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Патент USA US3074924

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United States Patent 0
Patented Jan. 22, 1953
reduced viscosity can be de?ned by and determined in and
with the following equation:
3 07 4 914
Viscosity of Solution
Ardy Armen, Concord, Cali?, assignor to The Dow Chem
ical Company, Midland, Mich., a corporation of Dela
Viscosity of Solvent
Reduced vlscosl'tyf Concentration of Solution
No Drawing. Filed Apr. 4, 1957, Ser. No. 650,570
8 Claims. (61. 260-78)
The difunotional cyclobutane groups that are free from
ring substituents may- be readily furnished in the poly
meric compositions ‘of the invention by utilizing such com
The chief aim and concern of the present invention is
to provide novel linear condensation polymers of the 10 pounds for the polymer preparations as are represented by
means of the following formulae:
polyamide, polyester and polyamide-ester types that con
tain various recurring cyclobutane derivative constituents
in their molecular con?gurations. The inventive design
also contemplates advantageously high molecular weight,
including ?ber-forming, embodiments of such polymeric
' '
The polymeric compositions that are within the pur
posive comprehension of the present invention are se
lected from the group of linear condensation polymers
consisting of those which are inclusively represented by 20
the following generic formulae:
in whichv E- and A may be selected, on an independent
basis, from the group consisting of hydroxy (—-OH),
25 amino (-—NHz), carboxy (-—COOH), and carboxy ester
(-—-COOR) radicals and s and d may be independent
numerical values from zero to 2.
Typical cyclobutane derivative compounds which may
in each of which B is a bivalent or difunctional cyclo
butane radical that is free from and does not contain sub
' be utilized with particular bene?t to provide linear con-'
30 densation polymers in accordance with the present in
vention include diphenyl cyclobutane-1,1-dicarboxylate;'
stituent groups on the cyclobutane ring structure, such
cyclobutane-1,2-dicarboxylic acid; cyclobutane-1,3-dicar
boxylic acid; spire-3,3-heptane-2,6-dicarboxylic acid; and
—<>(1,3-cyclobutylene) radicals
(1,2-cyc1obutylene) radicals
The polymeric compositions of the invention may be
prepared in ‘accordance with any of the several satis-v
factory procedures for the manufacture of condensation
polymers of the indicated types, depending upon the par
ticular starting materials that are employed.
Surprisingly enough, and contrary to what might be
expected from the propensity of thecyclobutane ring to
cleave under many conditions, the difunctional, unsub
stituted cycl-obutane derivatives are substantially vor com
(1,1-cyclobutylene) radicals
pletely stable under most polymerization conditions and
remain cyclically intact despite the elevated temperatures
that are encountered. In some cases it may be suitable to
.directly condense equivalent weight proportions of di
R is an alkylene group of from 2 to 10 carbon atoms; Y
verse, non~ring substituted cyclobutane derivative com-i
is a bivalent radical selected from the groupv consisting of
those included in the groups mentioned for the radicals 60 pound species that have appropriate functional terminal
groups for the intended purpose. More often, it may be
B and R; Z is selected from the group consisting of the
an advantage to condense each equivalent weight of a
dyads -—NH— and -—O--; X is selected from the group
cyclobutane derivative compound (or a mixture-of such
compounds) with an equivalent weight proportion of an
consisting of the dyads ——CONH—— and —-COO-—-; G is
a bivalent radical from a heterocyclic diamine (‘such as
piperazine and substituted piperazines);‘ Q is selected
from the group consisting ‘of 1,1-cyclobutylene and 1,2
cyclobutylene and k is a plural integer. Polymers in
which k has a numerical value ‘of at least about 20‘ may
frequently be found to be bene?cial for many purposes.
appropriate and desired diamine, alcamine, dihydroxy
‘compound, dicarboxylic acid or the like bifunctional com
pound including various heterocyclic diamines. As will
be obvious to those skilledin the art, the most favorable
reaction conditions, including the necessity for-employing
and the ‘choice of speci?c catalysts, will depend to a
Those in whichthe value of k is at least 50 may often be 60
great extent upon the particular reactants which may be
observed to possess advantageous ?ber-forming utilities
involved in a desired condensation.
and areusually'adapted to provide ?lamentous structures
that are orientable by stretching and the like procedures
after their initial formation. In this connection, the ?ber
Quite frequently, it may bemost bene?cial, in order
to readily prepare polyamide or polyamide-ester com
forming capabilities of polymeric compositions that are 65 positions, in accordance with the invention, to initially
form an amine salt of a cyclobutane derivative carboxylic
in accordance with the present invention generally stand
acid compound and to subsequently derive the condensed
in close relationship to the reduced viscosities of the poly
product from such, intermediate salt. In an
mers, as may be determined by measurement of a 0.5
analogous manner, polyesters may be furnished readily
percent by weight solution of the polymer in formic acid
by directly condensing cyclobutane derivative carboxylic
at a temperature ‘of about 35° C. Polymers whose so 70
acid compounds with suitable glycols.
measured reduced viscosities in formic acid are greater
than about 0.21 are ordinarily good ?ber'formers. The
Similar and re
lated techniques may be relied upon for the preparation
of other of the amide, ester and amide-ester linked poly
meric compositions that are within the purview of the in
As is apparent in the following speci?cation and de
scription, the polymeric compositions may vary from
those which are relatively low in molecular weight and
which may have viscid and elastomeric physical charac
teristics to crystalline high polymers that are fusible only
under the in?uence of heat at markedly elevated temper
atures. The ?rst-mentioned variations may frequently be
employed with advantage in adhesive and binding com
positions, for coatings of various sorts and to provide
the indicated diamines. If the salts that were formed did
not precipitate from methanol, ether was added until the
salts became cloudy and precipitation began. The iso
lated salts were then recrystallized and polymerized.
Table I.--Preparati0n of Linear Cyclobutane Derivative
Condensation Polymers
Pro Used to prepare
polymers 1
Details of procedures
3, 4, 5 and. 6--. The intermediate salt was heated in an evacu
atedsealed tube at a temperature of 20° C. for 2
hours. After cooling, the seal of the tube was
broken and the tube additionally heated for
molding and other shapable compositions by either direct
employment or in advantageous blends with other poly
mers. The latter variations, as has been indicated, are
oftentimes found to be eminently suited for ?ber-form
3 hours at a temperature of 260° to 280° C.
under an absolute mercury pressure of 0.5
to 2 mm.
1, 2, and 3_____ Diphenyl cyclohutane dlcarboxylate and an
equivalent weight of diamine were heated in
a sealed tube at 220° C. at 14 hours; then at
atmospheric pressure under a nitrogen atmos
phere at 260° C. for 45 minutes; and ?nally
at 3 mm. Hg pressure at 270° C. for 3 hours.
The diearboxylie acid was suspended in excess
ing and equivalent applications, probably because of the
sti?ening effect which is exerted on the polymer chain by
the cyclobutane derivative constituents thereof. In addi
tion, especially in the case of the polymers which contain
more symmetrical cyclobutane derivative constituents, the
ethylene glycol (1:3 mole ratio) and a catalytic
amount of litharge or zine borate was then
added. The resulting mixture was heated in
a nitrogen atmosphere at 210° C. for 4 hours;
then at 280° C. for 1 hour; and ?nally under
vacuum at 270° to 280° C. for 3 hours.
crystallinities and melting points of the polymer products
of the invention are considerably greater than are those
of their completely straight chain polymeric analogs with
which they may be compared. Likewise, the moduli of
1 See Table II for identi?cation 0! speci?c polymers.
elasticity of ?bers drawn from analogous linear, straight
Table Il.—-Cyclobutane Derivative Polymers
Prepared Melting
by pro- point of Melting
Table I
° 0.
1) sp./e.
salt, 0° C.
1 ........ .. ——C O
C ONH(CHg)5—-NH—
(lold-drawable ?bers [from color
Brittle polymer.
less polymer.
2 ________ __ —C 0
c o-N
3 ........ __ —C O
O 0NH(CHg)5—-NH—
A, D
200-201 ........ __
Colorless, sticky polymer.
4 ________ __ -o o-<>»o O—NH(CHg),NH-—
0. 21
Formed a nonviscous melt.
5 ........ _- —oo—<>»o o~1vn<emnoomomo(omnNH-
0 24 Ygellded
1rubber, cold-drawable
amen s.
6 ________ __ -O O~<>—C O—NH(CHg)wNH-—
Cold-drawable ?bers from melt.
7 ________ __ ——C O~<>-O O O CH¢OH¢0~
0. 34
Sticky at room temperature.
........ ..
1 Not involved.
chain, ?ber~forming condensation polymers are noticeably
It is interesting to note that polymer 3 was prepared by
less than are the same characteristic-s of ?bers drawn
both procedures A and DD, but neither polymer yielded
from polymeric compositions according to the present in
a viscous material.
vention, especially those containing symmetrical cyclo
The scope and purview of the present invention is to
be gauged in the light of the hereto appended claims
butane derivative constituents.
rather than strictly from the foregoing illustrative de
The various polymers, including certain ?ber-forming
scription and speci?cation.
‘embodiments, that, by way of further illustration, are
What is claimed is:
hereinafter speci?cally represented afford docent exempli
?cation of the multitudinous species that are advantage Ci 5 '1. A polymeric composition selected from the group
of linear condensation polymers consisting of recurring
ously possibilitated by practice of the invention. All of
units of the polymer units represented by the following
the cyclobutane derivative polymers that are included in
generic formulae:
Table II were prepared by one of the three procedures
that are set forth in the following Table I. The melting
points of the intermediate salts that were employed to
prepare the polyamides that were made according to pro
cedures A, B and C are also listed in Table II. All of the
intermediate salts that were employed were prepared by
combining methanolic solutions of equivalent amounts
of dihasic cyclobutane derivative of carboxylic acids in
in each of which B is a bivalent cyclobntane radical of 4
carbon atoms that is free from ring substituent groups;
[CO—B—X—Y-—Z] k
'18. A polymeric composition represented by the form
R is ‘an alkylene group of from 2 to 10 carbon atoms;
Y is a bivalent radical selected from the group‘ consisting
of those included in the groups mentioned for the radicals
B and R; Z is selected from the group consisting of the
dyads -—NH— and —O-—; X is selected from the group
consisting of the 'dyads —~CONH—~ and —COO—; G is
a bivalent radical from a heterocycl-ic diamine; Q is se
lected from the group consisting of 1,1-cyc1obutylene and
1,2-cyclobutylene' and k is a plural integer.
-2. A polymeric composition in accordance with claim 10
in which k is a plural integer.
1 in which R is 1,3-cyclobutylene.
3. A polymeric composition in accordance with claim
References Cited in the ?le of this patent
1 in which R is 1,2-cyc1obutylene.
4. A polymeric composition in accordance with claim
1 in which R is 1,1-cyclobutylene.
Carothers ____________ __ Sept. 20, 1938
5. A polymeric composition in accordance with claim
Gilrnan _______________ __ Jan. 6, 1942
1 in which 1: has a numerical Value of at least about 20.
‘6. A polymeric composition in accordance with claim
1 having 'a reduced viscosity greater than about ‘0.21 as
determined by measurement of a 0.5 percent by Weight 20
solution of the polymer in formic acid ‘at a temperature
of 35° C.
‘7. A ploymeric composition represented by the form
in which k is a plural integer.
Hanford et a1. ________ __ lune 2,
Fisher et a1 ___________ __ Nov. 27,
Fisher et a1 ___________ __ June 12,
Wittbecker ___________ __ Nov. 17,
Great Britain __________ __ Feb. 9, 1937
Patent No.- 3,074,914
January 22, 1963
Ardy Armen
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 4, Table 1, third column, line 2 thereof, for
"20° (3," read -~ 220° c, --9
Signed and sealed this 20th'day of August 1963.,
Attest: '
Attesting Officer
Commissioner of Patents
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