GB2052535A - A continuous method for the preparation of polyester resins and apparatus for carrying out the method - Google Patents

A continuous method for the preparation of polyester resins and apparatus for carrying out the method Download PDF

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GB2052535A
GB2052535A GB8017064A GB8017064A GB2052535A GB 2052535 A GB2052535 A GB 2052535A GB 8017064 A GB8017064 A GB 8017064A GB 8017064 A GB8017064 A GB 8017064A GB 2052535 A GB2052535 A GB 2052535A
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INST CHEMII PRZEMYSLOWEJ
INSTIYTUT CHEMII PRZEMYSLOWEJ
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/56Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/785Preparation processes characterised by the apparatus used

Abstract

A continuous method for the preparation of polyester resin by the reaction of an anhydride of a dicarboxylic acid with a compound containing active hydrogen atoms and with a monoepoxide compound in the presence of a catalyst, wherein the reaction is carried out in 2-10 stages, the catalyst being introduced in the individual stages in such amounts that its concentration in the first stage is 0.001-0.2% by weight and in the last stage 0.005-1.0% by weight in relation to the weight of the whole reaction mixture, wherein in all the stages a temperature in the range of 70-270 DEG C is maintained, and wherein the reaction is carried out in the liquid phase under a pressure of 4-100 atm. g.p. This method may be carried out in an apparatus which comprises a multi-sectional tubular reactor, which can be surrounded by a multi- segmental heating/cooling jacket, wherein before the inlet (6) to each reactor section (1) there is located a tube (2) with inlets (3, 4) and with an outlet (5) connected with the inlet (6), to the reactor section (1), static elements (7) being distributed in the tubes (2). <IMAGE>

Description

SPECIFICATION A continuous method for the preparation of polyester resins and apparatus for carrying out the method This invention relates to a continuous method for the preparation of polyester resins, more particularly a multi-stage, continuous method for the preparation of polyester resins by the reaction of anhydrides of dicarboxylic acids with compounds containing active hydrogen atoms-and with monoepoxide compounds in the presence of a catalyst at elevated temperature and under elevated pressure.

Polyester resins are prepared by many known methods, mainly intermittent or semi-intermittent methods, such as those described in U.S. Patent Nos. 2 779 793, 3 254060, 3 254 063, 3 382 217 and 2 662 024, Federal Republic of Germany Patent Nos. 1 000 534 and 1 900 181, French Patent Nos. 1 046 418 and 1 062 756 and German Democratic Republic Patent No.89,710 among others.

These methods consist in mxing all the components and catalyst in a reaction vessel, into which they are introduced in determined sequence and intervals of time, and in keeping them at a desired temperature, which is sometimes changed during the synthesis, and under desired pressure. In connection with the limited possibility of heat removal from the reaction vessel (a small heat exchange surface area per unit volume of the reaction space), the reaction conditions are selected to that the time of duration of the reaction is from several to a dozen or so hours.

A much more advantageous relation of the heat exchange surface area to the volume of reaction space is obtained in continuous reactors, as a rule of prolate shape. It is, however, difficult to prepare by a continuous method a polyester resin with desired characteristics, in particular of desired colour.

From U.S. Patent No. 3 374 203 it is known to pass a mixture of reactants through a tube reactor with a mobile stirrer which reaches the walls of the apparatus, this apparatus being surrounded by a multi-sectional cooling jacket; thus this reactor is quite complicated from the point of view of its structure. A similar method is described in French Patent No. 2 108 840.

Continuous methods for the preparation of polyester resins are also described in German Democratic Republic Patent No.112 657, in Federal Republic of Germany Patent No. 2 359 502, and in Hydrocarbon Processing 56, Dec. 1977 by J. C. Zimmer. On a commercial scale only the method described by Zimmer is used as well as the method described in U.S. Patent No. 3 723 390. The last mentioned method consists in introducing into a reactor a mixture of reactants together with a catalyst containing a deficient amount of monoepoxide compound, this compound being, moreover, introduced in portions to various places of the reaction space which contain mobile structural elements, these places being at different distances from the inlet of the reaction mixture.In the reaction space, a temperature of 1 65-2600C and a pressure of at least 25 atm.g.p. is maintained. The means residence time of reactants in the reaction space is below 20 minutes.

This synthesis is carried out in a complicated multi-segmental reactor constructed from special steel having a high heat conductivity and a high corrosion resistance, equipped with a high-speed stirrer necessary for a rapid intermixing of the reactants in the individual segments of the reactor and for ensuring high values of the heat exchange coefficients from the reaction mixture to the reactor walls.

The method presented now, though involving relatively high expense due to the cost of machinery and problems normally encountered when sealing pressure apparatus, makes it possible to obtain a product of desired characteristics and of an appropriate colour.

Colour is an important feature of a polyester resin. It is desired to have resins of colour below 50 on the Gardner scale. Up to now, neither the character of substances causing colouration of polyester resins, nor the mechanism of their formation are known. According to some indications, the coloured substances are formed during a prolonged maintaining of anhydrides at elevated temperatures, in particular in an oxygen-containing atmosphere, although it has nqt-been unequivocally stated whether the coloured substances are formed from the anhydrides themselves or from their contaminants. The results of other investigations seem to indicate that coloured substances are formed as a result of disruption of ether linkages in polyester resins at a slightly increased temperature.Finally, the colouration of the product can also be due to such overheating of the reaction mixture in the reactor or its components before their introduction into the reactor that carbon black or pitchy substances are formed.

Unexpectedly, it has now been found that a clear product having other desired properties can be prepared by a continuous method which is much more simple than those hitherto known and during a period of time which is much shorter than for a synthesis carried out in an intermittent or semiintermittent manner.

The present invention in one aspect provides a continuous method for the preparation of polyester resin by the reaction of an anhydride of a dicarboxylic acid with a compound containing active hydrogen atoms and with a monoepoxide compound in the presence of a catalyst, wherein the reaction is carried out in 2-10 stages, the catalyst being introduced in the individual stages in such amounts that its concentration in the first stage is 0.001-0.2% by weight and in the last stage 0.0051.0% by weight in relation to the weight of the whole reaction mixture, wherein in all the stages a temperature in the range of 70-2700C is maintained, and wherein the reaction is carred out in the liquid phase under a pressure of 4-100 atm. g.p.

In the method of preparation of polyester resins according to the invention anhydrides of dicarboxylic acids, compounds containing active hydrogen atoms and monoepoxide compounds are preferably introduced continuously or pulsatorily from one side into a prolate reaction space together with a catalyst taken in such a concentration as to obtain the mean conversion rate of anhydride during 4 minutes at a rate equal to 0.520% per minute, which corresponds to a concentration of catalyst of about 0.0010.2% by weight in relation to the whole reaction mixture, and to this region of the reaction space, in which a reaction mixture having undergone a degree of conversion of anhydride of 4098% is contained, an additional amount of catalyst is introduced such that its concentration in the reaction mixture which is leaving, continuously or pulsatorily, the reaction space would be equal to 0.005-1 .0% by weight. At the same time a temperature of 70-2700C is maintained in the reaction space, which is sufficient to keep the reaction mixture in the liquid state under the pressure applied, which is equal to 4-100 atm. g.p. It is desirable that the molar ratio of the whole amount of oxide introduced into the reaction space in a unit time to the amount of anhydride introduced during that time is from 0.8:1 to 5:1.

Compounds containing active hydrogen atoms are advantageously introduced into the reaction space in the form of a solution or a suspension in one of the reactants or in a mixture of a part or all of the reactants. It is advantageous to introduce the catalyst in the form of a solution in a mixture of molten anhydride with a compound containing active hydrogen atoms, this compound being at least partially reacted with the anhydride.

It is preferred to use LiCI or ZnC12 as the catalyst.

It is preferred to use maleic anhydride, phthalic anhydride or a mixture thereof as the anhydride.

As the compound containing active hydrogen atoms in the molecule, it is preferred to use 1,2propylene glycol, ethylene glycol or a mixture thereof.

As the monoepoxide compound, it is preferred to use epoxyethane, 1 ,2-epoxypropane or a mixture thereof.

The invention in another aspect provides apparatus for preparing polyester resin, comprising a multi-sectional tubular reactor for the synthesis of polyester resin, wherein before the inlet to each reactor section there is located a tube with inlets and with an outlet connected with the inlet to the reactor section, static elements being distributed in the tubes.

It is preferred to carry out the method according to the invention in the reactor according to the invention.

The invention will be further described, by way of example only, with reference to the accompanying drawing, which is a schematic view of a reactor for carrying out the method according to the invention.

The reactor shown in the drawing comprises 2-10 sections 1 which can be surrounded by a heating-cooling jacket and before which there are situated tubes 2 containing static elements 7 which cause multiple changes in the flow direction of the reactant streams, their division into smaller streams and thus intermixing. Into a tube 2 placed before the first reactor section 1' there are introduced through inlets 3 and 4 streams of the components of the reaction mixture containing a part of the catalyst to be introduced to the reaction space. After being intermixed with each other, these streams leave the tube 2 by an outlet 5 which is connected with an inlet 6 to the first section 1' of the reactor.The reaction mixture flows out of the section 1' by an outlet 8 connected with an inlet 3 to the next tube 2, the latter being placed before the subsequent section 1 of the reactor. Through the inlet 4 there is introduced to this tube the next part of the catalyst together with other components of the reaction mixture or an additional part of the components of the reaction mixture only. Streams introduced into this tube 2 through the inlets 3 and 4 are intermixed, then they are introduced into the next section of the reactor, and so on.

It is advantageous to also place static mixing elements 9 in the first section 1' of the reactor.

These elements 9 should be distributed along a distance corresponding to a ratio of L2/D of from 2 to 40, and the start point of this distance should correspond to a value of a ratio of L,/D of from 0 to 20, wherein D is the effective diameter of the reactor, in mm, L1 is the distance of the start point of the mixing elements from the inlet 6, in mm, and L2 is the length of the distance of the section 1' occupied by these elements, in mm.

The invention will be further described with reference to the following illustrative Example.

EXAMPLE A mixture of a composition given in the following table was introduced into a tubular reactor surrounded by a two-sectional jacket containing a heat carrier. The reactants were introduced into the reactor through a tube containing spiral elements. In several experiments, an additional amount of catalyst was introduced into the reactor after the first section, in which the degree of conversion of acid anhydride was from 40 to 98%. In each of the two sections of the jacket a constant, in the majority of cases different, temperature was maintained. These temperatures, together with other conditions of the reaction, are given in the table. The same table also gives some characteristic properties of the thusprepared polyester resins.

It follows from experiments A, G, H, L and N that when carrying out the synthesis under such conditions that the rate of reaction in the initial period of 4 minutes is higher than 20% per minute, there is obtained a polyester resin with a low acid number, but which is very dark. In all the other cases, the polyester resins obtained had a good colour and, at the same time, if neither the jacket temperature in the second section nor the catalyst concentration in that section were increased, polyester resins of a high acid number (experiments D, E, J and P) were obtained, even for a long residence time of the reaction mixture in the reactor.

TABLE <img class="EMIRef" id="027057248-00040001" />

Rate <SEP> of <tb> Molar <SEP> ratio <SEP> conversion <SEP> Catalyst <SEP> Temperature <tb> Average <SEP> of <SEP> anhy- <SEP> concentration <SEP> in <SEP> the <SEP> jacket <SEP> Acid <SEP> Colour <tb> anhydride <SEP> monoepoxide <SEP> of <SEP> residence <SEP> drides <SEP> in <SEP> % <SEP> by <SEP> weight <SEP> of <SEP> reactor, <SEP> in <SEP> C <SEP> number <SEP> of <SEP> the <tb> time <SEP> of <SEP> during <SEP> 4 <SEP> of <SEP> the <SEP> product, <SEP> on <tb> maleic <SEP> phthalic <SEP> ethyl- <SEP> cyclo- <SEP> 1,2- <SEP> 1,3- <SEP> reactants, <SEP> min., <SEP> in <SEP> 1st <SEP> 2nd <SEP> 1st <SEP> 2nd <SEP> Pressure <SEP> product, <SEP> Gardner <tb> acid <SEP> acid <SEP> ene <SEP> propylene <SEP> hexane <SEP> butylene <SEP> ethylene <SEP> in <SEP> %/min. <SEP> section <SEP> section <SEP> section <SEP> section <SEP> in <SEP> atm.<SEP> mgKOH/g <SEP> scale <tb> A <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 30 <SEP> 23 <SEP> 0.1 <SEP> 0.1 <SEP> 120 <SEP> 120 <SEP> 15 <SEP> 0.3 <SEP> 13 <tb> <SEP> B <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 30 <SEP> 15 <SEP> 0.01 <SEP> 0.1 <SEP> 120 <SEP> 150 <SEP> 15 <SEP> 1.5 <SEP> 1 <tb> C <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 30 <SEP> 15 <SEP> 0.01 <SEP> 0.01 <SEP> 120 <SEP> 190 <SEP> 2.3 <SEP> 2 <tb> D <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 30 <SEP> 15 <SEP> 0.01 <SEP> 0.01 <SEP> 120 <SEP> 120 <SEP> 15 <SEP> 47.0 <SEP> 2 <tb> E <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 240 <SEP> 15 <SEP> 0.01 <SEP> 0.01 <SEP> 120 <SEP> 120 <SEP> 15 <SEP> 22.8 <SEP> 2 <tb> F <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> - <SEP> 0.05 <SEP> - <SEP> 0.05 <SEP> - <SEP> 30 <SEP> 17 <SEP> 0.02 <SEP> 0.15 <SEP> 110 <SEP> 110 <SEP> 80 <SEP> 1.3 <SEP> 3 <tb> G <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> - <SEP> 0.05 <SEP> - <SEP> 0.05 <SEP> - <SEP> 30 <SEP> 25 <SEP> 0.15 <SEP> 0.15 <SEP> 110 <SEP> 110 <SEP> 80 <SEP> 0.8 <SEP> 10 <tb> H <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> - <SEP> 0.05 <SEP> - <SEP> 0.05 <SEP> - <SEP> 30 <SEP> 21 <SEP> 0.15 <SEP> 0.15 <SEP> 140 <SEP> 140 <SEP> 80 <SEP> 0.9 <SEP> 8 <tb> I <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> - <SEP> 0.05 <SEP> - <SEP> 0.05 <SEP> - <SEP> 60 <SEP> 25 <SEP> - <SEP> 0.15 <SEP> 140 <SEP> 140 <SEP> 80 <SEP> 5.7 <SEP> 3 <tb> J <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> - <SEP> 0.05 <SEP> - <SEP> 0.05 <SEP> - <SEP> 30 <SEP> 17 <SEP> 0.02 <SEP> 0.02 <SEP> 110 <SEP> 110 <SEP> 80 <SEP> 31.2 <SEP> 2 <tb> K <SEP> 1 <SEP> - <SEP> 5 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> 40 <SEP> 12 <SEP> 0.2 <SEP> 0.2 <SEP> 50 <SEP> 130 <SEP> 95 <SEP> 3.2 <SEP> 2 <tb> L <SEP> 1 <SEP> - <SEP> 5 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> 40 <SEP> 22 <SEP> 0.2 <SEP> 0.2 <SEP> 100 <SEP> 130 <SEP> 95 <SEP> 0.7 <SEP> 11 <tb> M <SEP> 1 <SEP> - <SEP> 5 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> 120 <SEP> 1.5 <SEP> 0.05 <SEP> 0.2 <SEP> 50 <SEP> 130 <SEP> 95 <SEP> 4.2 <SEP> 1 <tb> N <SEP> - <SEP> 1 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 24 <SEP> 0.1 <SEP> 0.1 <SEP> 130 <SEP> 200 <SEP> 20 <SEP> 2.8 <SEP> 9 <tb> O <SEP> - <SEP> 1 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 16 <SEP> 0.02 <SEP> 0.1 <SEP> 130 <SEP> 200 <SEP> 20 <SEP> 4.6 <SEP> 3 <tb> <SEP> P <SEP> - <SEP> 1 <SEP> - <SEP> 1.25 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 16 <SEP> 0.02 <SEP> 0.02 <SEP> 130 <SEP> 200 <SEP> 20 <SEP> 23.5 <SEP> 2 <tb> Q <SEP> - <SEP> 1 <SEP> - <SEP> 1.25 <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> 40 <SEP> 14 <SEP> 0.02 <SEP> 0.1 <SEP> 130 <SEP> 200 <SEP> 20 <SEP> 5.7 <SEP> 2 <tb> R <SEP> - <SEP> 1 <SEP> 0.5 <SEP> 0.75 <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> 30 <SEP> 15 <SEP> 0.02 <SEP> 0.1 <SEP> 120 <SEP> 190 <SEP> 30 <SEP> 4.8 <SEP> 3 <tb> S <SEP> - <SEP> 1 <SEP> 0.5 <SEP> 0.75 <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> - <SEP> 30 <SEP> 16 <SEP> 0.02 <SEP> 0.1 <SEP> 120 <SEP> 190 <SEP> 30 <SEP> 3.6 <SEP> 2 <tb> T <SEP> - <SEP> 1 <SEP> - <SEP> - <SEP> 1.25 <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> 40 <SEP> 12 <SEP> 0.03 <SEP> 0.12 <SEP> 120 <SEP> 170 <SEP> 5 <SEP> 6.5 <SEP> 1 <tb> U <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> - <SEP> 1.25 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 13 <SEP> 0.03 <SEP> 0.12 <SEP> 110 <SEP> 190 <SEP> 5 <SEP> 5.2 <SEP> 2 <tb> W <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> - <SEP> 1.25 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 13 <SEP> 0.03 <SEP> 0.03 <SEP> 110 <SEP> 230 <SEP> 5 <SEP> 6.4 <SEP> 3 <tb> Z <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> - <SEP> 1.25 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 11 <SEP> 0.02 <SEP> 0.12 <SEP> 110 <SEP> 250 <SEP> 5 <SEP> 3.7 <SEP> 2 <tb> X <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 1.05 <SEP> - <SEP> - <SEP> 0.1 <SEP> - <SEP> - <SEP> 30 <SEP> 15 <SEP> 0.01 <SEP> 0.1 <SEP> 120 <SEP> 150 <SEP> 15 <SEP> 7.1 <SEP> 2 <tb> Y <SEP> 0.5 <SEP> 0.5 <SEP> - <SEP> 01.05 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0.1 <SEP> 30 <SEP> 12 <SEP> 0.01 <SEP> 0.1 <SEP> 120 <SEP> 170 <SEP> 15 <SEP> 6.8 <SEP> 2 <tb>

Claims (10)

1. A continuous method for the preparation of polyester resin by the reaction of an anhydride of a dicarboxylic acid and with a compound containing active hydrogen atoms and with a monoepoxide compound in the presence of a catalyst, wherein the reaction is carried out in 2-1 0 stages, the catalyst being introduced in the individual stages in such amounts that its concentration in the first stage is 0.0010.2% by weight and in the last stage 0.0051.0% by weight in relation to the weight of the whole reaction mixture, wherein in all the stages a temperature in the range of 70-2700C is maintained, and wherein the reaction is carried out in the liquid phase under a pressure of 4-100 atm.
g.p.
2. A method as claimed in claim 1, wherein the catalyst is introduced in the form of a solution in one of the reactants or in their mixture.
3. A method as claimed in claim 1, wherein the catalyst is introduced in the form of a suspension in one of the reactants or in their mixture.
4. A method as claimed in any of claims 1 to 3, wherein an anhydride of a dicarboxylic acid is introduced together with a compound containing active hydrogen atoms, the said compound containing active hydrogen being already reacted with the anhydride in an amount of 5100%.
5. A method according to claim 1 for the preparation of polyester resin, substantially as herein described with reference to the accompanying drawing.
6. A method according to claim 1 for the preparation of polyester resin, substantially as herein described in any of the experiments of the foregoing Example.
7. Apparatus for preparing polyester resin, comprising a multi-sectional tubular reactor for the synthesis of polyester resin, wherein before the inlet to each reactor section there is located a tube with inlets and with an outlet connected with the inlet to the reactor section, static elements being distributed in the tubes.
8. Apparatus as claimed in claim 7, wherein in the first reactor section at a distance from the inlet thereof corresponding to a ratio of L1/D of from 0 to 20 and along a length corresponding to a ratio of L2/D of from 2 to 40 there are distributed static elements, wherein D is the effective diameter of the reactor, in mm, L1 is the distance of the start point of the mixing elements from the said inlet, in mm, and L2 is the length of the distance of the said section occupied by the said elements, in mm.
9. Apparatus as claimed in claim 7 or 8, wherein the reactor is surrounded by a multi-segmental heating/cooling jacket.
10. Apparatus according to claim 7, substantially as herein described with reference to, and as shown in, the accompanying drawing.
GB8017064A 1979-05-23 1980-05-23 A continuous method for the preparation of polyester resins and apparatus for carrying out the method Withdrawn GB2052535A (en)

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JPS5626930A (en) 1981-03-16 application
DE3019155A1 (en) 1981-05-14 application

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