Abstract
The present invention relates to a method for separating volatile substances, particularly iodine, diiodised aromatic compounds and/or mixtures thereof, from material mixtures containing said compounds. The invention further relates to a device for producing polyarylene sulphides, by means of which volatile substances, particularly iodine and diiodised aromatic compounds, can be separated from the polymers.
Claims
1. An apparatus for producing polyarylene sulfides including at least one repeat unit in accordance with the general formula I ##STR00003## (where A represents a bivalent aromatic radical) produced by condensation polymerization of a di-iodized aromatic compound in accordance with the general formula II
I-A-I Formula II using a sulfidation agent, comprising a) a precondensation stage comprising an agitating tub or a cascade of agitating tubs composed of a plurality of agitating tubs connected one after the other, wherein the agitating tub and/or the first agitating tub of the cascade of agitating tubs has at least one input possibility for the reactants, and has an outlet for the prepolymer, and downstream of the agitating tub or the cascade of agitating tubs further comprising; b) a condensation polymerization step comprising at least one condensation polymerization reactor or a cascade of a plurality of condensation polymerization reactors connected one after the other, wherein the condensation polymerization reactor and/or the first condensation polymerization reactor of the cascade of a plurality of condensation polymerization reactors has an input possibility for the prepolymers obtained from the first step and has an output possibility for the polycondensate, wherein the precondensation stage is connected to the condensation polymerization step via a product line, characterized in that the agitating tub or at least one agitating tub of the cascade of agitating tubs has at least one drainage possibility for gaseous side products and/or non-reacted reactants; the condensation polymerization reactor or at least one condensation polymerization reactor of the cascade of condensation polymerization reactors connected one after the other has at least one drainage possibility for gaseous side products and/or non-reacted reactants; wherein the at least one drainage possibility of the agitating tub or at least one tub of the cascade of agitating tubs opens into a condensation apparatus and/or a distillation column for the separation by distillation of the gaseous side products and/or non-reacted reactants; and wherein the at least one drainage possibility of the condensation polymerization reactor or at least one condensation polymerization reactor of the cascade of condensation polymerization reactors connected one after the other opens into at least one desublimator, wherein the at least one distillation column is connected downstream of the at least one desublimator, and the distillation column being connected to the at least one desublimator via a line and having a head side drain and a sump side drain.
2. The apparatus in accordance with claim 1, the distillation column of the at least one drainage possibility of the agitating tub or at least one tub of the cascade of agitating tubs has a feedback of non-reacted reactants into the agitation tub or into the first agitation tub of the cascade of agitation tubs respectively.
3. The apparatus in accordance with claim 1, wherein the distillation column the at least one drainage possibility of the agitating tub or at least one tub of the cascade of agitating tubs has a drain at the head side, the drain being connected to at least one condenser or desublimator via a supply.
4. The apparatus in accordance with claim 1, wherein the head side drain a) opens into a condenser or into the at least one desublimator; or b) is combined with the product flow stemming from a condenser.
5. The apparatus in accordance with claim 1, wherein it comprises an apparatus for generating vacuum which a) is connected to the at least one desublimator via at least one connection line; and/or b) is connected to at least one condenser or to the at least one desublimator via at least one connection line.
Description
(1) The present invention will be described in the following by means of the subsequent descriptions and by the Figures in detail, however, without limiting the invention to the specific parameters illustrated there.
(2) In this connection there is shown
(3) FIG. 1 a first variant of the method guidance in accordance with the invention as well as an associated apparatus for carrying out the method; and
(4) FIG. 2 a second variant of the method in accordance with the invention, as well as an apparatus for carrying out this method.
(5) In the following a preparation method is described which, in a highly economic and efficient kind and manner, separates gaseous substances (iodine and di-iodized aromatic compounds in accordance with formula II) either as a solid and/or as a liquid (molten solid) from specific method steps combines these meaningfully and feeds back a few flows into the process, preferably discharges iodine containing flows from the plant.
(6) Particularly for continuous processes the iodine flows and the p-DIB flows must be removed from the process without interruption of the vacuum at vacuums of 0.1 to 300 mbar and also there above, since the final product must be constant with respect to its quality.
(7) For reasons of cost and for energetic reasons the desublimation and/or recovery process components and the plant have to be optimized particularly well with respect to the costs of invest and operating costs.
(8) The preparation method is generally characterized in that the gaseous iodine/p-DIB flows exiting at different positions from the main flow are purified and/or discharged and preferably iodine containing flows are separated from the process and p-DIB-containing flows are fed back into the process for the purpose of further reaction; all iodine/p-DIB gas flows which lie above the triple point of iodine are initially condensed and/or rectified; all those iodine/p-DIB gas flows which lie beneath the triple point of iodine are discharged from the method are initially solidified by means of specific desublimators and are subsequently liquefied in a further step thereafter above the triple point; it is thereby enabled to completely meaningfully combine the different iodine/p-DIB flows and to separate these by means of specific separation operations such as e.g. rectification below over-pressure up to and down to vacuum and to add or to discharge at corresponding positions of the method.
(9) FIG. 1 shows a flow diagram of a method guidance in accordance with the invention in which also an apparatus in accordance with the present invention is used. The reactants sulfur and, for example, para-di-iodobenzene are supplied from corresponding storage containers via supply lines 11 and/or 12 to an agitation tub 10 as a first step of the condensation polymerization reaction. This first step is carried out at relatively high pressures, this means pressures of >126 mbar. In the agitation tub 10 and/or in a corresponding cascade of agitation tubs the reactants sulfur and p-DIB are converted to a prepolymer with relatively low viscosity. Elemental iodine arises as a side product during the condensation polymerization reaction. Additives, such as e.g. catalysts can be introduced at suitable positions via supply lines 14, e.g. into the supply lines 11 or 12, the agitation tub 10 or the condensation polymerization reactors 20a and/or 20b. The agitation tub 10 has a drain 101 via which the accruing iodine as well as e.g. non-reacted p-DIB can be supplied to a distillation column 102. In the distillation column 102 a separation of the iodine and of the p-DIB takes place, which p-DIB can be fed back to the agitation tub 10 via a supply line 15, for example, as a product discharged sump side and can thus be recycled. The iodine can be discharged at the head side via a drain 103 and can be supplied to a condenser 104 where a corresponding condensation of the iodine to molten iodine can take place.
(10) The agitation tub 10 is in this connection operated at temperatures at which iodine is present in the gaseous state at the corresponding pressures of 126 mbar and can thus be correspondingly easily removed from the accruing prepolymers. The prepolymer is supplied via a connection line 13 to a condensation polymerization reactor which in the case of the example illustrated in FIG. 1, is of two-step design and which has a first condensation polymerization reactor 20a and a second condensation polymerization reactor 20b. The condensation polymerization reactors are connected to one another via a melt line 21. Alternatively, the two reactors 20a and 20b can also be formed as a unit in which the corresponding steps are separated internally from one another. In the consecutive condensation polymerization reactors 20a and 20b a build-up of the degree of polymerization of the corresponding polyarylene sulfide, for example of the polyphenyl sulfide (PPS) takes place. In this connection iodine again arises as a gaseous side product and/or not yet reacted p-DIB can be included in the arising polymer melts. Both condensation polymerization reactors 20a and 20b have drains 201 and 201 via which the gaseous products can be supplied from the respective condensation polymerization reactors 20a and/or 20b to a desublimator 202. Likewise the possibility is given that a plurality of desublimators are connected one after another in order to increase the separation performance. Since pressures are present in the condensation polymerization reactors 20a and 20b which lie beneath the pressure present at the triple point of iodine (<126 mbar) no solidification of the iodine separated from the reactors 20a and 20b in the gaseous aggregate state is no longer possible under these conditions; merely a solidification and/or desublimation of the iodine can still take place. In the desublimator 202 thus a separation of iodine as a solid substance at, for example, cooled parts of the desublimator with which the iodine flows withdrawn from the reactors 20a and 20b come into contact takes place. The pressures in the condensation polymerization reactors 20a and 20b are in this connection set in such a way that lower pressure conditions are present in the reactor 20b than in the reactor 20a. The final polymer melt can take place via a output possibility 22 from the reactor 20b. Iodine separated in the desublimator 202 can be supplied via an output possibility and a supply line 205 to a further column 206 where a separation by means of distillation of the iodine at suitable pressure conditions at which the iodine undergoes a phase transition from liquid to gaseous can take place. In this connection iodine is discharged as a gaseous head side product 207 and is withdrawn and can be extracted for the external recylcing of the column. In this connection likewise a combination of this flow 207 with the iodine flows 103, extracted from the distillation column 102 and condensed in the condenser 104 is possible, wherein a line 105 is combined with the head side extraction possibility 207 of the column 206 from the condenser. Instead of the condenser 104 also a desublimator can be provided. The combined iodine flows 209 can thus be supplied to an external recycling. Likewise it is possible that the iodine flow 207 extracted at the head side of the column 206 is supplied to the condenser 104 in order to initially achieve a liquification of the iodine there. The column 206 at the sump side has a further outlet 208 for side products or reactants, such as for example p-DIB. The extraction of the iodine separated in the desublimator 202 can, for example, take place thereby that the temperature in the desublimator is time-wise increased so that again a phase transition from solid to gaseous of the iodine separated there takes place and thus a gaseous iodine flow can be provided in the column 206 via the supply line 205. Alternatively or additionally it is also possible to increase the pressures so that iodine separated in the desublimator 202 can run through a phase transition from solid to liquid so that a liquid iodine flow can be supplied to the column 206 in the supply line 205. Moreover the apparatus in accordance with the invention in accordance with the example in FIG. 1 has an apparatus for the generation of a vacuum 30 which is connected to the desublimator 202 and/or to the condenser 104 via corresponding vacuum lines 32 and 33. The apparatus for the generation of the vacuum 30 moreover has an outlet for exhaust gases 31.
(11) FIG. 2 shows a further embodiment of the apparatus in accordance with the invention in which like components as are illustrated in FIG. 1 are provided with the same reference numerals. Also the apparatus in accordance with FIG. 2 has an agitation tub 10 with supply lines 11 for sulfur and supply lines 12 for p-DIB, wherein, for example, in the supply line 12 and/or the agitation tub 10 further additives and/or catalysts can still be supplied via supply lines 12a and/or 14. A condensation polymerization of the reactants to a prepolymer takes place in the agitation tub 10. In analogy to FIG. 1 also the agitation tub 10 in accordance with FIG. 2 has a drain 101 and is connected to a distillation column 102. The prepolymer is supplied via a supply line 13 to a condensation polymerization reactor 20 designed as a multistep condensation polymerization reactor which has drains 201a and 201b at different positions for gaseous side products such as, for example, iodine and/or reactants, such as, for example p-DIB. These drains 201a and 201b respectively lead to a desublimator 202a and/or 202b. The desublimators 202a and 202b are connected to an apparatus 30 for the generation of vacuum via respectively separate vacuum lines 32a and/or 32b. The iodine flows from the desublimators 202a and/or 202b are respectively supplied to a collector 204 via a supply line 203a and/or 203b and from there are supplied to a downstream distillation column 206 via a supply line 205. The iodine flow 207 extracted at the head side is condensed and/or solidified in a condenser 104 and/or a desublimator together with that extracted from the distillation column connected downstream of the first step 10 and can, for example, be extracted as a so-called collected iodine flow 105 and/or as solid iodine. For the further purification likewise a feedback 106 into the column 102 is possible. Moreover, the column 206 can have a further drain 210 via which, for example, p-DIB purified there can initially again be supplied to the condensation polymerization reactor 20. However, likewise also a discharge into the condensation polymerization reactor 10 is possible.
