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Патент USA US2404720

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Patented July 23, 1946
2,404,720
UNITED STATES PATENT OFFICE
2,404,720
POLYMER PRODUCTS
Ray Clyde Houtz, Snyder, N. Y., assignor to E. I.
du Pont de Nemours & Company, W
Del., a corporation oi’ Delaware
on,
No Drawing. Application November 4, 1944,
Serial No. 562,018
10 Claims. (0:. zoo-o2)
1
This invention relates to a new composition of
2
at least 85% by weight of the polymer is acrylo
matter and shaped articles produced therefrom.
nitrile, in a solvent which does not react with or
More particularly, this invention reiates to an
organic solvent solution of polyacrylonitrile, i. e.
decompose the polymer, the solution being suit
able for the formation of commercially useful,
substantially void free articles of polyacrylo
polymerized acrylonitrile or polymerized vinyl
cyanide (CHFCHCNlr, and copolymers and in
terpolymers of acrylonitrile in which at least
85% by weight of the polymer is acrylonitrile,
and to the production of shaped articles from
said organic solvent solution of said polymers
of acrylonitrile.
This application is a continuatlon-in-part of
nitrile.
'
It is another object of this invention to pro_
duce a solution of polyacrylonitrile, or a co
polymer or interpolymer of acrylonitrile in which
at least 85% by weight of the polymer is acrylo
nitrile, in a volatile organic solvent, which solu
tion is stable over extended periods of time at
the copending application of Ray Clyde Houtz,
room temperature or elevated temperatures.
Serial No. 447,446, ?led June 1'7, 1942.
It is a further object of this invention to pro
Polyacrylonitrile, and copolymers and inter 15 duce, from solution, polyacrylonitrile, or a co
polymers of acrylonitrile with other polymer
polymer or interpolymer of acrylonitrile in which
izable substances, for example vinyl or acrylic
at least 85% by weight of the polymer is acrylo
compounds, in which at least 85% by weight of
nitrile in its substantially undecomposed and
the polymer is acrylonitrile have been known for
chemically unchanged state.
some time and recognized as possessing desirable 20
It is still another object of this invention to
physical and chemical properties including tough
produce, from solution, polyacrylonitriie, or a
ness and insolubility in and insensitivity to com
copolymer or interpolymer of acrylonitrile in
mon organic solvents such as methyl or ethyl alco
which at least 85% by weight of the polymer is
hol, acetone, ethyl ether, ethyl acetate, hydrocar
acrylonitrile which is tough, ?exible, tenacious
bon solvents, chlorinated hydrocarbons and the 2-5 and free from voids.
like. Because of these facts, numerous attempts
have been made to form these polymeric materials
into yarns, films and other shaped articles.
Other objects of the invention will appear
hereinafter.
The objects of the invention may be accom
The copending application of George H. La
plished in general by dissolving polyacrylonitrile,
tham, Serial No. 562,012, ?led of even date here 30 or a copolymer or interpolymer of acrylonitrile
with discloses solutions of polyacrylonitrile in
in which at least 85% by weight of the polymer
dimethyl carbamyl compounds and the produc
is acrylonitriie, in an aromatic diamino com
tion of extruded and otherwise shaped articles
pound taken from the group consisting of:
and structures from such solutions. The above
NE:
said application of George H. Latham represents 35
NH:
the first successful dissolution of polyacrylonitrile
in a solvent to produce a solution which is suit
able for the production of commercially useful
textile yarns or wrapping tissue ?lms and simi
40
lar tough, ?exible structures.
The present application relates to a similarly
satisfactory dissolution of polyacrylonitrile in an
organic solvent taken from a di?erent class of
organic compounds.
It is therefore an object of this invention to 45
dissolve polyacrylonitrile, or a copolymer or inter
polymer of acrylonitrile in which at least 85% by
weight of the polymer is acrylonitrile, in a sol
vent which does not react with or decompose
Ortlio phenylone dimino
NH:
Hr
Meta phonylcne diamlne
NHI
the polymer and which may be substantially 50
v(,zoiripletely removed from structures formed of
" was a solution.
It is another object of this invention to pro
duce a solution of polyacrylonitrile, or a co
polymer or interpoiymer oi acryionitriie in which 65
HI
Para phenylene diamine
2,404,720
templates solid solutions of acrylonitrile poly
mers containing at least 85% by weight of acryl
CH1
NH:
H:
OH;
NE:
NH:
H:
2,2’,4,4’-l.etramino 5,5’-dimethyl diphenyl methane
C0
NE’:
onitrile as well as liquid solutions thereof.
Shaped articles obtained from solvent solutions
of polyacrylonitrile in accordance with the in
vention and from which the solvent is subse
quently removed are substantially free oi’ for
eign matter and voids and substantially unde
composed and chemically unchanged from the
10 simple polymer prior to its solution.
The polyacrylonitrlle for use with the inven
tion is preferably prepared by the ammonium per
sulfate catalyzed polymerization of monomeric
acrylonitrile dissolved or emulsi?ed in water. It
15 can, however, be prepared by any other suitable
_ type of polymerization reaction such as, for ex
NH!
ample, the emulsion type reaction disclosed by
U. S. Patent No. 2,160,054 to Bauer et al. The
polymer preferably possesses a molecular weight
4,4'-diamlno benzophenone
20 within the range of 15,000 to 250,000 or even
higher, as calculated from viscosity measurements
by the Staudinger equation:
N/
Molecular weight=l1{V
2,0-dian1lno pyridine
C H:
HIN'
25 wherein:
HI
K ,,= 1.5)( 10"
=
.
‘
.
.
N" speci?c vlscoslty
.
=Vl8008lt! of solution __
viscosity of solvent
1
and
30
C=
concentration of the solution expressed as the
2,4,0‘triamino toluene
number of moles of the monomer (calculated) per
These acrylonltrile solutions may be formed
liter of solution.
into a shaped structure and the aromatic di
The molecular weight of the polymer obtained
amino solvent removed from the so formed struc
ture. The solvent may be removed by evapo 35 is dependent on such factors as the concentra
tion of the monomer in the water, the amount
ration under vacuum, or it may be removed by
NH:
leaching the solvent from the structure by means
of a liquid, for example water, which will dis
solve the solvent but which is inert to the acrylo
and type of catalyst present, the temperature of
the reaction, etc. For example, polyacrylonitrile
having a molecular weight of approximately
nitrile structure. If desired, a structure can be
formed from the solution and a portion of the
solvent retained in the structure as a plasti—
60,000 can be prepared as follows: To 94 pounds
of distilled water heated to 40° C. add 40 grams
of ammonium persulfate catalyst and 80 grams
of sodium bisul?te activator. Then add 16
cizer.
A number of the above-mentioned solvents
become colored on exposure to air, especially
at temperatures above their melting points. It
is therefore desirable, if a substantially colorless
product is required, to prepare the solutions and
to form the structures therefrom while excluding
oxidizing atmospheres. This may be done by
forming the solutions and subsequently forming
structures from the solutions in the presence of
nitrogen gas.
'
The solutions are prepared by dissolving the
polyacrylonitrile, or copolymer or interpolymer '
of acrylonitrile with one or a mixture of the
above-mentioned solvents. These solvents are
solid at ordinary temperatures and dissolve or
retain the polymer in clear solution, sometimes
only at elevated temperatures, for example at
temperatures of 100° C. or higher, below which
temperature the composition often resembles a
gel. In all cases. when the polymer is dissolved
in a solvent of the above class, the resulting com
position while hot has the appearance of a true
solution. When cooled to room temperature, the
composition frequently takes on the appearance
of a gel, which gel may on prolonged standing
undergo syneresis. Reheating of this gel or gym
ersed mass however causes it to again return to
solution form.
pounds of acrylonitrile slowly with stirring over
a period of two hours. The polyacrylonitrile
having the above said molecular weight will pre
cipitate from the solution. Increasing or decreas
ing the amount of the catalyst, while maintain
ing the other conditions constant, decreases or
increases the molecular weight of the polymer.
Acrylonitrile copolymers and lntei'polymers con
tainlng at least 85% by weight of acrylonitrile
and likewise preferably having a molecular weight
of 15,000 to 250,000-or higher can be prepared in
a similar manner.
The following example illustrates a preferred
method of preparing a solution of polyacrylo
nitrile in accordance with the principles of this
invention. The invention is not to be limited by
the details set forth in the example.
Example I
Ten (10) parts by weight of an acrylonitrile
polymer prepared by the polymerization of mon
omeric acrylonitrile in accordance with the
teachings of U. 8. Patent No. 2,160,054 to Bauer
et a1. and possessing an average molecular weight
of 120,000 are ground to an average particle size
of 200 mesh and intimately mixed with 100 parts
by weight of meta-phenylene diamine ground to
a similar particle size. The mixture is heated
over a period of thirty minutes to a temperature
of 200° C’. in a closed container, in the presence
of nitrogen, to form a fluid. homogeneous mass
In view of the relatively high melting points
of some of the solvents of this invention, they
are useful as solvent plasticizers for polyacrylo
nitrile. The present invention therefore con 75 or solution. The solution may be extruded
5
2,404,720
through a i5-hole spinneret at a temperature of
200° 0. into 9. glycerol bath heated to 115° C. to
form a l5-?lament yam. A bath travel 01' 24
inches may be employed and the yarn subjected
to a tension of 0.5 gram per denier (based on the
6
invention, it is preferred to spin under vacuum to
avoid the use of unduly high temperatures.
Shaped articles 01' acrylonitrile polymer can
also be formed by extruding the spinning solu
tion into a suitable precipitating bath compris
ing a liquid that is miscible with the solvent but
?nal yarn denier) during its travel through the
bath. The phenylene diamine is removed or
is a chemically inert non-solvent for the acrylo
leached from the yarn by the glycerol, thereby
nitrile polymer. As examples oi such a liquid
coagulating the polymer.
may be mentioned water, glycerin, organic sol
As above indicated, it is possible by the prac 10 vents such as alcohol, ether, etc.. or aqueous so
tice of this invention to obtain a solution of poly
lutions oi.’ salts, alkalies or acids. The copend
acrylonitrile, or a copolymer or interpolymer of
ing application oi’ William W. Watkins Serial No.
acrylonitrile which may be used in the manu
496,376, ?led July 28, 1043, covers the use of give
facture oi’ shaped articles such as yarns, ?lms
erol and aqueous solutions or salts or baths, pref
or molded articles. These solutions are also 15 erably at elevated temperatures, for the wet spin
suited for use as lacquers or coating compositions.
ning of acrylonitrile polymer yarn, from solutions
They are especially useful in the coating or wire
of the polymer, preferably with substantial ten
and electrical parts where the high chemical and
sion and stretch being applied during spinning.
electrical resistance of the polymer is impor
The article of acrylonitrile polymer thus ob
tant.
As also shown, the solvents of the invention
are useful not only in connection with the poly
acrylonitrile, but also with copolymers and inter
20 tained can advantageously be subjected to a
stretching operation or the type employed in the
above examples. This stretching is preferably
performed by passing the yarn between two pos
polymers of acrylonitrile with other polymeriz
itively driven rollers, the peripheral speeds of
able substances such as, for example, compounds
containing one or more ethylenic linkages in
cluding vinyl and acrylic compounds as well as
which are so adjusted that the article is stretched
ole?nic or diole?nic hydrocarbons such as iso
butylene, butadiene, etc., They are eminently
to from two to ten times its original length, pref
erably approximately six times its original
length. This stretching of‘ the formed article
may be performed at any suitable time. However,
satisfactory for use with those polymers that 30 in the case of articles formed by the wet spin
plug or casting technique, it is preferably per
contain a large amount oi’ acrylonitrile, for ex
ample polymers, or copolymers or interpolymers
formed before the article has been completely
dried. The orientation of the structure thus ob
that contain at least 85% by weight of acrylo
tained greatly improves the physical properties of
nitrile and that have generally been regarded by
the art as being completely insoluble in all com 35 the structure including its tenacity, its resilience,
etc.
mon organic solvents. Nor are these solvents
This stretching oi’ the shaped article can also
limited to use with a polyacrylonitrile of any
be accomplished by causing the article, while
given molecular weight. They can be used with
passing between stretching rollers, to contact a
a polymer of almost any given molecular weight
and are especially satisfactory for use with those 40 heated stationary pin, or to pass through an inert
medium such as air, water, glycerin, etc., heat
polymers having an average molecular weight
ed to a high temperature. Obviously, the article
within the range of 15,000 to 250,000 as deter
must not be exposed to this high temperature for
mined by viscosity data using the Staudinger
a period sufficiently long to decompose the poly
equation and intended for use in the manufac
ture of yarns or ?lms.
The solution of acrylonitrile polymer dissolved
in an organic solvent in accordance with this in
vention must be of such a concentration that its
viscosity at the operating temperature is within
45 mer. In general however, the time of contact of
the article with the heated medium is so short
that temperatures up to 250° C. can be employed.
it is generally preferred to heat the article to a
temperature of at least 100° C. during the
a workable range. When it is to be employed in 50 stretching operation. The stretching of acrylo
nitrile polymer, particularly under the in?uence
the spinning of yarn or the casting of film, the
0! heat, is described and claimed in the copend
solution should preferably have a viscosity within
ing application of Daniel T. Meloon Serial No.
the range of 25 to 750 pulses. When the polymer
496,397, ?led July 28, 1943.
has a molecular weight or 250,000 or more, this
requires that the maximum concentration of poly 55 In addition to acting as solvents for poly
acrylonitrile, or copolymers or interpolymers of
mer in the spinning solution be of the order oi’
acrylonitrile, the aromatic compounds of this in
10%. Generally. it is preferred that the spin
vention. when present in small amounts, can also
ning solution contain at least 10% 0! the poly
be used as plasticizing agents for the polymer
mer because of the diillculty of rapidly remov
and the higher boiling compounds oi’ the inven
ing large amounts of solvent from the solution
tion are especially suited for such use. At the
in the spinning operation. Moreover, it is eco
same time, it is, of course, to be understood that
nomically undesirable to use such large amounts
non-solvent softeners such as glycerol, etc. can
or solvent for the spinning of a given amount 01'
also
be incorporated in the solutions of this in
polymer although it is true that the solvent can
vention, these materials remaining in the sub
be completely recovered from the spinning oper
sequently formed articles to impart a softening
ation and reused. For these reasons, it is pre
effect. If it is desired to use such plasticizing
ierred to employ a Polymer having an average
or softening agents with polyacrylonltrile, they
molecular weight of between 40,000 and 150,000
are preferably added in the desired amount to an
since such a polymer forms a solution of the de 70 already formed solution 01' the polymer in a lower
sired viscosity in concentrations 0! the order of
boiling solvent.
15% to 25%, and at a desirable spinning tem
This invention is primarily concerned with the
perature.
steps of dissolving polyacrylonitrile in a suitable
In employing the evaporation method of spin
solvent to form a. stable solution adapted for use
ning ?laments and yarns in accordance with this 75 in the manufacture of shaped articles of poly
9,404,120
7
1. As a new composition of matter. a polymer
acrylonitrlle. It is characteristic oi the inven
tion that the solvents do not cause a decomposi
tion or chemical alteration of the dissolved
of acrylonitrlle containing in the polymer mole
cule at least 85% by weight oi.’ acrylonitrile dis
acrylonitrile polymer. At the same time, it is also
characteristic that the solvents provided by the
invention are also useful in the dissolving 01' mix
tures of polyacrylonitrile and adjuvants such as
dye modi?ers. linear polyamides such as nylon,
derivatives of cellulose including cellulose ethers
and esters, polymers of vinyl compounds such as
Ortho phenylene diamine
Meta phenylene diamine
Para phenylene diamine
2,224, '-tetramino 5,5'-dimethyl dlphenyl
methane
vinyl chloride. vinyl acetate, acrylic acid. etc.,
which adiuvants may be incorporated in the
acrylcnltrlle polymer solution to modify the prop
erties, both chemical and Physical. oi’ the result
ing shaped articles.
This invention provides a class oi’ solvents for
poiyacrylonitrile and copolymers and interpoly
mers of acrylonitrile, i. e. compounds which, when
solved in an aromatic compound taken from the
group consisting oi :
in
4,4'-diamino benzophenone
2.6-diamino pyridine
2.4.6-triamino toluene.
2. A new composition 0! matter as de?ned in
351m 1, in which said polymer is polyacryloni
e.
3. A new composition of matter as defined in
claim 1, in which said polymer of acrylonitrile is
nonreactive with said aromatic compound.
an appreciable amount, e. g. 5% or more by 20
4. A new composition of matter as de?ned in
weight of the polymer. The invention also pro
claim 1, in which said polymer has a molecular
vides a class of materials that is eminently suited
weight oi between 15,000 and 250,000.
for use in plasticizing structures comprising the
5. A new composition of matter as de?ned in
acrylonitrile polymers. The materials provided
claim 1, in which said polymer has a molecular
by this invention are apparently tr-ue solvents 25 weight
of between 40,000 and 150,000.
for the above-mentioned acrylonitrile polymers.
liquid, will form molecular dispersions containing
They do not tend to react with or decompose the
6. As a new composition of matter, a polymer
of acrylonitrile containing in the polymer mole
polymer. the polymeric material obtained irom
cule at least 85% by weight of acrylonitrile and
the solution of this invention apparently being of
an aromatic compound taken from the group
the same identical chemical composition as the 80 consistingot:
initial polymer.
Orthc phenylene diamine
Reference, throughout the speci?cation and
Meta phenylene diamine
claims. to acrylonitrlle polymers, polymers of
Para phenyiene diamine
acrylonitrile. and copolymers and interpolymers
oi’ acrylonitrile “containing at least 85% by 35 2,2',4,4'-tetramino 5,5’-dimethyi diphenyl
methane
weight of acrylonitrile" signi?es Polymers con
4,4'-diamino benzophenone
taining in their molecules at least 05% by weight
2.6-diamino pyridine
of the acrylonitrile unit which is considered to be
2,4,8-triamino toluene.
present in the polymer molecule as the group
40
7. The composition oi claim 1 in which the
solution contains at least 10% of said polymer oi’
that is. at least 85% by weight of the reactant
acrylonitrile.
material converted into and forming the poly
8. The composition of claim 1 in which the
mer is acrylonitrile.
45 solution has a viscosity within the range 25 to
Since it is obvious that many changes and
'ltopoisec.
9. The composition 01' claim 1 in which the
modifications can be made in the above described
details without departing from the nature and
spirit of the invention. it is to be understood that
the invention is not to be limited to the details
described herein except as set forth in the ap
pended claims.
I claim:
polymer is polyacrylcnitrile having a molecular
weight of between 15,000 and 250,000.
10. The composition of claim 1 in which the
polymer is polyacrylonitrile having a molecular
weight of between 40,000 and 150,000.
RAY CLYDE HOU‘I‘Z.
Certi?cate of Correction
Patent No. 2,404,720.
July 2a, 1946.
RAY CLYDE HOUTZ
It is hereby certi?ed that error appears in the printed s _eci?cation of the above
correction as follows: Column 6, me 14, for "or” read as;
numbered atent requ
and that t c said Letters atent should be read with this correction therein that the
same may coniorm to the record of the ease in the Patent Oi?ce.
a
o
Signed and scaled this 15th day of October, A. D. 1946.
[mm]
LESLIE FRAZER,
First Assistant Omission" of Patents.
9,404,120
7
1. As a new composition of matter. a polymer
acrylonitrlle. It is characteristic oi the inven
tion that the solvents do not cause a decomposi
tion or chemical alteration of the dissolved
of acrylonitrlle containing in the polymer mole
cule at least 85% by weight oi.’ acrylonitrile dis
acrylonitrile polymer. At the same time, it is also
characteristic that the solvents provided by the
invention are also useful in the dissolving 01' mix
tures of polyacrylonitrile and adjuvants such as
dye modi?ers. linear polyamides such as nylon,
derivatives of cellulose including cellulose ethers
and esters, polymers of vinyl compounds such as
Ortho phenylene diamine
Meta phenylene diamine
Para phenylene diamine
2,224, '-tetramino 5,5'-dimethyl dlphenyl
methane
vinyl chloride. vinyl acetate, acrylic acid. etc.,
which adiuvants may be incorporated in the
acrylcnltrlle polymer solution to modify the prop
erties, both chemical and Physical. oi’ the result
ing shaped articles.
This invention provides a class oi’ solvents for
poiyacrylonitrile and copolymers and interpoly
mers of acrylonitrile, i. e. compounds which, when
solved in an aromatic compound taken from the
group consisting oi :
in
4,4'-diamino benzophenone
2.6-diamino pyridine
2.4.6-triamino toluene.
2. A new composition 0! matter as de?ned in
351m 1, in which said polymer is polyacryloni
e.
3. A new composition of matter as defined in
claim 1, in which said polymer of acrylonitrile is
nonreactive with said aromatic compound.
an appreciable amount, e. g. 5% or more by 20
4. A new composition of matter as de?ned in
weight of the polymer. The invention also pro
claim 1, in which said polymer has a molecular
vides a class of materials that is eminently suited
weight oi between 15,000 and 250,000.
for use in plasticizing structures comprising the
5. A new composition of matter as de?ned in
acrylonitrile polymers. The materials provided
claim 1, in which said polymer has a molecular
by this invention are apparently tr-ue solvents 25 weight
of between 40,000 and 150,000.
for the above-mentioned acrylonitrile polymers.
liquid, will form molecular dispersions containing
They do not tend to react with or decompose the
6. As a new composition of matter, a polymer
of acrylonitrile containing in the polymer mole
polymer. the polymeric material obtained irom
cule at least 85% by weight of acrylonitrile and
the solution of this invention apparently being of
an aromatic compound taken from the group
the same identical chemical composition as the 80 consistingot:
initial polymer.
Orthc phenylene diamine
Reference, throughout the speci?cation and
Meta phenylene diamine
claims. to acrylonitrlle polymers, polymers of
Para phenyiene diamine
acrylonitrile. and copolymers and interpolymers
oi’ acrylonitrile “containing at least 85% by 35 2,2',4,4'-tetramino 5,5’-dimethyi diphenyl
methane
weight of acrylonitrile" signi?es Polymers con
4,4'-diamino benzophenone
taining in their molecules at least 05% by weight
2.6-diamino pyridine
of the acrylonitrile unit which is considered to be
2,4,8-triamino toluene.
present in the polymer molecule as the group
40
7. The composition oi claim 1 in which the
solution contains at least 10% of said polymer oi’
that is. at least 85% by weight of the reactant
acrylonitrile.
material converted into and forming the poly
8. The composition of claim 1 in which the
mer is acrylonitrile.
45 solution has a viscosity within the range 25 to
Since it is obvious that many changes and
'ltopoisec.
9. The composition 01' claim 1 in which the
modifications can be made in the above described
details without departing from the nature and
spirit of the invention. it is to be understood that
the invention is not to be limited to the details
described herein except as set forth in the ap
pended claims.
I claim:
polymer is polyacrylcnitrile having a molecular
weight of between 15,000 and 250,000.
10. The composition of claim 1 in which the
polymer is polyacrylonitrile having a molecular
weight of between 40,000 and 150,000.
RAY CLYDE HOU‘I‘Z.
Certi?cate of Correction
Patent No. 2,404,720.
July 2a, 1946.
RAY CLYDE HOUTZ
It is hereby certi?ed that error appears in the printed s _eci?cation of the above
correction as follows: Column 6, me 14, for "or” read as;
numbered atent requ
and that t c said Letters atent should be read with this correction therein that the
same may coniorm to the record of the ease in the Patent Oi?ce.
a
o
Signed and scaled this 15th day of October, A. D. 1946.
[mm]
LESLIE FRAZER,
First Assistant Omission" of Patents.
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