaporizer is joined by pipeline and solvent recovering system (15).
5. the application of arbitrary described device in the preparation aliphatic polycarbonate in the claim 1 to 4.
6. the application of arbitrary described device in the aliphatic polycarbonate washing coagulation devolatilization in the claim 1 to 4.
7. the washing coagulation devolatilization method of an aliphatic polycarbonate is with the described device of claim 2 the aliphatic polycarbonate glue to be carried out the washing coagulation devolatilization, comprises the steps:
Aliphatic polycarbonate glue in the polymerization reaction kettle (1) enters flash devolatilization glue jar (2), and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still (3) by described toothed gear pump (6), spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still (3) inlet (3-1), solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system (4), isolates solid polymer; Solid polymer enters polymer dry drying system (5), obtains the aliphatic polycarbonate after the washing coagulation devolatilization.
8. method as claimed in claim 7 is characterized in that: described device also comprises MONOMER RECOVERY jar (11), monomer-flocculation agent withdrawing can (12), water cooler and condenser;
The pneumatic outlet (1-2) of polymerization reaction kettle (1) joins by the inlet of pipeline and water cooler; The pneumatic outlet (2-2) of flash glue solution jar (2) joins by the inlet of pipeline and water cooler; The outlet of water cooler and MONOMER RECOVERY jar (11) join; The pneumatic outlet (3-4) of washing coagulation still (3) joins by the inlet of pipeline and condenser; The outlet of condenser and monomer-flocculation agent withdrawing can (12) joins;
Aliphatic polycarbonate glue in the polymerization reaction kettle (1) enters flash devolatilization glue jar (2), and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still (3) by described toothed gear pump (6), spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still (3) inlet (3-1), solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system (4), isolates solid polymer; Solid polymer enters polymer dry drying system (5), obtains the aliphatic polycarbonate after the washing coagulation devolatilization;
Volatilization gas in the flash devolatilization glue jar (2) enters water cooler, enters MONOMER RECOVERY jar (11) after being cooled; Volatilization gas in the washing coagulation still (3) enters condenser, enters monomer-flocculation agent withdrawing can (12) after being condensed.
9. method as claimed in claim 7 is characterized in that: described device also comprises high pressure separating tank (13), low pressure separation pot (14), solvent recovering system (15), water cooler and vaporizer;
The pneumatic outlet (1-2) of polymerization reaction kettle (1) joins by the inlet of pipeline and water cooler; The pneumatic outlet (2-2) of flash glue solution jar (2) joins by the inlet of pipeline and water cooler; High pressure separating tank (13) joins by the outlet of pipeline and water cooler; Low pressure separation pot (14) is joined by the outlet of pipeline and water cooler;
The pneumatic outlet (3-4) of washing coagulation still (3) joins by pipeline and solvent recovering system (15);
Described pipeline 10 (10) is provided with water cooler; Described solid-liquid separation system (4) is provided with the gas recovery mouth; Described gas recovery mouth joins by the inlet of pipeline and vaporizer; The outlet of vaporizer is joined by pipeline and solvent recovering system (15);
Aliphatic polycarbonate glue in the polymerization reaction kettle (1) enters flash devolatilization glue jar (2), and along with stirring is carried out, the partial monosomy solvent evaporates becomes gas to be removed, and obtains spissated glue; Spissated glue sprays into washing coagulation still (3) by described toothed gear pump (6), spray into the washing coagulation agent of boiling point ± 5 ℃ from the washing coagulation agent of washing coagulation still (3) inlet (3-1), solvent monomer, catalyzer and oligopolymer are washed, and evaporate into gas and are removed, and obtain the solid-liquid suspension thing; The solid-liquid suspension thing enters solid-liquid separation system (4), isolates solid polymer; Solid polymer enters polymer dry drying system (5), obtains the aliphatic polycarbonate after the washing coagulation devolatilization;
Volatilization gas in the flash devolatilization glue jar (2) enters water cooler, enters high pressure separating tank (13) or low pressure separation pot (14) after being cooled; Volatilization gas in the washing coagulation still (3) enters solvent recovering system (15); Liquid in the solid-liquid separation system (4) evaporates into gas through vaporizer, enters solvent recovering system (15).
10. as arbitrary described method in the claim 7 to 9, it is characterized in that: the condition that described washing coagulation agent need be satisfied is as follows: boiling point is higher than the monomeric boiling point that is used to prepare aliphatic polycarbonate, and aliphatic polycarbonate is insoluble to it.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206334A (en) * | 2011-05-05 | 2011-10-05 | 中国海洋石油总公司 | Method for removing volatile matters from aliphatic polycarbonate by washing and condensing |
| CN104910401A (en) * | 2015-04-17 | 2015-09-16 | 聊城鲁西聚碳酸酯有限公司 | Polycarbonate and solvent separation system, and method thereof |
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| CN102206334A (en) * | 2011-05-05 | 2011-10-05 | 中国海洋石油总公司 | Method for removing volatile matters from aliphatic polycarbonate by washing and condensing |
| CN102206334B (en) * | 2011-05-05 | 2013-01-23 | 中国海洋石油总公司 | Method for removing volatile matters from aliphatic polycarbonate by washing and condensing |
| CN104910401A (en) * | 2015-04-17 | 2015-09-16 | 聊城鲁西聚碳酸酯有限公司 | Polycarbonate and solvent separation system, and method thereof |
| CN109758994A (en) * | 2019-03-11 | 2019-05-17 | 浙江信汇新材料股份有限公司 | A kind of butyl reactor cleaning device and its cleaning method |
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| WO2022138409A1 (en) * | 2020-12-23 | 2022-06-30 | 住友精化株式会社 | Resin purification method |
| CN112898551A (en) * | 2021-03-11 | 2021-06-04 | 中山大学 | Post-production treatment device and method for semi-aromatic polyester-polycarbonate copolymer |
| CN114292290A (en) * | 2021-12-13 | 2022-04-08 | 华陆工程科技有限责任公司 | Reverse-sequence forward-flow energy-saving method and device for organic silicon crude monomer separation system |
| CN115716911A (en) * | 2022-11-18 | 2023-02-28 | 山东联欣环保科技有限公司 | Devolatilization method and devolatilization system |
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