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Патент USA US3063797

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Nov. 13, 1962
H. J. RYNKIEWICZ ETAL
3,063,787
PROCESS OF WET SPINNING STEREOREGULAR POLYVINYL ALCOHOL
Filed June 17, 1960
WUPIND
RPVA
IN
SOLVENT
INVENTORS
HENRY J. RYNKIEWICZ
EUGENE W. K. SCHWARZ‘
IRVING SKEIST
BYWWMEOMW
ATTORNEYS
3,063,787
United States Patent 0 ”ICC
Patented Nov. 13, 1962
1
2
This invention has as an object an oriented high-tensity
3,063,787
polyvinyl alcohol ?ber which, without the well-known
insolubilizing treatments, is insoluble in boiling Water.
Henry J. Rynkiewicz, Danbury, Conn., Eugene W. K.
Schwarz, Brooklyn, N.Y., and Irving Skeist, Summit,
N.J., assignors to Diamond Alkali Company, Cleve
A further object is a method of preparing such ?bers from
polyvinyl alcohol resins which are substantially insoluble
in boiling Water. Other objects will be obvious from a
careful study of the following description of this invention.
PROCESS OF WET SPINNING STEREOREGULAR
POLYVINYL ALCOHOL
land, Ohio, a corporation of Delaware
Filed June 17, 1960, Ser. No. 36,739
9 Claims. (CI. 18—54)
Conventional polyvinyl alcohol is obtained by saponi?
cation, hydrolysis or alcoholysis of polymerized vinyl
10 esters, especially vinyl acetate. The molecular weight of
This invention relates to the production of ?lms, ?bers,
the polyvinyl alcohol is dependent upon that of the ester,
threads, ?laments and similar articles. More particu
i.e., a high molecular weight polyvinyl alcohol is obtain
larly, it relates to the production of such articles from
able from an ester having a correspondingly high molecu
polyvinyl alcohol.
lar weight. The conventional polyvinyl alcohol having
It is known that polyvinyl alcohol, which is soluble in 15 a reduced viscosity of 1.0 is completely soluble in water
water, can be spun into ?bers by wet or dry spinning
methods from an aqueous solution of the resin. Such
at a temperature of about 70° C.
Accordingly, an aque
ous solution of polyvinyl alcohol may be employed to
?bers, however, are characterized by their sensitivity, to
water, particularly to hot water. If dipped in water at
normal temperature, the ?ber will shrink by more than 20
10% of its original length, and if the temperature of the
water is around 70°-90° C., the ?ber will dissolve.
produce ?bers, ?lms, etc. therefrom. v
The polyvinyl alcohol of this invention, hereafter re
ferred to as “Stereoregular polyvinyl alcohol” or “RPVA,”
is obtained by alcoholysis of polymerized vinyl halo
esters, especially vinyl chloroacetates and vinyl ?uoro
Polyvinyl alcohol (PVA) ?bers have been made resist
acetates, as disclosed in US. patent application Ser. No.
ant to water by various methods including modi?cation
of the alcohol prior to spinning and by after-treatment 25 689,768, ?led October 14, 1957, and now Patent No.
2,901,341. The Stereoregular polyvinyl alcohol having
of the ?ber. ‘It has been known to incorporate into the
' polyvinyl alcohol spinning solution a compound such as
a reduced viscosity of 1.1 will not dissolve in water at a
a dicarboxylic acid which is capable of forming a cross
linked structure under the in?uence of heat. It has also
temperature of 100° C. RPVA may be dissolved in
water at a temperature of 1l5°-120° C. The insolubility
of Stereoregular polyvinyl alcohol in water at 100° C.
has been attributed to the syndiotacticity of the alcohol
been known to acetalize the polyvinyl alcohol, then form
a ?ber and follow up ‘with a heat treatment of the ?ber.
Fibers, after being spun from a PVA solution, have
as contrasted to an atactic structure possessed by conven
been made resistant to water by various treatments such
tional polyvinyl alcohol.
Since pressurized equipment is necessary to maintain
as stretching and heat-treating, stretching and reacting
with a material such as an aldehyde, ketone or dibasic
a water temperature in the neighborhood of 120° C., it
may be desirable to employ an organic solvent to form
acid, exposure to formaldehyde vapors or elevated tem
peratures and treatment of the ?ber surface with waxes,
etc. Such treatments are expensive and often introduce
the spinning solution. Stereoregular polyvinyl alcohol
is not only insoluble in boiling water but is also insoluble
40 in most solvents or combinations thereof. In order to
treated ?bers.
determine the effect of various solvents on RPVA, a ?lm
As with other types of synthetic ?bers, a moderate
of the material was cast from a water dispersion of the
amount of drawing or stretching orients the molecular
resin. The dispersion was spread on a glass plate and
structure and results in high tensile strength. This orien
the water evaporated therefrom to form a ?lm. Small
tational drawing, however, is distinguished from the
sections of this ?lm were immersed in the solvents tested
stretching which accompanies the aforementioned insolu
and the effect of numerous solvents is shown in Table I.
bilizing treatments.
undesirable physical characteristics and impurities in the
TABLE II
Reagent
After 5 hrs. at room
After 24 hrs. at room
Additional 5 hrs. at
Additional 2 hrs. at
temp.
temp.
50—55° C.
90—95° 0.
Water ____________________________________ __ NNE.--
NE.
NNE.
NNE.
Ethylene diamiue ________________________ .-
Dissolved _____________ __
Dissolved _____________ .-
Dissolved _____________ __
Dissolved.
Acetic acid, glacial“
NN _
N NE.
NN -
V. sl. swollen.
Acetic anhydride-“
NNE-
NN
_
_
NNE}-
'
NNE.
_
Ammonium thiochauate (sat. sol.)-_.___ ____ Considerable swelling___ Considerable swelling... Considerable swelllng___ Considerable swelling.
Formic acid (ea-100%) _ _ _ _ _
_ _ _ __do
Lithium bromide (60% sol.)
S1 swollen
Zinc chloride (60% sol.) __________________ __
N
Ethylene chloride ________________________ __
Propylene carbonate- _
NNE at 50° C ________ _.
NNE .
Znitropropane- _ -
_____do
Degradation.
_____do
Greatly swollen.
______________________ __do ________________ ._
Dissolved-pink.
NNE at 50° C_____---_.
NNE_
NNE.
NNE.
NNE
NNE _
NNE.
Butyrolactoue
NNE _
NNE
Tetrahydroiurfuryl alcohol
NNE_
NNE_
Chloromaleic anhydride.
NNE _
NNE- __
NNE.
_
NNE
Triethylene diamine (sat. sol.) ___________ __ Apparently dissolved.-. Apparently dissolved--.
Morp holine.
NNE _ _
NNE_NN E
NNE.
_
Apparently dissolved.
V. sl. swollen.
N-methyl ________________________________ __
NNE _________________ __
NNE _________________ _.
Degradation
Piperdine-_
Pyridine
NNE.
NNE-
NNE.
NNE-
Swollen.
NNE-darkened.
v.
v.
sl.
swollen.
N
Piperazine (sat. sol.) _____________________ __ Appears to be dissolved- Appears to be dissolvedTriethanolamine_
NNE_
N N ENN
Appears to be dissolved.
NN E.
Diethaunlamine
NNE.
NNE...
Nitroethaue ______________________________ __
Acetonitrile _________ _.
N-acetylmorpholine ...... __
NNE _________________ _.
_
__
NNE .
NNE _________________ ..
NNE. --
NNE
NNE
.._-
NNE _________________ __
NNE.
N
NNE.
1,6-hexanedian1ine-—72% __________________ _- Appears to be dissolved. Appears to be dissolved. Appears to be dissolved. Appears to be dissolved.
'
See footnotes at end of table.
3: 063,787
4
' TABLE I—Continued
Reagent
7
After 5 hrs. at room
After 24 hrs. at room
Additional 5 hrs. at
Additional 2 hrs. at
temp.
temp.
50-55‘7 C.
90-95“ C.
_
Resorcinol (sat. sol.) ______________________ ._
Swollen _______________ ..
Considerable swelling-.-
Caprolactarn (set. sol.
NN E
V. sl. swollen ...... _.
Considerable swelling. ._
_ ...._do __________ __
Sl. swollen ________ __
__
Do.
Considerable swelling... Considerable swelling. _.
IDo.
Trioresyl phosphate.
NNE ___________ _.
_.
Swollen _________ __
Do.
Dimethyl sulione (sat. sol.)-.
Dime yl
{oxide
_.
Greatly swollen.
_.
N NE _________________ __
N N E.
Chloroform ______ _.
NNE-_ _
NNE
Sanoticizer 141
NN _____
N NE.
Diaeetiu _____ - .
NNE _____ __
Formamide _____ _ .
Sl. swollen- .
Triisooetyl phosph e _____________________ ._
NNE.
Sl. swollen.
NE--...
Bis (2-ethylhexyl) hydrogen phosphate"...
NNE.
NNE.-.
#:Hydroxypropionitrile ___________________ ._
NNE.
NE _______ _ .
2(2-‘am1noethylamine) ethanol ____________ .. NNE
Swollen.
V. sl. swollen-_
2-pyrrolidinone ........................... _.
Appears to be dissolved.
NE _____ ..
N-methylacetamide.
....... ..
Propargyl alcohol--.
V sl. sw ollen_.
Shell curing agent Tel.
Greatly swollen.
S1. swollen.
V. si. swollen.
N E _____ ._
N N E.
Diglyme __________________________ ._
NNE_
NN E.
Tetramethyleno sulione __________________ _-
NNE _____ _ .
NN E.
?-Alanine (sat. sol.) _________________ _.
V. s1. swollen_.
__
Swo1len--...
._
Glycine (sat. sol.) ___________________ __
Guanylurea phos hate (sat. sol.) _ _ _ . _ _
Methylannne (30 @ sol.) ............. ..
. . . “do ...................... ..do _________________ ..
Swollen.
o.
Greatly swollen _______ __
Greatly swollen.
-._ Appears to be dissolved. Appears to be dissolved- Appears to be dissolved. Appears to be dissolved.
Menthaue diamine _______________________ ._
NNE ................. _ .
NNE ................. . _
NNE ................. ..
NNE.
?-Hydroxyethyl
V. 51. swollen __________ -_
V. s1. swollen .......... ._
S1. swollen ____________ ._
Swollen.
trimethyl
ammonium-
bicarbonate-4 %.
Cyanamide .(sat. sol.) ____________________ ..
Considerable swelling.-.
Considerable swelling. ..
Greatly swollen _______ __
B-Propiolactone _____________________ -_
NNE ____________ ..
NN E ........... . .
..
NNE _________________ __
Si. swollen.
Urea (sat. sol.) ........................... ..
Greatly swollen ....... ..
Greatly swollen ....... ..
Greatly swollen _______ __
Disslolved (may contain
Considerable swelling.
.
.
.
.
.
go
Onyx ETC-50% 1 ......................... ._
Considerable swelling-..
Considerable swelling- __
Considerable swelling. _.
H01 (oone.)._-...-_
Dissolved ........ _.
Dissolved ....... ._
Dissolved _____________ __
i
Dissolved.
)
..
Swollen- -
.
.
d
SOz/dimethyl fomamide, saturated.---
NE- _
sozftetrahydroiuran, saturated ...... __
NNE. _
LiBr/dimethyl formarnide, saturated__
NNE. .
Greatly swollen _______ __
Greatly swollen.
LiBr/drmethyl sulfoxrde, saturated- _. .
NNE. .
Extremely swollen ____ ._
Extremely swollen.
NNE- .
N
LlBr/tetrahydroiuran, saturated ..... -.
ZnClz/dimethyl iormarnide, saturated.
znchldlmelhyl Sulfornde, saturated-..
ZnCn/tetrahydroiuran, saturated.-.
Dimethyl i’ormamide/HaO, 4:1 ratio--.
N
NN E.
(2).
...... _.
_
_
. _ _ . . _ . . . . . .
. . . __
_________________ _ _
NNE.
Partially dissolved.
NN E _________________ _ _
__.
Dimethyl suli'oxide/HzO, 4:1 ratio ........ . .
2
V. v. s1. swollen _______ ._
Extremely swollen ____ ..
2).
Extremely swollen.
S1
D0.
BIO/ethylene glycol, 4:1 ratio ............. ..
Greatly swollen.
Triton X-lOOfH1O, (cone. sol.)Diacetone alcohol ........... ._
Tetrahydropyran—2-inethanol-.
Extremely swollen.
NNE‘
NNE.
Ethyl oarbamate ........ ._
NNE.
Ethylene glycol _________________ ._
Urea/tetrahydroiuran, saturated .......... __
Swollen.
(2).
Urea/dimethyl iormamide, saturated _____ ._
Urea/ethylene glycol, saturated ___________ __
Sl. swollen.
NNE. _.
Swollen.
Urealdimethyl sulfoxide, saturated ....... ._ Sl. swollen_
Extremely swollen.
Urea/Z-pyrrolidone _______________________ __
Swollen.
NNE
Cyanamideltetrahydroiuran, saturated-____ NNE.-.
(I).
Cyanamide/dimethyl formamide, saturated. NNE__
V. v. 51. swollen.
Cyanamide/ethylene glycolksaturated ____ . .
Swollen.
NN E. _
Cyanamide/dimethyl sulfoxide. saturated- _ Swollen-
Considerable swelling- -_
Triethylene diamine/tetrahydrofuran__-_. ..
N N E _____________ ..
NN
__
.-
Considerable swelling.
(3).
Triethylene diamine/dimethyl formamide._ NNE. .
S1. swollen.
'l‘riethylene diamine/ethylene glycol ...... ..
Swollen.
Triethylene diamine/Q-pyrrolidone ....... .. NN
Extremely swollen.
Triethylene diamine/dimethyl sulioxide..._
Considerable swelling.
Caprolactamltetrahydroturan. _ _ _ _
_
(2)‘
Csprolaetam/dirnethyl formamide.
_
S1. swollen.
Caprolaetamlethylene glycol ...... - .
_
Do.
Piperazine (hydrate) ltetrahydrofuran _____ _ _
(1) .
Piperazine (hydrate)/dimethyl i’ormamide- _
NNE.
Piperazine(hydrate)/ethylene glycol ______ _.
Swollen.
Piperazine (hydrate)/dirnethyl suli'oxide. ___
Guanylurea phosphate/tetrahydrofuran-__ _
Dissolved.
(2)_
Guaniylurea phosphate/dimethyl iorma-
S1. swollen.
m! e.
Guanylurea phosphate/ethylene glycol- _ - ._
Swollen.
Guanylurea phosphateldimethyl sulfoxide"
Diehloroaeetio acid/glycerine ________ __
Dichloroacetic acidltetrahydroiuran. -_
_._
_
Considerable swelling.
NN
V. s]. swollen.
(z)_
‘.Diehloroecetie acid/dirnethyl iormamide
.
Diehloroaoetic aoid/dimethyl sulfoxide
_
Considerable swelling. . .
Extremely swollen. _
Formio acid/ethylene glycol- _ .__
.
NNE .... _ .'._ -_-
_'.
NN E
Triethylamine .......... .-
_
NNE _________ _-
--
NNE ................. .-
NNE ____________ __
Considerable swelling. __
Considerable swelling. _ .
Considerable swelling...
Duponol WA/HzO ....................... -_
___________ .-
._
S1. swollen.
Extremely swollen.
Considerable swelling.
.__
NNE.
Considerable swelling.
I Solvent boiled off.
1 Alkyl (CrCm) dimethyl benzyl ammonium chloride-25% sol.
Note-NNE =No noticeable e?eot; v.=very; sl.=silghtly; conc.=concentrated; sat.=saturated; and sol.=solution.
centrated HCl is very di?icult to handle and therefore is
‘From Table I it will be noted that ethylene diamine,
saturated solution of triethylene diamine, saturated solu 65 undesirable as a solvent. For preliminary Work, ethylene
diamine was selected as the solvent in the preparation of
tion of piperazine, 72% solution of 1,6-hexanediamine,
the spinning solution.
30% solution of methylamine and concentrated hydro
Typically, a solution of stereoreguiar polyvinyl alcohol
chlo'ric‘acid apparently dissolve the stereoregular poly
in ethylene diamine is extruded by means of a gear pump
vinyl alcohol. The ‘aqueous solutions of ‘triethylene di
amine, piperazine, herranediamine and methylamine all 70 through a multihole spinnerette into a coagulating bath
of methanol or other lower aliphatic alcohol containing
are quite ‘alkaline, having a pH in the neighborhood of
up to four carbon atoms. From the coagulating bath the
about 12. Films of RPVA which were reciprocated from
these solutions were found to be water-soluble and this
?ber or yarn is’ led to a positively-driven Godet and then
led to the belief'that such materials cause a possible deg
through air to a positively-driven Wind-up bobbin. BY
radation of the alcohol, accounting for its solubility. Con 75 adjusting the speeds of the various drives, the fiber can
3,063,787
5
6
be stretched or drawn in controllable amounts either in
the coagulating bath or in air between the Godet and
wind-up or both. It has bec 1 found advantageous to pro—
vide a heat-setting operation following the drawing which
comprises immersing the ?ber or passing it through a hot
load. At the same time the other hand wheel is turned
to lower the clamp, thus keeping the balance pointer at
the center mark. When the thread sample breaks, rota
tion of both hand wheels is stopped. At this point the
sample is checked to ascertain whether the break occurred
at the nip of the clamps and, if such is the case, that read
mineral oil bath at a temperature of about 120° to 180° '
C. This heat-setting operation may be accompanied by
a hot-stretch operation whereby the ?ber, while hot, is
ing is discarded. Using the sliding weights of the bal
ance, the weight of the chain is balanced and the reading
stretched 4 to 8 times its original length. The combina—
on the scale is the breaking point. The distance the
tion of heat and stretch not only increases the insolubility 10 lower clamp has moved from its original position deter
of the ?ber in hot water but also orients the ?ber and in
mines the ultimate stretch. The arithmetic mean of 10
creases its tensile strength.
breaking strength determinations is divided by the denier
Fibers produced from water-insoluble stercoregular
of the thread to give the grams per denier. The average
polyvinyl alcohol having a reduced viscosity of 1.5, in
of 10 ultimate stretch values, calculated as a percentage
accordance with this invention, have a tenacity of at least 15 of 5 inches, gives the ultimate stretch percent.
7.5 grams per denier. Such ?bers ‘are important in- in
Tenacity in grams per denier is converted to pounds per
dustrial uses such as cords for ?res, ?re hoses, industrial
square inch by the formula:
cords and belting, and in reinforcing ?bers for many ap
plications.
Reference has been made to the reduced viscosity 20
wherein :
(Nred) of polyvinyl alcohol. This value is an indication
of the molecular weight of the polymer and is equal to
the speci?c viscosity (N51,) divided by the concentration
S=strength in pounds
A=cross sectional area of the ?ber in square inches
solution In and the ?ow time of the solvent t0 are usually 25 d=density of the ?ber in grams per cubic centimeter
of polymer in the solution. The ?ow timeof the polymer
measured by the capillary method. *From these values the
g=strength or tenacity in grams per denier
speci?c viscosity is computed according to the formula
tc—to
The density of RPVA has been determined as 1.30
Nap:
to
30 gr./cc. Substituting this value in the above formula,
The reduced viscosity has a logarithmic relationship to
the tenacity in pounds per square inch is equal to
the molecular weight of the polymer and, in general, the
16,000Xgrams per denier.
'
range is:
In order that those skilled in the art may more com
Nred
Molecular weight
.
______________________ __
40,000—60,000
1.0—1.5 ___________________ ....
100,000-200,000
3.0
______________________ __ 500,000-l,000,000
Since conventional polyvinyl alcihol is soluble in water,
water generally is used as the solvent in determining the
reduced viscosity. Reduced viscosity of RPVA cannot
be determined in this manner, however, since it is insol
uble in water. Accordingly, the reduced viscosity of the
precursor, i.e., polyvinyl chloroacetates or polyvinyl
?uoroacetates, is determined and, as is common practice
in the polymer ?eld, this value is assumed to be propor
pletely understand the present invention and the preferred
35 methods by which the same may be carried into effect, the
following speci?c examples are offered.
Example 1
A prototype laboratory spinning apparatus such as is
shown schematically in the attached drawing is employed
which comprises a reservoir for the spinning solution
which feeds two positive displacement metering pumps
which are so interconnected and are run by variable
speed motor so as to permit the accurate metering of as
little as 3><10—3 cc. per minute of the spinning solution.
This apparatus is designed as a precision meter to extrude
tional to the reduced viscosity of the polyvinyl alcohol.
a uniform ?lament of spinning solution through the spin
Denier of ?bers is de?ned as the weight in grams of
a 9,000-meter length of thread and is determined by meas~
uring 9 meters of thread on a standard textile skeiner.
The thread is removed from the skeiner and wound into
nerette ori?ce. A candle ?lter, using muslin as the ?lter
ing medium, is mounted in such a Way as to permit the
spinnerette to be raised from and lowered into the co
a small loop about 1 inch in diameter. The loop of
thread is agitated in isopropyl ‘alcohol to remove any oil
ning solution. The main purpose of the ?lter is to mini
or other material which may be present on the thread
The spinnerette is attached to the ?lter through a glass
tube. The coagulating bath is contained in a stainless
steel tray, 24 inches long, with an effective ?ber im
surface and then airedried. The weight of the loop in
milligrams, as determined on an analytical balance, equals
the denier of the sample.
Apparatus for determining tensile strength and ultimate
agulating bath without interfering with the flow of spin
mize the incidence of clogging of the spinnerette ori?ce.
mersion length of 18 inches. Single-stretching of the
?ber is eifected by wrapping the ?ber once around a step
strength consists of a triple-beam laboratory scale. To
on a step cone, then to a rewind spool. The diameters
one pan of the scale is attached a #25 chain which then 60 of the steps are calculated to permit any elongation from
loops over a sprocket and hand wheel near the level of
0 to 1000% in 50% increments. Sequential stretching is
the balance, such that turning the hand wheel adds more
chain to the pan of the balance, thus gradually adding
effected by two step cones mounted parallel and rotating
at the same speed. The ?ber is fed around the two small
weight to that pan. The second pan of the balance has a
est diameter steps, then around successive larger steps
drum-type ?ber clamp attached below it. Directly below 65 and is ?nally wound on a rewind spool. The diameters
this clamp is a second clamp mounted with a rack and
of the steps vary fromrlAa inch to 4 inches and 1As-inch
pinion which, through a hand Wheel, can raise or lower
increments, permitting up to 700% stretch by this method.
the clamp. In operating the apparatus, the chain and
An ethylene diamine solution containing 24% stero
sliding weights on the balance are set at 0. The lower
regular polyvinyl alcohol having a reduced viscosity of
clamp is raised so that the clamps are 5 inches apart. The 70 about 0.4 is extruded through the spinnerette at a rate of
thread sample is clamped in the upper clamp and then
1.5 feet per minute into a coagulating bath of absolute
pulled through the lower clamp to a point where the
methanol. At this extrusion rate the coagulation time is
balance pointer reads 0 to insure that the sample is
60 seconds. The ?ber is subjected to a total stretch or
caught between clamps. The chain hand wheel is turned
elongation of 450% and is then dried at 130° C. for a
at a rate so as to add about 1 gram per second to the 75 period of 16 hours in order to remove all of the ethylene
3,063,787
7
8
diamine. The ?ber thus produced is insoluble in boiling
and the bath temperature is varied. Results of this test
water.
are set forth in Table IV.
Example 2
A quantity of stereoregularpolyvinyl alcohol resin hav
TABLE IV
ing a reduced viscosity of 1.5 is dissolved in ethylene di
amine to provide a solution of about 10% solids. Using
the vapparatus of Example 1, this solution, at room tem
perature, is ‘extruded through an eight-hole spinnerette
Strength (grams)
Hot
stretch
Thread
ternpera-
denier
Range
Aver-
ture, ‘’ 0.
at a rate of 1.5 feet per minute into a coagulating bath
of absolute methanol. The RPVA ?ber is stretched a 10
total of eight times in two’ stages at ambient temperature,
pressure and humidity. After drawing, the ?ber is given
Ulti
Grams
per
Pounds
per
denier
sq. in.
age
mate
elonga
tion
(per
cent)
134—136__-__
18.0
82. 6-103. 2
01. 7
5. 1
82,000
7. 8
157-160. __ __
18. 5 102. 8-115. 4
108. 4
5.9
04, 000
6. 6
a heat-setting treatment by immersion in a mineral oil
Example 5
bath at 130° to 160° C. for a period of 30‘ seconds. The
In order to determine the eifect of size or denier per
?ber thus produced is an eight-?lament yarn of which each 15
?lament on physical properties, a 10% solution of RPVA
?lament'is slightly less than one denier. This ?ber is in—
in ethylene diamine is spun into ?lbers as in Example 3.
soluble in boiling water.
Variation in denier is effected by changing the speed of
Water resistance and dry tenacity of various ?bers are
the solution feed pump and the resultant drawdown at the
presented in Table II:
‘
20 spinnerette ori?ces. Results are set forth in Table V.
TABLE H
TABLE V
Material
Water resistance
Tenacity,
g. /d.
Conventional PVA Nred 0.9
(tire cord ?ber).
Insoluble in cold water, 501uble in hot water.
5-9
Conventional PVA Nred 1.0.-.
Dissolves at 75-80‘3 0 ______ __
2-5 '
RPVA Need 1.25 ____________ _. Insoluble in boiling water___.
5-7. 5
Nylon:
'
Thread
denier
Filament
denier
Range
Aver-
Grams Pounds Ultimate
per
per
elongation
denier sq. in. (percent)
age
Tire cord ?ber ......................................... __
5-8
Textile ?ber
4-5
Tire cord ?ber ____ __
3-4
Textile ?ber
2-3
Rayon:
Strength (grams)
25
5.6.--_._.--.
0.7
34. 2-
.3
37.8
6 8 i 109,000
6 4
7.6.._-_
0.9
45.0- 53.2
48.4
6 4
103,000
6 4
2.2
826-1032
91.7
5 1 ‘
82,000
78
_
.
Example 6
In order to determine the effect of varying both the
Example 3
hot-stretch bath temperature and mono?lament size,
A 10% solution of stereoregular polyvinyl alcohol in 35 a 10% solution of RPVA in ethylene diamine is spun in
ethylene diamine is made by placing 140 grams of an
to ?bers as in Example 3, except that the solution is spun
hydrous ethylene diamine in a wide-mouth glass jar. To
through a 16 ori?ce spinnerette. The amount of hot
this is added a quantity of 15.5 grams of RPVA having a
stretch is maintained at 8 times the original length.
reduced viscosity of 1.5. The mixture is shaken vigor
TABLE VI
ously to form a thin slurry and then is heated for 3 hours
in a water bath at 55°—60° C.
The solution is spun
through a spinnerette containing 8 ori?ces, each of which
is 0.003 inch in diameter, into an absolute methanol bath
Denier
16 ?lament Mono?lament
Hot stretch Tensile Grams
tempera- strength
per
ture, ° 0. (grams) denier
Pounds
per
sq. in
at a speed which permits approximately 45 seconds co
agulation bath exposure. The strand is wet-stretched 45
1.5 times and wound on a supply spool. The supply spool
1. 2
135-140
110
5. 6
90, 000
l. 7
171-175
188
6. 6
106, 000
is placed on a hot-stretch machine where the strand is
0. 6
171-175
86
9. 0
144, 000
passed through a bath of mineral oil maintained at a
temperature of about 135-140" C. The exposure time
It is to be understood that although the invention has
of the strand in the bath is about 20 seconds. The amount 50
been described with speci?c reference to particular em
of stretch applied to the strand is varied by changing the
bodiments thereof, it is not to be so limited, since changes
gear ratio of either the feed or take-01f capstan wheels
and alterations therein may be made which are within
so that the speed of the take-0E wheel is 3 to 10 times
the full intended scope of this invention as de?ned by the
that of the feed wheel. Table III gives the properties of
55 appended claims.
the ?bers thus produced.
What is claimed is:
TABLE III
1. The method of producing stereoregular polyvinyl
alcohol ?bers which are insoluble in water at 100° C.
UltiTensile strength
and have a tenacity of at least 6.8 grams per denier
Denier
mate
(grams)
Grams Pounds
Hot
(8 ?lastretch
per
per sq. 60 which comprises the steps of forming a solution of stere
stretch
ments)
(percent)
Range
Aver
denier
in.
age
13. 6
12. 1
9. 8
6. 9
7. 3
6. 1
5. 6
13. 5
12. 7
10. 0
6. 5
7.2
5. 2
6. 4
23. 2-42. 9
36. 2-38. 5
33. 5-39. 1
25. 4-29. 6
26. l-39. 8
28. 0-36. 9
34. 2-41. 3
35. 7
37. 6
36. 8
27. 7
34. 4
32. 3
37. 8
2. 6
3. 1
3. 7
4. 0
4. 7
5. 3
6. 8
41, 000
50, 000
59, 000
64, 000
75, 000
85, 000
109, 000
Example 4
In order to determine the elfect of hot-stretch bath tem
perature, a 10% solution of RPVA in ethylene diamine
is spun into ?bers as in Example 3, except that the amount
of hot-stretch is maintained at 8 times the original length
oregular polyvinyl alcohol in ethylene diamine contain
ing about 3% to 24% by weight polyvinyl alcohol, ex
truding the solution through a spinnerette into a coagulat
ing bath of lower aliphatic alcohol containing up to 4
carbon atoms, wet-stretching the ?ber to about 1 to 3
times its original length and hot-stretching the ?ber about
4 to 12 times its original length at a temperature of
about 120”—180° C.
2. The method of claim 1 wherein the solution con
70 tains about 10% polyvinyl alcohol.
3. The method of claim 1 wherein the polyvinyl al
cohol has a reduced viscosity within the range of 0.4
to 1.5.
4. The method of claim 1 wherein the coagulating bath
is absolute methanol.
3,063,787
5. The method of claim 1 wherein the polyvinyl a1
cohol has a reduced viscosity of at least 1.5.
6. The method of claim 1 wherein the ?ber is Wet
stretched about 1.5 times its original length and is hot
stretched about 8 times its original length at a tempera
ture in the neighborhood of 130°-l60° C.
7. The method of claim 1 wherein the ?ber is hot
stretched in a bath of hot mineral oil.
10
the ?ber about 4 to 12 times its original length at a tem
perature of about 120°—180° C.
9. The method of claim 8 wherein the stereoregular
polyvinyl alcohol has a reduced viscosity of about 1.5 the
5 ?ber has a denier of 0.6 denier per ?lament, the hot
stretch temperature is 171°-175° C. and the tenacity of
the ?ber is 9.0 grams per denier.
8. The method of producing stereoregular polyvinyl
alcohol ?bers which are insoluble in water at 100° C. and 10
have a tenacity of at least 6.8 grams per denier which
comprises dissolving in ethylene diamine about 10% by
Weight of stereoregular polyvinyl alcohol which is insolu
ble in boiling water and has a reduced viscosity of at
least 1.2, extruding the solution through a spinnerette
into a coagulating bath of lower aliphatic alcohol con
taining up to 4 carbon atoms, wet-stretching the ?ber to
about 1 to 3 times its original length and hot-stretching
References Cited in the ?le of this patent
vUNITED STATES PATENTS
2,447,140
2,517,694
2,610,359
2,610,360
2,642,333
2,715,763
Shelton et al _________ __ Aug. 17,
Merion et al. ________ __ Aug. 8,
Hatchard et al. ______ __ Sept. 16,
Cline et al. ________ __ Sept. 16,
Tomonari et al. ______ __ June 16,
Marley ____________ __ Aug. 23,
1948
1950
1952
1952
1953
1955
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No‘, 3,063,787
November ~l3-V 1962
Henry J“ Rynkiewicz et al.
It is hereby certified that error appears in the above vnumbered pat
. ent requiring correction and that the said Letters Patent should read as
corrected below.
'
Column 2, lines 25 and 26g strike out “n and now Patent
No‘, 2,901,341"; columns 1 and 2?, TABLE IV under the column
heading "Reagent" line 5, for "'thiochanate‘" read——_-thiocya~nate
——; same table, same column lneadinghI line 18‘, for "Fiperd-ine"
read —— Piperidine —-; column 3‘, line 727 for "reciproEa-t-ed‘"
read —— reprecipita'ted ——; column 57 line 391, for ,“al-cihol‘"
read —— alcohol ——; column 10, line 4g afterl'la5‘" insert a
comma .
Signed and sealed this 24th day of‘S-eptember 1963,
(SEAL)
Attestz’
ERNEST w. SWIDER
Attesting Officer
DAVID L- LADD
Commissioner of Patents
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