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Патент USA US2403464

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Patented July 9, 1946
2,403,464
‘UNITED STATES PATENT OFFICE
2,403,464
HYDROLYZED VINYL ESTER INTER
POLYMER FIBERS
Albert Faris Smith, Wilmington, Del., assignor to
E. I. du Pont de Nemours & Company, Wil
mington, DeL, a corporation of Delaware
‘ No Drawing. Application July 22, 1942,
Serial No. 451,891
17 Claims. (01. 8—115.5)‘
1
This invention relates to novel arti?cial ?bers,
and to methods for preparing the same. More
particularly it relates to novel oriented ?bers of
ented ?bers according to this invention are-con
veniently made by interpolymerizing a vinyl or
ganic ester with one or more other polymerizable
hydrolyzed interpolymers of vinyl organic ester
substances, such as ethylene, vinyl cyanide, vinyl
with another polymerizable substance, and to 5 chloride, vinylidene chloride, methyl vinyl ke
tone, methyl acrylate, and methyl methacrylate,
methods involved in the manufacture of said
?bers.
Interest in the commercial possibilities of wa
esters of maleic and fumaric acid, and thereafter
hydrolyzing the vinyl organic ester portion of the
interpolymer to form the hydroxylated inter‘
ter-sensitive hydrolyzed interpolymers of vinyl
organic ester with another polymerizable sub 10 polymer.
The molar ratio of other polymerizable sub
stance, as a ?ber-forming material has lagged
stance to vinyl organic ester in the interpolymer
because of the adverse results encountered in
must be greater than 1:9 to satisfy the require
connection with the related polyvinyl alcohol
resins. Thus, it is known that polyvinyl alcohol
ment that less than 45% of the carbon atoms in
the polymer chain be attached to hydroxyl groups
is a ?lament-forming material and that such ?la
or organic groups hydrolyzable to hydroxyl
ments may be oriented to give strong ?exible
groups. Organic groups hydrolyzable to hydroxyl
?bers. However, these ?bers are not of general
utility as they dissolve in water, and in every
groups are ester groups of formula
instance attempts to make these oriented ?bers
0
insensitive to water by after-treatments have 20
I! g
,
-—C—-0-R
failed to give satisfactory results.
ether groups of formula —O--R, and acetal
An object of this invention, therefore, is to
groups of formula (—-O-~R)2, wherein R is a
provide water-insensitive, oriented ?bers of hy
monovalent. hydrocarbon radical.
drolyzed interpolymers of vinyl organic ester
The monomers from which the interpolymers
with another polymerizable material.
25
are prepared can be emulsi?ed in water and poly
A further object is to render oriented ?bers of
merized in the presence of catalysts, such as am
hydrolyzed interpolymers of vinyl organic ester
monium persulfate and benzoyl peroxide, gener
with another polymerizable substance insensitive
ally at temperatures above 40° C. The preferred
to water by a suitable after-treatment of said
?bers.
30 interpolymers with which this invention is par
ticularly concerned are the interpolymers of eth
A still further object is to provide oriented
ylene with a vinyl organic ester, e. g. vinyl acetate.
?bers of hydrolyzed interpolymers of vinyl or
A charge consisting of vinyl acetate, water, dis
ganic ester with another polymerizable sub
persing agent and catalyst is placed in a pres
stance, which ?bers are characterized by rela
sure vessel, ethylene pressure is applied, and the
tively high sticking points, by relatively low de
mixture is agitated at 60°~75° C. After several
grees of retraction in boiling water, and by sub
hours, the interpolymer which has formed is
stantial insolubility in boiling water.
taken out and unreacted vinyl acetate is removed
Still another object is to after-treat oriented
?bers of hydrolyzed interpolymers of a vinyl or
ganic ester with another polymerizable substance
whereby to increase the sticking points of said
?bers, to decrease the retraction of the same in
boiling water, and to render said ?bers substan
tially insoluble in boiling water.
These and other objects will more clearly ap
by steam distillation. Details of the polymeriza
tion are given in U. S. application Serial No
446,116, ?led June 6, 1942.
' The next step is hydrolysis of the interpolymer.
Ethylene-vinyl acetate interpolymers, for ex
ample, are dissolved in alcohol or a toluene- or
,4; Cal. benzene-alcohol mixture, and then sodium hy
droxide or potassium hydroxide in alcohol is
added. After hydrolysis has been carried out to
the desired degree, the resulting ethylene-vinyl
hydroxylated vinyl interpolymers in which less
alcohol interpolymer is isolated, e. g. by steam dis
than 45% of the carbon atoms of the polymer
chain are attached to groups from the class con
50 tilling to remove solvent, washing the residual
polymer, and drying. In general, it is preferred
sisting of hydroxyl groups and organic radicals
to use a highly hydrolyzed product, i. e. a product
hydrolyzable to hydroxyl groups, are treated with
wherein the hydrolysis is at least 95% and prefer
polyfunctional substances, one mole each of
ably 98 to 100% complete.
which is reactive with a plurality of moles of di
ethylamine, there results ?bers which do not 55 Filaments are prepared from the hydrolyzed
interpolymer by melt or solution spinning
disintegrate in water at 100° C. and have a sub
stantially higher melting point and show sub
methods. In melt spinning the hydrolyzed inter
polymer is heated and pressure is applied to the
' stantially less retraction in hot water than the
untxeated ?bers.
molten or softened material to force it through
Tie interpolymers used in preparing the ori-'
the fine openings of a spinneret in the form of ?la
pear hereinafter.
,
'
I have found that if oriented ?bers made from
2,403,464
.
ments. These ?laments are cooled and mechan- .
.
4,
N-chloromethyldiamides, Examples are oxydi
methylene bis-pyridinium chloride and adipyl
bis-aminomethyl pyridinium chloride.
ically wound on a bobbin which can be operated
at various speeds. In solution spinning the poly; (9)_ Dithiols, e. g. ethanedithiol.
mer is dissolved in a suitable solvent to form a
The general procedure for treating oriented
viscous solution. Suitable solvents are aqueous Cl
?bers by the process of this invention consists
pyridine and other aqueous amines, aqueous
in dissolving a substance of the above mentioned
type, hereinafter referred to as the "after-treat
.ing agen ,” in a solvent which will not vitiate
solution is forced through holes in a spinneret
into a heated column where the solvent is ?ashed 10 the action of the substance, and then soaking,
spraying or otherwise treating the oriented ?ber
off, or into a liquid non-solvent for the interpoly
with this solution at a suitable temperature.
mer which coagulates the interpolymer in ?la
Thereafter, the ?ber can be rinsed, dipped in a
ment form.
catalyst solution if required, dried, and baked
After the spinning operation, the ?laments are
usually twisted together and the thread is drawn 15 if necessary. In the case of some easily vapor
izable after-treating agents, it is possible to treat
or stretched to produce molecular orientation
the ?bers with the reagent‘ in the vapor phase,
' along the longitudinal axis of the ?lament. The
thus eliminating the use‘ of solutions.
‘
drawing is done by unwinding the twisted ?la
The exactdetails of the treatment of the ori
ments from the bobbin, passing them through a
liquid or gas held at a suitable temperature, 20 ented ?ber with the after-treating agent will de
pend upon the physical and chemical character
usually higher than room temperature, and wind
istics'of the particular agent used. For example,
ing them on a second bobbin operating at a greater
in the case. of methoxymethyl derivatives of
peripheral speed than the ?rst bobbin. In this
melamine, uron, urea and diamides, a 6% solu
way, molecular orientation is produced in the
?ber as revealed by X-ray diffraction patterns, 25 tion of the reagent in water is generally used.
The ?bers are soaked overnight in this solution
and the tenacity of the ?ber is much greater
containing a small amount of ammonium chlo
than that of the undrawn ?lament.
ride as a catalyst and then air dried at elevated
Polyfunctional substances, one mole of each
temperature, e. g. at about 85° C., and baked at
of which will react with a plurality of moles of
diethylamine, and which when applied to 30 about 135° C. Formaldehyde may be utilized in
, a similar procedure. Water-reactive agents,
oriented ?bers of the hydroxyl-containing inter
such as hexamethylene diisocyanate and adipyl
polymers serve to substantially eliminate the
chloride, are used in inert organic solvents. The
water-sensitivity thereof, may be classi?ed as fol
?bers can be soaked in a 10% solution of hexa
lows:
(l) Methylol and alkoxymethyl derivatives of 35 methylene diisocyanate in toluene for one hour‘
at ‘70° C. Treatment of the ?bers with adipyl
uron, i. e., the chemical compound having the
chloride is carried out in the same manner ex
structural formula
cept that a temperature of 25°-50° C. is su?lcient.
After this treatment the ?bers are rinsed with
40 toluene or other non-reactive solvent and the
chloroform-methanol mixtures, aqueous allyl
alcohol, piperidine, morpholine, and phenol. The
HN
NH
solvent is allowed to evaporate.
H143
CH:
Someafter-treating agents, e. g. those of class
4, are especially effective in raising the melting
point of the ?bers while others, e. g,'those of class
1, are most effective in reducing retraction in
\0/
melamine, urea and diamides in general. Spe
ci?c examples are dimethyloluron, trimethylol
melamine, dimethylolurea, N,N'-dimethylolsuc
cinamide, N,N'-dimethyloladipamide, etc., and
the methyl ethers of these compounds.
(2) Polybasic acids-and their acid halides.
Speci?c examples are adipic acid, adipyl chloride,
sebacic acid, sebacyl chloride, phosgene, boric
acid, thionyl chloride, sulfuryl chloride, and
'
water. For this reason it may be desirable to
treat the ?ber with more than one agent. A pre
ferred treatment for the ?bers is to use dimethyl
olurea ?rst, followed by treatment with hexa
methylene diisocyanate, thus giving the ?bers the
improvements of both reagents. The reverse or—
der of treatment can be used with like effect.
This invention is further illustrated by the fol
chromic acid. Of these, the acid chlorides of
lowing speci?c examples, wherein parts are by
polybasic acids are best.
weight unless otherwise indicated.
(3) Polyhalogen compounds in which the halo 55
gen is attached to a carbon atom which in turn'
Example I
is attached to other atoms by single bonds only.
This includes alpha, alpha'-dichlorethers, as
Oriented yarn prepared from hydrolyzed eth
alpha, alpha’-dichlorodimethylether and dichlo
ylene-vinyl acetate interpolymer having a mole
60
rodioxane. Other examples are 1,4-dichloro-2
ratio of 2.9/1, hydrolyzed 95% (12.1% of the car
butene and omega, omega’-dichloroxylene,
bon atoms of the polymer chain attached to hy
(4) Compounds having a plurality of _
droxyl and 0.6% attached to acetyl groups) is
treated as follows: A skein of the yarn is sub
merged in a relaxed condition for 1/2 hour at 50°
groups, where X is C or N; Y is O, S or NR. The 65 C. in a. solution of 85 parts of toluene, 2 parts of
most important examples are the diisocyanates.
pyridine, and 2 parts of adipyl chloride. After
(5) Certain conjugated unsaturates as quinone,
washing and drying, the treated yarn does not
acrolein, acrylonitrile.
stick to a block until a temperature of 220° C.
(6) Aldehydes, particularly formaldehyde. >
70 has been reached. It has a dry linear tenacity of
Others are acrolein, glyoxal, acetaldehyde, and
butyraldehyde.
(7) Chromic, ferric, and other heavy metal
salts.
-
I
(8) Diquatemary ammonium compounds de
rived from alpha, alpha'-dichloroeth§r$ 01.‘ D15
1.4 g./denier with 50% elongation and a loop te
nacity of 1.1 g./denier. Untreated yarn shrinks
70% in water at 100° C., sticks to a block at 105°
C., and has a dry linear tenacity of 2.4 g./denier
75 with 11% elongation.
2,403,404
‘
_ 5
Example II
(a) Oriented yarn prepared from hydrolyzed
ethylenevinyl acetate having a mole ratio of 3/1.
hydrolyzed 99% (12.4% of the carbon atoms in
the polymer chain attached to hydroxyls and '
Another sample of this same oriented yarn that
had been wound around a bobbin is treated for
14 hours in a mixture of 40 parts of water and 2
parts of glyoxal sulfate. The treated yarn is
rinsed with water, dried, and baked in air one
hour at 125° C. and ,1/2 hour at 135° C.-- It
shrinks 8% in water at 100° C. (d) Afurther
sample of untreated oriented yarn is wound
0.1% attached to acetyl groups‘) is wound around
a bobbin and treated at 102° C. for ‘la-hour in a
solution of 3 parts of sodium sulfate and 15 parts
of water to effect “heat setting." A skein of this 10 ?rmly around a bobbin and boiled in toluene for
5 minutes. Su?icient hexamethylene diiso
yarn is submerged in a relaxed condition for 11:
cyanate is added to make a solution of 2 parts
hour in water at 90° C., dried, wound around a
in
98 parts of the toluene. The solution is boiled
bobbin, soaked brie?y in a solution of one part of
' pyridine and 20 parts of benzene, and treated for
V5 hour in a solution of one part of adlpyl chlo
ride and 50 parts of kerosene at 70° C. The
product shrinks 3% in water at 100° C. and sticks
to a block at 185° C. It has a tenacity of 2.6 g./d_
with 12% elongation. vThe untreated yarn
shrinks 70% in water at 100° C., sticks to a block
at 105° C., and has a tenacity of 2.2 g./d. with 20
14% elongation.
one hour ‘and the yarn washed with toluene,
and dried. The treated yarn sticks to a block
at 250° C., shrinks 25% in water at 100° C., and
has a tenacity of 2.7 g./d. with 5% elongation.
Oriented, untreated yarn of this composition
sticks to a block at 140° C., disintegrates in water
at 100° C. and has a tenacity of 3 g./d. with 10%
elongation.
'
_
Example V
Oriented yarn of the same composition de
scribed in Example II is wound around a bobbin
and soaked in a solution of N,N'-bis(methoxy
yarn is wound around a bobbin and heated at
70° C. in water for 1,30 hour. After drying, the 25 methyl) urea in 98 parts of water“ for 14 hours
at 25° C. It is rinsed in distilled water and a
bobbin of heat-set polyvinyl alcohol is treated
(b) Oriented polyvinyl alcohol (50% of car
bons in polymer chain attached to hydroiwls)
solution of 90 parts of water and 10 parts of
with pyridine and adipyl chloride solution as in
part (a) above. Although the product does not
ammonium chloride, dried at 25° C. and baked
one hour at 125° C. and 1/2 hour at 135° C. The
dissolve, it shrinks 60% in water at 100° C., and
has a tenacity of less than 0.5 g./d. Polyvinyl 30 treated yarn shrinks 21% in 6 minutes in water
at 100° C. and sticks to a block at 135° C. The >
alcohol yarns therefore do not respond to this
yarn is thoroughly washed with distilled water
treatment as do yarns prepared from hydrolyzed
ethylene-vinyl acetate interpolymers.
to remove ammonium chloride, retreated with the
solution
of N,N’-bis(methoxymethyl) urea and
Example III
35
washed with water and the ammonium chloride
A sample of the untreated oriented yarn de
solution. After baking for one hour at 135° C.
scribed in Example 11 is' heat-set while under
the yarn shrinks 3% in water at 100° C. and
tension (held at constant length) in aqueous
sticks to a hot block at 145° C. The yarn is '
sodium sulfate solution at 102° C. and then sub 40 washed while still on a bobbin with a solution
merged in a relaxed condition in water at 90° C.
of 1.5 parts of soap and 98.5 parts of water and
The yarn is wrapped around a bobbin and heated,
then with distilled water and dried. A portion of
for one hour at 80° C. in‘ a 5% solution of hexa
this yarn is heated in'water for 10 minutes at
methylene diisocyanate in kerosene. The yarn,
100? C. and dried. It has a tenacity of 1.6 g./ .
after drying, does not stick to a block until the
with 21% elongation. The remainder of the
temperature reaches 210° C. and does not shrink
yarn is relaxed in 90 parts of toluene and 10 parts
in water at 100° C. It has a tenacity of 2.0 g./d.
of hexamethylene diisocyanate at 70° C. for one
with 12% elongation which is raised to 2.9 g./d.
hour. The yarn is washed in toluene, dried and
with 12% elongation by heating the yarn under
relaxed in air at 110° C. It has a tenacity of
tension in n-butanol at 80° C. for 11; hour. The 50 2.2 g./d. with 16% elongation, a loop tenacity of
original untreated yarn, as stated in Example 11,
1.5 g./d. with 16% elongation. It does not
shrinks 70 % in water at 100° C., sticks to the block
shrink in water at 100° C. and does not stick to
at 105 C., and has a tenacity of 2.2 g./d. wit
a block until a temperature of’ 220° C. has been
14% elongation.
'
reached.
Example IV
Example VI
55
A skein of unoriented ?laments of the same
Oriented yarn prepared from hydrolyzed
composition described in Example II is soaked
ethylenevinyl acetate ‘ interpolymer having a
14 hours at 25°-30° C. in a solution of 6 parts
mole ratio of 1.2/1, substantially completely hy-'
of N,N'-bis(methoxymethyl)urea in 94 parts of
drolyzed (23% of the carbon atoms in the poly
mer chain attached to hydroxyls) is wound 60 water. It is rinsed with distilled water and ace
tone and dried. It is drawn immediately 320%
around bobbins and treated for 14 hours
in mineral oil at 90° C., wound on another bobbin
at 25°-30° C. in the following solutions: (a)
under tension, soaked brie?y in a solution of 10
2 parts of N,N’,N"-tris(methoxymethyl)mel
parts of ammonium chloride and v90 parts of
amine, 2 parts of formaldehyde, and 53 parts of
water; and (b) 4 parts of N,N'-'bis(methoxy 65 water, dried and baked in air at 135° C. for one
hour. The treated yarn shrinks 6% in -water
methyDurea, 10 parts of water and 30 parts of
acetone. The treated yarns are rinsed once in
water and once in solution of 10 parts of ammo
nium chloride and 90 parts of water, dried and
baked for 2 hours at 130° C. The yarn treated
with‘ solution (a) shrinks 2% in water at 100°
C. and sticks to a block at 120° C., while yarn
treated with solution (b) shrinks 5% in water
at 100° C., sticks to a block at 130° C. and has a
at 100° C. and sticks to a block at 162° C.
The
N,N'-bis(methoxymethyl)urea does not react
with the ?bers during drawing, but during the
baking at 135° C. in the presence of the ammo
nium chloride. That is, reaction takes place on
the oriented material.
Example VII
(a) Oriented yarn prepared from hydrolyzed
tenacity of 2.4 g./d. with 20% elongation. (c) 75 ethylenevinyl acetate interpolymer, having a
2,403,464
8
.
‘mole ratio of 1/2.1, substantially completely
so treated sticks to a block at 195° C. and shrinks
hydrolyzed (33.9% of, the carbon atoms in the
polymer chain attachedvto hydroxyls) is wound
5° C. with a solution of 10 parts of N,N',N’f-tris
(methoxymethyl) melamine, 2.5 parts of ammo
20% in boiling water. Untreated yarn disinte
grates in boiling water and sticks to a_ block at
160° C.
It is understood of course that the‘ above ex
amples are for purposes of illustration only and
nium chloride, and 87.5 parts of water.
that the invention is not limited to the materials,
around a bobbin and treated for 16 hours at 0° to
After
reagents, and conditions therein set forth, but
drying at 25°—30° C., the yarn is baked one hour
is susceptible rather to wide variationv as will
in air at 135° C. It sticks to a block at 155° C.,
shrinks 8% in water at 100 C., and has a tenacity 10 more clearly be pointed out hereinafter.
of 4.0 g./d. with 8% elongation; Untreated
‘
yarn sticks to a block at 140° C., disintegrates
in water at l00f’,'C.,-.and has a tenacity of 4.7 g./d.
more of ethylene with vinyl organicesters, any
other hydrolyzed interpolymer of a vinyl organic
with 9% elongation.
' ester with another polymerizable compound, hav
,
In place of the preferred hydrolyzed interpoly
(b) Another portion of untreated oriented yarn 15 ing less than 45% of the carbon atoms attached
to hydroxyl groups, may be treated according to
described under (a) is 'wound around a bobbin
this invention. The interpolymer chain will thus
and heated at 102° C.,for 11; hour in a solution
contain —CHOH-—CH2-- units together with
of 3 parts of sodium sulfate in 15 parts of water
other units the exact character of which is large
and submerged in a relaxed condition for 112 hour
at 90° C. in water. A skein of the yarn is soaked 20 ly irrelevant except, of course, that it is derived
16 hours in a relaxedcondition in a solution of 3
from a ‘polymerizable monomer other than a
parts of N,N',N"-tris(methoxymethyl)melamine,
vinyl organic ester and which does not hydrolyze
to yield alcoholic hydroxyl groups under the con
ditions used to hydrolyze the interpolymer. A
and after baking for 3 hours at 85° C. and 14 25 large number of monomers of this type are
known. Particularly well known are vinyl com
hour at 135° C., it does not shrink in water at
pounds of formula CI-Iz=CHX, where X is a
100° C. and sticks to a block at 145° C. Its tenac
monovalent atom or radical such as halogen,
ity, which is substantially unchanged by heat
cyano, carboxy, carbalkoxy, acyl, or amide. An
ing the yarn in water at 100° C. for 5 minutes,
is 4.0 g./d. with 17% elongation. This ?ber gives 30 other class of polymerizable substances are the
vinylidene compounds of ' formula CI-llz=CXz,
an X-ray diifraction pattern typical of an ori
where X is a monovalent atom or radical and
ented crystalline polymer in that it contains
where the X’s may be the same or different. Ex
sharply de?ned interferences.
amples are vinylidene chloride and methyl meth
(c) Oriented polyvinyl alcohol (50% of the
carbons in the polymer chain attached to hy 35 aerylate.
In the case of the preferred hydrolyzed eth
droxyls) yarn that has been heat-set under
1 part of ammonium'chloride, and 96 parts of
water. The dried yarn is wound around a bobbin
tension on a bobbin in water at 70° C. for 2 min
utes, is treated while still on the bobbin in a solu
ylene-vinyl acetate interpolymers, those having
an ethylene/vinyl alcohol molar ratio of from
49/1 to 1/3 (hydroxyls on 1 to 38% of the carbon
and baked substantially as described under (b). 40 atoms of the polymer chain) give after-treated
?bers with good water resistance. The inter
Although the product does not dissolve in water
polymers with an ethylene/vinyl alcohol ratio of
at 100° C., its tenacity is less than 0.5 g./d. and
from 3/1 to 1/3 (hydroxyls on 12 to 37.5% of the
it shrinks about 70%. Polyvinyl alcohol yarn
carbon atoms of the polymer chain) give after
does not respond to these treatments as well as
yarn from hydrolyzed ethylene-vinyl acetate in 45 treated ?bers of the greatest general utility. For
some uses it is possible to obtain su?lcient hot
terpolymers.
water resistance in ?bers made from polymers
Example VIII
tion of N,N’,N"-tris(methoxymethyl) melamine
having as much as 45% of the carbon atoms
One skein each of oriented yarn prepared from
the polymer chain attached to hydroxyl groups
hydrolyzed ethylene-vinyl acetate interpolymer, 50 of
or groups hydrolyzable to hydroxyls.
having a mole ratio of 1/2.3, 93% hydrolyzed
Part of the hydroxyl groups may be convert
(32% of the carbon atoms in the polymer chain
attached to hydroxyls and 2.4% attached to
acetyl groups) is treated one hour at 25°-30° C.
in the following solutions: (a) 1 part of am
monium chloride, 3.7 parts of formaldehyde, and
95.3 parts of water; (1)) 2.5 parts of N,N’-bis
(methoxymethyDuron, 97.5 parts of water and
0.001 part of 85% phosphoric acid. After drying,
ed into other groups, as acetals or ketals. That
is, a hydrolyzed interpolymer may be .treated
with an aldehyde such as formaldehyde or bu
55 tyraldehyde under mild conditions to form afor
mal or butyral with some of the hydroxyl groups.
The treatment of the oriented ?bers of such ma
terials comes within the scope of this invention.
The acetals may be spun, oriented, and then
both skeins are baked one hour at 130° C.
baked as an after-treatment. The aldehyde used
Neither of the skeins shrinks in water at 100° C. 60
in making the acetal serves as the after-treating
nor sticks to a block below 225° C.
Untreated
yarn disintegrates in water at 100° C. and sticks
to a block at 160° C.
agent under the conditions of baking.
>
Heat treatment of the untreated oriented ?
bers at constant length reduces their shrinkage
Example IX
when placed in water at 100° C. in a relaxed con
A skein of oriented yarn prepared from hy
dition. This heat treatment or “setting" at con
drolyzed ethylene-vinyl acetate interpolymer,
stant length can be effected by heating the fi
,havinga mole ratio of 1/3.6, hydrolyzed 95.2%
bers in air, water, aqueous salt solutions, or bu
(37.3% of the carbon atoms of the polymer chain
tanol, or in other organic liquids which do not
attached to hydroxyls and 1.8% attached to ace 70 dissolve the ?bers. The setting treatment is fa
tyl groups) is treated 1/2 hour ‘in a. solution of 1
cilitated by heating the ?bers in contact with a
part of hexamethylene diisocyanate and 640 parts
small amount of dilute acid such as hydrochloric,
of boiling toluene. Forty parts of mineral oil is
sulfuric, phosphoric, or acetic acid. Such acid
added and the temperature gradually raised to
heat treatment aids in making the ?bers less wa
160° C. while the toluene is distilled. The yarn 75 tor-sensitive. However, in order to obtain ?bers
2,403,404
.
9
having good resistance to shrinkage in boiling
‘organic ester in which from 1% to less than 45%
water, particularly in the case of hydrolyzed in
of the carbon atoms of the polymer chain are
attached to groups from the class consisting of
terpolymers relatively high in hydroxy1 content,
it is necessary to subject the oriented ?bers to
the chemical after-treatment of this invention.
hydroxyl groups and organic radicals hydrolyz
able to hydroxyl groups, which comprises react
It is desirable to apply this chemical after-treat
ing said oriented ?bers in one or more stages
ment to ?bers which have been heat-set since
with a solution of a polyfunctional substance or
this combines the useful e?ects of both treat
substances one mole each of ' which will react
ments.
with a pluralityof moles of diethylamine, said
The after-treating agent used in the process 10 substance being selected from the group consist
of this invention can be applied to the ?laments
ing of methylol and alkoxymethyl derivatives of
before orientation if the agent does not react im
uron, melamine, urea and diamides.
mediately. The ?ber can then be oriented by
3. The method of improving oriented ?bers of
drawing, and the agent already present can be
hydrolyzed interpolymers of ethylene with a
caused to react with the oriented ?ber by heat, 15 vinyl organic ester in which from 1% to less
catalyst or aging. If the ?bers are treated to
than 45% of the carbon atoms of the polymer
raise the melting point before orientation, sub
chain are attached to groups from the class con
sequent orientation is not so successful as when
performed ?rst.
sisting of hydroxyl groups and organic radicals
hydrolyzable to hydroxyl groups, which comprises
This emphasizes the impor
tance of carrying out the reaction after orien
tation.
'
20 treating said oriented ?bers in one or more stages
with a solution of a polyfunctional substance or
substances one mole each of which will react
‘
The ?bers can be given more than one treat
ment with the same after-treating agent or with
with a plurality of moles of diethylamine, said
different agents. In the case of using more than
substance being selected from the group consist
one agent, the treatments can be successive, or
ing of methylol and alkoxymethyl derivatives of
a plurality of after-treating agents can be ap
uron, melamine, urea and diamides, then remov
plied at the same time, providing they do not re
ing the solvent from the treated ?bers, and there
act with each other or the solvent. The appli
after subjecting said ?bers to baking tempera
cation of more than one after-treating agent to
tures.
'
the same ?ber possesses an advantage in that 30
4. The method of improving oriented ?bers of
each may impart valuable properties to‘the ?ber.
hydrolyzed interpolymers of ethylene with a
The after-treating agents can be applied to ?
vinyl organic ester wherein from 1% to less than
45% of the carbon atoms of the polymer chain
bers containing other modifying substances pro
viding that the modifying substance does not re
are attached to hydroxy1 groups which com
act with all of the after-treating agent. Such 35 prises reacting said oriented ?bers with a com
modifying substances are dyes, pigments, sizes,
weighting, lubricants, plasticizers, and ?llers.
position comprising essentially polyfunctional
substances one mole each of which is reactive
with a plurality of moles of diethylamine, said
The ?ber may contain substances which can be
dissolved out, leaving interstices into which the
substances being selected from the group consist
40 ing of methylol and alkoxymethyl derivatives of
after-treating agent can penetrate.
If the ?ber is ?rst swollen by soaking in an ap
uron, melamine, urea and diamides.
propriate liquid, the after-treating reagent will
5. The method of improving oriented ?bers of
react more readily with the ?ber.
hydrolyzed interpolymers of ethylene with a vinyl
The procedure which leads to the best ?bers,
organic ester wherein from 1% to less than 45%
particularly‘ from the standpoint of tensile 45 of the carbon atoms of the polymer chain are at
strength and resistance to shrinking, consists in
tached to hydroxyl groups, which comprises re
(1) heat setting the oriented ?berat constant
acting said oriented ?bers in one or more stages
length at 95°—102° C. prior to treatment with the
with a solution of a polyfunctional substance or
after-treating agent, (2) avoiding the use of ex
substances one mole each of which will react
cess after-treating agent, and (3) applying all 50 with a plurality of moles of diethylamine, said
heat or baking treatments to the ?ber while it is
substance being selected from the group consist
held at constant length.
ing of methylol and alkoxymethyl derivatives of
.
. The after-treated, oriented ?bers of this in
uron, melamine, urea and diamides.
vention are of general utility, including use for
hosiery yarn, weaving, felts, pile fabrics, sewing
thread, cordage, nets, screens, ?shline, electrical
, insulation;
and mono?ls as racket and bow
strings, ?shing leaders, bristles, etc.
I claim:
‘ 6. The method of improving oriented ?bers of
55
hydrolyzed interpolymers of ethylene with a vinyl
. organic ester wherein from 1% to less than 45%
of the carbon atoms of the polymer chain are
attached to hydroxyl groups, which comprises
treating said oriented ?bers in one or more stages
. 1. The method of improving oriented ?bers of 60 with a solution of a polyfunctional substance or
hydrolyzed interpolymers of ethylene with a yinyl
organic ester in which from 1% to less than 45%
substances one mole each of which will react
of the carbon atoms of the polymer chain are
attached to groups from the class consisting of
substance being selected from the group consist
with a plurality of moles of diethylamine, said
ing of methylol and alkoxymethyl derivatives of
hydroxyl groups and organic radicals hydrolyz 65 uron, melamine, urea and diamides, then remov
able to hydroxyl groups, which comprises react
ing the solvent from the treated ?bers, and there
ing said oriented ?bers with a composition com
prising essentially polyfunctional substances one
' _mole each of which is reactive with a plurality
after subjecting said ?bers to baking tempera
tures.
-
7. The method of improving oriented ?bers of
of moles of diethylamine, said substances being 70 hydrolyzed interpolymers of ethylene with vinyl
selected from the group consisting of methylol
acetate wherein from 1% to less than 45% of the
carbon atoms of the polymer chain are attached
and alkoxymethyl derivatives of uron, melamine,
to hydroxyl groups, which comprises reacting said
urea and diamides.
2. The method of improving oriented ?bers of
oriented ?bers with a composition comprising es~
hydrolyzed interpolymers of ethylene with a vinyl 75 sentially polyfunctional substances one mole each
2,403,464
11
12
of which is reactive with a plurality of moles of
lower degree of retraction in water than the un
reacted ?ber.
diethylamine, said substances-being selected from
the. group consisting of methylol and alkoxy
methyl derivatives of uron, melamine, urea and
diamides.
~7
13. Oriented ?bers of hydrolyzed interpolymers I
of ethylenewith a vinyl organic ester, which ?
> bers have been reacted subsequent to orientation
with polyfunctional substances one mole each of
which is reactive with a plurality‘oi.’ moles of di
ethylamine, said substances being selected from
acetate wherein from 1% to less than 45% of the
the group consisting of methylol and alkoxy
carbon atoms of the polymer chain are attached
to hydroxyl groups, which comprises reacting 10 methyl derivatives of uron, melamine, urea and
diamides, said hydrolyzed interpolymer before re
said oriented ?bers in one or more stages with
action having from 1% to less than 45% ‘of the
a solution of a polyfunctional substance or sub
carbon atoms of the polymer chain attached to
stances one mole each of which will react with
hydroxyl groups, said reacted ?bers being further
a plurality of moles of diethyiamine, said sub
stance being selected from the group consisting 15 characterized by being substantially insoluble in
‘water at 100° 0., and having a lower degree of re
of methylol and alkoxymethyl derivatives of uron,.
traction in water than the unreacted ?ber.
melamine, urea and diamides.
14.‘ Oriented ?bers of hydrolyzed interpoly
9. The method of improving oriented ?bers of
8. The method of improving oriented ?bers of
hydrolyzed interpolymers of ethylene with vinyl
hydrolyzed interpolymers of ethylene with vinyl
mers of ethylene with vinyl acetate, which ?bers
acetate wherein from 1% to less than 45% of the 20 have been reacted subsequent to orientation with
polyfunctional substances one mole each of which
carbon atoms of the polymer chain are attached
is reactive with a plurality of moles of diethyl
to hydroxyl groups, which comprises treating
amine, said substances being selected from the
said oriented ?bers in one or more stages with
group consisting of methylol and alkoxymethyl
a solution of a polyfunctional substance or sub
stances one mole each of which will react with 25 derivatives of uron, melamine, urea and diamides,
said hydrolyzed interpolymer before reaction hav
a plurality of moles of diethylamine, said sub
ing from 1% to less than 45% of the carbon atoms
stance being selected from the group consisting of
of the polymer chain attached to hydroxyl groups,
said reacted ?bers being further characterized by
solvent from the treated ?bers, and thereafter 30 being substantially insoluble in water at 100° C_.,
and having a higher melting point and a. lower
subjecting said ?bers t0 baking temperatures.
degree of retraction in water than the unreacted
10. The method of improving oriented ?bers of
hydrolyzed interpolymers of ethylene with vinyl
?ber.
15. Oriented ?bers of hydrolyzed interpolymers
acetate wherein the mole ratio of ethylene to
vinyl alcohol varies from 3/1 to 1/3, which com 35 of ethylene with vinyl acetate which ?bers have
been reacted subsequent to orientation with poly
prises-reacting said oriented ?bers in one or more
methylol and alkoxymethyl derivatives of uron,
melamine, urea and diamides, then removing the _
stages with a solution of a polyfunctional sub
stance or substances one mole each of which will
functional substances one mole each of which is
of uron, melamine, urea and diamides.
hydrolyzed interpolymer before reaction having
reactive with a plurality of moles of diethylamine,
react with a plurality of moles of diethylamine,
said substances being selected from the group
said substance being selected from the group con 40 consisting of methylol and alkoxymethyl deriva
sistlng of methylol and alkoxymethyl derivatives
tives of uron, melamine, urea and diamides, said
11. The method of improving oriented ?bers of
hydrolyzed interpolymers of ethylene with vinyl
acetate wherein the mole ratio of ethylene to
vinyl alcohol varies from 3/1 to 1/3, which com
prises treating said oriented ?bers in one or more
stages with a solution of a polyfunctional sub
stance or substances one mole each of which will
from 1 to 38% of the carbon atoms of the poly
mer chain attached to hydroxyl groups, said re
acted ?bers being further characterized by being
substantially insoluble in water at 100° C., and
having a higher melting point and a lower degree
of retraction in water than the unreacted ?ber.
16. An oriented ?ber of a substantially com
pletely hydrolyzed interpolymer of ethylene with
said substance being selected from the group
vinyl acetate, which ?ber has been reacted sub
consisting of methylol and alkoxymethyl deriva
sequent to orientation with N,N'-bis(methoxy
methyl) urea, said hydrolyzed interpolymer before
tives of uron, melamine, urea and diamides, then
removing the solvent from the treated ?bers, and
reaction having from 12 to 37.5% of the carbon
thereafter subjecting said ?bers to baking tem 55 atoms of the interpolymer chain attached to hy
peratures.
droxyl groups, said reacted ?ber being further
12. Oriented ?bers ofhydrolyzed interpolymers
characterized by substantial insolubility in water
react with a plurality of moles of diethylamine, -
of ethylene with a vinyl organic ester which have
been reacted subsequent to orientation with poly
at 100° C. and a higher melting point and a lower
degree of retraction in water than the unreacted
functional substances one mole each of which is 60 ?ber.
reactive with a plurality of moles of diethylamine,
17. The method of improving an oriented ?ber
of a substantially completely hydrolyzed inter
said substances being selected from the group
consisting of methylol and alkoxymethyl deriva
polymer of ethylene with vinyl acetate wherein
tives of uron, melamine, urea and diamides, said
from 12 to 37.5% of the carbon atoms of the in
interpolymer before reaction having from 1% to 65 terpolymer chain are attached to hydroxyl groups,
which comprises treating said oriented ?ber with
less than 45% of the carbon atoms of the polymer
a solution of N,N’-bis(methoxymethyl) urea, re
chain attached to groups from the class consist
ing of hydroxyl groups and organicv radicals hy
moving the solvent from the treated ?ber, and
thereafter subjecting said ?ber to a baking tem
drolyzable to hydroxyl groups, said reacted ?bers
‘
being further characterized by being substantial 70 perature.
AILIBER'JI'v FARIS SMITH,
ly insoluble in water .at 100° C., and having a
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