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It will be apparent that the first of the above reaction according to this invention should be
reactions involves the interaction of at least two above the melting point of the reaction mixture
molecular proportions of the glycol per mole and above the boiling point of the alcohol or phe
cular proportion of the acid. It will be noted from nol to be displaced, but not substantially above
the above equations that glycol is liberated as the the boiling point of the glycol; temperatures ap
condensation proceeds. This glycol should, of proximating the boiling point of the glycol are
course, be removed from the reaction Zone.
Alternatively, the highly polymeric polymethyl under conditionsThe
4 advantageous.
such
heating should be effected
that the displaced alcohol
ene terephthalates of this invention can be made or phenyl can be removed from the reaction zone,
by heating terephthalic acid bodies, such as ester usually by means of conventional distillation
forming derivatives of terephthalic acid with gly equipment. The heating is usually at atmospheric
cos of the series HO(CH2)CH, where 72 is an in SO pressures, but higher or lower pressures may be
teger within the range of 2 to 10. Suitable ester used if desired. Preferably the heating is effected
forming derivatives are aliphatic or aromatic in an inert atmosphere, e. g. in the presence of
esters of tercphthalic acid, for instance, low an inert gas, such as nitrogen or hydrogen.
molecular alkyl esters such as methyl, ethyl, pro
pyl, butyl, amyl, hexyl and heptyl terephthalates, 55 Heating is continued until the distillation of the
and aryl estcr's such as those from phenol, creSols displaced alcohol or phenol ceases, at which stage
and other homologues. The reaction involved is the ester interchange can be assumed to be com
an ester interchange reaction. In practice it is pleted.
preferred to use the methyl or ethyl terephthal When using the ester interchange method, the
ates, since these are cheap and the most readily 60 time required to form the gycol terephthalates
available. Other terephthalic acid bodies can be may be considerably shortened, as compared with
used which are capable of forming terephthal the direct method, i. e. from terephthalic acid
ates under the conditions of the reaction, such itself and a glycol. ;:
as the terephthalic acid dihalides, including the The reaction between the terephthalic acid di
dichloride/the dibromide and the diiodide, but of 65 halides and the glycols is best carried out in the
these the dichloride is preferred on the grounds
of cost and availability.
presence of a diluent, for example, an inert or
ganic Solvent Such as chloroform or tetrachlor
Ester interchange reactions are reversible re ethane and in the presence of a base, usually a
actions and may be represented by the following
equation: tertiary organic base such as pyridine, N-methyl
70 piperidine, N-dimethyl-aniline or N-diethyl
ROAc--ROHeeR'OAc--ROH aniline. Any inert Organic Solvent can be used
A factor which displaces the equilibrium in the in this process.
required direction is the presence of an excess The initial reaction involved in the production
of the displacing alcohol; also, in practice, the 7s of the polymeric polymethylene terephthalates of
2,405,819
5 6
this invention by the ester interchange method of non-metallic ester interchange catalysts, for
is represented graphically below: example, boron, or by purely surface catalysts,
Such as broken glass or Silica gel, in the presence
of a small amount of an alkali metal ester inter
2EO (CH), OH -- Roock Xcoor - change catalyst. As a matter of fact any of the
known compatible ester interchange catalysts
Hoch).oock Xcooch).oh. -- 2 ROH can be employed.
The products of the ester interchange reaction,
Similarly, the production of the polymeric poly or the low molecular weight polymeric poly
methylene terephthalates of this invention from () methylene terephthalates otherwise obtained, can
terephthalic acid dihalides involves initially the be converted into the highly polymeric products
production of glycol esters of terephthalic acid, of this invention by heating them at a temperature
as is represented graphically below: above the boiling point of the corresponding glycol,
under conditions effecting removal of the glycol.
2HO (CH), OH -- zock Dooz a-m- 5Advantageously, during the heating or during
part of the heating, the pressure is reduced SO
Irocit).oock Doooch-oh --2H2 as to facilitate rapid distillation of exceSS of
glycol present. The pressure may be reduced in
In the above equations R repesents an alkyl successive stages so that the heating begins at
or aryl residue, Z represents a halogen and 7. 20 normal pressure, is continued at a reduced pres
is an integer from 2 to 10. An inspection of these sure and is completed at a still further reduced
equations will show that if the products of the pressure. Pressures of from 20 down to 1 mm.
initial reactions are to be the diesters from the of mercury are particularly suitable. Higher or
glycols used, then at least two molecular pro lower pressures may be used if desired. The ma
portions of the glycol per molecular proportion 25 terials used as catalysts may also be present during
of terephthalic acid are required. If, aS may be this stage of the reaction. Metal catalysts may
the case, Smaller proportions of the glycols are
used, then the products of the initial reaction will be used in the second part of the process when
starting from terephthalic acid or a terephthalic
consist of or comprise various low molecular
weight polymeric polymethylene terephthalates, 30 acid dihalide to accelerate conversion of the low
polymeric alklyene terephthalate into high poly
and thus the products of the ester interchange mers poSSessing Cold drawing properties.
reaction are the more accurately represented The heating Should be conducted under condis
as mixtures of products of the formula:
Hoch).oock Xc ooch).o.ocx >coloch).of
tions to prevent oxidation, that is, the presence
where n has its former significance and ac is
Zero or a Small integer. of oxygen should be avoided and a slow stream
The ester interchange reaction is advan of an inert gas, for example, nitrogen or hydro
tageously carried out in the presence of ester gen, is advantageously passed through and/or
interchange catalysts. If no catalyst is present Over the molten maSS.
the reaction proceeds very slowly. Ester inter During the heating, the melting point and the
change catalysts which have been tried and viscosity of the melt gradually increase; the tem
found to be suitable to a varying degree are perature must be maintained high enough to keep
the
lithium, sodium, potassium, calcium, beryllium, s of the mass in the molten state during the whole
magnesium, zinc, cadmium, aluminum, chromi heating period.
um, molybdenum, manganese, iron, cobalt, nickel, The heating is continued at least until a fila
copper, silver, mercury, tin, lead, bismuth, anti ment formed from the melt possesses the property
mony, platinum and palladium. Some of these, of cold-drawing. After the heating is completed,
such as Sodium, lithium, potassium, calcium, 50 the moved
product may be extruded or otherwise re
from the reaction vessel in molten form,
magnesium, zinc, cadmium, manganese, iron, and Subsequently cooled. The extruded material
nickel, cobalt, tin, lead and bismuth have been may be formed into blocks, chips and the like.
found to be efficient ester interchange catalysts The products of the invention are linear highly
when used alone, but good results are also ob polymeric esters having recurring structural units
tained when using small amounts of an alkali of the following formula:
metal, e.g. 0.025% to 0.1%, on the weight of the 55
initial terephthalic ester, and one or more of -() (CH) () () (c x(t)
the metals beryllium, magnesium, zinc, cadmium,
copper, silver, aluminum, chromium, molybdenum, where n is an integer within the range of 2
manganese, iron, nickel, cobalt, mercury, tin, 60 to 10. The three lower members of this series,
lead, bismuth, antimony, platinum and palladium. namely the ethylene terephthalate, the tri
The quantities of the latter metals present can methylene terephthalate and the tetramethylene
be varied widely. terephthalate contain the following recurring
The ester interchange catalysts may be added Structural units.
in the form of powder, chips, shavings, ribbon,
wire or in any other convenient form. The alkali -o CHCH. () () ('g X(
metals, the alkaline earth metals or magnesium
are conveniently used in the form of alcoholates,
formed by dissolving them in the gylcol to be
used or in another alcohol such as methyl or
ethyl alcohol. Further, the alkali metals may be and
-och.ch.crooc{ Xco
used in the form of their carbonates or other
alkaline reacting Salts, for example, borates. -oct.(H,cil, 1so occ X( )
Magnesium may be used in the form of its oxide,
It has also been found that the ester inter respectively.
change process is accelerated by the presence 5 The esters of this invention when freshly formed
2,405,819
7 8
and in the undrawn state are sometimes merization to a remarkable extent and reach val
amorphous in character. They become micro ues much in excess of those of the aliphatic poly
Crystalline upon standing. They are highly esters. Thus, esters isolated at an early stage of
viscous, transparent to slightly opaque liquids, de the reaction between terephthalic acid and ethyl
pending on the presence or absence of inorganic ene glycol have melting points in the region of
materials added as CatalystS, at temperatures 130° C., but the higher polymers do not melt below
slightly above their melting points. If the melts 240° C.
are allowed to cool slowly or if the esters are Again, in the case of the aliphatic polyesters,
heated at a temperature somewhat below their the free solubility which they display in many
melting points, crystallization Suddenly occurs 10 organic solvents is a property substantially inde
and the glassy Solids become porcelain-like, pendent of their molecular weight, but this is not
opaque Solids. The esters have melting points true of the highly polymeric polymethylene ter
ranging up to about 258 C. for the ethylene ephthalates, the solubility of which markedly
terephthalate, these melting points increasing diminishes as polymerization proceeds.
rapidly with their degree of polymerization. The l5. These differences in properties between the
lower members of the series have melting points products of the present invention and those
above 200° C. They have solubilities in Organic similar materials hitherto described are of out
liquids which decrease with their polymerization. standing importance, and considerably enhance
They are resistant to hot and cold dilute acids the utility and widen the field of application of
and, when formed into filaments by drawing or 20 the products of the present invention, particularly
extrusion the flaments are capable of being cold in the textile industry.
drawn to the extent of several hundred per The invention will now be further described
cent of their original length to form fibres. The with reference to a number of specific examples,
fibres thus formed show by characteristic X-ray which are to be regarded solely as illustrative, and
patterns molecular Orientation along the fibre
axis. They have great strength and pliability, 25 notTheas restricting the scope of the invention.
following examples illustrate the produc
are highly lustrous and are insoluble in most tion of the preferred product of the invention,
Organic liquids. highly polymeric ethylene terephthalate:
When extruded or drawn in the molten state,
the highly polymeric polymethylene terephtha 30 Eacample 1
lates yield flaments which can subsequently be 50 grams of terephthalic acid and 89 grams
cold-drawn to the extent of several hundred per ethylene glycol were refluxed for about 72 hours
cent of their original lengths, whereby molecularly until solution was effected. The resulting glycol
oriented structures, i. e. fibres of great strength terephthalate was then washed with water, dried
and pliability are obtained, and it is in the form sis in vacuo, and further heated in a stream of
of such flaments and fibres that the highly poly nitrogen for 84 hours at 280 C. The resulting
meric polymethylene terephthalates of the inven polymer of melting point 254-255 C. was very
tion find their greatest utility in the art. viscous and possessed good cold-drawing prop
The flaments can be formed by extrusion or erties.
by drawing from the melt directly after the coma (0 Eacample 2
pletion of the heating during which the highly
polymeric product is formed. Alternatively, 10 grams of methylterephthalate, 4.85 grams of .
blocks or chips or like shapes may be remelted ethylene glycol, and 0.003 grams of sodium were
and thereafter formed into flaments. Any suit heated in a distilling tube in a stream of Oxygen
able apparatus can be used. 5 free nitrogen for about 3 hours at 97 C., until
The cold-drawing operation may be carried most of the methyl alcohol was removed and the
out on flaments which have been allowed fully ester interchange reaction was practically con
to cool and solidify after their formation, or it plete. The resulting low polymeric glycol tere
may directly follow the formation of the flaments phthalate was then further heated at 280 C.
as one part of a continuous process. Any suit
able apparatus and process may be used for cold 50 for
under ordinary pressure for 30 minutes, and then
a further 10 hours in vacuo, a slow current
drawing. For instance, the flaments may be of nitrogen being introduced through a capillary.
wound from one roller to another, the second The resulting product was a while polymer, melt
roller rotating at a higher speed than the first ing at 256° C. to a highly viscous liquid, and pos
roller, for example, at a speed up to about 4 or 55 sessing cold-drawing properties.
5 times that of the first roller. Alternatively, Example 3
the cold-drawing may be effected by employing
a snubbing pin. 15 grams of methyl terephthalate, 7.27 grams
The term cold-drawing, as used herein, in of ethylene glycol, 0.0075 grams of sodium, and
cludes warming the filaments to facilitate
stretching, for instance, bypassing them through
so six inches of clean magnesium ribbon (1 gram)
- were heated as in Example 2 at 19. C., and the
warm or hot water or steam before and/or dur ester interchange was practically completed at
ing the cold-drawing operation. the end of one hour only. The low polymeric
In respect of their fairly definite melting points glycol terephthalate thus obtained was further
and their ability to yield fibres the highly poly 85. heated at 280° C. as in Example 2, but the high
meric polymethylene terephthalates resemble the polymer possessing the desired properties was al
corresponding polymethylene esters from ali ready obtained after 2 hours.
phatic acids of the series HOOC(CEa)COOH,
where n is greater than unity, but no such be Eacample 4
havior is shown by the corresponding esters de 70 The process was exactly as described in Exam
rived from phthalic acid. ple 3, except that 0.1 gram of boron was added
While the melting points of the aliphatic poly in place of the magnesium ribbon.
esters are substantially independent of the de cample 5
gree of polymerization, the melting points of the
terephthalates increase with the degree of poly TS The process was the same as in Examples 3 and
9
a405,810 10
4, except that manganese chips were used as the in an atmosphere of nitrogen, by means of a bath
secondary catalyst in addition to Sodium. at 200-210 C. After 18 hours all of the acid had
Eacample 6 dissolved. The temperature was then raised and
15 grams of methyl terephthalate, 727 grams the excess of glycol was removed from the reac
tion mixture by distillation. The temperature
of...ethylene glycol, and 0.005 gram of lithium (as was brought up to 287 C. and maintained for 7A,
lithium methoxide dissolved in methyl alcohol) hours. After the first hour at 287° C., the pres
were heated at 197 C. as described in Example 2. sure was reduced to about 15 mm. of mercury,
The ester interchange reaction was practically and after a further 1% hours the pressure was
completed after 45 minutes, and on subsequent O again reduced to 1%-2 mm. of mercury. Fila
heating as described in Example 2, a cold-drawing ments formed from the molten mass could be
polymer was obtained after 2% hours. extended by cold-drawing into fibres.
Eacample 7. The product of all the preceding examples is a
15 grams of methyl terephthalate, 7.27
highly polymeric ethylene terephthalate; it has
5 recurring structural units with the following gen
grams of ethylene glycol and a small quantity of eral formula:
magnesium turnings (0.1 gram) were heated at
197° C. as in the preceding examples. The ester
interchange reaction was practically completed
after 30 minutes only. On further heating at it has a melting point lying between 254 and
280° C. a cold-drawing polymer was obtained 258 C. when measured in a capillary tube in the
after 4 hours. absence of air. It is a white, hard, porcelain like
Eacample 8 material; when molten it can be formed into
filaments which can be extended by drawing to
22.2 grams of ethyl terephthalate, 9.3 grams 2. as much as five times their original lengths form
of ethylene glycol, 0.006 gram of lithium (as ing flexible and strong fibres; the latter show,
lithium ethoxide dissolved in ethyl alcohol) and by characteristic X-ray patterns, Orientation
0.5 gram of magnesium ribbon were heated to along the fibre axis. The product is not dis
gether at 197 C. in a distilling tube in a slow solved by the usual organic solvents and it dis
stream of oxygen-free nitrogen for 45 minutes by 30 Solves with difficulty and only to a slight extent
which time the ester interchange was complete in highly polar solvents such as formamide, ni
and the ethyl alcohol liberated had been dis trobenzene, phenol and m-cresol, at relatively
tilled off. The temperature was raised to 280 C. high temperatures. At temperatures up to
for 20 minutes and a vacuum then applied. The 140 C. the Crystalline or micro-crystalline form
heating at 280 C. in vacuo was continued for 2% 35 is undissolved and otherwise unaffected by amyl
hours by which time the melt was highly viscous benzoate, amyl phthalate, amyl salicylate, benzyl
and filaments drawn from the melt possessed benzoate, benzyl butyl phthalate, dibutyl phthal
good cold-drawing properties. ate, ethyl acetate, ethyl benzoate, ethyl alcohol,
Eacample 9 benzyl alcohol, diethylene glycol, formic acid,
6 grams of phenyl terephthalate, 2.4 grams of acetic acid, amyl benzyl ether, dibenzyl ether,
m - dimethoxybenzene, dioxan, dimethylform
ethylene glycol and 0.005 gram of potassium car- . amide, pyridine, acetone, chloroform, carbon
bonate were mixed together and heated in a tetrachloride and benzene. It is practically un
stream of oxygen-free nitrogen at 197 C. for 1. affected by hot or cold dilute acids, and it shows
hour under conditions whereby the phenol formed a surprisingly good resistance to degradation by
by the ester interchange reaction could distill 45 strong acids. For instance, it is practically un
off. Under these conditions most of the phenol affected by boiling for 1 hour in 10% aqueous
was removed; the remainder was removed by fur hydrochloric acid, in 30% sulphuric acid or in
ther heating the mixture at 280° C. for 30 min glacial acetic acid. It is surprisingly stable to
utes. The pressure was then lowered to about 1 50 hot or cold alkalis.
mm. of mercury and the heating continued at The following examples illustrate the produc
280° C. for a further 5 hours. Highly polymeric tion of highly polymeric polymethylene tere
ethylene terephthalate was obtained. phthalates from glycols other than ethylene
Eacample 10 glycol:
Eacample 12
9.15 grams of terephthalyl dichloride was 55 15 grams of methyl terephthalate, 8.9 grams of
added slowly to a mixture of 3.45 grams of eth
ylene glycol, 8.5 grams of pyridine and 75 grams trimethylene glycol, 0.0013 gram of sodium, and
of chloroform. The mixture was then, gently six inches of clean magnesium ribbon (1 gram)
boiled under reflux for one hour, COOled, and were heated together at 197 C. in a distilling tube
poured into ether. The oil which separated was 60 in a stream of oxygen-free nitrogen, for 1A
removed and shaken With an excess of dilute hours, when the ester interchange reaction was
hydrochloric acid and a white solid, a low poly practically completed. The resulting low poly
meric ethylene terephthalate, With a melting meric trimethylene glycol terephthalate was then
point of about 130° C. was obtained. The white 65
heated at 280 C. for 30 minutes at ordinary pres
solid was well washed with water, dried, and sure and for a further 3 hours in vacuo, when a
heated in a stream of oxygen-free nitrogen in the cold-drawing polymer of melting point 221 C.
presence of 1 gram of magnesium ribbon firstly was obtained.
at 197 C. for 15 minutes, and then at 280 C., Ecample 13
with the pressure being gradually reduced to 1.
mm. of mercury for 6 hours. Highly polymeric 70 tetramethylene glycol wereacid
1.7 grams of terephthalic and 4.5 grams of
heated together at
ethylene terephthalate was obtained.
Eacample 11 220-240 C. for about 3 hours until solution was
effected. The resulting melt was heated for 2%
300 grams of terephthalic acid and 550 grams hours at 249 C. with a stream of nitrogen pass
of ethylene glycol were mixed together and heated s ing through the molten mass, and then for a
2,465,819
11 12
further 12 hours at 249c. under vacuum. The still showed X-ray patterns giving no appearance
resulting highly polymeric tetramethylene ter of orientation of the molecules, but they showed
ephthalate cooled to a crystalline, porcelain-like a distinct appearance of crystallinity. The sub
polymer of melting point 208° C. which could be stantially fully drawn flaments, i. e. the fibres,
melt-spun to give filaments possessing good cold showed characteristic X-ray patterns for molec
drawing properties. ular Orientation along the fibre axis.
Eacample 14 3acample 18
4.8 grams of methyl terephthalate, 4.45 grams A quantity of highly polymerized highly
of hexamethylene glycol, 0.0015 gram of lithium O polymeric ethylene terephthalate was cast in the
dissolved in 0.5 gram of methyl alcohol and 0.5 form of a rod and melt extruded in a rod spin
gram of magnesium ribbon were mixed together ning apparatus of the kind described in British
and heated for 1% hours at 197 C. in a stream of Patent No. 527,532 using a plate spinneret have
oxygen-free nitrogen under conditions whereby ing 5 holes each of 0.254 mm. diameter. The
the methyl alcohol was removed. The so ob 5 temperature in the melt chamber was 280° C.
tained low polymeric hexamethylene glycol and the rod passed into the apparatus at the rate
terephthalate was then heated at 245 C., in of 1 cm. in 2% mins. The spun flaments were
vacuo, for 2 hours, when a cold-drawing polymer, wound up, drawn in Water at 55-60 C. at a ratio
highly polymeric hexamethylene terephthalate, of 4.7/1, twisted, doubled and coned by conven
melting at 136 C. was obtained. tional methods. The ten strand yarn so "ob
Eacample 15 tained was highly lustrous. When tested in the
Cambridge fibre extensometer at 70 F. and 65%
2.4 grams of methyl terephthalate, 3.2 grams RH its tenacity was 3.2 grams per denier and its
of decamethylene glycol, 0.0024 gram of Sodium extension at break was 16.5%.
and 4 inches of clean magnesium ribbon (0. What is claimed is:
gram) were heated together at 197° C. for 1% 1. A series of highly polymeric linear tereph
hours, and at 280° C. in vacuo for 3 hours, under thalic esters composed of recurring structural
the conditions described in the preceding units of the formula
examples. The result was a white, cold-drawing
polymer of melting point 123° C., highly polymeric
decamethylene terephthalate, which was Softer -och. oocK Xc 0
at room temperature than the one obtained from wherein m represents an integer within the range
ethylene glycol. of 2 to 10, the three lowest members of the series
The following examples are illustrative of the having melting points above 200° C.; said esters,
production of filaments and fibres from the here 35 when formed into flaments, having the charac
inbefore described highly polymeric esters of this teristic property of being capable of being cold
invention. drawn to the extent of several hundred per cent
Eacample 16 of the original length to form fibres of great
A quantity of highly polymeric ethylene strength and pliability.
terephthalate was heated in the absence of O
2. A highly polymeric linear terephthalic ester
oxygen to a temperature of 280 C. and extruded composed of recurring structural units of the
through a single hole spinneret. The so obtained formula
filament had a moisture regain of 0.7% at 21 C.
and 65% RH, and the maximum absorption of
water at 21 C. was only 4.4% by Weight.
-ochschoock Xc 0
said ester having the characteristic property,
The filament was cold drawn at a draw ratio when formed into filaments, of being capable of
of 4.7/1 to give a strong, flexible fibre of diameter being cold-drawn to the extent of several hundred
0.075 mm. On testing in the Cliff autographic per cent of the original length to form fibres of
recorder (Journal of the Textile Institute, (1933), great strength and pliability, said ester having a
24, T 351) at 16° C. and 65% RH the fibre showed melting point above 200 C.
a breaking load of 180.5 grams corresponding to 3. A highly polymeric linear terephthalic ester
a tensile strength of 40.75 kg./mm. The exten composed of recurring structural units of the
sion at break was 10% on the original length. formula
Eacample 17 55
A quantity of highly polymeric ethylene
telephthalate was spun at a temperature of 286
-och.ch.choock Do O
said ester having the characteristic property,
C. and the filament obtained was drawn at a ratio when formed into flaments, of being capable of
of 4.43/1 giving a strong, flexible fibre with a being cold-drawn to the extent of several hundred
diameter of 0.11 mm. When tested in the Good 60 per cent of the original length to form fibres of
brand single thread tester at 22 C. and 65% RH, great strength and pliability, said ester having
the breaking load was 348 grams which corre a melting point above 200° C.
sponded to a tensile strength at break of 36 4. A highly polymeric linear terephthalic ester
kg/mm.. The extension at break was 18.5% composed of recurring structural units of the
of the original length. The Same fibre, when 65 formula
thoroughly wet with water, showed a tensile
strength at break of 30 kg/mm.
The cher highly polymeric polymethylene -och.ch.ch.choocKXC ()-
terephthalates of this invention can be formed said ester having the characteristic property,
into filaments and fibres in a similar manner. 70 when formed into filaments, of being capable of
When examined under X-rays, the undrawn being cold drawn to the extent of several hundred
filaments showed patterns which indicated that per cent of the original length to form fibres of
they were entirely amorphous and that there great strength and pliability, said ester having a
was no orientation of the molecules. After heat melting point above 200 C.
ing at 100° C. in water for 2% hours, the filaments 75 5. A series of highly polymeric linear polye
2,465,819
13 14
methylene terephthalates having from 2 to 10 moving by distillation the polymethylene glycol
carbon atoms in their polymethylene groups, in which is liberated, and continuing the heating
the form of cold-drawn fibres of great strength until a stage is reached at which flaments formed
and pliability, showing by characteristic X-ray from the mass possess the property of cold draw
patterns molecular orientation along the fibre ing.
axis; the three lowest members of said series hav 13. The process of claim 12 followed by the
ing melting points above 200° C. steps of forming the product into filaments and
6. A highly polymeric linear ethylene tereph cold drawing said filaments,
thalate in the form of cold-drawn fibres of great 14. In the manufacture of highly polymeric
strength and pliability and showing by character O materials which are capable of being formed into
istic X-ray patterns molecular Orientation along filaments having cold drawing properties, the
the fibre axis, said terephthalate having a melt process which comprises heating and reacting an
ing point above 200° C. ester of terephthalic acid and an alcohol of the
7. A highly polymeric linear trimethylene formula R-OH where R is an alkyl group having
terephthalate in the form of cold-drawn fibres of s from 1-7 carbon atoms with an excess of poly
great strength and pliability and showing by methylene glycol having from 2 to 10 carbon
characteristic X-ray patterns molecular Orien atoms, said glycol having a boiling point above
tation along the fibre axis, said terephthalate the boiling point of said alcohol, in the presence
having a melting point above 200° C. of an ester-interchange catalyst, removing the
8. A highly polymeric linear tetramethylene alcohol formed by the reaction by heating to
terephthalate in the form of cold-drawn fibres of temperatures above the boiling point of said alco
great strength and pliability and showing by hol, then further heating the resulting glycol
characteristic X-ray patterns molecular orienta terephthalate at temperatures above its melting
tion along the fibre axis, said terephthalate hav point to produce a high polymer, removing by dis
ing a melting point above 200° C. tillation the polymethylene glycol which is lib
9. In the manufacture of highly polymeric mas erated, and continuing the heating until a stage
terials which are capable of being formed into is reached at which flaments formed from the
filaments having cold drawing properties, the mass possess the property of cold drawing.
process which comprises heating polymerizable 15. The process of claim 14 wherein said ester
polymethylene terephthalate having from 2 to 10 SO interchange catalyst comprises an alkali metal.
carbon atoms in its polymethylene group at tem 16. The process of claim 14 wherein said estero
peratures above its melting point to produce a interchange catalyst comprises an alkali metal
high polymer, removing by distillation the poly together with another metal.
methylene glycol which is liberated, and continu JOHN REX, WHNFIELD,
ing the heating until a stage is reached where JAMES TENNANT OICKSON.
filaments formed from the melt possess the prop
erty of cold drawing. REFERENCES CTED
10. The process of claim 9 followed by the steps The following references are of record in the
of forming the product into filaments and cold file of this patent:
drawings said filaments. (0
11. The process of claim 9 wherein the heating UNITED STATES PATENTS
step is conducted in the presence of a polymeriz Number Name Date
ing catalyst. 2,071,250 Carothers ---------- Feb. 16, 1937
12. In the manufacture of highly polymeric 2,249,950 Fuller -------------- July 22, 1941
materials which are capable of being formed into 45 2,282,827 Rothrock ---------- May 12, 1942
filaments having cold drawing properties, the 2,312,879 Christ -------------- Mar. 2, 1943
process which comprises heating and reacting 2,437,046 Rothrocket al. ------- Mar. 2, 1948
an alkyl ester of terephthalic acid having 1-7
carbon atoms in the alkyl group with an excess FOREIGN PATENTS
of a polymethylene glycol having from 2 to 10 50 Number Country Date
carbon atoms, under conditions producing ester 414,665 Great Britain -------- Aug. 7, 1934
interchange and the formation of the correspond
ing glycol terephthalate, then further heating OTHER REFERENCES
said glycol terephthalate at temperatures above Carothers: Collected Papers (1940), pages
its melting point to produce a high polymer, re- 55 26-27, 156-164.