Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
-"- 10 ~2~7~ 7
B~CKUROUND OF ~HE I~VENTION
A cla~ Or polyeaters having certa~n adVantaB~
orer polyethglene tsrephthalato 18 dlsclosed ln ~erman OS
2,520,819 (Schasrgen). mese polye~tora exhlblt optlcal
ani~otropy ln the molton atate and can be ~elt ~pun lnto
~ibers ~hich on heat treatment by tochniques dlsclo~ed
in Germ~n OS 2,520,820 (L*lae) increa~e in tenaclt~. ~uch
heat treated polyester nber~ are sugge-ted ror u~e in tlre
cord~ and ln other industrial nd con~umer products where
the hlgh atrength permit~ uae Or less yarn ~ith lt~
attendant economlc and other adv~nt~ges. In ~uch end-use
appllcatlons, partlcularly ln truck tires, except~onally
high temperatures, e.g. ln excess o~ 150C, mag be
encountered. Thererore it 18 important that the yarn oi
the cord be Or high atrength at roo~ te~peratur and also
possess high strength at such elevated temperature~. ~arn~
irom polyesters of the pre~ent lnvent~on satlsry this
requlrement.
SU~MARY OF THE INVE~TIO~
mis lnventlon provides norel polyesters Or rlber-
~ormlng molecular ~eight cond stlng ossentlally Or recurring
unit~ o~ the ~ollo~ing ~ormula~:
I ~ II
- ~ - and -C ~ C-
and or rrom O to lO mol % (based on total mols Or unlt~) of
other aromatlc or c~cloallph~tic polyoster-~ormln~ units,
as ~ell as ~ibers, rllms and molded artlcle~ thereo~.
A
..
,.. - .. . . . . ............................. ~ .
. ... . .. ... .. . . ~ . .
10~9274~
The fiber-rormlng polyesters are optically aniso-
tropic in the melt, are melt splnnable and exhlblt an
lnherent vlscosity o~ at least 0.7, measured as descrlbed
herelna~ter. The flbers rormed therefrom may be heat
treated to yield rlbers with tenaclty in excess o~ 18 grams
per denier and a ret~ntion of at least 65Z of such tenacity
at ]50C. DRAWINGS
Figure 1 is a plot of tenacity (grams per denier)
vs. temperature ~C) for yarn Or a polyester Or the lnven-
tion (Curve A) and ~or yarn Or two controls, namely the
polymers of Examples 2 and 3, Curves B and C, respectively.
The control polymers are mentioned ln German OS 2,520,~19.
Flgure 2 is a plot of tenaclty retentlon (%) vs. temperature
(C) ~or the same set of polymers.
DETAILED DESCRIPTION OF THE INVENTION
The polyesters of the lnvention may be prepared,
spun and the ~ibers heat treated to increase tenaclty by
the general procedures shown in German OS 2,520,819 and
2,520,~20 and specl~ically illustrated ln Examples 1 and
4-~ hereln.
The novel polyesters are prepared ~rom phenylhydro
qulnone and terephthalic acid or their functlonally
equlvalent derlvatlves. If comonomer reactantY are to be
employed, they too may be added as their functlonally equlvalent
~ derlvatlves. Among such comonomers may be mentloned resorcinol,
`~ isophthalic acld, hydroqulnone, p-hydroxybenzoic acld, and
4,4'-dlhydroxybiphenyl which provide the ~ollowlng repeatlng
unlt~, respectively:
' ' O O
-0 ~ , -C ~ , -0- ~ 0- , -0 ~ C- and
O C~= o
... . .
.' ' ' ~ ~
tog2747
-o~o-
Mlxtures Or comonomers, such as hydroqulnone and resorclnol
may also be used. The presence Or comonomer unlts depresses
the meltlng point as would be expected and may asslst ln melt-
splnning processlng. In some lnstances additlonal advantages
are obtalned such as rllament abraslon reslstance, fllament
adheslon to rubber, etc. The fibers Or the lnventlon that
are made from a homopolymer are Or partlcular economlc
advantage over a copolymer since rewer reactants are requlred
to make the homopolymer.
The term "conslstlng essentially or" ls intended
to have lts customary meanlng: namely, that all speclfled
` materlals and condltions are very lmportant in practlclng
the lnvention but that unspeclrled materials and condltions
are not excluded so long as they do not prevent the benePlts
of the inventlon from belng realized.
Melt polymerization, preferably under anhydrous
~ condltions ln an lnert atmosphere, is used for the polymer
synthesls. Generally, polymerization is contlnued untll the
polyester has a molecular weight sufficlent for flber
formatlon. Inherent vlscosities Or at least 0.7, measured
as described hereinafter, are userul for preparatlon of
shaped articles.
~, The novel polyesters exhiblt optlcal anisotropy
ln the molten state as determlned by the technlque shown in
German OS 2,520,~19. The polyesters have excellent thermal
stability in the molten state and may be readily formed into
flbers, films, bars or other shaped ob~ects. While withln the
scope Or but not speclflcally mentloned ln the aforementloned
~30 German OS 2,520,819 and OS 2,520,820, the heat treated
`
. ~ . .
10927~7
lbers Or this lnventlon are unusual in that they possess
both hlgh strength and excellent strength retentlon at 150C.
The novel heat treated polyester flbers of the lnven-
tlon have tenacitles in excess of 18 grams per denler and
retaln at least 65%, more preferably at lea~t 70% of such
tenaclty at 150C. Bars Or the polymers Or the lnventlon
exhlblt high torsion modulus at elevated temperatures and
hlgh heat deflectlon temperatures (heat deflectlon tempera-
tures measured by A.S.T.M. D648 at 264 p81 on a slngle
ln~ectlon molded bar.)
Retentlon Or tenaclty and modulus ln rlbers at
elevated temperatures ln the range Or 100-200C 18 lmportant
in a number Or relnforclng appllcatlons, e.g., ln tlres
[R.E. Wllfong and J. Zlmmerman, J. ApplledPolymer Scl., 17,
? 2039-2051 (1973)], where heat bulldup and hlgh operatlng
temperatures to 150C are frequently encountered, partlcularly
ln truck tlres, [F. S. Conant, Rubber Chem. and Technology,
44, 397-439 (1971) and P. Kalnradl, G. Kaufmann and F. Schmldt,
Kautschuk and Gumml-Kunststoffe 19, 27-36 (1966) ] and ln such
2~ other appllcatlons as clutch faclngs, brake llnlngs, conveyor
belt reinforcement ln glass manufacture, ropes and cables ln
sucker rods for oll well use. It ls also lmportant that the
flbers possess hlgh tenaclty at elevated temperature~ slnce
~l` yarn tenacity determlnes the amount of yarn needed rOr the
~` truck tlres or for relnforce~ent ln other hlgh temperature
appllcatlons. The heat treated flbers of thls lnventlon are
~ partlcularly useful for these purposes slnce they have a hlgh
`~ retentlon of tenslle properties at elevated temperatures a~
well as hlgh absolute tensile values at elevated temperatures.
, 30 It should be recognized that fllaments Or lower
.
-- 5 --
. , .
'V
,~ , ,
.' ' , ,, ' , ,:
~0'3 '~47
strength than demonstrated hereln have been obtalned. It i8
belleved that care~ul and thorough mlxlng o~ reactants durlng
polymerlzation ls at least partly responslble for the hlgher
propertles. Proportlons and ldentlty of the comonomer may
also effect the propertles. Other ractors may be purlty Or
lngredlents and the partlcular heat treatment condltlons
selected.
Preparatlon of Shaped Artlcles
For flber preparation, the molten polymer mass,
obtalned elther directly from the melt polymerizatlon of
the polymer-forming lngredlents or vla the meltlng of polymer,
ls processed, e.g., through a melt splnning unit and extruded
through a spinneret into a quenchlng atmosphere (e.g., air
~ malntalned at room temperature) and wound up.
r Flbers may be melt spun in a conventlonal fashlon
,. . . .
from single or multi-hole spinnerets. In the melt spinnlng
cell, the melt zone temperature can be ln the range Or
from about 310C to about 370C,dependlng on the sample.
Higher temperatures are used for samples exhibiting hlgher
2~ lnherent vlscosltles or hlgher flow temperatures. Slml-
larly, spinneret temperatures can be in the range o~ from
about 320C to about 375C,depending on the melt zone
temperature and the melt viscosity of the polymer. Filter
packs may ~e employed in the splnneret aæsembly. The as-spun
rlbers may be wound up over a broad range o~ speeds, preferably
from lOO m~mln to 4,500 m/min. The as-spun ribers are oriented,
having orientation angles o~ less than 65, preferably less
than 25, measured as described herein.
Films may be prepared by melt-presslng or melt
~30 extruslon techniques. Exceptionally tough bars may be
:i , .
~ - 6 -
~ . .... . ' ' . ' ' ' . ` ' - ' ' ' '' . '
10~3 ''7~17
prepared by ln~ection moldlng. The relatlvely low vlscosity
Or the melts is an advantage in processing.
When heat treating the yarns, it is often deslrable
to coat them with graphite or other inert materlal to help
prevent contacting fibers from adhering to each other.
Flber samples as skelns or on bobblns may be heated
in an inert atmosphere (e.g., nltrogen) under a variety Or
conditions. Heating is normally conducted ror from about 30
minutes to 4 hours or longer at a maximum temperature
close to but below the filament fusion DOint.
Interfilament fuslon should be avoided so that the yarn~ are
rewindable. It iS preferred that the maximum temperature be
reached in a stepwise or 810w contlnuous fashlon.
When the fiber samples are wound on bobbins, it is
prererred that a soft, yielding surface be present on the
~' bobbin, e.g., a coverlng of Fiberfrax~ (batted ceramlc lnsula-
tlon Or the Carborundum Company). The lnert atmosphere withln
the oven or other heat-treatlne chamber ls changed durlng the
treatlng perlod by causlng a rlow Or the inert gas (e.g.,
~;2~. nltrogen) to enter and to leave the oven at a rate surficient
j to remove by-products from the vlclnlty Or the flber.
As can be seen from the rigures, the heat treated
flber Or Example 1 (Curve A) a flber Or the lnvention, has a
tenaclty that ls high, that ls greater at 150~C than that Or
heat treated flbers Or Example 2 (Curve B) or Example 3
(Curve C) and has lost significantly less of lts strength
at the elevated temperatures than have the other flbers.
; Moreover, as shown ln Examples 7 and 8 ~products Or the
lnventlon) the absolute value of tenacity at 150C ls sub-
~30 stantlally higher than that Or the controls, (Ex. 2 and 3).
.''` ~
, .
_ 7 _
,
..; '
lO'~Z747
It lill be noted th~t the rib-r~ Or E~ples 7 and 8 re Or
high~r ton~clty than that Or l~plc 1 ~lo the ~ retent~on
Or ten~,city ha~ remainod at a high level~
Measur~nts
Inher nt Viscoslt~ rent viscodty (~i~h) as
r~portod h roln 18 de~in~d by the rolloldng eq~tion:
l~herdn (~rol) reprosent~ the relati~e vi~co~lty an~l C ropre-
~ont~ a concoatration o~ 0.5 gru- Or the poly~er in 100 ~
or ~ol~nt. Tho relativo vi~coslty (~r-l) is d ten~in ~I b~r s
dividlnt tho r10~ tl ~ in a capi~lary viscoqlleter or a ~lluto
~oluti0n o~ th poly~er by th~ nO~ tim~ rOr the pur- ~ol~ nt
Th~ dilute ~olutions used heroin ror d~termlnlng ~rel) are
the conc-ntratlon e~pres~-a by (C), ~bo~e; r10~ ti~e~ are
det-rEln~ at 30-C3 the ~olvent is 1,1,1,3,3,3-hexarluoroi~o-
pr0panol/chloro~or~ (50/50, vol/~ol)
nd 1~ Proportl-~ Yarn tensile prcp-rti~ aro
~a8Ure~ with an "Instronn* ~niversal T stlng Instrument
;'2 ~20 (In~tron Gorp0ration, C~nton~ ~as~.) providea ~ith an "rnstron"
`3 ~nviron~ental Ch~b-r Sy~tem for t~st~ at a~ovo ~mbl-nt tempera-
tur-. Specim~n~ to b- t-~to~ ar- conditloned at l~a~t one hour
at 70-F an~ 65% r~l~tlv~ h~n~dity Y~rn~ are t~i~ted 3 tu m 8
por inch (or a~ indicated), Z t~i~t, at 0.1 gr~m per denier
ten d on Denl-r~ Den , i8 det-rmined as in U ~. Patent
3,869,429 Th~ ssme yarn ll~nier 1~ us~d ~or anblent and
higher tallper~ture testing to dcter~ine prq~erty rotention
at el~te~ t~qp-~tur~ ~or a giv-n ~ibor. The tlist-d ~ra~
ou~te~ l ith "Ilutron" ~C clu~p8 ~uch that the ~ge l ngth
30 Or ~r~a (dis~;~nce bet~en Ja~) 1- 10.0 + 0.1 inches t25.4 +
.
* de~otes tr~de mark
-- 8 --
-
,B
.~ .
.
, .................................. .. .
....
'747
0.25 cm). Amblent temperature testlng ls made ln the flber
condltionlng envlronment. Hlgher temperature testlng is made
by enclosing yarn and clamps ln the Environmental Chamber
controlled at the deslred temperature. Such speclmens are
held ln the chamber for three minutes before testlng. Testlng
is conducted by elongatlng yarn speclmens to break at a
constant rate Or extenslon of 50% per min. based on the flber
gage length. ~he stress-strain cur~e i8 plotted automatlcally
on the "Instron" recorder and/or the load/elongatlon data are
fed lnto a computer. From these data or the stress-straln
curve, the breaklng tenaclty, T, ls computed as grams per
denler, elongatlon, E, as lncrease ln length at break,
expressed as a percentage of the nominal gage length, and
initial modulus, Mi, as grams per denler from the slope Or
a llne drawn tangent to the lnltlal llnear part of the stress-
straln curve. These terms and thelr calculation are further
deflned ln A.S.T.M. D2101, Part 25, 196~. Average values
computed from two or more breaks are reported.
. Orlentatlon Angle - OA (arc) lndlcate the
orientatlon angle and (2~ speclfic arc) as in U.S. 3,671,542,
and were measured by method (2) therein.
In the examples which follow, the perlods glven
for flber heat treatment lnclude bOth the tlme used to arr$ve
at the lndicated temperature and the time the fiber ls maln-
tained at that temperature.
EXAMPLE 1
~ hls example lllustrates preparation o~ poly(phenyl-
1,4-phenylene terephthalate), i.e. consisting only of
-O- ~ O- and -C i C- units ln substantially
equimolar amounts, and strong fibers thereof. These flbers
_ g _
10'~'7~`7
oxhibit xccptionally hl~h le~ l~ o~ t~uclty retention at
ele~rate~ t~eratu~s.
In a 250~1. three~ck, roun~otto~ ~k eq!~ip~ed
~ith a ~tirrer, nltrogon inlet port, ~ tlll~tion b~, ar~l
a colloction ~el, are pl~co~ 5~.0g(0.2 D~le) Or pl~rl-
l~roguinono dlacetat- an~ 31.6 t (O.l9 molo) Or tercpmh-lic
acld Tho reactlon ~C88~ thrlce e~acuat-~ and p~ th
dry nitrog n The roaction ve-~-l i8 pl~co~ in a W00~8
~otal bath ~t 290-C, ~tlrrlng 1~ bogun an~ a nitrogon ~lo~
10 ~ intainea In about 13 m1~.~ th- first ac tlc a¢ld 1~
collectea T~enty ~inutc~ l~tor tho bath teqp-r~tur~ i8
ralse~ to 300C. A~ter an a~dltlonal 27 min , tho temperature
o~ the bath i8 ralscd to 310C; in another 40 ~in to 320C;
in an~thor 35 ~in. to 340-C Aft-r 23 ~ln more, th nltrogcn
'~ nOY i8 halto~ and the roaction systo~ pl~c~ under ~ cuu~,
all at 340-C. A~tcr 8 dn moro, th pressure i8 reaUCOd to ~!
about 10 D~ Hg. T~ n. later th~ v~c~ 1~ relea-ea ~th
nitrog-n, stlrring i~ st~pp~l ~ th~ ~olt~n pol~r iB allo~ed
to cool un~or nitrogon. Tho ylola i~ 56 g; ninh ~ 1.03.
A plug Or thls poly~or is D~lt ~pml into alr
thro~gh a ~lti~ol ~ eret ~ in~r t holc dlamc*or - 0.023
., ~lt tO~ t~porat~ (llZT) - 3~1-343-C, ~pin~rct
t~raturo - 346C~ th res~ltlng yarn ~u~ p at 457
.hin.
Throe bobbln~ of ya~n ar~ col~ ctea, and aro pl~ed
t-geth-r to r~orDI a y~rn o~ bout 400 denier ~ich cxhibits
3 T/~ 3.4/~.9/448, O.A. ~ 14- (20.3-).
A portlon of the p~iod ~ ~uDd on a Flber-
:~,. Erax0~0~oroa bob~ln (in eXC1~8~ 0~ 0~ lay~r) and hoatod in
a nitroeen-~pt o~ron under the rollo~ ucce~iv~ con~ltio~:
10 -
lB
;
. . . ~ .. .
., ., ~ . .~
7'17
roo~ t~p-rsture - 230C/1.5 hr., 230-275C/1.5 hr., 275~95C/
1.5 hr., 295-312-C/1.5 hr., 312-325-C/12.5 hr. Thc bobbln 1
allo~d to cool and theso yarn properties are ob~er~ d at
roo~ ta~ T/~/~i/Den.: 21.4/3.5/546/371. Portio~a of thi~
ya~ arc testo~ rOr tensile strength retention at elo~t~
t~per~t~s by the proced~ pre~lowl~ describ-d under
~M~suremcnts~ with the rollo~dng ~snlts:
TABI$ I
Br~klag % Rotentlon
10 Te-t Ten~clty Of Or~gl~l
T~erature, C At Te~t T~D. Breaking Ten~city
21 21.4 100
100 18.9 88
125 17.4 81
150 17.1 80
175 15.6 73
2~ 15.2 71
EXA~PIE 2 ~ iTROL
~is ~le lllwt~tes that ~lbers Or ~poly
2Q (chloro-1,4~hen~rlene terephthalate/2,6-napht~late)(70/30,
~le bads) are lnfes~lor to the ribers o~ thl~ lnventlon ln
retention of te~cit~r at ele~ate~ te~erat~.
Copol~r(chloro-1,4i~h~1ene teraphthalate/2,6-
~aphth~late)(70/30, ~ole ba~i~) i8 p~pared aml spun into
~i ~ibers by Dletho~l~ slailar to tho~e de~cribed in G~an OS
~l 2,520,819 to yield an a~ rn ha~rlng the~- proportio~:
T/E~/Dcn.: 7.0/1.8/533~499 ~ured on yarn l~ith 3.6 t~/
lnch, 2-direction). A yarn s~le collected on a di~rent
bobbin a~ng the sa~e ~pinnin.g operatlon i~ ~ppea on ~
30 Fiber-E~-co~er d bobbi2~ and heat treated irl . nitrogen-
~ept o~n u~der the~e succe~ o conditiQns: 220C/l hr.;
.~ .
-- 1 1 -
` B
~n~3~747
t-~per~ture ralsed to 260C and held thereat rOr 1 hr ;
t~æ~rature rai~d to 285-C and held thcreat rOr 1 hr.;
toqperature r~ised ln 0 4 hr to 300-C and held theroat ror
12 hr. The bobbin i8 allo~ed to cool and the~e proportie~
are obscr~e~ at roo~ te~p-rature Th/hl/bon.: 3~.9/4.7/
597/419. Portiona Or th heat tr~at~d yarn ars te~to~ ror
ton~city ret-ntlon a~ ol~bte~ tcmperature- a~ ln
E~a~plo 1 ~lth the follo~lng result~:
TABLE 2
Bre~king % R~t-ntlon
10 Te~t Tonacity or Original
T--poratureJ C At T- t TemD. Broaking Tonacity
21 3~.9 100
100 25.1 72
125 19 4 56
150 13.7 39
175 11.1 32
200 11.5 33
PLE 3 ~ ROL
~ple lJlustrates t~t ~lbcrs Or pol~ nro-
20 l~h~l~n~ h~rotereq?hthalate) are inrerior to tho
ib~r~ o~ this inventio~ in ret~tlon Or t~aclty at
ele~t~l taq~-rature~.
Pol~(~hloro -1, 4~h~10no ha~droterephtha~te ~
px~par d rr~ chloro~roq~0ne diac~tate and h~dro-
, ~
t~rephthalic acld ana ~pun into ~ib-r~, all b~ m~hods
s~m~lar to thn~ ae~crlbed ln ~ r~an OS 2,520~819. Thc
aJ-spun yarn i~ plied 6X to gi~e a yarn ~ith T~E/Ml/ben. ~
3.2/1.7/206/110 (measured on yarn ~ith throe turns/i~ch, Z-
direction). A uample of the pliod ysrn i8 wrapped on a
Fiber-Fra~-covered bobbin and heat troated in a nitrogen-
s~ept o~en under these succes d ~e conditlon~: 170-C/ 1 hr ;
_ 12 -
::
B
;; ; ` ~ . :
lO~Z7~7
tqperaturc r~se~l to 230 C~l hr; t~peraturo r~ed to
2~0-C/2 hr.; t~poratur raised to 290C an~l held th-r-at
~or 2 1/4 hr The bobbln i8 allo~d to cool ~nA these
prop-rtl-~ ar~ obserred at roo~ t~p-rAtur~s T/l~h~. -
9~3/2 0/389/105. Portion~ o~ the h~t treated ga~ ar
t-~t-d rOr ton~cit~ retention at elevated teqp-rat~
a~ ln E~qpl~ 1 ~lth the ~ollo~ ult~
T~Bl,E 3
Br~ Rot~tion
10 Test T~clty or
TemDerature, C At To~t T~.
21 9.3 1~0
: 100 6.6 71
~: 125 6.2 67
~ 150 5.2 56
`. 17~ 4.2 45
200 3.0 32
l~ 4
,c
;~ Thi8 aqple 8ho~ tbat ~ tltution Or 8.1 ~1 %
..
20 or p~lro~b-~oic acid ~ori~ Ul~it~ rOr part o~ the ph~yl-
l,~h ~rlo~o torephthalate u~it~ in poly(phetlgl-1,4-ph~lene
ter~htl~late) gl~ lth high te~city aDd high t~eity
rotention at 150-C.
~i A mlxture Or 663 g (2.45 ~oles) o~ phenylhgdroquinone
diacetate (7 ~ole % excess), 381 g (2.29 ~les) o~ ter~phthalic
ac~d and 73 g (O.4O ~oleJ) Or p-Qcetox~benzoic aci~ i~ placod in
~ a 2-liter rcd n kettle equlpped ~lth an er~iclent corrosion re-
``' si~tant m~tal ~tlrrer, nitrog~n inlet port, and fr~ctlonatlon
colu~n ~lth conaonser and variable take-o~ head. Th ~ottlo iB
pur~ed several times by evacuation and ~ ng ~ith nitrogen
- 13 -
B
~,.... ..
.. , ~ ... . .
i()t~ 7~
and then is placed ln a Woods metal bath at 195C. The bath
and kettle are heated at atmospheric and then at reduced
pressure, the reaction is stirred and the acetic acid reaction
product is collected. m e temperature of the reaction mixture
is monitored by a sheathed thermocouple in the meit. Nltrogen
M ow at 1 ~t3/min i8 maintalned and 810wly dlminlshed to zero
~as the kettle i8 evacuated. As the polymerization progresseg, the
rollowlng temperatures (C)/elap8ed t1me8 (m1n)/pressures (mm or Hg)
; are observed: 148/15/760, 274/26/760, 336/74/380, 341/76/250,
; 10 343/78/120, 343/80/50, 344/82/1-5, 348/93/1-5. After 93 mlnutes,
the reaction mixture i~ cooled, and the kettle is broken to
; rree the polymerJ which then is cut to a size that ~111 pass
through an one-eighth inch mesh screen. The polymer i8 then
sub~ected to a purification procedure. It 18 agitated with 10
wt. % aqueous (NH4)2C03 solution and collected and then washed
in turn with distilled water, 10% aqueous acetic acld, water,
acetone, refluxing acetone, (while stirring), additional acetone,
and then is dried at 115C at reduced pressure. Purification ls
found to improve spinning performance. The yleld is 662 g (~6%)
Or polymer with a ~inh of 2.12.
~he polymer is redrled for several hours at 110C at
reduced pressure and transferred to and spun from an one inch
single screw extruder equipped with a pump block and filter pack
assembly and a 100 hole spinneret, each hole with a diameter of
0.013 cm. The temperature in the screw fed zone is ad~usted so
that the polymer melts (maximum temperature in block is about
350C) and is uniformly fed to the spinneret (maintained at about
~.. . ~,.
345C) and extruded at a throughput o~ }2.4 g/min. The yarn
take-up rolls rotate at a surface speed o~ 220 m./mln. The yarn
30 then is passed through an alr Jet to consolldate lt and wound up
r
~' ' .
- 14 -
.
10~74'7
on a shaft drlven bobbln taklng care to avold mechanlcal
damage to the yarn. The yarn exhibits a T/E/Ml/den of
6.1/1.6/400/496 (at 3.6 turns/lnch); O.A. - 16~ (20.1).
A clrcular skeln of yarn i8 heat-treated ln an oven
purged wlth nltrogen (wlth exclu~lon of alr) at these tempera-
ture~ (~C)/times (hrs): gradually from 25-200/1.3, slowly
from 200-30~/4.0, 30~/12, cooled from 30~-25/1.3. The heat-
treated yarn exhlbits T/E/Mi/den of 24. ~/4.3/485/486 ~at 3.7
turns/lnch). At 150C lt exhlblts T/E/Ml/den of 1~. 9/3. ~/335/
487. Tenacity retentlon is 76%. Some sticking 19 observed
; between lndividual fllaments.
EXAMPLE 5
. Thls example shows that substltutlon of 2.5 mol %
of resorclnol derlved unlts for part of the phenylhydroqulnone
derlved unlts in poly(phenyl-1,4-phenylene terephthalate)
glves yarn with high tenacity and hlgh tenacity retention at
- 150C.
This polymer ls prepared essentlally by the method
of ~xample 4 from 741 g. (2.74 moles) of phenylhydroqulnone
diacetate, 2~ g (0.14 mole) of resorcinol diacetate, and 44~ g
~; (2.70 moles) of terephthalic acid to obtain 7~4 g (93%) of
~ ,
product wlth an nlnh f 1.54. The total tlme of polymerlzatlon
ls 76 minutes, 16 mlnute of whlch ls at reducedpressure and at
338C-341C.
~; Thls and a slmilar preparation (nlnh of 1.66) of
extracted, washed and drled polymer are physlcally blended,
x .
~ dried and then spun ln the extruder of Example 4 under similar
:.,::
conditlons; spinneret temperature ls 335C. The yarn exhlbits
~~; T/E/Mi/den of 6.3/1.7/434/531.
A skein of thls yarn is heat-treated as in Example 4
: , .
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-.
':
10'.~2'747
at the~e temperatures (C)/time~ (hrs~: 25-200/2, 200-312/5.3,
312/6.7, 312-25/2.7. The heat-treated yarn exhlblts a T/E/Ml/den
Or 29.7/4.4/559~506. At 150C it exhibits T/E/Mi/den Or
22.9/3.8/392/510.
EXAMPLE 6
This example shows formation of yarn with high
tenacity and high tenacity retention at 150C ~rom a copolymer
of poly(phenyl-1,4-phenylene terephthalate) in which 5 mole ~
Or the terephthalic acid derived units are replaced wlth units
; 10 derived from trans-hexahydroterephthalic acld.
This polymer is prepared essentlally by the method
~, of Example 4 from 790 g (2.89 moles) of phenylhydroquinone
diacetate, 426 g (2.56 moles) of terephthalic acid and 23.2 g
,~,
(0.135 mole) of trans-hexahydroterephthalic acid. The poly-
merization is conducted for 66 minutes, 18 minutes Or whlch ls
:, .
at 334C-344C under reduced pressure. The yleld ls790 g (93%)
f polymer with anq inh Or 1.76.
The polymer is dried and then ~pun ln the extruder of
~; Example 4 under simllar condltions. The yarn exhlblts a T/E/
.~ ao Mi/den of 6.3/1.6/420/493 (3.6 turns/lnch); O.A. 16 (20.1).
A skeln of thls yarn ls heat-treated as ln Example 5.
..
The heat-treated yarn exhiblts T/E/Ml/den o~ 23.0/3.4/602/483.
. At 150C it exhiblts T/E/Mi/den of 16.~/3.0/335/4~9.
EXAMPLE 7
is example shows the preparation Or poly(phenyl-
1,4-phenylene terephthalate) yarn wlth high tenaclty and hlgh
;; tenacity retention at 150C from phenylhydroqulnone and
terephthalic acid.
In a 2-llter resin kettle with a dome shaped lid and
heated ~ractionation column equipped otherwlse as ln Example 4
., :
;
~; - 16 -
..
. . . . . . .. . .
10'3, '747
i8 placed 545 g (2.93 moles - 3 mole ~ excess) Or phenyIhydro~
quinone, 471.4 ~ (2.~ moles) of terephthalic acld and 0.01 g
Or titanium tetramethoxide in 90 ml tetramethylene cyclic
sulrone (aids in returning monomers and ollgomers to the
polymerlzatlon). The heated column and dome shaped lld ald in
~eparating the monomers, partlcularly the phenylhydroqulnone,
efficiently from the water reaction product. m e reaction ls
conducted wlth a nitrogen purge in a manner similar to Example 4 at
the followlng temperatures (C)/èlapsed tlmes (mln)/pressures (mm o~
Hg): 220/12/760, 276/32/760, 324 /60/760, 326/85/630, 324/100/
510, 329/115/380, 332/130k250J 336/145/12~, 338/160/~5, 336/184/2,
338/228/2, 340/247/2. After 255 minutes, the reaction is cooled,
the polymer isolated, cut into small pieces and extracted
essentially as in Exam~le 4. The yield is 591 g (66%) of
polymer with an ~lnh of I.6~. ~
The polymer ls dried and then spun as ln Example 4;
splnneret temperature ls 354C, throughput ls 9.7 g/mln. The
yarn ls collected at 165 m/mln. and exhlblts a T/E/Ml/den o~' 5.6/
1.5/42~/511 (3.6 turns/lnch); O.A. = 17 (20.1).
A skeln o~ yarn ls heat-treated as ln Example 4 at
these temperatures (C)/tlmes (hrs): 25-200/1.3, 200-316/10,
316/6, 316-25/1.3. The heat-treated yarn exhlblts T/E/Ml/den
o~ 22.3/3.6/573/490 (3.6 turns/lnch). At 150C lt exhlblts a
; T/E/Ml/den of 18.2/3.3/394/488.
EXAMPLE 8
miS example illustrates preparation of poly(phenyl-
1,4-phenylene terephthalate) ~ibers with exceptionally high
levels of tenacity at 150C.
m is polymer is prepared essentially by the method of
Example 4 from 780 g (2.89 moles) of phenylhydroquinone diacetate
. . .
ln~ 747
and 448 g (2.70 moles) of terephthallc acld to obtaln 760 g
(89S! o~ product wlth an ~inh ~ 1.8. The total tlme of
polymerization is 90 minutes, 20 minutes of which is at
reduced pressure and at 343C-366C, The polymer is isolated,
ground up, and purified by pa~sing a stream of heated nitrogen
(250C) upward through the finely divided polymer in a column
for two hours.
Thls and rour simllar preparatlon~ are physically
blended, dried, pelletlzed, then spun essentlally as in
Example 4 but through a 70 hole splnneret; throughput 1~
9.9 g/mln; take-up roll speed ls 256 m./mln. The orlented
yarn exhlblts T/E/Ml/den Or 5.~/1.3/473/342 (4.4 turnQ/lnch).
A skein of yarn is heat-treated as in Example 4 at
these temperatures (C)/times (hr) = 25-200/2, 200-317/10.7,
317/3.3, 317-25/2. The heat-treated yarn exhibits T/E/Mi/den
- of 28.4/3,4/710/335 (4.4 turns/inch). At 150C it exhibits
T/E/Mi/den of 21.5/3.2/421/347,
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