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Патент USA US3028374

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United States Patent 0 "ice
3,028,364
Patented Apr. 3, 1962
2
1
of the present invention will appear from the following
description and claims.
It has now been found that if diphenols and dicar
boxylic acids are condensed in a two-phase mixture of
liquids, the acid chloride of the dicarboxylic acid being
dissolved in organic liquid which is a solvent for the
reaction product formed, and the bis-phenol being dis
solved in another liquid which is immiscible with the
former, it is possible to carry out the condensation reac
3,028,364
PRODUCTION OF LINEAR AROMATIC
POLYESTERS
André Jan Conix, Hove-Antwerp, and Urbain Leopold
Laridon, Mortsel-Antwerp, Belgium, assignors to
Gevaert Photo-Producten N.V., Mortsel, Belgium, 2!
company of Belgium
No Drawing. Filed Apr. 1, 1958, Ser. No. 725,498
Claims priority, application Great Britain Apr. 2, 1957
3 Claims. (Cl. 260-47)
10 tion at room temperature and to obtain high molecular
weight products which dissolve in low-boiling solvents.
This invention relates to the production of polymeric
It has further been found that this condensation method
materials and particularly of linear aromatic polyesters.
can be applied for obtained polyesters of high molecular
It is known to prepare aromatic polyesters by causing
Weight, starting from a wide variety of bis-phenols and
terephthalic acid and derivatives to react with glycols
having 2 to 12 carbon atoms. The most valuable rep 15 dicarboxylic acids.
According to the present invention, a process for the
resentative of the series of polyesters thus obtained is
polyethylene terephthalate.
production of linear aromatic polyesters comprises react
ing phenolate of a diphenol of the general formula
It has also been proposed to produce aromatic poly
esters by substituting diphenols for glycols in reactions
with dicarboxylic acids but it Was found di?icult or im 20
possible to obtain polyesters having su?iciently high mo
lecular weights. Accordingly for the production of poly
with a diacid chloride of an aromatic dicarboxylic acid
_ esters of this type recourse has been had to the reaction
between the free diphenol and the dihalide, usually the
dichloride of the dicarboxyl acid, the reaction being car 25
of the general formula
'
1100c
00011
ried out in the presence of a base for instance sodium
j hydroxide. It is very di?icult, however, to obtain ac—
in which formulae the hydroxyl groups and the carboxyl
cording to this method really high-molecular polyesters
groups may be in the para- or meta-position and wherein
which can be formed in ?laments and ?lms; moreover
the reaction is not smooth and the reaction mass tends 30 each of the R and R’ represents a single bond or an alkyl-,
aryl- or halogen substituted methylene group or a carbon
to become pasty, the end product frequently being yellow
atom which forms part of the cycloaliphatic ring, or
to brown.
one represents such a group or form parts of such a ring
Products of high-molecular weight can be obtained,
or such a carbon atom, and the other represents an oxy
however, according to British patent speci?cation No.
621,102, by condensing the dicarboxylic acid with the
35 gen atom or a carbonyl- or sulphonyl group, or a satu
rated hydrocarbon radical such as a methylene- or ethyl
diacetate of the diphenol or by reacting the dicarboxylic
ene group, the said reaction being carried out by dissolv
acid with the diphenol in the presence of acetic anhydride.
ing the aromatic dicarboxylic acid chloride in a solvent
In the copending US. patent application Serial No.
702,252, a process is described for the production of 40 for the reaction product and adding thereto the diphe
nolate dissolved in a solvent which is immiscible with
linear ‘aromatic polyesters by polycondensation of diphe
the solvent in which the acid chloride is dissolved while
nols with aromatic dicarboxylic acids accordingv to which
maintaining the temperature at substantially room tem
high molecular linear aromatic polyesters are obtained
perature and precipitating the reaction product, e.g. by
which dissolve in low boiling solvents by selecting as the
diphenols those of the general ‘formula
45 pouring the reaction mixture into boiling water. ‘The
following are examples of such radicals:
or chemically equivalent derivatives thereof, such as di
acetates and other diesters, and as dicarboxylic acids those 50
of the ‘general formula
HO O C
C OOH
@WQ
55
or chemically equivalent derivatives thereof, such as
and
esters or anhydrides, wherein each of the R and R’ rep
resents an alkyl- or aryl-substituted methylene group or
forms part of a cycloaliphatic ring, or one represents
such a group or forms part of such a ring, and the other 60
represents an oxygen atom or a methylene- or carbonyl
group.
The polycondensation is carried out according to the
above-mentioned copending application by heating the
a.
on3
l
(0112)::
(($111) n1
Ha
wherein n and n’ each represents a positive number from
dicarboxylic acid and the diphenol, preferably in the form 65 1 to 7,
of the diacetate e.g. to a temperature of 305° C.
It is therefore an object of the present invention to
provide new linear aromatic polyesters which dissolve
quite well in low-boiling solvents and show high soften
ing temperature. A further object of the present inven 70
tion is to provide a suitable method for the production
of such linear aromatic polyesters. Still further objects
3,028,364
wherein R and R’ represent radicals as de?ned above.
The following examples illustrate the invention with
out limiting, however, the scope thereof. The softening
points are obtained on ?lms prepared from the polyesters.
Especially high-molecular weights are obtained if the
reaction is carried out in the presence of a suitable cat
alyst, such as a quaternary ammonium compound. Ex
10 The elongation of strips of ?lms subjected to a load of
0.17 kg/mm.2 is measured in function of the tempera
ture. The temperature where a large rise in elongation
is observed is taken as the softening temperature. It is
to be emphasized that these temperatures have only a
amples of- such catalysts are trimethylbenzyl ammonium
chloride, triethyl benzyl ammonium hydroxide, and tri
ethyl benzyl ammonium chloride.
It is an important advantage of the present invention
that the reaction may be carried out at room temperature 15 comparative value and are not to be confounded with
consisting of non-miscible solvents which separately keep
melting temperatures. In fact they correspond more or
less with glass transition temperature.
in dissolution the sodium diphenolate and the acid chlo
Example 1
and at atmospheric pressure in a liquid reaction medium
ride together with the polyester formed.
' We use Water as the solvent for the diphenolates and 20
methylene chloride as common solvent for the acid chlo
A ?ltered solution of 3.15 g. of di-p-carboxy-phenyl
2,2-propane di-acid chloride in 20 cm.3 of methylene chlo
ride is brought into a vessel, ?tted with a stirrer and a
dropping funnel. To this solution is added 0.05 g. of
rides and the polyester formed during the reaction. Other
water immiscible organic solvents can be used in associ
triethylbenzyl ammonium chloride. Under stirring and
ation with water, such as dichloroethane, tetrachloro
25 during 30 minutes, a solution of 2.3 g. of di-p-‘iydroxy
ethane, benzene and toluene.
phenyl-2,2-propane and 0.8 g. of sodium hydroxide in 20
The diphenolates can be formed by dissolving the di
cm.3 of water is dropwise added. The reaction tempera—
phenols in water in the presence of equivalent quantities
ture is held by cooling to approximately 25° C. The
of metal hydroxides such as sodium- or potassium hy
solution is subsequently stirred for 75 minutes. After
droxides. The dichlorides can be obtained a.o. by re—
this
period, the reaction mixture became extremely vis
30
action of the respective dicarboxylic acids with thionyl
cous. The viscous mixture is brought into boiling water
chloride.
whereupon the polymer precipitates. The polymer is
The following are examples of aromatic dicarboxylic
isolated
by ?ltration and dried. The intrinsic viscosity
acids the dihalide of which can be used for preparing the
of the polymer determined in dichloroethane solution at
polyesters according to the present invention:
35 25° C. is 1.9. The polymer dissolved in methylene chlo
4,4’-dicarboxy-diphenyl,
4,4'-dicarboxy-diphenyl ether,
4,4’-dicarboxy-diphenyl sulphone,
4,4’-dicarhoxy-diphenyl methane,
1,2- and 1,1-(4,4'-dicarboxy-diphenyl)ethane,
4,4'-dicarboxy-benzophenone,
4,4’~dicarboxy-diphenyl dichloromethane,
2,2-(4,4'-dicarboxy-diphenyl)propane,
2,2-(3,3'-dicarboxy-diphenyl)propane,
2,2-(4,4'-dicarboxy-diphenyl) 1,1-dimethylpropane,
3,3-(4,4'-dicarboxy-diphenyl)heptane,
3,3-(3,3'-dicarboxy-diphenyl)heptane,
1,1-(4,4’-dicarboxy-diphenyl)propane,
1,1-(3,3'-dicarboxyediphenyl)propane,
ride can be cast to tough, transparent, colorless ?lms
which are characterized by a low water-absorption and
a high softening point (225° C.). This ?lm material is
particularly useful as base for photographic materials.
40
29.5 g. of the di-acid chloride of di-(p-carboxy-phenyl)
ether and 0.5 g. of triethylbenzyl ammonium chloride is
brought into a vessel, ?tted with a stirrer and a dropping
funnel. To this solution is dropwise added under vigor
ous stirring and during 35 minutes a solution of 22.8 g.
di-(p-hydroxy—phenyl)-2,2’-propane and 8 g. of sodium
hydroxide in 200 cm.3 of Water. The reaction mixture
50 is subseduently stirred for 3 hours at a temperature of
approximately 25° C. The viscous solution is brought
1,1 or 2,2-(4,4'-dicarboxy-diphenyl)butane,
1,1 or 2,2-(4,4'-dicarboxy-diphenyl)pentane.
into boiling water, whereupon the polymer precipitates,
The following are bis-phenols the metal phenolates of
which can be used for preparing the polyesters according
to the present invention:
and can be isolated by ?ltration. The polymer has an
intrinsic viscosity of 0.76 measured in a dichloroethane
55 solution at 25° C.
which are characterized by a low water-absorption and a
l-phenyl- 1 , 1- (4,4’-dihydroxy-diphenyl) methane,
high softening point (200° (1.). Similarly, the polymer
l-phenyl- 1 , 1- ( 4,4’-dihydroxy-diphenyl) ethane,
2,2- (4,4’-dihydroxy-3 ,3 '-dimethyl-diphenyl ) propane,
can be moulded into transparent objects showing a high
'60 impact
1,1,1-trichloro-2,2-(4,4'-dihdroxy-diphenyl) ethane,
a particularly high-distortion
'
Example 3
2,2-(4,4'-dihydroxy-diphenyl) 1,1-vdimethylpropane,
1, 1-(4,4'-dihydroxy-diphenyl) propane,
1,1 or 2,2-(4,4'-dihydroxy-diphenyl) butane,
1,1-, 2,2- or 3,3- ( 4,4'-dihydroxy-diphenyl ) pentane.
strength and
temperature.
2,2- ( 4,4'-dihydroxy-diphenyl ) propane,
3 ,3- (4,4'-dihydroxy-diphenyl ) heptane,
The polymer can be cast from a
solution in methylene chloride to tough, transparent ?lms
1,1-(4,4'-dihydroxy-diphenyl)-cyclohexane, >
4,4'-dihydroxy-diphenyl-sulphone,
Example 2
A solution consisting of 100 cm.3 of methylene chloride,
A polyester is prepared by proceeding as in Example 2
65 but using 1 mol of the di-acid chloride of 2,2-(4,4'-di
carboxy-diphenyl)propane and -1 mol of the di~sodium
salt of 4,4'-dioxy-diphenyl~phenyl methane of the formula
The invention includes polyesters obtained by reacting
a mixture of two or more of the speci?ed diphenolates 70
With one or more of the speci?ed aromatic dicarboxylic
acid chlorides or mixtures of two or more of these acid
chlorides with one or more of the said diphenolates.
In this way, polyesters are obtained containirsY the re
curring structural units according to the general formula: 75
A'polyester, soluble in low-boiling chlorinated hydro
8,028,364
6
carbons such as methylene chloride, is obtained. The
softening point of the ?lms cast from solution, is 218° C.
rated by ?ltration. The polymer is soluble in tetrachloro
ethane. From this solvent the polymer can be cast into
but using as starting materials the di-acid chloride of
solution amounts to 0.95.
colorless, transparent ?lms showing good ?exibility and
Example 4
a high softening point (220-250° C.). The intrinsic
A polymer is prepared by proceeding as in Example 3 5 viscosity of the polymer, determined in tetrachloroethane
2,2-(4,4’-dicarboxy-diphenyl)propane and 4,4'-dioxy-di~
phenyl-l,l-cyclohexane of the formula
Example 7
CH3
[
OYHIB
|
_l
~000Q000C>OC0~
l- .
([1113
Y_
J
15
H2O
CH2
solution was added over a period of 20 minutes to a
A polyester soluble in methylene chloride and showing
l.
CH3
1 3
(I:
000
4,4'_dicarbony1_ch10ride in 50 cm’s of 1,1,Ltrich1oro
ethane.
Example 5
OH
5.127 g. (0.02 mol) of 2,2-(4,4'-dihydroxy-3,3'-di~
methyl-diphenyl)propane and 150 mg. of triethylbenzyl
20 vigorously stirred suspension of 5.583 g. of diphenyl
a softening Point of about 170° C’ is obtamai
l
, I
ammonium chloride were dissolved in 40.4 cm.3 of
NaOH N. At a temperature not exceeding 23° C. this
CH’
—o
(‘1113
Stirring was continued for an additional 4 hours,
subsequently the upper layer was decanted and replaced
s02
l
oo—
v ..l
4.566 g. (0.02 mol) of 2,2-(4,4'-dihydroxydiphenyl)pro- 30 by 100 cm.3 of distilled Water. The mixture was again
pane and 150 mg. of triethylbenzylammonium chloride
stirred for 30 minutes. Subsequently the aqueous layer
were dissolved in 40.4 cm.3 of NaOH N and 20 cm..3
was decanted and removed. Upon pouring the organic
of 1,1,2-trichloroethane were added. At a temperature
layer into an excess of ethanol, a ?brous white polymer
not exceeding 19° C., a solution of 6.864 g. of sulphone
precipitated which could be isolated by ?ltration. The
4,4'-dibenzoylchloride in 60 cm.3 of 1,1,2-trichloroethane 35 polymer is soluble in methylene Chloride, 1,2-dich10r0
was added over a period of 15 minutes to the vigorously
ethane, 1,1,2-trichloroethane, tetrachloroethane and di
stirred mixture. Stirring was continued for an additional
oxane; from these Solvents the Polymer can be cast into
150 minutes. Subsequently the upper aqueous layer was
colorless, transparent ?lms Showing good ?exibility and
decanted and replaced by 50 cm.3 of distilled water;
a_ high Softenlhg P0111t (230—2_50°
the mixture was again Stirred for 30 minutes_
The intrinsic
This pl.o_ 40 vlscosity of the polymer, determined in tetrachloroethane
cedure was repeated once more. The polymer was precipitated into an excess of ethanol and is found to ‘be
solut1on amounts to 1'45‘
Example 8
2111:
5.128 g. (0.02 mol) of 3,3-(4,4'-dihydroxy-diphen
soluble in methylene chloride, 1.,2-dichloroethane, 50
yl)pentane and 100 mg. of triethylbenzylammonium
1,1,2-trichloroethane and tetrachloroethane. From these
solvents the polymer can be cast into colorless, trans
chloride Were dissolved in 40.4 cm.3 of NaOH N.
pafeht ?h'hs Showing gohd heX'ibili'ty ?hd a high Softening
temperature not exceeding 20° C., this solution was
At a
Polht (200° C)’ The mtrlnslc VISCQSIW of the Polymer’
added over a period of 15 minutes to a vigorously stirred
determined in tetrachloroethane solut1on amounts to 0.64. 55 mixture of 5583 g‘ of diphenyl_4,4I_dicmbonyl chloride
Example 6
in 60 cm.3 of 1,1,2-trichloroethane. Stirring was con
tinued for an additional 2 hours. Subsequently 40 cm.3
5.006 g. (0.02 mol) of 4,4’-dihydroxydiphenylsulphone
and 200 mg. of triethylbenzylammonium chloride were
of l,1,2~trichloroethane and 100 cm.P of water were
dissolved in 40.0 cm.3 of NaOH N and 20 cm.3 of
added to the viscous mixture and stirring continued for
l,l,2-trichloroethane were added. At a temperature not 65 30 minutes. Subsequently the upper aqueous layer was
exceeding 20° C. a solution of 6.424 g. of 4,4'-(2,2-pro-
decanted and replaced by 100 6111-3 0f W?tef- The miX~
pylene)dibenzoylchloride in 40 cm.3 of l,l,2-trichloroethane was added over a period of 20 minutes to the
. ture was again Stirred for 1 hour. Subsequently the
Polymer Was Precipitated into an eXCeSS of ethanol- The
vigorously stirred mixture. Stirring was continued for
?brous white polymer is soluble in methylene chloride,
an additional 4 hours, subsequently the upper layer was 70 1,2-dichloroethane, 1,1,2-trichloroethane and tetrachloro
decanted and replaced by 100 cm.3 of distilled Water.
ethane; from these solvents the polymer can be cast into
The mixture was again stirred for 30 minutes. Subsecolorless, transparent ?lms showing good ?exibility and
quently the upper layer was decanted and removed. Upon
a high softening point (260-290“ C.). The intrinsic
pouring the organic layer into an excess of ethanol, a
viscosity of the polymer, determined in tetrachloroethane
?brous white polymer precipitated which could be sepa- 75 solution amounts to 2.25.
3,028,364
‘Z
Example 9
5.808 g. (0.02 mol) of 1,l-(4,4'-dihydroxy-diphenyl
ture.
Stirring was continued for an additional 3 hours.
phenyl) ethane and 150 mg. of triethylbenzylamrnonium 10 The upper aqueous layer was decanted, and the residue
chloride were mixed with 40.4 cm.3 of NaGH N and
washed with 20 crn.3 Water by stirring during 15 minutes.
10 crn.3 of 1,1,2-trichloroethane at a temperature not
exceeding 10° C. Over a period of 20 minutes a mixture
The aqueous layer was decanted and the residue was
poured into ethanol. A ?brous white polymer was
of 5.583 g. of diphenyl-4,4’-dicarbonyl chloride and
obtained, with an intrinsic viscosity determined in tetra
50 crrr.3 of 1,1,2-trichloroethane was added at a tem 15 chloroethane of 0.92 and a softening point of 180° C.
perature not exceeding 28° C. Meanwhile the reaction
it is soluble in methylene chloride, 1,1,2-trichloroethane,
mass was vigorously stirred.
Stirring Was continued for
l,2—dichloroethane, tetrachloroethane, dioxane and tetra
hydrofurane.
an additional 3 hours, subsequently the aqueous layer was
decanted and replaced by 100 cm.3 of distilled water;
Example 12
CCls
the mixture was again stirred for 30 minutes. Subse
quently the aqueous layer was decanted and the polymer
precipitated into an excess of ethanol.
9.525 g. (0.03 mol) of 1,1,1-trichloro-2,2-(4,4’-dihy
droxy-diphenyl)ethane was mixed with 45.5 cm.3 of
The ?brous white
NaOH 1.5 N at a temperature not exceeding -—-l0° C.
and a solution of 150 mg. of triethylbenzylammonium
chloride in 50 (1111.3 of methylene chloride was added.
At a temperature not exceeding —5° C. a solution of
polymer is soluble in methylene chloride, 1,2-dichle-ro
ethane, 1,1,2-trichloroethane, tetrachloroethane and di
oxane; from these solvents the polymer can be cast into
colorless, transparent ?lms showing good flexibility and
a high softening point (280-309° C.). The intrinsic
viscosity of the polymer, determined in tetrachloroethane
solution amounts to 1.95.
.85 g. of diphenylether 4,4’~dicarbonylchloride and 150
mg. of triethylbenzylarnmonium chloride in 50 cm.3 of
methylenechloride was added over a period of 10 minutes
35
Example 10
to the vigorously stirred. mixture.
Stirring was continued
for an additional 5 hours at a temperature not exceeding
1
CH3
1
4.566 g. (0.02 mol) of 2,2-(4,4'-dihydroxy-diphen
0° C. Subsequently the upper aqueous layer was decanted
and replaced by 100 cm.3 of distilled water. The mixture
was again stirred for 1 hour. Subsequently the aqueous
layer was decanted and the organic layer was poured
yl)propane and 150 mg. of triethylbenzylarnmoniurn
chloride were dissolved in 40.4 cm.3 of NaOI-l N and
20 cm.3 of 1,1,2-trichloroethane were added.
At a ten -
perature not exceeding 5° C., a. solution of 7.242 g.
into boiling water; a ?brous White polymer could easily
be separated. The polymer is soluble in methylene
30 cm.3 of 1,1,2-trichloroethane was added over a. period
chloride, 1,2-dichloroethane, 1,1,2-tricldoroet one, tetra—
of 25 minutes while the mixture was vigorously stirred.
chioroethane, dioxane and tetrahydrofurane. From these
Stirring was continued for an additional 3 hours at a 50 solvents the polymer can be cast into colorless, transparent
temperature slowly rising to 20° C. Subsequently the
showing good ?ex'bility and a high. softening point
upper aqueous laye was decanted and replaced by 101'.)
(‘180° C). The intrinsic viscosity of the polymer, deter
of 4,4’-benzophenone dichloride dicarbonyl chloride in
0111.3 of distilled water.
for 30 minutes.
decanted
The mixture was again stirred
mined in tetrachloroethane solution amounts to 1.3.
We claim:
Subsequently the aqueous layer was
removed. Upon pouring the organic layer
55
into an excess of ethanol, at ?brous white polymer pre
1. A process for preparing highly polymeric linear
polyesters, having an intrinsic viscosity of at least 0.4
cipitated which could be isolated by ?ltration. The poly
when measured in a solution of a chlorinated hydrocar
mer is soluble in methylene chloride, 1,2-dichloroethanc,
bon, which comprises condensing a diacid halide of an
1,1,2-trichloroethane, tetrachloroethane and dioxane; from
aromatic dicarboxylic acid, dissolved in an alkyl halide
these solvents the polymer can be cast into colorless, 60 which is a solvent for the polyester formed, with an
transparent films showing good ?exibility and a high
alkali metal salt of a bis-phenol dissolved in water, the
softening point (HO-260° C.). The intrinsic viscosity
aromatic dicarboxylic acid is a member of the group
consisting of
of the polymer, determined in tetrachlorocthane solution
amounts to 0.90.
Example 11
65
1.535 g. of 1,2-diphenylethane 4,4’-dicarbonylchloride 70
and 0.025 g. of triethylbenzyiammonium chloride were
dissolved into 15 crn.3 of 1,1.2-trichloroethane. A solu
tion of 1.14 g. of 4,4’-dihydroxy-diphenyl-2,2-propane
HO——CO—Ar'—R’—-—Ar’--CO—OH
and the bisphenol is a member of the group consisting of
I-IO-—Ar—Ar-—OH and HO-—Ar-—R—A1‘~—OH
in which formulae each of the links Ar and Ar’ represents
and 10.2 cm.3 of NaOH 1.0077 N was added over a period
of 10 minutes to the stirred solution at room tempera“ 75 a bivalent aromatic radical selected from the group con
3,028,364
9
sisting of an unsubstituted para-phenylene radical, a
metaphenylene radical, a methyl substituted paraphenyl
ene radical and R and R’ each represents a bivalent radi
cal selected from the group consisting of an ether radical,
a carbonyl radical, a sulphonyl radical, a saturated lower
10
2. A process according to claim 1, wherein the con
densation is carried out in the presence of a catalyst
selected from the group consisting of the quaternary am
monium compounds.
3. A process according to claim 1 wherein su?icien-t
water is added to the reaction mixture to precipitate the
hydrocarbon radical, and a carbon atom which forms part
polymer formed.
of a cycloaliphatic ring, at least one of the radicals R
and R’ is a bivalent saturated lower hydrocarbon radical
References Cited in the ?le of this patent
selected from the group consisting of a lower alkyl-sub
10
UNITED STATES PATENTS
stituted methylene group, an aryl substituted methylene
group, a lower alkyl- and aryl substituted methylene
2,595,343
Drewitt ______________ __ May 6, 1952
group, a halo-methyl substituted methylene group, a
halogen-substituted methylene group and a carbon atom
which forms part of a cycloaliphatic ring, whereby the
polyester is dissolved in the alkyl halide as it is formed, 15
permitting the formation of highly polymeric linear poly
esters.
2,600,376
Caldwell _____________ __ June 17, 1952
2,808,394
2,839,508
Speck ________________ __ Oct. 1, 1957
Williams _____________ __ June 17, 1958
OTHER REFERENCES
Conix: Ind. Eng. Chem., 52, 147-150 (1959).
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