US Patent 2602075: Production of thermoplastic resins and the production from such resins of threads, fibres, filaments, and the like

Patented July 1, 1952

2,602,07

UNITED

STATES PATENT
2,602,075
PtODUCTION OF THEI{MOPLASTIC I{ESINS
AND THE PRODUCTION FROVI SUCH RES-
INS OF THREADS, FIBRES, FILAVIENTS,
AND THE LIKE
Albert Snley Crpener Suton Coldfield, Bir-
mnghrn, nglnd, Frnk Reeder, Klly,
Swnse, Wle, nd Eric R. Wllsgrove, Cov-
entry, Engliml, ssgnors o Courulds Lim-
iel, Lonlon, Engliml,  Brish cornpny
No Drwing. Application Novernber 1, 1949, Se-
rial No. 124,944. In Gre Britin November
26 1948

12 Clims.
1
This invention relates fo the production of
therm_oplastic resins and fo the production from
such resins of threads, fibres, filaments, monofils
and the like, hereinafter generally referred fo as
"threads."
it is ki,own fo produce thermosetting synthetic
resins by condensing phenols with glycerine or
glycerine derivatives. Thus United States patent
specification No. 1,642,078 describes the produc-
tion of insoluble and infus}ble resins suitable as
shellc substitutes by heating a phenol with glyc-
erine or with a derivative of glycerine such as epi-
chlorhydrin, in the presence of small quantities
of a catatyst, which may be acidic or basic, fo
fore an initial condensation product and thon
condensing this product with a hardening agent
such as hexamethylene tetramine.
If is also known fo react phenols, which may
be monohydric er dihydric, with epichlorhydrin
in a]ka!ine solutionin order o produce a deriva «
tire which can thon be used for forming thermo-
sefting resins. For example in British specifica«
tion No. 518,057 it bas been proposed to forrn
thermosettin resins by condensing an ethylene
oxide-phenol derivative (obtained by reacting
phenol with epichlorhydrin in alkaline solution)
with the aïdaydride of an acid which is at least
dibasic, and in British spécification No. 579,698
if bas been proposed fo form thermosetting resins
by polymerising products containing at least two
ethylene-oxide groups and which are obtained
the fonction of the phenolic hydroxyl groups of
a dihydric phenol with epichlorhydrin or. alpha
di-chlorhydrin in the presence of alkalfl
In the leceuil des TTavaux Chimique de Pays
Bas, vol. 67 (1948), pages 438. fo 441, E. G. G.
Werner .and E. Farenhorst bave described the
production of aromatic bis-glycidyl ethers.by
acting a phenol such as hydroquinone or resor-
cinol with an excess of epichlorhydrin in the pres-
once of alkali; itis stated that in the presence of
excess alkali, high molecular polycondensäte
products may be f0rmed and also that the aro-
matic bis-lycidyl ether obtained from hydroqni-
none polymerises in the presence of sodium
droxide fo form an infusible, insoluble produc.
If bas been disclosed, for example in Jouïaal
de Pharmacie et de Chimie, volume 18 (1933),
page 189 and in British patent specification No.
420,078, that equimolecular proportions of epi-
chlorhydrin, pyrocatechol and caustic potash con-
dense with rin c!osure on bing heated ogether
in a stream of nitrogen fo form 5-(hydr0xy-
methyl)-2,3-benzodioxne 1,4.
The object of the present invention is fo pro-

OFFICE

(CI. 260--47)
2
duce therm0plstic resinons products which aïe
in general suitable for the production of threads,
particularly threads capable of being cold drawn.
In accordance with the present invention, a
5 process for the production of thermoplstic res-
ins comprises condensing by heating, substan-
tially equimolecular proportions of epichlorhydrin
and af least one aromatic dihydroxy compound
in which the hydroxy groups are phenolic and
10' the carbon: atoms linked to the hydroxyl groups
are separated by af least one other crbon atom,
together with a quantity of an alkali such that
the ratio of the numer of molecules of alkali
fo the number of molecules of the dihydroxy
15 compound is at least 1.0, the heting being con-
tinued until a fibre.-forming çesinous product is
0btained.
In accordancs with one modification of the
invention, thermoplastic resins are obtained from
20 substantially equimolecular proportions of an aro-
matic dihydroxy compound as defined and epi-
chlorhydïin, togeçher with a uantity of an alkali
such that th raf.io of the number of molecules
of alkali fo the number of molecules of the di-
2 hydroxy compound is ai least 1.0, by a two-stage
process in which the epichlorhydrin is first re-
acted.with from 50 fo 100 per cent of the dihy-
droxy compgund and the product obtained is then
heated with the alkaIi and any remaining dihy-
0 drçxy compound, until a fibre-forming resinous
pr0duct is ohtaned..
In accordance with a further modification of
the iAenien, thermoplastic resins are obtained
from substantial!y equimolecular pEoportions of
5 an aromatic dihydroxy compound as defined and
epich]orhydrin, together with a quntity of an
alkali such that the ratiD of the number of mole-
cules of a]kali fo the nurnber of molecules of the
dihydroxy compound is af least 1.0, by  two-
40 stage process in which one mol of the dihydroxy
componnd .is first reacted with two mols of epi- •
chlorhydrin and the alkali fo form an aromatic
bis-glycidyl ether and thon the aromatic bis-
glycidyl ether is heated with a further mol Of a
45 dihydroxy componnd as defined together with a
small proportion of an alkali catalyst, the heat-
ing being contined untfl a resinous fibre-form-
ing prodct is obtained. The aromatic bis-glycidyl
ethers prepared in the first stage of this re-
50 action may be ruade substantially as described
by E. G.. . Werner and. E. Farenhorst in the
pape" eferred o above; this paper states that
the aroms, tic bis-glycidyl ether obtined from
hydroquinone is olymerised in the presence of
55 sodium hydroxide to form an infusible, insoluble

2,609,075

product. When carrying out the second stage of
the process according fo the present invention
it is preferred to prevent as far as possible the
Ïormation oÏ infusible resins Ïor example by add-
ing the bis-glycidyl ether gradually to the mix-
ture of the dihydroxy compound and the catalyst.
Alternatively, the second-stage reactants may be
melted together in the absence of solvents or dil-
uents. The bis-glycidyl ether may be added
gradually to the mixture of the dihydroxy com-
pound and the catalyst in the f0Tn Of a solution
or suspension, for example in ethanoL
The two-stage process according fo the in-
vention involving the formation of an aromatic
bis-glycidyl ether as an intermediary, may be
employed Ïor producing copolymeric resins by
using in the second stage a different dihydroxy
compound from that used in the flrst stage to
produce the aromatic bis-glycidyl ether.
The single stage and two-stage processes ac-
cording fo the invention may be effected in the
presence of water, aqueous alcohol, aqueous di-
oxane or other suitable diluent. Itis preferred
fo carry out the condensation hile the reac-
tion mixture is stirred at high speed so that the
polymer is precipitated in the form oï a fine
powder which can be readily separated, washed
and dried.
The process according to the invention may
also be effected by heating the three reactants
together in the presence of a diluent untfl a
low molecular-weight polymer is precipitated,
separating this polymer and completing the con-
densation by heating the low molecular weight
potymer in the molten state for example at tem-
peratures of 200 ° centigrade or higher.
Examples of aromatic dihydroxy compounds
for use in the present invention are resorcinol,
hydroquinone, 3,3' and 4,4' dihydroxy diphenyls,
dihydroxy diphenoxy ethanes, dihydroxy di-
phenyl methanes and diphenylol propanes, and
1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 2:6 and 2:7 dihydroxy
naphthalenes. Mixtures of aromatic dihydroxy
compounds may also be used, the quantities used
being such that the total number of phenolic
hydroxyl groups is substantially equal to twice
the number of molecules of epichlorhydrin.
The dihydroxy compounds may also contain sub-
stituent gr0ups which are inert to the other re-
actants, examptes of such groups being halogen
at.oms, alkyl groups and alkoxy groups. The
compounds should be free from groups such as
amine or carboxyl groups which are reactive to-
wards epichlorhydrin. Itis also unnecessary fo
employ reactants of a particularly high degree
of purity and in many cases commercial grades,
for example of epichlorhydrin, may be used suc-
cessïully in carrying out the invention. Dihy-
ch'oxy compounds such as catechol or 1,2 dihy-
droxy naphthalene in which the OH groups are
on adjacent carbon atoms condense by ring clo-
sure when reacted according fo the invention
and do hot produce thermoplastic flbre-forming
poIymers.
The alkali is preferably caustic soda or caus-
tic potash. The ratio of the number of mole-
cules of alkali fo the number of molecules of
the aromatic dihydroxy compound is in the
range of ïrom 1.0 to 1.1. The actual propor-
tion of alkati used in a single stage process in
the presence oï a diluent has a marked influence
on the intrinsic viscosity of the product, the
higher the proportion of alkali, the higher the
intrinsic viscosity. This effect is shown by the
foLlowing table of results which were obtained

4
by condensing i mol of hydroquinone and 1 mol
of epichlorhydrin for 6 hours under a reflux con-
denser in aqueous alcohol (2 volumes of alcohol
fo 1 volume of water) with various initial quart-
5 tities of caustic soda:

10

]volecules of caustic
soda per molccule of
hydroquinone

1.015
1.035
1. O55
1. 075
I. 095

15

Intrinslc vlscosity of]
product (1 per cent
solution in meta-.
eresol).

.33
.48
.58
• 80

Intrinsic viscosity (i) as referred to in this
speciflcation is deflned as
20 i=log« o
c
where 1 Ls the relative viscosity at 25 ° centi-
grade of a solution having a concentration of c
grains per 100 grains of solution.
25 The single stage process according fo the in-
vention may be effected simply by heating the
three reactants together with the water, aqueous
alcohol or other diluent, under a reflux con-
denser ïor several hours, ïor example, 6 hours;
30 in this case a low molecular weight polymer is
flrst precipitated and then undergoes further
polymerisation on continued heating, the final
resinous product being obtained as a powder.
With this procedure the product is usually con-
35 taminated with alkali metal chloride formed in
the reaction. This salt mey be readfly separated
by boiling the product with water.
The process according fo the invention may
be effected in two stages by first heating the di-
40 hydïoxy compound and the epichlorhydrin,
preîerably in the absence of a diluent, under a
reflux condenser for example for 1 hour, then
adding the alkali, the desired diluent and any
further dihydroxy compound and continuing the
45 heating under reflux until a fibre-forming prod-
uct of the desired molecular weight is obtained.
It is preïerred to inhibit oxidation of the poly-
mer as far as possible during the condensation,
for example by conducting the reaction under
50 an atmosphere of an inert gas such as nitrogen
and/or by adding a small proportion of a reduc-
ing agent such as sodium stannite to the initial
reactants; alternatively a reducing agent may be
formed in situ in the initial reaction mixture.
55 By inhibiting oxidation as described, polymers oï
improved colour are obtained.
In accordance with a further embodiment of
the invention, the epichtorhydrin may be ïormed
in situ by using atpha- or beta-glycerol dichlor-
60 hydrin, or a mixture oï both, with 1 molecular
equivalent of caustic alkali in place of the epi-
chlorhydrin. In this case, the caustic alkali used
fo react with the glycerol dichlorhydrin is addi-
tional to the alkali required to effect the reac-
65 tions according to the invention.
The products obtained according to the in-
vention are in general thermoplastic polymeric
prod.ucts of high molecular weight which can
usually be drawn or melt-spun by standard meth-
70 ods to form threads generally capable of being
cold drawn. When the resinous products are to
be formed into threads by melt-spinning, it is
desirable to prevent as far as possible any fur-
ther polymerization during the heating and spin-
75 ning operations and this may be effected by add-

ing at any convenient stage-of the condensa-
tion a small proportion, for example about !
peï cent, of a monofunctional compound which
will react either with an aromatic hydroxyl
group or with an epoxide ring; examples of such 5
compounds are glycidol and phenol. These com-
pounds are preferably added-to the initial re
actants. Alternatively further polymerisàtion
may be substantially prevented by boiling fhe
product with dilute aqueous hydrochloric acid
or a sirnilar reagent which is capablè-of destr0y-
ing an epoxide ring.
The products marie accoïding fo the inven-
tion are general!y unaffected -by -mineral aCids
and alkalis and are generally insoluble in the ]5
usual organic solvents such as alcohol, acetoie,
benzene and carbon tetrachlor-ide.
The intrinsic viscosities of the bulk of the poly-
meric products can in general be increased by
extracting the polymer with :a liquid which dis- 20
solves lower molecular weight polymers whfle
having no appreciable solvent action on the
higher molecu!ar veight polymers; a suitable
liquid for this purpose is glacial acetic acid.
The intrinsic vicosities of those polymers 25
which have hot been treated .to prevent furfher
polymerisation as described above may be in-
creased by heating the polymers at high tem-
peratures, for example-of the ortier of 200 ° cen-
tigrade, in the absence of air, for example for '30
I to 3 hours.
The polymeric products obtained according to
the invention contain alcoholic hydrox:l groups.
They are therefore capable of reacting with com-
pounds such as acid chlorides, anhydrides 35
acrylonitrile and oxidising agents which are
known to react with such hydroxyl groups. In
particular, the products react with poly-func-
tional compounds capable of reacting With-hy-
droxyl groups to produce cross-lirked polymers. 40
Examples of such poly-functional compounds
are bi-functional compounds such as formalde-
hyde and its polymers, acetone, organic diiso-
cyanates, organic diisothiocyanates, dicarboxylic
acid chlorides, methylene diacetate and dibutyl 45
formal, and trifunctional compounds such as
organic tïiisocyanates. Specific examples of or-
ganic-diisocyanates are 2,4- and 2,6-tolylene diiso-
cynates. The cross-linking reactions are par-
ticularly suitable for increasing the heat-resist- 50
ance of the polymrs; thus threads which are un-
suitab!e for normal textile purposes because they
soften a low temperatures, for example below
100 ° centigrade, can be considerably improved
by treating them with polyfunctional compounds 55
as described. Such treatment also improves the
resistance of the threads fo hot and boiling water.
The treatment with polyfunctional compounds
may be eiïected by immersing the threads in a
bath containing the polyfunctional compound or 60
by possing the threads by means of suitable stor-
age devices such as reeis or rollers through a
bath containing the polyfunctional compound.
A catalyst may be added to the bath if desired and
the bath may also be-heated. The bath may also 6
contain a swelling agent for the threads.
The invention is illustrated by the following
examples in which the parts are by weight unless
otherwise stated. In all examples the alcohol
used was industrial spirit (64 overproof). 70
Example 1
A.mixture of 1!0 parts of hydroquinone and 185
parts of epichlorhydrin was boiled for 30 min-
utes under a reflux condenser. A solution of.ll0 .75

parts of hdroqunone in800 parts.of alCohol and
a solution consisting of 80 parts-of caustiC soda
in 500 parts of water were then 'added and the
resultant mixture was heated under reflux for
3/2 hours. The precipitate which formed Wïs
filtered off, washed with water and dried at bom
temperature in a vacuumdesiccator.
The Product, on heating, began fo soften af
about 100 ° centigrade and was m01ten at I20 °
centigrade; at this temperatUre it was drawn hto
threads Which were capáSle of being coll drawn
at least 100 per cent. A thread of denier 9 had a
dry tenacity of 0.8 and an extensibility of 35
per cor/t. The iintrinsc viscosi-ty of the product
measured as a P..per cent s61ution in metacresol
was 0.2.
Example 2
000 parts of hydroquinone an 185 .parts of
epichlorhydrin wererefluxed together for 1 hour
and thon co01ed. A .solution of 110 parts of hy-
droquinone-in 800 paoEs .of alcohol and asolution
of 80 parts of caustic-soda in 500 parts of water
were added fo the cooled reaction pr0duct and
the mixture was heated for 3 hours under a $efiux
condenser. The precipitated product was filtered
off, xzashed with bofling water till free from
sodium chloride, and then dried in  vacuum
desiccator.
A 1 per cent solution 'of the pr0duct in meta
cresol had an intrinSic visc0sity of 0.30. The
product me!ted af 143 ° fo 146 ° centigrade andin
the molten state was readily drawn out into
threads capable of being cold drawn at least 100
per cent.
Eïplë 3
The-procedure descr.ibed ïn Example 1 was .re-
peated but in this case resorcinol was .used in
place ofthe hydroquinone.
A reddish brown resin was obtained which
softened ai about 55 ° centigrade; on stretching,
the product had a copper-coloured lustre.
E xa rple 4
110 parts oï hydrOquinone dissolved in 800
parts oï alcohol, 92.5 parts Oï epichlorhydrin and
40 parts Oï Custic sda dissolved in 250 parts
water were mixed together and the mixture was
heated for 5 hours under a reflux condensèr.
The material which had separated was thon
boiled with N/100 hydrochloric acid and fhe
resinous product was powdered and dried.
The product was a buff-coloured resin soften-
ing at bout 138°to 142 ° centigrade;-above these
temperatures, it was drawn into fibres capable of
being cold drawn but to a lesser extent than the
product of Example 1. Its intrinsic viscosity,
measured as a 1 per cent solution in meta-cresol,
was 0.26.
Example 5
110 parts of hydroquinone and 92.5 parts of
epichlorhydrin were refluxed together and the
temperature indicated by a thermometer, the
bulb of which was immersed in the vapour, was
noted from rime forime. The temperature re-
mairïed constant ai 115 ° centigrade (the boiling
point of epichlorhydrin) until, after about 100
minutes' heating, if began fo fise sharply. Ai
this stage heating was stopped and, when the
mixture was sfficiently cool the contents of the
flask were dissolved in 400 parts of alcohol.
ttegting under reflux was thon resumed and
solution of 40 parts of caustic soda in 250 parts
of water was added over 25 minutes .down the
condenser. I-Ieating was continued for 3 hours

9609075

7
and the polymeric product which separated was
removed, washed severaI rimes by boiling with
water, and dried by vacuum desiccation af room
temperature. The final product, which was
similar to that of Example 1 had an intrinsic 5
viscosity of 0.23.
ExampIe 6
A product consisting oï the mixed stereoisomers
of l:4-bis(2:3 epoxypropoxy) benzene, (other-
wise known as hydroquinone bis-gIycidyI ether) lo
melting point 105 ° to 109 ° centigrade, was made
by the method oï Werner and Farenhorst reïerred
to above. A suspension o£ 12 parts oï this product
in 28 parts of ethanoI was added slowly and con-
tinuously over one hour, fo a solution of 6 parts of ] 5
hydroquinone and 0.25 part of caustic soda in
28 parts of ethanol and 1 part of water, the solu-
tion being boiled continuously under a reflux
condenser. When the addition was completed,
refluxing was continued for a further 3 hours. 20
The ethanol was then distilled off using a steam
bath, and the residue was washed with water,
dried in an oven at 110 ° centigrade, ground to a
coarse powder and fina]ly dried in a vacuum over
phosphorus pentoxide. The product melted at
140 ° centigrade and had intrinsic viscosities of
0.23 and 0.22 in 1 per cent solutions in morpholine
and m-cresol respectively. It drew out into
fibres at 140 ° fo 150 ° centigrade and the fibres
were capable of being cold drawn about 50 per
cent.
Example 7
The product obtained as desciibed in Example
4 was extracted in a Soxhlet ïor I hour with
glaciaI acetic acid. This treatment removed
lower molecular weight polymers with the result
that the intrinsic viscosity oï the main bulk
the polymer measured in a 1 per cent solution in
meta-cresoI was increased from 0.26 to 0.35.
Example 8
A polymer was made substantiaIIy as described
in ExampIe 5 with the only exception that the
heating under leflux in the second stage, after
the eddition of the caustic soda solution, was
carried out for oniy 194 hours. The product was
then heated in an off bath af 200 ° centigrade.
under a slow stream of oxygen-free nitrogen.
Samples were removed at intervals and their 5O
intrinsic viscosities were determined, with the
lowing resuIts:

ttealing tin:e Intrinsic iscosity (1
per cent so]ulion fi
(hous) -cresol)
Nil 0.149
t.0 0.195
1.5 0.209
2. 5 O, 232

55

Example 9
A polymer was oïotained from eplchlorhydrin
and hydroquinone as follows: 3
110 parts of hydroquinone dissolved in 220 parts
of alcohol, 92.5 parts of epich]orhydrin and 43
pasts of caustic soda dissolved in 130 parts of
water were mixed together and the mixbure heat-
ed for 6 hours under a reflux c6ndenser while 7o
stirrin-g vigorously. The precipitated polymer
was filtered off, washed with hot water, bofled for
30 minutes with N hydrochloric acid, washed
again and dried.
The product was melt-spun into threads of ap- 75

8
proximately 30 denier. A sample of the threads
produced was immersed for 90 seconds while un-
der slight tension in a .bath consisting of 25 vol-
umes of a .mixture of 2,4- and 2,6-tolylene di-
isocyanates, 75 volumes of car.bon tetrachloride
and 2 volumes of pyridine, the bath being heated
to .its boiling point. The threads were removed
from the bath, washed with cold carbon tetra-
chloride and dried.
The improved properties of the threads ob-
tained vere demonstrated .by the following tests:
(1) Sarnples of .both treated and untreaed
threads were dropped into ,boiling water. The
untreated threads shrivelled up while the treated
thread were unaffected.
(2) Samples of both treaed and OEmtreated
threads were put into narrow glass tubes which
were then immersed in an off bath, the tempera-
ture of which was then slowly raised. The un-
treated threads softened at about 5 ° centigrade
where as the treated threads retained theh" fl-
,brous structure even at 280 ° centigrade.
Example 10
The polymer fro*m hydroquinone and epichlor-
hydrin produced as described in Example 9 was
melt spun in'me threads of approxim«tely 20 de-
nier which were wound on to bobbins. One bobbin
was immersed for 3 hours in a .bath at 25 ° centi-
grade consisting of I volume of sebacyl chloride,
3 volumes of acetone and 9 volumes of carbon
tetrachloride. The resultant thread was resist-
ant to the action of boiling water and remained
coherent when head to 250 ° centigrade. The
thread had an extensibility suitable for textile
purposes and could `be stretched .when hot.
Example 11
A bobbin o'f 20 denier thread produced as de-
scribed in Example 10 was immersed for 18 hours
in a water-free solution at 25 ° centigrade consist-
ing of 10 volumes of acetone, 10 volumes of car-
bon tetrachloride and 0.1 volume of boron tri-
fiuoride etherate. The resultant thread was
herent at 250 ° centigrade.
A similar improvement in heat resistance was
obtained `by immersing the thread for 18 hours
at 25 ° centigrade in a 10 per cent solution of
methylene diacetate in a mixture of ethyl ace-
tare and caçbon tetrachloride containing 1 per
cent of boron trifiuoride etherate.
Example 12
A mixture of 328. parts of hydroquinone and
618 parts of industriaI alcohol were refiuxed on
a water oath for 15 minutes while stirring rapid-
Iy and a stream of oxygen-free nitrogen was
passed through the apparatus fo sweep out
mospheric oxygen. A solution of 126.1 parts of
caustic soda in 30 parts of wateï was then added
and refluxing continued, with stirring, for 10 min-
utes. With the water ,bath at ï0 ° centigrade,
26.6 parts of ePichlorhydrin were added at such
a rate that the reaction mixtm'e refluxed rapidly,
this operation taking about 15 minutes. The
temperature of the .bath was then raised fo 90 °
centigrade and the mixture was refiuxed for 6
hours,the rapid stirring being continued through-
ou.
The product, which was precipiçated as a finely-
divided white powder, was filtered off, washed
with hot distflled water, bofled with N/2 l,dro-
chIoric acid for ½ hour to destroy any epoxide
rings present, filtered, boiled wiih distiIled water
and filtered again; the product .was then dried,

firs at 110 ° centigrade in an air oven and flnal!y
in a vacuum desiccator.
The dried product was a white crystalline pow-
der, rnelting point 145 ° to 150 ° cen%igrade and
intrinsic viscosity, measured on a 1 per cent solu-
tion in meta-cresol, 0.43: It was readily rnelt
spun fo form threads capable of being cold drawn.
Example 13
A mixture, of 325.4 parts of hych-oqtùnone, 5.64
parts of phenol and 613 parts of alcohol was re-
fluxed on a water bath for 15 minutes while stir-
ring iapidly and passing oxygen-free nitrogen
through the apparatus to sweep out atmospheric
oxygen. The mixture was then treated with 126.1
parts of caustic soda and 276.6 parts of epichlor-
hydrin as described in Example 12.
The product, which was precipitated as a fine-
ly divided white powder, was isolated as described
in Example 12. The phenol added to the initial
reactants served to reduce or prevent polymerisa-
tion of the product during melt spinning.
The dried product was a white crystalline pow-
der with an intrinsic viscosity as a 1 per cent
solution in meta-cresol of 0.39. It was readily
melt-spun to form threads capable of being cold
drawn.
Example lg
A mixture of 321.6 parts of hydroquinone, 2.77
parts of phenol, 1 part of- stannous chloride di-
hydrate (SnC122H20) dissolved in 5 parts of
water, and 626 parts of alcohol were refluxed to-
gerber on a water bath, treated with 126.1 parts
of caustic soda and 271.3 parts of epichlorhydrin
as described in Example 12. The product ws
separated as described in Example 12.
The dried product was a white crystalline pow-
der having an intrinsic viscosity of 0.43 measured
on a 1 per cent solution in meta,cresol. It was
readily melt-spun to form threads capable of
being cold drawn.
Example 15
A mixture of 18.5 parts of epichlorhydrin, 22..0
parts of hydroquinone, a solution of 8.76 parts of
caustic soda in a mixture of 27.3 parts of water
and 17.5 parts of alcohol, and 25 parts of alcohol
was heated under reflux on a water bath wih
vigoioui itiiring for 6 hours.
The product, which was precipitated as ,a pale
brown powder, was washed twice by boiling with
distflled water and was dried in an air oven at
110 ° centigrade for 1 hour. The intrinsic viscos-
ity of the dried product,, measured on a 1 pe].
cent solution in meta-cresol, was 0.80.
Exaple 16
The procedure described in Example 15 was
repeated using 13.3 parts of epichlorhydrin in-
stead oî 13.5 parts and refluxing for 6½ hours 6O
instead of for 6 hours. A product similar to that
produced in Exemple 15 was obtained, its
trinsic viscosity also being 0.30.
Eæample 17
65
A mixture of 13.7 parts of epichlorhydrin, 22.0
parts of hydrequinone, a solution of 3.76 parts of
caustic soda in- a mixture Of 27.3 parts of water
and 17.5 pals of alcohol, and 25 parts of alcohol
was heated under reflux on a water bath with 7o
vigorous stirring for 3/2 hours. The product was
separated as described in Example 15; ifs intrin-
sic. viscosity measured as a 1 per cent solution in
meta,resol was 0.75.
In carrYng out the procedure describd in Ex- 7

.10
amples 15, 16 and 17 a considerable quantity of
heat is evolved particularly during the initial
stages of the. reaction and care should therefore
be taken to ensure that the reaction mixture does
 hot bol1 over.
Example 18
22.8 parts of diphenylolpropane
!0 -</---- -<
(Ho
9.25 parts of epichlorhydrir, 24 parts of alcohol
and a solution of 4.40 parts of caustic soda dii-
15 solved in i2.9 parts of water were heated together
under reflux and with stirring on a water bath for.
6 hours. The product was isolated as descrbed
in Example 12. It was a fibre-forming white
powder melting at 160 ° to 165 ° centigrade and
20 having an intrinsic viscosity, as a 1 Per cent solu-
tion in meta-cresol, of 0.43_.
Example. 19
18.6 parts of p,p"-dihydroxy diphenyl, 9.25 parts
2_5 of epichlorhydrin, 4.24 parts of caustic soda dis-
solved in 10.9 parts of water, and 78 parts of dii
oxane were heated under reflux with vigorous
stirring on a steam bath at 100 ° centigrade for
5½ hours.
30 The product, which was precipitated as a pale
yellow powder was iSolated as described in
ample 12. It had an intrinsic viscosity, measured
as a 1 per cent solution in morpholine, of 0.35
and it melted at approximately 300 ° centigrade;
35 threads were drawn from the melt.
Example 20
6.43 parts of epichlorhydrin, 11.7 parts of p,p'-
dihydroxy diphenyl, 0.77 part of hydroquinone,
, 3.02 parts of caustic soda dissolved in 7.3 parts of
water, and 72 parts of dioxane were mixed
gerber and heated under reflux with vigorous
stirring for 6 hours at 100 ° centigrade. The prod-
uct was isolated ag described in Example 12.
45 The product was a pale yellow powder having
an intrinsic viscosity, measured ,as a 1 per cent
solution in morpholine, of 0.29.
Example 21
50 9.25 parts of epichlorhydrin, 12.4 parts of p,p'-
dihydroxy diphenyl, 3.63 parts of hydroquinone,
4.32 parts of caustic soda dissolved in 11.0 parts
of water, and 96 parts of alcohol were heated
gerber under reflux with rapid stirring for 6
55 hours. The product, isolated as described in
ample 12, had an intrinsic viscosity, measured as
a 1 per cent solution in morpholine, of 0.20.
Example 22
A mixture of 321.6 parts of hydroquinone, 2.77
parts of phenoI, 1 part of stannous chloride di-
hydrate, dissolved in 5 part of water and 460
parts of alcohol was refluxed together on a water
bath for 15 minutes whfie stirring rapidly and
passLug a stream of oxygen-free nitrogen
through the apparatus to sweep out atmospheric
oxygen. A solution of 126.1 parts of caustic soda
disso!ved in 3i0 parts of water were then addd
and refluxing continued, with stirring, for 10
minutes. !99 parts of water were then added
and then 271.3 parts of epichlorhydrin were
added over a period of 15 minutes; the resultant
mixture was refluxed for 6 hours, the rapid stir-
ng being continued throughout.
The product was isolated as described in Ex-

2,602,075
 2
ample 12. if was a whie crystallie powder, The final thread was resistant fo boiling vater
melting point 145 « o 150 ° centigrade, and in- and was coherent at 230 ° centigrade.
tïinsic viscosity, measured on a 1 per cent solu- xampe 27
tion in mea-cresol o 0.51. it was readily melt
spun fo ïorm threads capable o being cold 5 A 130 denier monofil o the epichlorhydrin-
drawn, hydroquinone polymer obtained as described in

Exampte 23
A mixture of 9.3 parts of 4,4'-dihydroxy di-
phenyl, 11.1 parts of hydroquinone bis-glycidyl 10
ether and a trace of solid sodium carbonate were
heated for 3 hours at 240 ° to 260 ° centigrade in
a stream of oxygen-free nitrogen.
The product obtained was fibre-forming, had
a melting point of approximately 190 ° centi-
grade and an intrinsic viscosity, measured as a
1 per cent solution in meta cresol of 0.25.
Example 24
A mixture of 18.5 parts of epichlorhydrin, 22.0
parts of hydroquinone and a solution of 8.28
parts of caustic soda in 26.3 parts of water and
17 parts of alcohol was heated under reflux for
6 hours while stirring vîgorously. The product
was washed with boiling distilled water for /e 5
hour and dried, its intrinsic viscosity, meas-
ured as a 1 per cent solution in meta-cresol, was
.0.43.
The product was then heated to 200 ° centi-
grade in the absence of oxygen for 1/4 hours.
3O
The intrinsic viscosity of the product was there-
by raised to 0.55. it was readily milt spun to
form threads capable of being cold drawn.
If the original product is first stabilised by
boiling for 1 hour in N/5 hydrochloric acid, the
heat-treatment described only raises the intrin-
sic viscosity to 0.45.
Exampte 25
The hydroquinoni-epichlorhydrin polymeric 40
product obtained as described in Example 22 was
melt-spun to form a 6 filament, 30 denier per
filament thread and the thread was loassed
through a bath at 65 ° centigrade consisting of
57.5 volumes of a mixture of 2:4 and 2:6 tolylene .5
dfisocyanates, 155 volumes of xylene and 17.5
volumes of pyridine. The thread was stretched
80 per cent during its passage through the .bath.
The immersion rime in the bath was approxi-
mately 1 minute. The thread was thon washed 50
in carbon tetrach]oride and dried. The resulting
thread remained coherent af 250 ° centigrade and
was substantial]y unaffected by boiling water.
A similar effect was obtained using the saine
bath at 70 ° centigrade and washing 2th a mix-
ture of 4 volumes of carbon tetrachloridœe and 1
volume of alcohol.
ExampZe 26
The hydroquinone-epichlorhydrin polymer ob-
tained as describid in Exampli 22 was melt spun
fo form a 14 filament, 30 denier per filament
thread. The thread was passed through a bath
af 74 ° centigrade containing I volume of a mLx-
ture of 2:4 and 2:6 tolylene diisocyanates and
4 volumes of xylene; the immersion rime was 50
seconds and a stretch of 80 per cent was imposed
in the bath. T1]e thread was thon passed
through a second bath af 86 ° centigrade contain-
ing 57.5 volumes of a mixture of 2:4 and 2:6
tolylene diisocyanates, 155 volumes of xylene and
17.5 volumes of pyridine; the immersion time
was 50 seconds and a stretch of 5 per cent was
imposed in the bath. The thread was thon
washed with carbon titrachloride and dried.

Example 12 was immersed at 20 ° centigrade for
30 seconds in a bath consisting of equal volumes
of a mixture of 2:4 and 2:6 tolylene dfisocya-
nates, pyridine and carbon tetrachloride..The
monofil was thon washed in carbon tetrachloride
and dried. The final monofil was coherent at
temperatures abve 250 ° centigrade.
Example 28
1 22.2 parts of hydroquinone bis-glycidyl ether,
16 parts of 1:5 dihydroxynaphthalene and 0.08
part of sodium carbonate were heated together
at 200 ° centigrade for 2 hours. The product was
a fibre-forming polymer melting at 110 ° centi-
20 grade, approximate]y.
Exarnple 29
A mixture of 327.3 parts of resorcinol, 2.ï7
parts of phenol, 1 part of stannous chloride' dt-
hydrate dissolved in 5 parts of water, and 626
parts of alcohol were refiuxed together on a
water bath and thon treated with 126.8 parts
of caustic soda dissolved in 370 parts of water
and 273.8 parts of epichlorhydrin as described in
Example 12. The product was separated as de-
scribed in Example 12.
. The product was a white fibre-forming solid
melting.at 50 ° to 62 °centigrade.
What we c]aim is:
1. A process for the production of thermop]as-
tic fibir-forming resins which comprises con-
densing equimolecular proportions of epichloï-
hydrin and at least one aromatic dihydroxy com-
pound in which the hydroxyl groups are pheno]ic
and the carbon atoms linked to the hydroxy]
groups are sepa.rated by at least one other car-
bon atom, the said compound being otherwise
free from groups which are reactive towards epi-
chlorhydrin, together with a quantity of an alkali,
such that the ratio of the number of molecules
oî the alkali fo the ioEumber of molecules oî the
dihydroxy compound is within the range of 1.0
to 1.1, and heating until a fiber-ïorming resinods
condensation product is ormed.
2. A process as ciaimed in claire 1 wherein the
aromatic dihydroxycompound used is hydro-
quinone.
3. A pïocess as claimed fioE claire 1 wherein the
reaction is carried ut ïor ai least part of the
55 heating rime in the presence of a diluent.
4. A process as claimed in claire 3 wherein the
heating is caried out in the presence of a diluent
until a low molecular weight polymer is precipi-
tated, the low molecular weight polymer is sepa-
60 rated and the condensation completed by heating
the low molecular weight polymer in the molten
condition.
5. A process for the production of thermoplas-
tic fiber-forming resh]s which comprises con-
65 densing equimolecular proportioï]s of epich]orhy-
drin and af least one aromatic dihydroxy com-
pound in which the hydroxyl groups are pheno]ic
and the carbon atoms linked to the hydroxyl
groups are separated by at least one other car-
70 bon atom the said ccmpound being otherwise
free from groups which are reactive towards epi-
chlorhydrin, together witt] a quantity of an alka]i
such that the ratio of the number of molecules
of the alka]i fo the number of mo]ecules of the
75 .d.hydroxy compound is within tl]e range of 1.0

9,609075

13
to 1.1 in two stages comprising first reacting the
epichlorhydrin with from 50 to 100 per cent of
the aromatic dihydroxy compound and then
heating the product so obtained with the alkali
and from 50 to 0 per cent of the aromatic dihy-
droxy compound until a fiber-forming resinous
product is obtained.
6. A process as claimed in claire 5 wherein the
first stage oï the condensation is carried out by
heating the epichlorhydrin and the aromatic
hydroxy compound together in the absence of a
diluent and the second stage of the condensation
is carried out in the prescnce of a diluent.
7 A proccss as claimed in claire 5 wherein thc
aromatic dihydroxy compound used is hydro-
quinone.
8. A process for the production of thermoplas-
tic fiber-forming resins which comprises con-
densing equimolecular proportions of epichlor-
hydrin and at least one aromatic dihydroxy com-
pound in which the hydroxyl groups are phenolic
and the carbon atoms linked to the hydroxyl
grouPs are separated by at least one other car-
bon atom, the said compound being otherwise
free from groups which are reactive towards epi-
chlorhydrin, together with a quantity of an al-
kali, such that the ratio of the number of mole-
cules of the alkali to the number of molecules
of the dihydroxy compound is within the range of
1.0 to 1.1, in two stages comprising first reacting
two molecular proportions of epichlorhydrin with
one molecular proportion of the dihydroxy com-
pound to form an aromatic bis-glycidyl ether and
then heating the aromatic bis-glycidyl ether with
a further molecular proportion of a dihydroxy

30 Number
2,060,715
2,500,600
2,500,765
2,504,518
35

i4
compound as defined, together with a small pro-
portion of an alkali catalyst, until a fiber-form-
ing resinous product is obtained.
9. A process as claimed in claim 8 wherein the
5 second stage of the reaction is effected in the
presence of a diluent, the bis-glycidyl ether and
the .diluent being added gradually to a mixture
of the dihydroxy compound and the catalyst.
10. A process as claimed in claim 8 wherein
10 the second stage of the reaction is effected by
heating the bis-glycidyl ether, the catalyst and
the dihydroxy compound together in a molten
condition until a fibre-forming product is ob-
tained.
15 11. A process as claimed in claire 8 wherein
different dihydroxy compounds are used in the
two stages of the reaction.
12. A process as claimed in claire 8 wherein the
aromatic dihydroxy compound used is hydro-
20 quinone.
A. STANLEOE C_IPENTE1R.
IANK 1REEDE1R.
E. 1R. WALLSGtOVE.
25 REFERENCES CITED
The following references are of record in the
file of this patent:
UNITED STATES PATENTS
Naine Date
Arvin ............. Nov. I0, 1936
Bradley ........... Mat. 14, 1950
Montague .......... Mat. 14, 1950
Greenlee ........... Apr. 18, 1950