Note: Descriptions are shown in the official language in which they were submitted.
` 1~54745
BACKGROUND OF THE INVENTION
High molecular weight linear polyester compositions based
on bisphenols have been shown to be useful in the preparation of films
and fibers. These compounds, when molded into useful articles using
conventional techniques, offer properties superior to those articles
molded from other linear polyester compositions.
Bisphenol polyesters can be prepared by three condensation
techniques, i.e., melt, homogeneous and interfacial condensation
techniques. Melt or bulk polymerization is the simplest method and
10 in this technique the reactants are charged into a vessel and heated.
Homogeneous or solution polymerization generally offers a better rate
of reaction and temperature control than the melt process since
solubility of all reactants in a common solvent permits the reactants
to be more thoroughly dispersed and the resulting product is more
15 conveniently handled. In the interfacial method, the reactants are
dissolved in solvents which are immiscible with each other and their
reaction takes place at the interface of the solvents.
Of the three condensation techniques, homogeneous or solution
polymerization is the least often used for two reasons. The first is
that the interfacial technique provides all of the advantages of the
homogeneous technique and additionally provides means for maintaining
the concentration of the reactants in the reaction zone at a constant
level. The second reason is that it is difficult to produce high molecu-
lar weight polymers by solution polymerization while such high molecular
weight products are easily obtained using either the melt or inter-
facial techniques. Thus, in solution polymerization, the product
rarely has an intrinsic viscosity in excess of 0.6 deciliter per gram
~k
1al54745
of polymer when measured in a solution of symmetrical tetrachloro-
ethane at 30C., and indeed, most polymers produced by this method
have intrinsic viscosities of less than about 0.4 dl/g. The intrinsic
viscosity is, of course, a measure of the molecular weight of the
product and as the molecular weight decreases, the polyesters become
more brittle and lose strength. Thus, the molecular weight of the
polyesters produced by the solution process are usually not high
enough to produce a polyester having good impact strength.
The interfacial technique has several disadvantages. One
is the possibility of hydrolysis of some of the diacid chloride and
formation of carboxylic acid groups which can then react with more
diacid chloride forming anhydride linkages in the growing polymer.
Exposure to moisture during processing and/or use can result in
hydrolysis of the anhydride linkage which could seriously degrade
polymer properties. In a solution method, moisture can be excluded
by careful drying of all ingredients and solvents by known methods
such as distillation, azeotropic distillation or drying of solids in
suitable equipment such as vacuum ovens. Also in a solution poly-
merization method, if the hydroxyl-containing compound reacts very
rapidly with the diacid chloride it may not be necessary to eliminate
the very small amount of water that may be present as an impurity.
In an interfacial process, large amounts of water are always present
and thus the probability of reaction with the dihalide is increased.
Another disadvantage of the interfacial process is the low yield per
batch of 3%-5% polymer solids while the solution method affords up
to 11% polymer solids per inch.
In the solution condensation of a bisphenol and an aromatic
dicarboxylic acid halide, it is known to add the dihalide to
1(~54745
the bisphenol or glycol or to mix the two reactants followed by
addition of a suitable catalyst, and in both instances to initially
employ one diol so as to form a prepolymer and thereafter add the
second diol. See, e.g., Korshak et al, J. Poly. Sci., A-l, 11, 2209
(1973). The addition of the aromatic dicarboxylic acid halide to the
hydroxyl-containing component is standard procedure.
Copending Canadian application Serial No. 244,340, J. A.
Pawlak et al, filed January 23, 1976, discloses that adding the hydroxyl-
containing component to the diacid halide in solution polymerization
produces high molecular weight polyesters having a low melt viscosity.
This application is based on the finding that following the procedure
of the copending application and using certain sequential additions of
reactants will produce high molecular weight polyesters having an
ordered microstructure and a lower melt viscosity.
Accordingly, it is the object of this invention to provide a
new process for the production of novel high molecular weight aromatic
polyesters having an ordered microstructure, a low melt viscosity and
an improved yield per volume of reactants and solvents by the solution
or homogeneous polymerization technique. This a~d other objects of the
20 inYention will become apparent to those skilled in the art from the
following detailed description.
SUMMARY OF THE INVENTION
This invention relates to a solution polymerization process
for the production of high molecular weight, ordered microstructure,
25 linear aromatic polyesters, and more particularly to a process in which
the hydroxyl-containing component is added to the diacid halide in a
particular sequence.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, a solution
polymerization process for the production of linear aromatic
1054745
polyesters is carried out by adding the hydroxyl-containing com-
ponent to the diacid halide in a particular sequence under poly-
merization conditions.
The diacid halides which can be used in the process of
thc invention include oxalyl chloride and diacid halides of the
formula
X-Y-Z-Y ' -X
wherein Z is a bivalent or disubstituted radical of 1 to about 20
carbon atoms selected from the group consisting of alkylene, aryl-
ene, cycloal~ylene, alkylarylene, and arylene-B-arylene where B is
-O-, -S-, -SO-, -S02-, -S03-,-CO-, GP-0, GN~,-or al~ylene; Y and Y'
are independently selected from the group consisting-of C0, SO,
SO2; and X is halogen. G is defined hereinafter with respect to
the bisphenols. Additionally, mixtures of the diacid halides may
be employed to achieve a polymer with especially desired properties.
Among aromatic disulfonyl halides which can be used in
the polycond~nsation reaction according to the invcntion are:
1,4-benzene disulfonyl chloride; 1,3-benzene disulfonyl chloride;
1,2-benzene disulfonyl chloride; 2,7-naphthalene disulfonyl chlor-
ide; 4,4'-diphenyl disulfonyl chloride; 4,4'-diphenyloxide di-
sulfonyl chloride; 4,4'-diphenylmethane disulfonyl chloride;
4,4'-diphenylsulfone disulfonyl chloride; 3,3'-diphenylsulfone
disulfonyl chloride; bis-(4-chlorosulfonylphenyl)-2,2'-propane;
4,~-dichloro-1,3-benzene disulfonyl chloride; 4,6-dichloro-1,3-
benzene disulfonyl chloride; and 4,5,6-trichloro-1,3-benzene
disulfonyl chloride.
Among the diacid halides of dicarboxylic acids which
can be used according to the invention are: terephthaloyl chlor-
ide; isophthaloyl chloride; sebacoyl chloride; adipoyl chloride;
4,4'-diphenylether dicarboxylic acid chloride; fumaryl chloride;
and maleoyl chloride.
Diacid halides of aromatic monocarboxysulfonic acids in-
clude m-chlorosulfonylbenzoyl chloride; p-chlorosulfonylbenzoyl
chloride; ~nd 2-sulfonylchloride-1-naphthyl chloride.
lOS4~45
Other typical examples include the acid chlorides of bis
(4-carboxyphenyl)-sulfone; bis(4-carboxyphenyl-carbonyl; bis
(4-carboxyphenyl)-methane; bis(4-carboxyphenyl)-dichloromethane;
1,2- and 1,1-bis(4-carboxyphenyl)-ethane; 1,1- and 2,2-bis (4-
carboxyphenyl)-propane; 1,1- and 2,2-bis(3-carboxyphenyl)-propane;
2,2-bis(4-carboxyphenyl)-1,1-dimethyl-propane; 1,1- and 2,2-bis(4
carboxyphenyl)-butane; l,l-and 2,2-bis(4-carboxyphenyl)-pentane;-
3,3-bis(4-carboxyphenyl)-heptane; 3,3-bis(3-carboxyphenyl)-heptane;
and bis(4-carboxy)-diphenyl.
Although the preferred chlorides have been listed above,
the other halides, especially the bromides but also the flourides
and iodides, may be suitably substituted for the chlorides to ob-
tain good results.
When polymers of the invention having high percentage alter-
nating structure are desired, the acid halide should be one which
is capable of transmitting inductive effects. In such an acid
halide, when one acid halide group reacts with a diol, the reac-
tivity of the second acid halide group changes. Such acid halides
are those of the formula wherein Z is arylene or alkylarylene.
Also useful are oxalyl chloride, fumaryl chloride and maleoyl chlor-
ide.
The hydroxyl-containing component used in the present inven-
tion is a mixture of a bisphenol and a glycol or a mixture of two
different bisphenols or a mixture of two different glycols.
The bisphenols considered useful for the preparation of
high molecular weight polyesters according to the present inven-
tion correspond to the general formula:
... .
'~ _5_
1~54745
HO - Ar - Ed ~ Ar - OH
Tb Gm Tb
wherein Ar is aromatic, preferably containing 6-18 carbon atoms
(including phenyl, biphenyl and naphthyl), G is selected from the
group consisting of alkyl, aryl, haloaryl, haloalkylaryl, alkyl-
aryl, cycloalkyl, halocycloalkyl, and haloalkyl, and suitable
contains 1-14 carbon atoms; E is a bivalent (or disubstituted)
xadical selected from the group consisting of alkylene, haloalkyl-
ene, cycloalkylene, halocycloalkylene, arylene, haloarylene, -O-,
-S-, -SO-,-SO2,-SO3, -CO-, GP=O and GN~, and preferably contains
-5a-
1054745
1-14 carbon atoms; T is selected rom the group consistin~ of
halo~en, G or OG, Cl and l~r bein~ preferred halogens; m is 0 to the
number of replaceable hydro~en atoms on E; b is 0 to the number of
replaceable hydro~en atoms on Ar; and d is 0 or 1. When there is a
plurality of G and T substituents in the bisphenols accordin~ to
the above formula, these substituents may be the same or different.
The T substituents may occur in the ortho-, meta-, or para-position
with respect to the hydroxyl radical. Additionally, mixtures of
the above described bisphenols may be employed to achieve a poly-
mer with especially desired properties. The bisphenols can contain
12 to about 30 carbon atoms, preferably 12 to about 2S carbon atoms.
Bisphenols havin~ the above general formula and which
are suitab~e for being applied accordin~ to the present invention
include, but are not limited to, bis(4-hydroxyphenyl)-methane,
bis(3-methyl-4-hydroxyphenyl)-methane, bis(4-hydroxy-3,5-dichloro-
phenyl)-methane, bis(4-hydroxy-a,5-dibromophenyl)-methane, bis(4-
hy~roxy-3,5-difluorophenyl)-methane, bis(4-hydroxy~henyl)-2,2-
propane [common name - bisphenol-Al, bist3-chloro-4-hydroxy-
phenyl)-2,2-propane, bis(4-hydroxy-3,5-dichlorophenyi)-2,2-
propane, bis(4-hydroxynaphthyl)-2,2-propane, bis(4-hydroxyphenyl)-
phenylmethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-
hydroxyphenyl)-4'-chlorophenylmethane, bis(4-hydroxyphenyl)-2,2,2-
trichloro-1,2-ethane, bis(4-hydroxyphenyl)-1,1-cyclohexane, bis(4-
hydroxyphenyl)-cyclohexylmethane, 4,4'-dihydroxydiphenyl, 2,2'-
dihydroxydiphenyl, dihydroxynaphthalene, bis~4-hydroxyphenyl)-
2,2-butane, bis(3,5-dichloro-4-hydroxyphenyl)-2,2-propane, bis(2-
methyl-4-hydroxyphenyl)-2,2-propane, bis(3-methyl-4-hydroxyphenyl~-
l,l-cyclohexane, bis(2-hydroxy-4-methylphenyl)-1,1-b-ltane, bis(2-
hydroxy-4-tertbutylp}lenyl)-2,2-propane, bis(4-hydroxyphenyl)-1-
phenyl-l,l-cthane, 4,4'-dihydroxy-3-methyldiphenyl-2,2-propane,
4,4'-dihydroxy-3-methyl-3'-isopropyldiphenyl-2,2-butane, bis(3,S-
dibromo-4-hydroxyphenyl)-phenyl phosphine oxide, bis(4-hydroxy-
phenyl)-sulfoxide, bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxy-
lOS4745
phenyl)-sulfonate, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxy-
phenyl)-mcthylamine, 2,3,5,6,2',3',5',6'-octachloro-4,4'-hydroxy-
biphenyl, bis(3,5-dibromo-4-hydroxyphenyl)-Xetone, and bist3,5-
dibromo-4-hydroxy~henyl)-2,2-propane.
In addition to the above recited para hydroxy bisphenols,
the corresponding ortho and meta hydroxy bisphenols can be cm-
ployed in the process of this invention.
The bisphenols and glycols can be employed in proportions
from 0 to 100 percent of either, as long as two different compounds
are employed. The glycol is preferably employed in any amount from
5 up to about 95 mol percent of th~ hydroxyl-containin~ component
with the bisphenol constituting the balance. ~lore preferably, the
diol is 15-85 mol percent of the hydroxyl-containing component and
most preferably about 50 mol percent. In general, the glycols will
contain ~ 40 carbon atoms and typical examples include ethylene
glycol, diethylene glycol, triethylene glycol, tetraethylene ~lycol,
propylene glycol, dipropylene glycol, polypropylene glycol, hexyl-
ene glycol, 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexane-
diol, l,5-pentanediol, thiodi~lycol,-1,3-propanediol, 1,3-butane-
diol, 2,3-butanediol, 1,4-butanediol, 1,3-butylene glycol, neo-
pentyl glycol, 1,2-dimethyl-1,2-cyclopentanediol, 1,2-cyclohcxane-
diol, 1,2-dimethyl-1,2-cyclohexanediol, 2,2,4-trimethyl-1,3-
pentanediol, polyethylene glycol, hydroxyl-terminated aliphatic
polyeste~s of, e.g., about 1000 molecular weight, and the like.
In accordance with conventional procedure, any of those
materials which are known to be catalysts for the condensation
reaction can be employed in this invention. Such catalysts are
bases, such as tertiary amines such as trimethylamine, triethyl-
amine, pyridine and the like. The base catalyzes the reaction and
also neutralizes the hydrogen chloride that would otherwise be -
liberated during the condensation reaction. The catalyst (and
~ICl acceptor) is usually employed in twice the molar quantity of
thc diacid halidc although a slight exccss of up to about 15 molar
lOS4745
percent, preferably 5-10 molar percent, is generally employed to
ensure completeness of reaction and to compensate for any loss of
volatile base.
Any of the known inert organic solvents can be used in
the process of this invention. ~uitable inert solvents include
both aliphatic and aromatic hydrocarbons as well as simple and
cyclic ethers. Typical hydrocarbons include isooctane and benzene
fractions such as those having a boiiing range of 120-200 C.
Cycloaliphatic compounds such as decahydronaphthalene are also
suitable. Benzene, toluene, xylene, and isomeric mixtures of
hexylcumene, cyclohexyltoluene, cyclohexylethyl benzene, isopropyl-
ethyl benzene, dihexyl benzenes, and diphenyl, and the like are
examples of suitable aromatic hydrocarbons. The ethers include
diisopropylether, diisoamylether, dimethylethers of ethylene and
diethylene glycol, diphenylether, l,4-dioxane, and the li~e. Also
suitable are nitrobenzene, dimethyl sulfoxide and dimethyl formamide
as well as chlorinated aliphatic and aromatic hydrocarbons such as
methylene chloride, tetrachloroethane, tetrachloroethylcne, penta-
chloroethane, o-dichlorobenzene, trichlorobenzene, J~,~ -dichloro-
ethyl benzene, monochlorobenzene, and the like. The amount ofsolvent must be sufficient to avoid precipitation as the reaction
proceeds. The diacid halide is employed in the form of a 1-25
weight percent solution, preferably 10-25 weight percent, in one
of the foregoing solvents, although a more concentrated solution
can be used if additional solvent is added as the reaction con-
tinues. The hydroxyl-containing component can be employed in the
form of about a 15-100 weight percent solution (i.e., if the
hydroxyl component is a liquid, it can be employed without solvent)
and is preferably used as a 30-50 wei~ht percent solution. Suffi-
cient solvent is used to obtain a polyester concentration of 1-11%
or more, depending on viscosity, and preferably about 5-ln%.
The polymerization process is carricd out using the
standard solution polymerization techniqucs except that the
hydroxyl-containing component to~ethcr with the catalyst arc addcd
-8-
1054745
to the diacid halide, preferably with stirring. The addition is
preferably performed slowly but this is not necessary if the hcat
of the exotherm is controlled by cooling via ice baths or solvent
reflux. The particular temperatures maintained will depend on the
diacid halide. For example, in the case of isophthaloyl chloride, a
temperature of 0-5 C. is suitable while with terephthaloyl chlor--
ide a *emperature above 15 C. is used in order to maintain the
terephthaloyl chloride in solution. In general, the reaction tem-
perature will be from about 0 C. to the boiling point of the most
volatile reaction component, and preferably about 0-40 C. ~fter
the end of the addition period, which can last about 0.5-6 hours,
preferably about 2-4 hours, a reaction or stirring period is
preferably employed, usually lasting about 2-24 hours, depending
on the reactivity of the hydroxyl-containing component with the
diacid halide. The faster the reac*ion occurs, the less stirring
or reaction time is necessary to en~surc completeness of reaction.
. A second or third addition of a hydroxyl-containing component can
then be made in the same manner until all of the diacid halide has
reacted with stoichiometric amounts of the hydroxyl-containing
components. Thereafter any amine hydrohalide solids can be filtered
out of the solution, or the solution can be quenched with dilute
hydrochloric acid, washed with distilled water until the washings
are free of chloride and filtered. The polymer can then be re-
covered by the addition of an anti-solvent such as acetone, by
addition of the polymer solution to a non-solvent or by addition
of the polymer solution to warm or hot water under hi8h agitation
in cases where the solvent has a boiling point below that of
water.
The color of the composition of this invention is im-
proved by excluding oxygen from the reaction vessel. Phenols and
bisphenols upon slight oxidation discolor to a deep red. Since
pronounced colors are hard to mask, the ~olymer to bc most uscful
l~S4'745
should be colorless or nearly colorless. Therefore, an inert or
unreactive gas is employed to exclude oxygen from the reaction vessel.
While it has been convenient to use nitrogen, suitable unreactive
gases or mixtures can be employed including the inert gases such as
argon, helium and neon.
The process of this invention produces high molecular weight
polymers with low melt viscosities which make the polymers suitable for
use as engineering plastics, e.g., in the preparation of films and
fibers and molded articles. Without being limited to theory, we believe
high molecular weight polymers with ordered microstructures are formed
for several reasons. The addition of the hydroxyl-containing component
to an excess diacid halide prevents the formation of highly crystalline
and insoluble block polymers. Furthermore, the addition of the hydroxyl-
containing component in a sequential manner influences the formation
15 of definite microstructured linear polymers. In the case of diacid
halides, such as terephthaloyl chloride, the two acid halides are of
unequal reactivity (see Korshak et al, supra) further adding to the
ordering of the microstructure of the resulting polymers.
The following Examples are presented in order to further
20 illustrate the present invention. In the Examples, as well as through-
out the specification and claims, all parts and percentages are by
weight, all temperatures in degrees Centigrade, and all intrinsic vis-
cosities were determined in 1,1,2,2,-tetrachloroethane at 30~ C. unless
otherwise specified.
EXAMPLE 1
A poly(neopentylene-4,4'-isopropylidene diphenylene tere-
phthalate 50:50) was prepared by the process of the aforementioned co-
pending Canadian application Serial No. 244,340. A solution of dis-
tilled terephthaloyl chloride (0.40 mol) in distilled methylene
30 chloride (195 ml) was prepared in a 3-liter 3-necked flask equipped
- 10 -
105474S
with a mechan;cal stirrer, thermometer, reflux condenser with attached
drying tube, an inert gas inlet and a pressure equalized additional
funnel. The flask was immersed in an ice bath but the temperature
was maintained above 15C. to prevent the precipitation of the
terephthaloyl chloride. The solution was kept under a constant dry
nitrogen atmosphere with stirring. A solution of recrystallized
bisphenol-A (0.20 mol), recrystallized neopentyl glycol (0.20 mol)
and distilled triethylamine (0.88 mol) in distilled methylene
chloride (500 ml) was added to the terephthaloyl chloride solution
over a 6.5 hour period at a temperature range of 15-21.5C. while
maintaining a medium rate of stirring. The addition funnel was
rinsed with methylene chloride (200 ml). The reaction mixture was
stirred for an additional 2 hour period at temperatures of 18-23C.
The mixture was filtered to remove triethylamine hydrochloride.
Methylene chloride (400 ml) was used for rinsing. The solution was
washed with distilled water until the washings were free of chloride
ions, treated with activated carbon, dried over MgS04 and filtered.
The solid polymer was recovered by precipitation by addition of
acetone as a non-solvent. The so1ids were dried in a vacuum
desiccator at 91-100C. The properties of this polymer are given
in Table I.
EXAMPLE 2
A poly(neopentylene-4,4'-isopropylidene diphenylene tere-
phthalate 50:50) was prepared by the process of this invention by
adding a solution of 78.1 9 (0.75 mol) of recrystallized neopentyl
glycol and 151.8 9 (1.5 mols) of dried and distilled triethylamine
~S4745
dissolved in 200 ml of dried and distilled methylene chloride to a
solution of 304.5 9 (1.50 mols) of distilled terephthaloyl chloride
dissolved in 700 ml of dried and distilled methylene chloride in a
5-liter 3-necked Morton flask which was equipped in the manner des-
cribed in Example 1. The addition was conducted over a 4-hour period
with stirring at temperatures of 19-25C. The addition funnel
was rinsed with 200 ml of dried and distilled methylene chloride
and the reaction mixture stirred for 4 hours at temperatures of
21.8-24C. The mixture was allowed to react for an additional
20 hour period at room temperature without stirring. A solution
of 171.2 9 (0.75 mol) of recrystallized bisphenol-A and 151.8 9
(1.50 mols) of dried and distilled triethylamine in 600 ml of dried
and distilled methylene chloride was added to the reaction mixture
with stirring over a 6.1 hour period at temperatures of 18-26C.
Thereafter, 5.1 9 (0.05 mol) of dried and distilled triethylamine
dissolved in 100 ml of dried and distilled methylene chloride were
added to ensure complete reaction and an additional 700 ml of
methylene chloride was added to the viscous reaction mixture to
yield ~--solution calculated to have 10.9% polymer solids. The
solution was washed twice with 1500 ml and twice with 1000 ml of
distilled water. After the last washing, the solution formed an
emulsion which was precipitated by addition to hot distilled water
in a Waring blender. The precipitated polymer was washed three
times with distilled water in the Waring blender to remove all
traces of chloride ions. The properties of the polymer are set
forth in Table I.
1054745
TABLE I
Pro~ertics of Solution Poly~merized rolyesters
Product of Example 1 2
Type Addition One Step Sequential
[~ (dl/g)CD 0.77 Q 25 C. 1.27 Q 30 C.
38,100 (70,900) 79,000 (149,000)
~n~3 22,200 (38,500) 42,900 (77,100)
~hY/~ln~3 1 . 72 (1.84) l.B4 (1.93)
Tg, C.~ 137 137.5
Microstructure
(N~IR Analysis) Random 64.8% Alternatin~D
Yield (% of Theory) 68.4 98.0
~elt Viscosity at
300 C. at 1~] = 0.70,
Poises ca. 54,000 ca; 43,000
____ ___ ___ ______ _______ ____
n sym-tetrachloroethane
.el permeation chromatography analysis using a polyester
calibration curve which was derived from absolute values for
molecular weights (li~ht scattering for ~iw and membrane
osmometry for ~In). ~rw is the weight average molecular
weight while ~rn is number average molecular weight. Values
in parenthesis were obtained by usin~ a polystyrene calibra-
tion curve for the gel permeation chromatography analysis.
lass transition temperature by differential scanning
calorimetry.
CH3 O O CH
" " , 3
ercentage of -O ~ C- ~ OC ~ COC~I2C-CII-O- in the
c.~3 c~{3
microstructure of the polyester determined by N~SR. See,
Yamadera et al, J.roly.Sci., ~-1, 5, 2259-2268 (1967).
0.5 g samples of each polyester were pressed between
aluminum foil on a Carver press for one minute at 180 C. and
8000 psi. The product of Example 2 yielded a film which was pre-
dominantly clear while the product of Example 1 showed very littlc
flow as evidenced by a film which was almost completely opaque.
-13-
l~S4745
EXAMPLE 3
A poly(neopentylene-4,4'-isopropylidene terephthalate
50:50) prepared by the interfacial process described in United States
Patent 3,471,441 and molded was used as a control to compare physical
properties of the injection molded product from Example 2. The results
are tabulated in Table II.
TABLE II
Product of Example 2 Patent 3,471,441
Tensile, Yield
Strength (psi) 8203 8100-8300
10 Tensile, Ultimate
Strength (psi) 7513 7200
Elongation at Yield, % 10.9 7-9
Elongation, Ultimate, % 94.3 29-33
Flexural Strength (psi) 12,263 13,300
Flexural Modulus (psi) 2.7 x 105 3.2 x 105
Notched Izod Impact
(ft.-lbs/inch) 14.4 11-13
Heat Distortion Temp. C.
66 psi 129 128
264 psi 115 118
Rockwell Hardness
R Scale 118 122
M Scale 40 67-75
Abrasion Resistance -
CS17 Wheels - 1000 9 load
Mg lost/1000 cycles 15-16 11-13
EXAMPLE 4
A poly(neopentylene-4,4'-isopropylidene diphenylene tere-
phthalate 50:50) was prepared by the process of this invention.
3045.5 9 (15~00098 mols) of terephthalate chloride
(commercial grade) were charged into a 10 gallon Pfaudler reactor
through the charge port. The port was sealed and 56 pounds
- 14 -
lOS4745
(S gallons) of distilled methylene chloride were charged into the
reactor through a solvcnt charge line. The mixtur~ was stirred
at ~bout 21 C. to effect solution. 783.5 g (7.50049 mols~ of
commercial grade neopcntyl ~lycol (wei~ht adjusted for 0.30% water
content) were char~ed into a meltcr tank alon~ with one-half
~allon of C.P. benzene. The mixture was stirred and heated to
reflux using high pressure steam. The benzene was removed con-
tinually over a 1 hour period. The neopentyl glycol in the
melter tank was cooled and dissolved in 1518 g (lS mols) of dis-
tilled triethylamine and 12 pounds (about 1 gallon) of distilledmethylene chloride. The resulting solution was added to the
Pfaudler reactor via a metering glass and line at 55 ml~minute.
Total addition time was 2 hours. Temperature during the addition
was maintained at about Z2 C. by applying cooling water to the
reactor jacket. The reaction mixture was heated to 30-33 C.
for 3 hours and during this heating period, 7.50049 mols (1712.8 g)
of ~1itsui bisphenol-~ tweight corrected for a 0.03% water content~
were charged to the melter tank and dehydrated by the same pro-
cedure as described above for tXe neopentyl glycol. The dehy-
drated bisphenol-A was then dissolved (with heating) in the
melter tank in 1669.6 g (16.5 mols) of distilled triethylamine
and 12 pounds of distilled methylene chloTide. The resultin~
solution was added to the reactor at a rate of 63 ml~minute
(2-1/2 hour addition period) at 26-30~ C. The melter tank was
rinsed with approximately 1 gallon of distilled methylene chlor-
ide. The reaction mixture was stirred for 9 hours.
A sample of the polymer solution was neutralized with
dilute hydrochloric acid, the water layer removed and the polymer
recovered by precipitation in hot distilled water in a Waring
blender. After washing with distilled water to remove chloride
ions ~nd drying in a vacuum oven, a product was obtained which
exhibited an intrinsic viscosity of 0.83 dl/~.
1054745
EXAMPLES 5-6
Two poly(neopentylene-4,4'-isopropylidene diphenylene tere-
phthalate 50:50) were prepared by the process described in Example 4.
The reaction times and results are set forth in Table III.
TABLE III
SEQUENTIALLY POLYMERIZED POLYESTERS *
Example 5 6
Neopentyl Glycol
Addition Time 2-1/4 hours 2-1/4 hours
Rx Time 3-1/2 hours 14-1/2 hours
Bisphenol-A
Addition Time 3-1/4 hours 2-1/4 hours
[n] 0.70 1.08
10 % Alternating Structure 72.5 68.0
Molecular Weights by GPC
Mw 35,400 (65,600) 62,800 (117,000)
Mn 14,300 (23,400) 17,100 ( 30,900)
Mw/Mn 2.48 (2.80) 3.66 (3.79)
Melt V;scosity @ 300C.
at [n] = 0.70, Poises - ca. 43,000
* See footnotes to Table I.
EXAMPLE 7
302.5 9 (1.4900 mols) of commercial terephthaloyl
chloride and 2500 ml of dried and distilled methylene chloride
were charged into a 5-liter 3-necked Morton flask. The flask was
equipped with two Y adapters, a thermometer, a 5-bulb Allihn con-
denser, a mechanical stirrer, a nitrogen inlet and a steam jacketed
l-liter 3-necked addition flask. The steam jacketed addition flask
was equipped with a nitrogen inlet, mechanical stirrer, Dean-Stark
trap and a water cooled condenser. 77.76 9 (0.74500 mol)
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of commercial neopentyl glycol (weight corrected for presence of
0.22~ watcr) and 100 ml of dry benzene were char~ed into the
steam jac~tcd addition flas~. The contents wcre heated with
steam to rcflu~ and the mixture refluxed until the water was re-
~oved by azeotropic distillation. The benzene was then distilled
off, the contents of the flas~ cooled slightly and 150.8 ~ (1.49
mols) of dried and distilled triethylamine and 50 ml of dried and
- distilled methylene chloride were added through a dry water cooled
condenser. The mixture was stirred until solution was effected.
The neopentyl glycol/triethylamine/methylene chloride solution
was added to the terephthaloyl chloride solution over a 2.3 hour
period at lS.5-26 C. The addition flask was rinsed by refluxing
100 ml of dried and distilled methylene chloride. The rinse was
added to the reaction mixtuTe which was stirred for 6.7 hours and
allowed to react without stisring for 11-1/4 hours. A solution
of 81.31 g (0.37250 mol~ of commercial bisphenol-~ (weight ad-
justed to correct for 0.03% water), 84.3S g (0.36935 mol) of com-
mercial thiodiphenol, 0.9449 g (0.00629 mol) of 4-tert-butylphenol
and 165.8 g (1.639 ~ols) of dried and distilled triethylamine in
225 ml of dried and distilled methylene chloride was added to the
rea~tion mixture over a 175 minute period at 20-24 C. The re-
action mixture was stirred for 2-1/2 hours. 1000 ml of distilled
water containing 18.7 ml of concentrated hydrochloric acid were
then added to the reaction mixture. The water was separated and
approxi~.ately S00 ml of methylene chloride added to reduce vis-
cosity. The solid polymer was recovered by precipitation into hot
distilled water in a ~Yaring blender, washed free of chloride ion
with distilled water and dricd in a vacuum oven overnigllt at about
112 C. The final terpolymer was found to have an intrinsic vis-
cosity of 0.70 dl/g in sym-tetrachloroethane at 30 C. and a glass
transition temperature of 12~ C. (by differential scanning
(calorimetry).
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EXAMPLE 8
203.0 9 (1.000 mol) of commercial terephthaloyl chloride was
reacted first with 31.84 9 (0.300 mol) of 2,2'-oxydiethanol and 60.7 9
(0.60 mol) of distilled triethylamine followed by reaction with 159.36
9 (0.69791 mol) of commercial bisphenol-A (weight adjusted for a moisture
content of 0.015%), 0.6279 g (0.00418 mol) of 4-tert-butylphenol and
151.8 9 (1.50 mo~s) of distilled triethylamine by the procedure of
Example 7. The final polyester exhibited an intrinsic viscosity of
0.79 dl/g in sym-tetrachloroethane at 30C. and a glass transition
temperature of 135C. (by differential scanning calorimetry).
EXAMPLE 9
211.7 9 (1.0430 mols) of commercial terephthaloyl chloride
and 90.8 9 (0.4470 mol) of isophthaloyl chloride were reacted by the
procedure of Example 7 first with 77.72 9 (0.7450 mol) of commercial
neopentyl glycol (weight adjusted for a moisture content of 0.164%)
and 150-8 9 (1.490 mols) of distilled triethylamine followed by re-
action with 169.40 g (0.74189 mol) of commercial bisphenol-A (weight
adjusted for moisture content of 0.015~), 0.9359 9 (0.00623 mol) of
4-tert-butylphenol and 165.8 9 (1.639 mols) of distilled triethylamine.
The final product exhibited an intrinsic viscosity of 0.64 dl/g in
sym-tetrachloroethane at 30C. and a glass transition temperature of
123C. (by differential scanning calorimetry).
EXAMPLE 10
3066.4 9 (15.104 mols) of commercial terephthaloyl chloride
dissolved in 56 pounds of dry methylene chloride was reacted by the
procedure of Example 4, using triethylamine as catalyst, with 788.3 9
(7.552 mols) of commercial neopentyl glycol (weight adjusted for 0.22%
water content - water was removed by azeotropic distillation) followed
by reaction with 1718.2 9 (7.5239 mols) of commercial bisphenol-A
(weight adjusted for a
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0.03% water contcnt - water removed by azeotropic distillation)
and 8.4379 g of 4-tert-butylphenol. After work-up, a polymer
was obtained which exhibited an intrinsic viscosity of 0.83
dl/g in sym-tetrachloroethane at 30 C., a glass transition
(DSC) of 138 C. and NMR analysis indicated that the polyester
contained about 69.5~ of alternating microstructure. A sample
of the polyester when injection molded showed a Notched Izod
Impact of from 14.7 to 15.4 ft. lbs./inch.
The novel polyesters prepared according to this invention
are characterized by having an intrinsic viscosity of at least
0.6 dl/g in symmetrical tetrachloroethane at 30 C, preferably
at least about 0.7 dl/g. The polyesters also have a relatively
high degree of alternating structure compared to polyesters
made by processes that produce products having a random structure.
In the working examples provided herein, the amount of alterna-
ting structure is expressed as a percentage determined by NMR
(See footnote 4 in Table 1). The extent or degree of alterna-
ting structure has been expressed in the literature (See Yamadera
et al, J. Poly. Sci., A-l, 5, 2259-2268 (1967) ), as a B value
for polymers produced from a 50:50 mixture of two different
hydroxyl components (such as 0.5 mole fraction of bisphenol A
and 0.5 mole fraction of ethylene glycol). The B value is two
times the percent alternating structure divided by 100. (Thus,
the B value for the polymer of Example 2 herein is 1.296.) The
degree of alternating structure irrespective of the mole frac-
tions of the hydroxyl containing component can be expressed as
an Alternation Index (A) which is defined as follows:
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1054745
A = 1 + ( b~ ~ br )
wherein bf is the mole fraction of alternating copolymer
structure found in the polymer by NMR.
br is the mole fraction of alternating copolymer
structure that would be produced by a reaction
that produces random structure.
bm is the maximum mole fraction of alternating
copolymer structure that is theoretically
possible.
A polymer having all alternating structure has an A value of
2.0; a polymer having all random structure has an A value of
1.0~ wh~e~a polyme~~-havin~ c~mp~ete-l-y-block--structure has_
a va~ f=~. The polymers produced in the working examples
herein had proportions of alternating structures and Alterna-
tion Indices or A values as follows:
Percent Alternating Alternation
Example Wo. _ Structure Index
2 64.8 1.296
72.5 1.450
6 68.0 1.360
69.5 1.390
The novel polymers produced in accordance with this invention
have an Alternation Index of about 1.1 to 1.6, preferably
ab~t 1.2 to about l.S.
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Various changes and modifications can be made in the
process of this invention without departing from the spirit
and the scope thereof. For example, and as illustrated in the
Examples, by taking advantage of reactivity ratio differences
of different monomers (see Vinogradova et al, Vyso~imol Soed.,
pp 457-462 (19i2) by, e.g., varying addition order and ratios,
not only high molecular weight linear copolyesters but also
terpolymers, etc., can be prepared. Accordingly, it will be
understood that the various embodiments disclosed herein were
for the purpose of further illustrating the invention but were
not intended to limit it.
