CA1048691A - Method for preparing aromatic polyesters - Google Patents

Abstract

ABSTRACT

The method for preparing aromatic polyesters consists in the interaction between bis-phenols and dihalogenanhydrides of aromatic dicarboxylic acids taken at a molar ratio from 0.9 to 1.1, at a temperature from -10 to +30°C, in the presence of alkali taken in the quantity of 2 - 2.5 moles per mole of bis--phenols, is a system water-organic liquid, at their volume ratio from 0.2 to 5; said organic liquid is capable of dissolving dihalogenanhydrides of dicarboxylic acids, is chemically inactive towards the starting components, and is miscible with water in the quantity of not less than 25 per cent. The process is carried out in the presence of water-soluble salts of metals standing in the first and the second groups of the Periodic System, taken either separately or in combination, in the quantity from 5 to 45 per cent by weight with respect to the weight of water taken for the reaction. The reaction mixture which is formed, is emulsion containing the end product. The emulsion is ready for direct use.
The end product in the form of solution can also be obtained.
To that end the reaction mixture containing the end product is allowed to stand to separate into two phases, namely into an aqueous and an organic phases. The organic phase is a solution of the end product in a mixture with the organic liquid and water. The settled out phases are separated. The obtained solution is ready for direct use.

The end product can also be prepared in the form of powder, for which purpose the reaction mixture, containing the end product is mixed with water in the quantity from 30 to 200 per cent of the volume of the reaction mixture. The obtained suspension is passed through a filter to isolate the end product.
The proposed method provides for the preparation of high-molecular aromatic polyesters at yields to 99.7 per cent.

Description

)48~91 ~HOI) l~OR P:REPARLNG AROM~TIC POLYE6TERS

` The i~vention relates to methods for prepali~g aromatic : polyesters-S~id polyesters are widely used in electrotech~ical, electronic, radio, aircraft and machi~e-builing industries.
.: Plastics o~ the ba~is of aromatic polyesters have high strength, possess good dielectric properties~ thermal stability, w~ter resi~ta~ce, and are there~ore used in the manufacture oi articles ~or ele¢tro-, a~d radio-engin~ering i~du~try, e~g., ior the manuiacture o~ coil formers, bodies of capacitors, relays, . et¢.
~ ilms made of such polgmers ~re ~ood in~ulating material~
~or olectric motors (i~ter~ rer~ 810t la~ellar ~ulation) acld for trans~ormer~ ~hey ca~ al80 be u~ed~ ~or prepari~g capacitor~
Aromatic polye~ters ca~ be used ~180 as binding naterial for a~tifr~ction sel~-lubricatlng pl~ti~ articlc~ ~orking i~ vacuu~
~A ~ithout lubrica~ts~ for prepar~ng f$bres,~u~*~Uo~ a~d ~oams ~ta~ding temperature~ to 300 &.
,-~ Eno~n i~ the prior art are a fe~ methods for preparing aro-'~ matic polye~ters2 (a) by polycondensation o~ bis-phe~ol~ ~ith ~, diohloroa~hydrides of aromatic dicarbox~li¢ acida in high-boil~ng selvents at elevated temperature~; (b) by polyconden~ation of bi~-phe~ols ~ith dichloroaohydrides o~ aro~atic dicarbo~ylic a¢ids i~ a ~ediula of organic solvents in the presence o~ tertiary ` amine~.

.. ~

.`. ' ~

.: . .
, ... . . . .

. . ~ .
:- - ' . :
'. : : - . ' . ' :
,~ ~ . . . .

1~48691 Diæadva~tage~ i~herent in these method~ are the pre~ence of admixtul~s that are difiicult to reLove from the polymers after their synthesi~, the~e admiYtures may be residual qua~titie~
of the catalyst, or they may appear as a re~ult of ~rolonged heati~g of the reactio~ mixture at high temperatures. These adllLiYtures aIfect ~uc~ adversol~sr the quality of the end product to ~ecrea~e its thermal stability, impair physico-mechanical characteristicE and worki~g behaviour.
~ own 81~0 i8 the i~ter-phaee methcd for prapari~g aromatic polye~ter~ by the i~teractio~ of bis-phenols a~d dihalog~na~-hydrides of aromatic dicarboxylic acids i~ thæ presence o~ alkali.
The ~ynthe6i~ is ~i~rried out i~ the system ~a~er-organic liquid~
which is ¢apable o~ dis~olving dihalo~enanhydrides o~ dic~rboxyli¢
acids~ is chemically i~active ~ith respect to the ~tart~ng reactants o~ tho 8~8tem, and i8 i~miscible with ~ater.
Accordi~g to this method, bis-pho~ol a~d alkali, for eYampie NaO~ or ~0~ taken in the gua~tit~ o~ 2-3 mole per mole o~ b~s-phenol~ ~re di~solved in water. Dihalogenauhydride oi ~romatic dicarboxylic acid is dissolved in an organic liquid, ~or e~mple, in chlorofor~, or yyle~e. Bis-phenol and dihelogena~hyd- -ride are taken i~ equimolar ratio (or clo~e to it)~ ~he obtai~ed ~olution~ are poured together and stirred. ~he proce~ carried out predomi~antly in the presen¢e o~ an emulsifying aBe~t and a ~atalyst, viz., salt~ of guartern~ry ammonium base~.
Thi~ ~etho~l has 80me advanta~;5es. Thus, the reaction casl be carried out at room temperature, the process proceeds at high .

., . . .
, ' , . , - :
.: . . . .
.:~ ' . -':

1~48691 rates. But there are al80 disadv~ntage~ in thi~ method which reside i~ th~t the yield of the e~d product is rather low (80 -90 per ce~t), the molecular weight i~ al80 insufficiently high (the logarithmic viscosity 0.3 - 0.8). P~rthermore, the polyester obtPined i8 contami~ated with a~mixture~, e.g"
remnants of the eatalyst a~d emul~ifying age~t~
This i~volves thorough washi~4 of tho pol~mer which is complicated by th~ ~act that the pol~mer~ after sy~thesi~, is impregnated with th~ orga~i¢ liquid which i8 in~oluble i~ water.
Due to incomplete reaction (ths ~ield of the product i~ 80-90 ~er .
cent) the mother li~uor a~d the offl~o~ts ¢ontain great amounts of u~reacted mo~omers, the ¢atalyst, emulsi~ing agent, which i~volve~ a~;tionAl operations o~ special complicated pla~t~
where the ef~lu~nts are purified and ths mo~omsrs are recovered.
~he object of thi~ in~re~tion is to provide a met~od fo~ :~
prepari~g aromatic polyester~ that would mal~e it possible to prepare high-molecular end product at high yiold.
Another object of the i~vention i8 to 01mpli~y the process for preparing and treating th0 e~d produ~t~
In accordance ~ith thes~ and other object~, tho in~ention consi~ts i~ t~at bi~-phenol~ i~teract with dihalogenanhydrides oi aromatic dicarboxylic acids ta~Qn i~ the ~olar ratio ~rom 0.9 to 1~1, at room temperatur~ from -10 to +30C, in the pre~ence of alk~li takerl in the gua~tity o~ 2 - 2.5 mole p~r mole of bi~-phenol3~ in the 8y8tom water-org~ic liquid at their v~lu-metric ra~io of 0~2 to 5~ said o:rB;anic liquid being capable ~

.
;' - . .
- . . , - .
: ~ - ' ., , '. :
. ~ .
. ,.- ,` - ~ , . .

, - , , .

. .
1~48691 dissolving dihalog0na~h~drides of dicarboxyli¢ acid~, chemically inactive towardg the starting components, ~d miscible ~ith water in the qua~tity ~ot le88 than 25 per cent. The interaction b~tween the startin~ compo~ents i8 realized in the presence oi ~ater-soluble salts of metals, standi~g in ths first and seco~d ~roup~ of the Periodic System~ taken either ~eparately or in combination~ in the quantit~ from 5 to 45 per ¢ent o~ the water wei~ht; a~ a reeult, a rea¢tion mixture containi~g the end .
- product i8 obtained.
:, . .
; ~he introduction o~ said salts under the adopted conditions of re~lizing the propo~ed ~ethod, in particular in the presence of said organic liquid, chaQge~ the ratio o~ the mai~ and side ~, prOCe88e~ 80 that polyesters are produced at high yields, and their molecular ~eight is high, too. The poly~er ca~ be readily ; ~ashed o~t o~ the organic liquid, and it contain~ no admix~ures.
Bis-phe~ols, according to the i~ve~tion, ~ay be of ~arious ~tructure, containi~g both OE groups i~ one be~zene nucleus (for eYample~ resorcinol); bi~uclear~ cont~ g OH groups in :j ~arious ben~ene nuclei (ior examplo, 4,4'- dioxydiphen~lpropane);
bi~uclear~ containing OH groups in various benzene nuclei which are sephrated by a car~on atom ~ith a co~plez lateral substitute /~or eY~mple, phe~olphthale~n 9,9' (4-ox~phenyl)fluore~e/;-: poly~uclear b~s-phenols co~tai~ing, i~ additio~ to the 0~ group~
bo~dèd tQ the benzene ~uclei, also aliphatic OH groups l~or eYam~le~ 2-~ -o~yet~ 3-3~-bis (4-ox~yhe~yl) phthalimidi~e/ and ~180 mix*ures of bis-phenol~ of the above-named classesO

,, .... .

, _ 5 _ ~

-;
; ~he ~tarti~g dihPlo~enanhydride~ of alomatic dicarboyyli¢acids, accordin~ to the i~vention, can be diheloge~anh~dride~
o~ aromatic dicarboxylic acid~ of varioue ~tructures: phthalic (for e~ample iso- and terephthali¢ acid), aromatic dicarbo~ylic acids of the biphenyl series (fo~ example, diphenyloxide o~
4-4'dicarbox~1ic or diphe~ylhe~a$1uoropropa~e-4,4'dicarbox~1ic - acid); aromatic dicerbox~lic acids with condan~ed nuclei (for eYample~ 276-naphthalenedicarboxylic acid), and al80 their ~ixtu-,., res .
~he alkalis that ~re introduced i~to the sy~tem, ~e alkalis that ca~ convert bis-phenol into ionic ~or~ (for eYample~ NaOH, ~ ~0~, LiOH, and other~. The qu&~tit~ o~ the alksli added i~ fro~

2.0 to 2.5 ~oles per mole of bis-phe~ol or a m~xture of bis-phenol~, i.e., with a small excess ~hich i~ nece~ry to neutralize acid ~ormed in the hydroly8i8 0~ dihalo~e~anhydride of aromatic dicarboy~lic ~cids~
~ ~ccording to the invention, the orga~ic liquid~ u~ed in : the pro¢ess are liquids mi~cible with water i~ the qua~tit~ ~ot ,~ less tha~ 25 per cent. Su¢h liquid~ ~re aliphatic ketones (e.g., ~ethyleth~lketone), al~cylcic lower ether~ (~or e~ample, . ...
tetrahydroiura~e, dioYa~e), and al80 their mixtul~s~
~ he ge~eral principle ~ selecting the or~a~ic li~uid dur~g ~ynthesi~ of polymer~ from dih~loge~anh~drides i8 their .bility to di~olve dihalo~enanhydride a~d al~o inertness to~ar~
all starting compo~ents. The qua~tit~ oi the organic l~quid i~ ~ot important. ~he guantity o~ ~ater and oi the organic li~uid i8 take~ at their volume ratio ~rom 0.2 to 5.

, . . . . .
.~. .
, . . . . .
~i . .
~ , . .,. : .

, : :

10486~
In order to prepare high-molecular end product, pre-ference in selecting the organic liquid should be given to such an organic liquid that dissolves the end product or . causes its swelling.
Making use ~`f systems consisting of water and water-, miscible organic liquid for polycondensation of bis-phen~s and dihalogenanhydrides of aromatic dicarboxylic acids is theoretically of low probability due to the high possibil_ .
ity of hydrolysis of dihalogenanhydride. It has been i~ found that the introduction into the system water - water-miscible organicliquid of an additive of water-soluble ; salts of metals of the first and second groups of the ~- Periodic System drastically decreases the hydrolysis of :; ~
dichloroanhydride and results in obtaining a polymer hav-::. . .
~; ing high molecular weight. -~ The introduction into the reaction system of said i~ salts during synthesis of aromatic polyesters with the purpose of preparing high-molecular polyesters has not been practiced before.
. ~ccording to the invention, examples of such salts s ~ are KCl, CH3COONa, NaCl~,; BaC12, and also their mixtures.
The quantity of the additives (salts) is not of principal importance and it may vary within wide limits (over 5 per cent by weight) with respect to the quantity of water.

.
There exists, however, a lower limit (for each salt) of salt content in the system, and if this lower limit is trespassed the molecular weight of the polyester is very ~,~ low. The upper ~imit of the salt quantity is determined ; by its solubility in the system.
. The result of the synthesis carried out under -the . . .
~ thus selected conditions is the reaction ~ixture contain-;-~ ing the end ; . .:
. .
:
~; - 6 -, . . .
~' ,. ..
.~. .
.:.:.
. . ~ . . .
. ., 4869~
product. This reaction mixture iB a~ emulsion which i8 ready for direct u~e. The emulsion ¢on8i8t~ 0~ the orga~ic ~d aqueou~
phases. The organic phase of the emulsion co~si~ts of a mixtures o~ the orga~ic liquid taken ~or the ~thesis, ~ater (5-10 per ce~t by ~oight with respect to the orgaGic p~ase) and the end product dissolved i~ this mixture. The agueous phase is a solution Or ~alt~ in a misture o~ ~ater and the orgaGic liquid.
The end product can also be obtainsd as a solution or powder.
In order to prepare a solutioa o~ ~omatic polyesters it i8 recommendable to ~ettle ~aid reactio~ ~i~ture co~taini~g the ~d product ~o that the aqueous and or~a~ic pha6e~ are $or~ed, the latter being a solution of the e~d product in a mixture o~
water and the orga~ic liquid, as ha~ been stated abovc. ~he phases are then separated. ~aid 801utio~ iS stable in storage ~to 30 day~) and is ready ~or direct use.
Whenever ~ece~sary, aromatic polyester~ ca~ be pr0pared in the $o~m oi powder by precipitating them ~rom emulsions or solution~ In order to prepare po~d~r ~rom emulsion, it i~
recommendabie to add water to tho reaction mi~ture~ co~tainin4 the ~nd product (i.e., emul~ion~ and to separate the end product by pas~in4 the obtained su~pension through a ~ilter. ~The quantit~
of water added i8 from 30 to 200 per cent by ~olume with respect to the reaction mi~ture).
~ he proposed ~ethod for preparing aromatic polyest~rs as compared with the k~o~n methods, doe~ ~ot re~uire cataly~ts or '''",''; ' ;:'' :
:
' .;. . .
.. : . - - . .
~, - ' . . . ' ' .
. - - . .
'~ . ' .. .' ' . . . ::

.,. .' ' - :

" 1048691 , .
emuls~fying agents, and despite this it ensures preparation of the end ~-i product having high molecular weight (logarithmic viscosity to 2.5) at - high yields (to 99.7 per cent). Thus-obtained product has high thermal stability (stands temperatures over 280C.
Table 1 shows some characteristics of the proposed method, as compared to the inter-phase method for preparing aromatic poly-, esters in the system water-organic liquid immiscible with water. The Table is compiled with respect to the data obtained in preparing polyester of 4,4'-dioxydiphenylpropane with a mixture of dichloro-~: anhydrides of iso- and terephthalic acids). Table 1 ~,...................................................................... .

.
Nos Specification Water-organic liquid Water-organic liquid immiscible with wa- miscible with water ; ter system system tNaCl assalt) . .
l Organic liquid xylene tetrahydrofuran s 2 Dresence ofcata-bst in % by wt of water 5-10 none

3 Synthesis time, min. 45 6-10

4 Washing procedures (for powder) 10-15 3 Yield of product, %
~-~ of theory 85-90 98-99 . . , ; ~ 6 Content of bis-phenol in effluents ;~ in % of starting ; quantity ô-12 0.1 - 0.2 ::
,. . . .

, :
. .
,. ,.;.' ,. .
. :~

......
. ~, .
_ 8 -',i ., ...

.''.

1~48691 . . .
As it ha~ already been said, emulsionæ and solution~ of polyester~ prepared b~ the proposed method ~re ready for immediate use. Owi~g to this Iact, such labour-consumi~g opera-tio~s of the i~ter-pha~e method a~ filtration a~d ~shing o~ the polymers awalle~ at0r-immi~cible orga~ic liquid, ~tripping and distillatio~ of organic liquids that destroy the e~d product under the action of the remai~ing quantities o~ alkali a~d eleva-ted temp~ratures, are 01imi~ated. : :~
I~ the end product ia prepared as powder,.th~ operationsof filtration a~d washi~g are less labour-consumi~g~ a~d the time re~uired to proces~ the polymer is cut 3-5 tim0s.
The high depth of completene~s of the mai~ r~action~ the absence of catal~Qts or emulsifying agents, ensure the minimum contamination of the pol~mer ~d the ef~luents, which add~ to the e¢o~om~ o~ the process.
or the purpose o~ compari60n~ Table 2 giv~s charactefi ~tics ;,......... .
.: oi poly0ster powder on-tho basis of 4,4'- dio~ydlphe~ylpropaue : a~d dichloroauhydrid~ of iso-~ and terephthalic acids (50:50) . . .
: pr0pared by the proposed method a~ compared to the product .`. obtai~ed b~ the k~ow~ i~ter-phase method in the ~stem ~lene-~a~er~ :
,"'' -, :
, ;:

. . .

. . .
';.' ' . ', -.. . . . .
. -.. . .
, -: :

~048691 Table 2 - Aromatic polyester prepared in - - Nos Characteristics Xylene-water tetrahydrofura~ system 5ytsteemsslt ~; I Specific vi~scosity of 0.5 Z
S polymer solution in mixture wlth tetrachloroethane-phenol to 0.8 to 1.5 `5 2 X-ray structure slightly amorphous crystaline ; 3 Dispersity (mean particle - size~, mm 0.7 0.2 4 Bulk weight, g/cc 0.17 0.37 ~ 5 Loss in specific viscosity ; after treatment at 280C~ %
of initial 60 25 _ . .
The hi8h dispersity of the obtained aromatic polyesters offers good prospects for their use in the manufacture of antifriction -- f self-lubricating plastics, for which the high degree of miscibility of the polymeric binder (ln this case aromatic polyester) with the other components is guaran.eed by high dispersity. Cwing to high dispersity and increased thermal stability~ powdered polyesters accor-ding to the invention are readily pelletized and granulated and can successfully be used for the msnufacture of plastics by pressing~

moulding~ extrusion. Below given are mechanical characteristics of a plastic material prepared by moulding polyester on the basis of 4,4~-dioxydiphenylpropane and a mixture of dichloroanhydrides of iso-, and terephthalic acids;~

.,~ ~.

:;i ;'"~ - 10 . .

'`"
,' . :
: ,;

.

l. Ultimate compression strength, kg/sq.cm 900 2. Ultimate tensile strength~ kg/aq.cm 700 . , 3. Ultimate flexural strength, kg/sq.cm llO0 - 1200 4. Impact strength, kg-cm/sqcm:
; for a notched specimen 15 -~- for a solid specimen~ specimen re~ ;
mains intact

5. Vicat softening temperature, C 200 - 210 The abovel~ateindicate that the mechanical properties of the plastic on ehe basis of said aromatic polyester are not infer-ior to those in the widely known high-strength plastics, *~z., polycarbonates whole its, thermal stability is significantly higher.
(Gn the basis of the other bis-phenols, for example, phenolphtha-lein 9~9l-(4-oxyphenyl)fluorene~ plastics and other articles can be -~`! ' prepared, in which the Vicat softening temperature (is as high as 00 - 350C).
Aromatic polyesters prepared by the proposed method can be worked into films both by the pouring and by the extrusion method.

:~.
~ The specifications of such films made from aromatic polyesters on .: .
the basis of 4,4'-dioxydiphenylpropane and a mixture of dichloroanhy-drides of iso-, and terephthalic acids (obtained by ehe casting method) are as ~ollows:
' ~ 1. Ultimate tensile strength~ kg/sq.cm 700 2. Percentage elongation 10-20 3. Volume resistivity Ohm.cm 1ol6 .
4. Dielectric constant 3 5. Dielectric strength for a 30-micron thick specimen , kV/mm lO0 ~., : . ;
' - 11 -: .
,,',;'~' . .

:

t^: . 1048691 `. `
- The proposed method can be realized as this.
Bis-phenol, a water soluble salt and alkali are dissolved, `~ either in succession or simultaneously, in water or in a mixt~re of water and an organic liquid. Dihalogenanhydride of aromatic dicarbox~
lic acid is also dissolved in the organic liquid. The obtained sol-utions are poured together with stirring. Stirring is continued for 2 - 60 minutes~ with the result that an emulsion is formed which con-tains high-molecular end product. The process is carried out at a temperature of -10 to + ~0 C. All the named components can be taken `~ separately or as mixtures with compounds of the same class.
The order in which the components are loaded does not ; matter. It may be as follo~s:
1. Dissolution of bis-phenol in an organic liquid (solu-., .
tion A); dissolutlon of alkali and salt in water (solution B);

mixing together solutions A and B; dissolution of dihalogenanhydride .: -in an organic liquid (solution C); adding solution C to a solution (A+B).
:
,;'~ 2. Adding solution (A+B) to solution C.
~A~ 3. Dissolution of bis-phenol in an aqueous solution of alkali and salt and its mixing with solution of dihalogenanhy-.~...~
`; dride in an organic liquid.

~' The preferably order of operations is that described in , ., Item 1.
The obtained reaction mixture contains the end product and is actually an emulsion ready for direct use.

:'~' , _ 12 -. . .
,'' :

:
.

~ 104869~
In order to prepare a solution, the emulsion is separated (by settling) into an organic and an aqueous phases. Said phases ; are separated from each other. The organic phase~ which is a solu-tion of polymer in an organic liquid and water, can also be used as such.
Whenever necessary, the polymer can be prepared as a pow-` der.;~To that end~ to the obtained reaction mixture added is water - in the quantity from 30 to 200 per cent of the reaction mixt~re volume. The result is a suspension which is then filtered to iso-late the end product. The polymer is washed~ for example, with .~ .
water~ and dried.
-~ For a better understanding of the invention~ the following examples of its practical embodiment are given by way of illustra-` tion.
The values of logarithmic viscosity ¦ ~l i h are obtained ~ from the values of specific viscosities of the polymer solution ;~ (0.5~g/100 cc of solvent) at 250 C. The solvent is a mixture of tetrachloroethane and phenol (2:3).
,:
~ The yields of the polymer in per cent are given with ; respect to theory.
.,, Example 1 17.1 g of 4,4'-dioxydiphenylpropane are dissolved in 50 cc of tetrahydrofuran ~ To the obtained solution of bis-phenol added are 150 cc of an aqueous solution containing 6.6 g of NaOH
and 18 g of KCl. 7.67 g of dichloroanhydride of isoph thalic acid . . .

, ' ,; : ' ~ ', .
..:
.":
. ~:
. . . ..
.

; and 7.67 g of dichloroanhydride of terephthalic acid are dissolved in lOO cc of tetrahydrofuran at a temperature of -10 C.
The obtained solution of dichloroanhydride is added with : stirring to the solution of bis-phenol, salt and alkali, cooled to +S-C. After pouring together the solutions, stirring is continued ;~ for another 2-3 minutes. The result of this process is an emulsion r, . .
ready for use.

To this emulsion added with stirring are 150 cc of water to ` prepare a suspension of the polymer which is separated by filtration.

i~; The polymer is washed with water and dried.

~] inhof the polymer is 1.20. The yield of the polymer is 99.4 ~; per cent.

Example 2 3.98 of phenolphthalein are dissolved in 20 cc of tetrahydro-,.. .
~- furan and to the obtained solution added are 30 cc of an aqueous sol-ution containing l.l g of NaOH and 6.7 g of NaCl.
; 2.3 g of dichloroanhydride of terephthalic acid are dissolved in 30 cc of tetrahydrofuran at a temperature of -10C.
~ The obtained solution of dichloroanhydride is added with ; stirring to the solution of bis-phenol~ salt~ and alkali~ at a temp-erature of 20C. After pouring together the solutions~ stirring is continued for another 2-3 minutes to prepare~ emulsion which is an organic phase containing the polymer (8 per cent), tetrahydrofuran ~.:
s ~ (87 per cent), water (5 per cent) and an aqueous . . .
.
.~,, .
,;:
, . .
; - 14 -;:;
~ ::""
:
. ;"
:: .
;:-; ~:
,~

."' :

: .
;`
~,:

``;

~04869 phase which is an aqueous solution containing salts (22 per cent), tetrahydrofuran (8 per cent) and an insignificant amount of alkali which is neutralized with acetic acid. After settling and decant-` ing the aqueous phase, an organic phase y~ich is a solution of the polymer in tetrahydrofuran and water is isolated. The solution is ` ready for use. It can be used to manufacture articles of various : : :
`~ configurations.
of the polymer is 1.17.
Example 3 3.8 g of 4,4'-dioxydiphenylpropane and 2.06 g of KOH are --dissolved in 25 cc of water and to the obtained solution added are 25; cc of an aqueous solution containing 7 g of NaCl. 2.92 g of ~ d$fluoroanhydride of isophthalic acid are dissolved in 50 cc of `- tetrahydrofuran at a temperature of 10 C. The obtained solution of dif/luoranhydride is added with stirring to the solutinn of bis-phenol~ alkali and salt cooled to +5 C. After pouring to-, gether the solutions, stirring is continued for another 2-5 min-.: . .
utes, to prepare emulsion which is ready for use.
100 cc of water are added with stirring to the emul-sion to prepare a suspension of the polymer from which it is sep-arated by filtration. The polymer is washed with water and dried.
inh of the polymer is 0.67. The yield is 98.5 per cent.
Exa~ple 4 ',''' 5.7 g of 4~41-dioxydiphenylpropane are dissolved in 50 ml of cc of tetrahydrofuran. To the obtained solution of bis-' ; phenol added are 45 cc of an aqueous solution containing 2.25 g of ~ NaOH and 9 g of NaCl.

:~, - ~ - 15 -....

:
, .:

.
'''.' , ,.: .
... .

` ` 1048691 ,.
` 2.58 g of dichloroanhydride of isophthalic acid and 2.58 ` g of dichloroanhydride of terephthalic acid are dissolved in 55 cc of tetrahydrofuran at a temperature of -10C. The obtained solu-.
tion of dichloroanhydride is added with stirring to the solution o of bis-phenol~ salt and alkali at a temperature of ~20 C. After ` pouring together the solutions~ stirring is continued for another 2-5 minutes. The result of the process is emulsion which is an ' organic phase containing the polymer (12 per cent)~ tetrahydro-.
furan (83 per cent), water (5 per cent)~ and an aqueous phase -;.h . ~
which is an aqueous solution containing salt (22 per cent), tetrahydrofuran (10 per cent)~ and insignificant quantity of alkali which is neutralized with acid acetic acid. After settl-~..

ing and decanting the aqueous phase~ an organic phase, i.e.~ solu-,. ~
tion of polymer in tetrahydrofuran and water is obtained. The solution is ready for use. Articles of various configurations are ..~,.
~ manufactured therefrom.
:
inh of the Polymer is 1.89.
Example 5 1.51 g of 2-~ -oxyethyl-31-bis(4-oxyphenyl)phthalimidine and 0.95 g of 4,4'-dioxydiphenylpropane are dissolved in 30 cc :. ~
of tetrahydrofuran. To the obtained solution of bis-phenol added are 30 cc of aqueous solution containing 0.72 g of NaOH and 5.5 g of NaCl.

1.72 gfofidichloroanhydride of terephthalic acid are dissolved in 40 cc of tetrahydrofuran at a temperature of 10C~
the obtained solution of dichloroanhydride is added with stirring '.,; .
i;', : "~
~ - 16 -.. ~
:

. -,:;
. ..
:'.

.
:`
, -.

` 10~8691 to the solution of bis-phenol~ salt and alkali, at a temperature of 30 . After pouring together~ stirring is continued for another 2-3 minutes. The result is suspension of the polymer which is separated by filtration. The polymer is washed with water and dried. L ~1 inh :; :.,. . : . .
of the polymer is 1.15. The yield of the poly~er is 97 per cent.
Example 6 3.8 g of 4,4~-dioxydiphenylpropane, 9 g of NaCl and 1.5 g of NaOH are dissolved in a mixture consisting of 30 cc of methyl-ethylketone and 50 cc of water. 1.72 g of dichloroanhydride ofisophthalic acid and 1.72 g of dichloroanhydride of terephthalic acid are dissolved in 20 cc of tetrahydrofuran at a temperature of -10C. The obtained solution of dichloroanhydride is added with stirring to the solution of bis-phenol~ salt~ and -alkali, at a temperature of +20C. After pourhng together, the solution is stirred for another 3-5 minutes. The result is emul-sion which is ready for use. To the emulsion added with stirring are 200 cc of water. The result is suspension of the polymer which is separated by filtering. The polymer is washed with water and ~ inh of the polymer is 0.64.
, Example 7 ` ~ 3.38 g of dichloroanhydride of terephthalic acid are dissolved in 50 cc of tetrahydrofuran at a temperature of -10C.
Then 5.9 g of 9,9'-bis(4-oxyphenyl)fluorene, 1.5~g of NaOH and 7 g of ~Cl are dissolved in 50 cc of water at a tempera- -ture of +20C. The obtained solution of bis-phenol, alkali and , " ~
,,,, ~
. ,, , ...................................................................... ..
~-~ - 17 -~:, , .. .
f,~ ~
; `"

r r.

~ ' j ~ ' ' : 1048691 salt is added with stirring to the solution of dichloroanhydride.
., After pouring together the solutions, stirring is continued for another 3-5 minutes. The resultant emulsion is ready for use.
To the e~ulsion added with stirring are 50 cc of water. As a result~ a suspension of the polymer is prepared, which is then separated by filtering. The polymer is washed with water and dried.

inh f the Polymer is 0.60 Example 8 3.8 g of 4,4'-dioxydiphenylpropane are dissolved in 25 cc of water containing 0.92 g of LiOH. To the obtained solution of bis-phenol added are 25 cc of an aqueous solution containing

6 g of LiCl. Then~ 1.72 g of dichloroanhydride of isophthalic acid and 3.64 g of dichloroanhydride of diphenylhexafluoropropan-edicarboxylic acid are dissolved in 60 cc of tetrahydrofuran at a temperature of -10 C. The obtain solution of dichloroanhydride is added with stirring to the solution of bis-phenol~ salt~ and alkali~ at a temperature of 10C. After pouring the solutions together~ the mixture is stirred for ano~hèr 3-5 minutes. The resultant emulsion is ready for use. To the emulsion added with stir~ing are 220 cc of water to prepare a suspension of the polymer which is separated by filtration. The polymer is washed with water and dried. L ~ i h of the polymer is 0.73.
Examples 9 through 19 were carried out under the same conditions as in Example 1. The results of the experiments are summari~ed in Table 3.

~, .~:
....
.,; ~

- 18 _ :
: .
:., :;-'"'''"~,;
. .~
..:

J-;'' - ~ - . , ' ' ' '` -~48~91 ~ , ~ Nos, Bls-phenol, ln g A~ i, in g Salt, in g . .
1 2 _ _ 3 4 .~ 9 11.41 of dioxydiphe- 4.4 of NaOH 10 of KCl nylpropane - 15 of NaCl ditto 6.18 of KOH 10 of NaCl ~ 10 of BaCl : 11 ditto 4.4 of NaOH 18 of LiCl `

:i :
12 ditto 4.4 of NaOH 25 of KBr 13 ditto 4.4 of NaOH 20 of NaCl . .
,, .
; :
;: 14 3.8 of ditto 1.1 NaOH 6.6 of NaCl ~:' 15 ditto 0.92 of LiOH 6 of LiCl ,.,:;. :' , 0 16 5.42 of resorcinol 4.4 of NaOH 30 of BaCl ~:
~.,~ . .
-;: 17 11.41 of dioxydiphe- 4.5 of NaOH 20 of K CO
,.jj nylpropane 2 3 I'i.1~'; ' .. 18 ditto ditto 50 of NaNO3 ~:~ 19 ditto 4.7 of NaOH 20 of Ca(CH3COO)2 -.

., ' ~li'' t,:.' .
,.~

, ~i, . . .

~'' , ~' ~, ' ~ri' ~ ~ ~048691 ~ I ~
.. o ~
. ~. ~ U~
~ o c~ ~ 0 0 t~
o~
: ,. ~
'~ ~

~ ..
.. ,. ~
~' .,1 0 ~ t` I~ o ,.. - ~ ~ o o o o ,., .. .
`~1''' ~
.~ .~ U 1~ ~ ~ o ~
,,.~,, ,~ ~
,`........... .
~,,. .., ~U ~ o O O "~ ' ~ ~ o ,,.',~,", ~ a~
"",, .

I L I I ~ ~ '1 ~ 'I ~ ~ U nl ~
r a) U ~ I ~ ~ ~ U ~ tU
U ~ ~ 1 U ~ ~ ~
r~ O ~ 1 Vrl ~ 1 rl U 1~ 0 U ~ 0 ~. ~ In a ~ O ~
~, ~:: ~ ~ ~ h ~ 5 N~
,............ ~ u"~ u U~ ~ ~u i~ ~1 O ~ ,S ~1 ~ o R rl ~ R
." ~ ~-~ O ~-~ O O O ~1~ 0 0 ~0 ~0 ~ ~/ ~0 ~ O ~1 ~ q'~ o ~
Q oo~O O ~ 0 `1 o .~, ~ ~ ~ O ' ~ 1 0 u~
.
. al~ -~ -19a-.

:

4 ~ ~9 1 1~
. ~ o~ ~ ~0 ~0 ~ " ' , . '~ ~ ~ ,~
..:..':
'.~ ~
,.,. . 0 ~ ~D o 0 ' ~ j ~ o ~
~. ~ 3 3 .. ~.

~. . .
1 9b-~,

Claims (3)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A method for preparing aromatic polyesters consisting in the interaction between bis-phenols and dihalogenanhydrides of aromatic dicarboxylic acids taken at the molar ratio from 0.9 to 1.1, at a temperature from -10 to +30°C, in the presence of alkali taken in the quantity of 2 - 2.5 mole per mole of bis-phenols, in the system water-organic liquid at their molar ratio from 0.2 to 5; said organic liquid is capable of dissolving dihalogenanhydrides of dicarboxylic acids, is chemically inactive towards the starting components, and is miscible with water in the quantity not less than 25 percent, the said starting compo-nents are reacted in the presence of water-soluble salts of metals selected from the first and second groups of the Periodic System and taken in the quantity from 5 to 45 per cent by weight with respect to the quantity of water: as a result a reaction mixture containing the end product is obtained.

2. A method according to Claim 1, wherein the reaction mixture containing the end product is settled to separate into an aqueous and organic phases, the latter containing organic liquid, water, and the end product, said phases are separated from each other.

3. A method according to Claim 1, wherein the reaction mixture containing the end product is mixed with water in the quantity from 30 to 200 per cent by volume with respect to said reaction mixture, the resulting suspension is filtered, to separate the end product in the form of powder.