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Патент USA US2412034

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2,412,034
Patented Dec. 3, 1946
UNITED STATES PATENT OFFICE
2,412,034
SYNTHETIC COMPOSITIONS AND PROD
UCTS HAVING MOLECULARLY ORIENTED
STRUCTURE
I Gaetano F. D’Alelio, Pitts?eld, Mass., assignor to
General Electric Company, .a corporation of
New York
No Drawing. Application June 4, 1942,
Serial No. 445,808
2 Claims. .(Cl. 28-42)
2
1
may then be cold-drawn to produce a
molecularly oriented structure which exhibits
This invention relates to novel synthetic com
positions wherein the molecules have been
oriented so that they are parallel with the major
surface. More particularly this invention re
lates ‘to formed structures which exhibit char
the characteristic crystalline X-ray pattern.
Threads made from such compositions have out
acteristic crystalline X-ray diffraction patterns
standing tensile strength of the order of 40,000
50,000 pounds per- square inch. The threads are
and comprise a molecularly oriented copolymer
of acrylonitrile and an acrylic ester having th
without breaking.
structural formula
-
‘f
capo-coon’
very ?exible and can be tied into tight knots
_
‘
Copolymers of acrylonitrile and acrylic esters
10 having substantially greater than 80% acryloni
trile are too hard and brittle, and have too high
consisting of hydrogen and monovalent alkyl
a melting point to be readily adaptable to the
methods of forming molecularly oriented‘ struc
tures. Copolymers comprising substantially less
radicals having a maximum of four carbon
atoms, and R’ is a radical selected from the class
than 40 per cent acrylonitrile cannot be cold
drawn to, produce a {molecular oriented struc
where R' is a radical selected from the class
consisting of alkyl radicals, aralkyl radicals, aryl
ture which exhibits the characteristic crystalline
radicals and alkaryl radicals.
X-ray patterns.
Illustrative ex
The
components , themselves
amples of radicals represented by R in the above
cannot be cold drawn. Polymeric acrylonitrile
formula are: methyl, ethyl, propyl, isopropyl, 20 is far too hard and brittle and has too high a
butyl, isobutyl, tert.-butyl, sec.-butyl. Prefer
softening point to prepare extruded or precipi
ably R is hydrogen or the methyl radical. Illus
tated ?bers or the like. Likewise the esters of
trative examples of radicals represented by R’
acrylic acid and/or substituted acrylic acids are
in the above formula are: alkyl, e. g., methyl, '
unsatisfactory when polymerized alone or with.
ethyl, propyl, isopropyl, vbutyl, isobutyl, sec. 25 copolymerizable materials other than acryloni
butyl, amyl, hexyl, decyl, etc.; cycloalkyl, e. g.,
trile, e. g., ethyl acrylate, ethyl methacrylate,
cyclopentyl, cyclohexyl, methyl cyclopentyl,
propyl cyclopentyl, amyl cyclopentyl, methyl
styrene, ethyl acrylate-styrene, benzyl acrylate
cyclohexyl, dimethyl cyclohexyl, etc. ; aryl, e. g.,
' materials cannot be cold drawn to yield articles
styrene, etc.v Copolymers of these and related
phenyl, xenyl, naphthyl, etc. ; alkaryl, e. g., tolyl, 30 ‘having molecularly oriented structure. Even
acrylonitrile ‘cannot be cold drawn to give
xylyl, ethyl phenyl, propylphenyl, isopropyl
vphenyl, etc.; aralkyl, e. g., benzyl, phenethyl,
oriented products when copolymerized with such
phenylpropyl, phenylbutyl, etc.
unsaturated compounds as butadiene, styrene,
Acrylonitrile and its copolymers possess out
vinyl acetate, etc. For example,'a mixture com
standing properties which make them useful in 35 prising ' ‘,
,
.
the plastics art. For example, they have a de
Parts by weight
sirably high softening point and are very re-'
sistant to the action of chemicals. However,
Acylonitrile
although polymeric acrylonitrile and copolymers
Butadiene _________________________ __.,_ 30
Benzoyl peroxide ________ _.' ____________ __
0.25
of acrylonitrile are known, as far as I am aware 40
noone has successfully produced articles from
these polymeric bodies which possessed a molec
ularly oriented structure. This has excluded
their use in the preparation of ?bers and other
objects requiring a molecularly oriented struc; 45
ture.
'
-
'
__________________________ _.. 70
‘was sealed in an autoclave and exposed to in
creasingly more drastic polymerizing conditions.
The autoclave was ?rst kept at room tempera
ture for 42 hours and then at 45° C. for 7 hours.
Following this the autoclave was heated to 60° C.
for '72 hours and then at 80-90? C. for 48 hours.
The polymer was removed from the autoclave
I have now discovered that it acrylonitrile is
copolymerized with an acrylic or alpha-sub
and sheeted between the differential 1 rolls at
loo-120° C. to remove any entrapped monomers
stituted acrylic ester in the proportions of from
40 to 80 per cent nitrile to from 60 to 20 per 50 or low molecular weight polymers. Fibers made
from this composition could not be cold drawn.
cent ester and preferably from 50 to'80 per cent
The preferred method for forming the oriented
nitrile to from 50 to 20 percent ester a copoly
mer is obtained which may be formed into the
articles of this invention involves first the co- 1 I
shape of ?laments, foils, tubes, etc. by extrusion
polymerization of the selected'monomers. Two
or precipitation methods. These shaped articles 55 satisfactory methods of polymerization may be
2,412,034
used. An emulsion method may be carried out
by placing the mixture of monomers in water
tion may be carried into effect the following ex
amples are given. All parts are by weight.
containing a small amount of an emulsifying
Example 1
agent, e. g., polyvinyl alcohol, polymethacrylic
acid, starch acetate, Aerosol, Tergitol, etc., and 5
‘
_
,
‘
Parts by weight
a polymerization catalyst. The mixture of
monomers may be emulsi?ed in the water prior
to or after an initial polymerization has been
Acrylonitrile ____________________________ __
40
Ethyl acrylate __________________________ __
60
effected. By rapid agitation under the in?uence
Polymethacrylic acid ___________ ___ _______ __
Water _________________________________ __ 500
2.5
of heat, e. g., 70-85° C., a latex is obtained which 10 Hydrogen peroxide (30% aq. sol’n) ______ __ 1.7
may be coagulated by the usual methods, e. g.,
The above ingredients were mixed together in
by addition of coagulants. Alternatively the
a three-neck one-liter ?ask equipped with a
mixture of monomers may be heated alone in
,stirrer and a reflux condenser. The reaction
the presence of an activating catalyst at tem
mixture was heated initially at 60-700 C. for a
15
peratures substantially below the boiling point
period of 1 hour and following this at-70-80° C.
of the mass in a sealed container. As the poly
for 40 hours. The resulting product was a latex.
merization proceeds, the temperature may be
type material. The copolymer was coagulated
from this latex by application of heat and the
addition of sodium chloride. The removal of the
monomer or low molecular weight substances by 20 chloride ion from the polymer wasthen e?ected
any one of several methods, e. g., by sheeting
.by continually washing with warm water and
increased as the vapor pressure of the mass de
creases. The copolymers are freed from any
with resultant evaporationIor by use of selective '
then with cold water. The product was now dried .
and any remaining easily vaporizable monomers
solvents.
The copolymers of this invention may be made
or low molecular weight polymers were removed
into ?bers, threads, ?laments, ?lms, tubes and 25 by sheeting on differential rolls at 150° C. The
the like by any suitable method. For example,
yield of product was 91%. This composition, now
I may extrude the copolymer under pressure
in a state ready for fiber formation, was pre
through a die at elevated temperatures or I may
dissolve the polymer in a suitable solvent and
molded into a pill, dimensioned to fit snugly into
the heating chamber of the extrusion’ apparatus.
reprecipitate it in the desired shape by’forcing 30 By making this preform, the presence of any air
entrapped in the ?bers would be virtually impos
the solution through a die, followed by either
evaporation of the solvent or passing into a pre
cipitant for the polymer. I prefer to use the
extrusion method for shaping the articles, using 35 ‘
chamber to 140-165° C. and a piston pressure of
temperatures ranging from 150-250° C., depend
ing upon the particular type of polymer being
the molten copolymer through the ori?ce. The
extruded ?lament was virtually ‘colorless, semi
used, since each polymer has a different soften
opaque, and slightly elastic.
sible. The preform wasiheated in the heating
800-1200 pounds per square inch used to extrude
The ?lament was .
maintained under slight tension during the ex
heated to ‘some temperature above the softening 40 trusion process and was cooled quickly by a stream
of cold air directed at the exterior of the ori?ce.
point, e. g., 15-25° C. above, extruded and rapidly
The extruded ?lament possessed a diameter of
cooled. After the article is formed it is cold
approximately 0.012". When cold drawn at room
drawn, during which process molecular orienta- _
temperature to 100-200% elongation, a ?ber ex
tion along the major surface takes place, The
extruded or precipitated articles are not in them 45 hibiting crystalline orientation along the main
ing point. Generally speaking the polymer is
selves molecularly oriented. It is only after the
cold drawing process that they exhibit the .char
?ber axis and possessing considerable strength
acteristic X-ray patterns indicative of the crys
ular orientation of the ?ber structure was evi
and excellent ?exibility was obtained. The molec
denced by the typical crystalline X-ray diffrac
talline orientation. The increase in tensile
strength and ?exibility after the cold drawing 50 tion pattern obtained. Further indication of an
oriented structure was manifested by the con
process is remarkable.
‘
version of the semi-opaque ?lament to an opaque
Any activating (polymerization) catalyst may
- one during the cold drawing operation.
be used in making the copolymers. For example,
I may use ozone, ozonides, inorganic super-oxides
Example 2
such as barium peroxide, sodium peroxide, etc., 55
Using the method of preparation described in
aliphatic acyl peroxides, e. g., acetyl peroxide,
Example 1' a copolymer prepared from 50 parts
lauryl peroxide, stearyl peroxide, tertiary-butyl
acrylonitrile and 50 parts ethyl acrylate was pro
peroxide, etc., peroxides of the aromatic acid
duced in a 98% yield.
'
series, e. g., benzoyl peroxide, aoetyl benzoyl per
The copolymer was now extruded in the same
oxide, various per compounds, e. g., perborates, p60
manner as described in the preceding example
persulfates, perchlorates, etc., aluminum salts "
or fed directly to a ?lament extruding machine.
such as the halides, e. g., aluminum chloride,
However, the temperature and pressure conditions
organic and inorganic acids such as methacrylic
used in this example were those of 150-190“ C.
acid, hydro?uoric acid, etc., metal compounds of
the unsaturated acids as, for instance, cobalt and 65 and 1000-1500 pounds per square inch. The ?la
ment was subjected to a tension su?lcient to
manganese resinates, linoleates, maleates, etc.
elongate it 100-150% at room temperature. The
Benzoyl peroxide is a preferred catalystin mass
oriented ?ber was tough and su?lciently?exible
polymerizations and hydrogen peroxide or benzoyl
so
that it could be tied into tight knots. The di
peroxide in emulsion polymerizations. Any
amount of catalyst may be used, but, in general, 70 ameter was approximately 0.012". This cold
u
for economic reasons the .catalyst concentration
will be within the range of 0.1 to 2.0 per cent
by weight of the whole.
In order that those skilled in the ‘art may
. better understand the means by which this inven
drawing operation as in the previous example
effected a molecular orientation along the main
?ber axis as indicated by the typical crystalline
X-ray diffraction patterns obtained from ?bers.
75 The‘ cold drawn ?lament possessed a tensile
2,412,084
5
01’ a heavy sirup was rapidly agitated by stirring.
strength of 40,000 pounds per square inch based
on the original diameter. Filaments of this com
position possessed excellent resistance to many
solvents, namely aliphatic hydrocarbons, alcohols,
ethers, mixtures of aliphatic and aromatic hydro
carbons, etc.
Example 3
A ?ber-forming composition was prepared in
the same manner as in Example 1 with the excep
Five hundred parts water containing 2 parts by
weight of polyvinyl alcohol were added. The
partially polymerized mass was thus dispersed
5 into bead form throughout the water. Heating
was continued at'80-85° C. for 55 hours.
The
product of small copolymer beads was ?ltered,
washed well with warm water and dried at 80°
C. for several hours. The yield of product was 85
10 parts. The copolymer was sheeted on the differ
ential rolls for 5 minutes at 150° C.
The extrusion of the preformed ?ber-forming
material was done at 140-180° C.,,employing a
piston pressure of 1000 pounds per square inch.
Extrusion was carried out at 170-220° C. in the 15 These ?bers were practically colorless and of
uniform cross-section. Cold drawing to produce
same apparatus used for the previous examples.
an elongation of about 100% produced a ?lament
The pressure used during the extrusion was 1000
that showed by X-ray photographs that a crys
2000 pounds per square inch. The extruded ?la
talline orientation along the major ?ber axis had
ment was cold drawn at 30-35° C., undergoing
in the process about 150% elongation. Whereas 20 taken place. The ?laments'produced by this cold
drawing process could be drawn into tight knots
the ?lament was somewhat brittle at room tem
tion that 60 parts acrylonitrile and 40 parts of
ethyl acrylate were used. The copolymer was pre
pared for extrusion in the usual manner. The
yield of polymer in this case was 850%.
without breaking. They exhibited good strength.
perature following the extrusion, after cold draw
ing it was extremely ?exible.
The cold drawn
' Example 6 ~
?ber showed by X-ray photography a typical
The preparation of a copolymer from a mono
meric mixture of 60 parts of acrylonitrile and 40
crystalline diffraction pattern, indicating orien
tation along the major ?ber axis.‘ Tensile
strength tests on several samples of the oriented
?ber gave values of 40,000-50,000 pounds per
parts ethyl methacrylate was carried out in the
same manner as described in Example 5.
Sim
ilarly the copolymer was prepared for extrusion
square inch.
The ?bers possessed excellent resistance to a 30 and then forced through an ori?ce to form the
?ber. The temperature required by this composi
great many solvents, e. g., aliphatic hydrocarbons,
tion was ISO-200° C. The ?laments produced .
ketones, alcohols, ethers, mixtures of aliphatic
could be cold drawn into oriented ?bers. These
and aromatic hydrocarbons and to naturally
possessed good ?exibility and a tensile strength
occurring liquids, as petroleum and its distilla
35 of about 40,000 pounds per square inch. The ?la—
tion products.
ments displayed excellent resistance to such sol
Example 4
vents as aliphatic hydrocarbons, alcohols, ethers,
Cellosolve, and to a limited extent to dioxane and
acetone.
Beginning with a monomeric mixture of '70
parts acrylonitrile and 30 parts ethyl acrylate a
copolymer was prepared by the method of Ex 40
ample 1. ‘This copolymer was sheeted to rid the
?ber-forming material of low molecular weight g
The product was now
‘ polymers and monomers.
Example 7
The preparation of ?bers from a copolymer
obtained from a monomeric mixture of 80 parts
acrylonitrile and 20 parts ethyl methacrylate fol
prepared for extrusion. The temperature re
lowed the same procedure as described in Ex
quired for satisfactory extrusion was 190-230° C. 45 ample 5. The temperature required for extrusion
and the pressure from 1500-2500 pounds per
was 180-220° C. and the pressure required was
square inch. The ?laments following extrusion
1000-1500 pounds per square inch. The ex
were pale yellow and somewhat brittle. It was
truded ?laments were brittle and lacked good
not possible to tie knots with these fibers with
strength qualities. However, when cold drawn,
out breaking them. After cold drawing to 100%
thus causing an orientation parallel to the major
elongation, the ?bers were much improved with
?ber axis, the ?laments exhibited excellent ?ex
‘regard to ?exibility and strength. The cold
ibility and a tensile strength between 40,000
drawing was carried out at 40-50° 'C._ Tensile
50,000 pounds per square inch. The resistance
strength tests gave values of from 40,000-50,000
of these products to hydrocarbons, alcohol, ether,
pounds per square inch. The solvent resistance 5 ketone, naturally occurring oils and chlorinated
of these ?bers was even better than those of the
previous examples.
Cloth
woven, from
these .
solvents was excellent.
Example 8
A copolymer of 70 parts acrylonitrile and 30
As in‘the previous cases the cold drawn ?laments 60 parts benzyl aorylate was produced by mass poly
showed marked molecular orientation along the
merization, using 0.15 part by weight of benzoyl
major ?ber axis.
peroxide as an activating catalyst. Copolymeri
Example 5
zation was accomplished by heating the mixture
?bers may be used in contact with petroleum,
gasoline. kerosene, alcohols, esters, ethers, etc.
Parts by weight
__________________________ __
50
Ethyl methacrylate _______ __- ____________ __
Acrylonitrile
50
_ at 65-80° C. over a period 01 '12 hours in a sealed
6” container. The copolymer was sheeted on the
differential rolls at 150° C. to remove any vola
tile components.
‘
Benzoyl peroxide ____ __:_ ________________ __ 0.05
Extrusion through an ori?ce of 0.012" diame
ter of a preformed pellet was carried out at 160
The above ingredients were mixed in a three
neck one-liter ?ask equipped with a stirrer and 70 190° C. and 1000 pounds per square inch pres
sure. The extruded ?ber was cold drawn to cause
a re?ux condenser. These reactants were heated
the molecular orientation parallel to the major
1% hours at 70-82° C. This temperature was ob
tained by gradually raising the temperature and
noticing the increase in viscosity. The partially
polymerized mass which was of the consistency
?ber axis. The product had good ?exibility and
a tensile strength of the order of 40,000 pound
76 per square inch.
-
9,419,084
.
r ‘
7
“ In‘ producing the molecularly oriented ?bers of
this invention I may use in addition to the ethyl
acrylate, ethyl methacrylate and benzyl acrylate,
such copolymerizable materials as any ester of
acrylic acid, e. 3., methyl acrylate, propyl acry
late, isopropyl acrylate, butyl acrylate, isobutyl
acrylate, amyl acrylate, octyl acrylate, decyl ac
rylate, cyclopentyl acrylate, cyclohexyl acrylate.
phenyl acrylate, ?uorophenyl acrylate, tolyl ac
rylate, xylyl acrylate, chloroethyl acrylate, etc.;
esters of methacrylic acid, e. g., methyl methac
rylate, ethyl methacrylate, propyl methacrylate,
butyl methacrylate, isobutyl methacrylate, cyclo
hexyl methacrylate, cyclopentyl methacrylate,
benzyl methacrylate, phenyl methacrylate, iodo
phenyl methacrylate, tolyl methacrylate, phen
ethyl methacrylate, xenyl methacrylate, etc.;
esters of ethacrylic acids, e. g., methyl ethac
rylate, ethyl ethacrylate, propyl ethacrylate,
bromopropyl ethacrylate, benzyl ethacrylate,
phenyl ethacrylate, tolyl ethacrylate, etc.; es
ters of propacrylic acid, e. g., methyl propac
8
,
.
molecularly oriented ?ber possessing ‘good
strength and ?exibility. A speci?c composi
tion which may be used to yield excellent re
sults is: acrylonitrile-70 parts, ethyl acrylate25 parts, and ethyl methacrylate-5 parts.
Example 10
'
Parts by weight
Acrylonitrile _____________________ __ X (50-80)
Ethyl acrylate ____________________ _- Y (45-5)
10 A third component _____________ __ 100-(X+Y)
The third component may be methyl acrylate,
propyl acrylate or butyl acrylate. As in the pre
vious example the mixture of monomers is poly
15 merized in the usual manner and then extruded
or precipitated into a form which may be cold
drawn. Molecular orientation parallel to the ma
102' surface is accomplished by cold drawing.
Instead of extruding the ‘above compositions
20 in the shape of a thread or ?lament, I may ex
trude them in the shape of tubes, rods, or sheets
which similarly can be cold drawn to yield molec
ularly oriented objects which exhibit character
istic crystalline X-ray diffraction patterns.
The ?bers and similar articles produced ac
etc.; esters of butacrylic acid, e. g., methyl butac 25 cording to this invention may be woven into
rylate. benzyl butacrylate, phenyl butacrylate,
highly insoluble and chemical resistant cloth for
iodophenyl butacrylate, etc.; and other esters of
use as ?lter cloths in handling chemicals and the
acrylic acid and substituted acrylic acids in which
like. They may also be used for textiles, e. g.,
R and R’ may have the meaning previously de
cloth, hosiery, etc. Textile materials made from
‘ ?ned. Although copolymers of any of the above 30
the herein described ?bers, ?laments or threads
rylate, ethyl propacrylate, propyl propacry
late, benzyl propacrylate, phenyl propacrylate,
or related compounds may be used in preparing
the oriented ?bers of] this invention, nevertheless
I do not mean to limit these preparations to co
polymers containing only two constituents, e. g.,
are superior to silk, cotton, linen, wool, rayon or
synthetic condensation polymers from the stand
point of their resistance to water, chemicals, sol
or combination thereof. ‘They are also
acrylonitrlle and ethyl acrylate. That portion of 35 vents
lighter in weight and considerably tougher and
the copolymer other than the acrylonitrile may
more ?exible than the recently developed glass
be one or any plurality of esters of acrylic or sub
stituted acrylic acids. Thus I may use a copoly
fabrics,
What I claim as new and desire to secure by
mer of acrylonitrile, methyl acrylate and methyl
methacrylate; acrylonitrile, ethyl acrylate and 40 Letters Patent of the United States is:
l. A molecularly oriented ?ber showing a char
methyl methacrylate, acrylonitrile, benzyl acry
acteristic
crystalline X-ray diffraction pattern
late and propyl acryiate; acrylonitrile, ethyl ac
which comprises a cold-drawn copolymer of (1)
rylate, methyl methacrylate, benzyl acrylate and
acrylonltrile, (2) ethyl acrylate and (3) ethyl
isobutyl ethacrylate, etc.
'
methacrylate, the acrylonitrile being present in
For example, I may also use a multicomponent 45
the proportion of 40% to 80% and the ethyl
system of the following types:
'
esters of the acrylic acids being present in total
Example 9
proportion of 20% to 60%, the sum of (1). (2),
Parts by weight
and (3) in said copolymer being equal to 100%.
2. A molecularly oriented ?ber showing a char-v
Acrylonitrile ______________________ __ X (50-80)
Ethyl acrylate ____________________ __ Y (45-5)
Ethyl methacrylate ____________ __ 100—(X+Y)
The above ingredients are polymerized in the
usual manner. Extrusion of the ?ber-forming ma
terial. and subsequent cold drawing results in a
50 acteristic crystalline X-ray diffraction pattern
which comprises the cold-drawn copolymer of‘
70% acrylonitrile, 25% ethyl acrylate and 5%
ethyl methacrylate.
GAETANO F. D'ALELIO.
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