close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3084155

код для вставки
United States Patent 0
M
ICC
Zi?hlhll?
Patented Apr. 2, recs
2
1
treating the copolymer solution with a brominating agent.
The brominating agent is employed in quantities which
will produce brominated copolymers having from 1 to
BROMHNATED AMUH‘QUS CGP-JLYMERS (ll?
ETHYLENE AND HEGHER ALPHA @LEFiN?
WITH AMINES
50 wt. percent bromine, preferably 1 to 10 wt. percent
and more preferably from 1 to 5 wt. percent bromine
Henry g. Malrowsld, Roselle Bath, and Charles ‘W. Secl
bach, Cranford, NJ?” assignors to Esso Research and
Engineering Company, a corporation of Delaware
No Drawing. Filed Jan. 13, 1953, Ser. No. 708,370
6 Claims. (Cl. 260-88.2)
therein. The amount of brominating agent used is cal
culated on 100% bromination. If bromination takes
place to an extent less than 100%, the quantity of bro
minating agent is adjusted to obtain brominated copoly
10 mers having the desired amount of bromine therein. The
This invention relates to the preparation of brominated
copolymers. More particularly, the invention relates to
the preparation of brominated rubbery amorphous co
polymers of ethylene and higher alpha ole?ns and to the
preparation of synthetic rubbers therefrom.
15
bromination is carried out at temperatures of from 20°
to 130° C. preferably 75 to 110° C. The brominated
copolymers are then isolated by standard techniques
known to the art.
The curing agents which react with the brominated
copolyniers to form the synthetic rubbers of the invention
ethylene and higher alpha ole?ns by the low pressure
are metal salts, metal oxides, metal powders, amines and
polymerization process is described in copending appli
polyamines. in general, the metal components of the
cation 672,435, ?led July 17, 1957.
metal salts, metal oxides, and metal powders are chosen
It has now been found that amorphous rubbery copoly 20 from groups HA, KB of the periodic table, and tin,
The preparation of amorphous rubbery copolymers of
mers of ethylene and higher alpha oletins can be bro
minated to form brominated copolyiners which then can
be treated with certain curing agents to form synthetic
rubbers having excellent mechanical, dynamic and aging
properties.
i
The amorphous rubbery copolyrners of ethylene and
copper and iron.
Particularly useful are the metal oxides,
sul?des, nitrates, phosphates, sulfates, and organic acid
salts of groups HA and 11B metals particularly Zn, Cd,
Mg, iron and lead. Also particularly preferred are
25 amines and polyamines; in particular, any diamine, tri
amine, and higher polyarnine having one or more of the
higher alpha olefins used to form the brominated copoly
mers and the corresponding synthetic rubbers of the
invention contain from 5 to 95 mol percent, preferably
following types of amino groups; (a) unsubstituted amino
groups, (b) mono-substituted amino groups, (c) di
substituted amino groups, and (d) heterocyclic amines
30 to 70 mol percent of ethylene with 95 to 5 mol per
cent, preferably 70 to 30 mol percent of an alpha ole?n
containing 3 to 6 carbon atoms, have a tensile strength
in the range of from 2 to 500 p.s.i., a melting point below
about 50° C., a solubility in xylene at 100° C. greater
than 15 wt percent, an apparent modulus of elasticity
at —50° C. of less than 1>< 105 psi, a crystallinity of
less than 10% as shown by X-ray analysis, and a molec—
such as pyridine. The substituents on the mono- and di
substituted amino groups are one or more of alkyl, aryl
ular weight of from 5,000 to 500,000. 1]‘hese copolymers
and heterocyclic groups. ‘An added advantage in using
these polyarnines is that they not only effectively produce
the cured copolymers of the invention but they also act
as antioxidants and stabilizers.
The reaction between the brominated copolymers and
the curing agent is carried out by mixing from 1 to 40
parts, preferably 5 to 20 parts, and more preferably 5
can be prepared by any known process, such as the low
to 10 parts by weight of a metal salt or oxide with
pressure polymerization process or the high pressure 40 100 parts by weight of copolymer. When the compound
polymerization process; see e.g. Belgian Patent 533,362,
is a polyarnine, from 0.5 to 15 parts, preferably from 1
“Chemical and Engineering News,” April 8, 1957, pages
to 8 parts, and more preferably from 2 to 6 parts by
weight of polyamine per 100 parts by weight of copolymer
12 through 16, “Petroleum Re?ner,” December 1956,
pages 191 through 196 and copending application 672,435,
is used. The reaction temperature employed is in the
?led July 17, 1957. Ethylene-propylene copolymers are 45 range of from 225° F. to 350° F. preferably 280 to
preferred due to their low cost. These amorphous rubbery
320° F. and more preferably about 310° F.
copolymers do not contain su'?icient unsaturation to
Fillers such as carbon blacks, silica, mica, various
enable them to be cured by conventional curing agents
clays and the like can be used, and in general their use
Such as sulfur or resins.
lso, these copolyiners contain
is preferred. From 5 to 150 parts, preferably 30 to 60
such a slight amount of unsaturation that they cannot be
parts of ?ller per 100 parts of polymer is used. Highly
brominated to any appreciable extent ‘by the addition of
desirable cured copolymers are prepared with 50 parts of
bromine across their double bonds.
carbon black per 100 parts of copolymer. A wide
variety of carbon blacks can be employed as ?llers, e.g.
Surprisingly therefore, it was discovered that these
copolymers can be brominated when the bromination is
furnace black , channel blacks, thermal blacks, lamp
blacks, acetylene blacks and the like.
carried out in solvents which are capable of dissolving
or swelling the copolymer and which do not react rapidly
The reaction is carried out by mixing the brominated
with the brominating agent. Satisfactory solvents are
copolyrner, the compound adapted to react with the bro.
aliphatic and aromatic hydrocarbons and their halogen
minated copolymer, and the ?ller, if any, in a rubber
mill and heating the mixture to reaction temperature.
ated derivatives, such as n~heptane, benzene, chloroform,
carbon tetrachloride, ethylene dichloride, and chloroben (10 The mixing can also be carried out in other rubber com~
pounding equipment such as Banbury mixers or kneaders.
The invention will be better understood from the
followinCy examples. It is to be noted that values given
power and nonreactivity with the brominating agents.
in the examples and tables for tensile strength and elon
The bromination of these copolymers is carried out by
treatment of the copolymer in an appropriate solvent with 65 gation are measured on 20-25 mil thick micropads unless
otherwise noted.
a brominating agent which is preferably elemental bro
EXAMPLE I
mine, although other bromine-ting agents such as N-bromo
succinimide can also be used. In particular, the bromina
90.0 grams of an ethylene-propylene copolymer having
tion of the copolymers is carried out by ?rst preparing a
the properties shown in Table I were mixed with 1.4 liters
copolymer solution having from 20 to 150 grams of
of CCL, in a 3-liter 3-necl; ?ask. The mixture was heated
copolymer per liter of solvent, preferably from 80 to
to 70° C. with stirring, which was continued at this tem
100 grams of polymer per liter of solvent, and then
erature until a homogeneous paste. was obtained. There
Zene; with carbon tetrachloride and chlorobenzene being
particularly preferred because of their excellent solvent
egos/1,1115
1.1
3
was then added to this paste with stirring a solution of
30.0 grams of bromine in 100 ml. of CCl.; over a period
of 30 minutes. The reaction mixture was then stirred for
another 4 hours at 70° C. During the last two hours
Examples IX to XIV relate to the curing of the bromi
nated copolymers of the invention with polyamines.
ably a mixture of HCl and HBr.
halogen was mixed with 50 g. of carbon black on a warm
EXAMPLE IX
nitrogen was bubbled through the reaction mixture to 5
100 g. of the brominated copolymer prepared by the
facilitate the removal of hydrogen halide, which was prcb~
process of Example I, which contained 10.35 wt. percent
Then a volume of
acetone equal to the volume of the reaction mixture was
rubber mill. 2 g. of m-phenylenediamine was then added
added to the reaction mixture, resulting in precipitation of
to the polymer mixture at room temperature. The mix
the copolymer which was then isolated, thoroughly Washed, 10 ture scorched badly during IIliXiIl". From this it can
and kneaded with acetone. The copolymer was then
be seen that brominated polymers having halogen con~
banded on a warm mill, partially dried, formed into a
sheet, and dried under vacuum at 50° C. The solid 00-
tents above 10 wt. percent are di?icult to process when
amines and polyamines are used as curing agents. Spe
polymer product weighed 95.5 grams and contained 10.35
cial precautions are required to prevent scorching of high
Wt. percent halogen (Paar determination). Some of the 15 bromine content copolymers.
halogen present was chlorine, which was introduced into
the copolymer by reaction involving the COL; diluent.
EXAMPLES XTHROUGH XII
Evaporation of the mother liquor from the reaction left
The brominated copolymers of Examples VI, VII and
as a resldue 4-1 g. Of an Olly copolymer. The PIOPEIUCS
VIII respectively were treated according to the process of
of the bromrnate'd copolymer, the reaction conditions, and 20 Example IX with either curing mixture A which is com
the properties of the unsubstituted copolymer are listed
posed of 100 parts brominated copolymer, 4 parts m
in Table I.
phenylenediamine, and 4 parts stearic acid, or curing mix~
EXAMPLES H THROUGH VIII
ture B which is composed of 100 parts brominatcd copoly
mer, 50 parts carbon black, 4 parts m-phenylenediarnine,
Copolymers having the properties and compositions 25 and 4 parts stearic acid. The curing mixture used, the
shown in Table I were brominated by the procedure of
conditions of cure, and the properties of the cured copoly
Example I using the quantities or reactants and reaction
mers are also given in Table II. Additionally, the prop
conditions given in Table I.
erties of the corresponding brominated copolymers and
Table I
I
II
III
1V
V
VI
VII
VIII
Ethylenepropylene copolymcr used:
Mole percent propylene ___________ __
14.1
9. 2
9.1
42
15
42
42
42
Inherent viscosity, vi 1..
Tensile strength, p.s.i---
__
1.75
128
1. 42
170
1. 50
630
1.86
145
1.06
123
1. 4S
285
1. 48
285
1. 48
285
Elongation, percent ________________ ._
Softening point, ° C _______________ ..
Melting pooint, ° C ................ __
660
52
s2
360
20
34
180
<31
75
444
31
5s
660
so
70
80
<30
<30
80
<30
<30
80
<30
<30
CO1;
CC];
(3C1;
00110
CcHu
Cal-I0
CoHu
1500
90
1500
100
1500
100
1200
70
1200
70
1500
100
1500
100
1500
100
60
67
67
58
58
07
67
67
30.0
7
4.5
11.1
7
3 5
29.1
70
6.5
22.4
70
1
15.0
75
2
30.0
70
5.5
20.0
70
3. G7
10.0
70
3.5
90.6
100.4
103.7
75.6
77.7
101.9
09.9
102.8
Reaction conditions:
Solvent ____________________________ .._
Total volume, ml .......... ._
Copolymcr, grams ..... __
Copolymcr c0110., g./1_Bromine, g ________ ..
Temperature, ° C_
__
Reaction time, hr __________________ -_
(2)
Product:
Total copolymer, g ________________ __
Percent yield
05
05
90
03
100
so
00
4.1
4.4
6.1
2.4
1.2
4.7
4.6
6.5
95. 5
11.03
96. 0
0. 871
97. 6
10.517
73. 2
1.00
76, 5
1. 00
07. 2
10.002
95. 3
1.27
96. 3
1. 25
Halogen, weight percent 8 _____ _. 3 10. 35
3 0.93
4 8.77
5 4. 96
5 2. 93
5 5. 7G
5 1. 80
l 2. 30
Oily copolymcr ____ __
Brorniuatcd copolymcnInherent viscosity, 111' I...
.
0s
1 In tatralin at 125° C. at a concentration of 1 g./litcr for the solid copolymer only.
1 Based on assumption that the bromine present reacts completely with all the copolymer present and only
by substitution.
3 Paar bomb determination.
a Dictert determination: 1.37 Weight percent chlorine and 7.40 weight percent bromino.
5 Dietort determination.
5 Of solid copolymer.
7 0n the soluble portion of the solid copolyrncr.
1‘ n-lieptanc.
It can be seen from Table I that amorphous copolymers
can be successfully brominated using a wide variety of re
action conditions and solvents.
the corresponding unbrominated copolymers from which
the brominated copolymers were prepared are also given
in Table II for comparison purposes.
Table II
X
XI
Tensile
Elong-
p.s.1.
percent
strcngth,
ation,
XII
Tensile
Elong-
p.s.i.
percent
strength,
atlon,
Tensile
Elong
p.s.i.
percent
strength,
atlon,
Unbrominatcd copolymer-
285
80
285
80
285
80
Brominatcd copolymer- _ _
251
108
232
160
223
116
510
430
560
70
00
580
620
790
620
530
050
635
420
380
300
Curing mixture A:
310°
00' at 310° F__
S0’ at 310° F__
120’ at 310° F _______ _-
480
645
430
30’
310° F ________ -00’ at 310“ F ________ __
00' at 310° F ________ __
120' at 310° F _______ _-
l, 470
1,4105
1, 620
1, 5-10
1, 340
1,490
1,500
1, 510
380
420
430
‘150
Curing mixture 13:
3,084,145
5
Table IV
It can be seen from the above table that the physical
properties of the polyamine cured brominated copolymers
are markedly improved compared to those of both the
unbrominated and the brominated copolymers. Also, it
Example XIII
can be seen that the addition of carbon black to the curing 5
Tensile
EXAMPLES XIII AND‘ XIV
‘Brominated copolymers were prepared from amor
phous ethylene-propylene copolymers by brominating the
Unbrominated copolymer__._
570
80
Brominated copolymer ____ _.
420
130
10 Control:
30’ _____________________ __
510
60'.-.
90’.
latter in benzene according to the process of Example I.
The properties of these unbrominated and brominated co
120’ _ _ .
Tensile
Elonga
290
220
340
470
. _ . __
270
Ouringm ture
polymers are given in Table III.
30' at 308° F. _
._
Table III
XIII
XIV-
mer
Elonga~
strength, tion, strength, tion,
p.s.i.
percent
p.s.i.
percent
mixture (as is in curing mixture B) is highly advantageous.
Unbro- Brominminated
ated
copoly- copoly-
Example XIV
Bromin
ated
copoly
mer-1
mer
755
220
795
265
840
240
830
250
1, 320
1, 350
1, 310
140
230
230
1, 400
240
610
620
630
320
330
340
600
320
.................. __
1, 480
2, 880
2, 870
40
90
40
__________________ __
1, 625
1, 635
1, 780
330
300
300
__________________ ._
1, 750
1, 840
1, 910
Inherent viscosity, vi
Softening point, ° 0
Melting point, ‘’ O
200
190
240
Curing mixture E:
Tensile strength, p.s
Elongation, percent _____ _.
._
80
130
220‘
Apparent modulus of elasticity, p.s.i.
‘5 _________________________________________ -.
Bromine, weight percent _____________ __
0
1. 05
1. 09
3.03
4. 35
30’ at 308° F- _
1, 380
60
60’ at; 308° F__
1, 970
1, 670
90
100
90’ at 308° F ___________ -_
1The corresponding unbrominuted copolymer is a blend of three
l, 710
1, 580
70
70
1, 820
70
ethylene-propylene copolymers having the following properties:
It can be seen from the data in Table IV that the
brominated copolymers of the invention are cured suc~
Grams
Copolymer
Tensile
inblend strength,
.
p.s.i.
Elonga- Inherent 35
tion,
viscos
percent
ity, vi
cessfully by various polyamines to rubbers having high
tension strength and elongations. The addition of ?llers
320
265
1.41
328
1
3082
it‘?
.6
such as carbon black to the curing mixtures provides
products ‘after curing which have even higher tensile
strengths.
40
'
oxides.
Portions of the above brominated copolymers were
used to prepare the following curing mixtures:
I
EXAMPLES XV THROUGH XXII
The prominated copolymers prepared in Examples I,
III, V, VII, VIII and VI were cured using the curing
mixtures and conditions listed in Table V for Examples
Curing mixtures A and B-Compositions as. shown for
Examples X through XII.
XV through XX respectively. The brominated copoly
Curing mixture C:
mer of Example XXI was prepared by brominating an
Parts
Brominated copolymer _______________ __-____ 100 50
Carbon black
'
Examples XV through XXIII are examples of bromi
nated copolymers cured with either metal salts or metal
_____
_
Curing mixture D:
___
50
amorphous ethylene-propylene copolymer in benzene and
had 0.03 wt. percent bromine and an apparent modulus
of elasticity of 1.05 X10“5 p._s.i, at —50° C. The bromi
nated copolymer of Example XXII was prepared by
brominating an amorphous ethylene-propylene copolymer
I
Brominated copolymer ___________________ __ 100
Carbon black ________________________ _..____ 50
in benzene and had 4.35 wt. percent bromine and an
Stearic acid _____________________ __r_____-__
4 55
inherent viscosity of 1.48. The brominated copolymers
Z-aminopyridine ________________________ __
4
4 60
of Examples XV through XXII were formed into vari
ous curing mixtures and cured. The properties of the
brominated and the cured copolymers, the conditions of
cure, and the curing mixtures used are given in Table V.
The curing mixtures referred to in Table V have the
4
following compositions:
Curing mixture E:
'
,
Brominated copolymer ___________________ __ 100
Carbon black ___________________________ ___
Stearic acid
2,6-diarninopyridine
__
____________________ __
50
Curing mixture F:
‘
Brominated copolymer ____ __a ____________ __
Carbon black
_
Stearic acid ____________________________ __
p-Phenylenediamine _____________________ __
100
50
4 65
4
The above curing mixtures were prepared by mixing
the components in a cool rubber mill (the stearic acid
was added before the polyamine). The mixtures were 70
then cured. The tensile strengths and elongations for
the cured brominated copolymers are given in Table IV
Curing mixture G:
Parts
Brominated copolymer ___________________ __ 100
Carbon black
___
I
_
50
Zinc oxide _____________________________ __
5
Stearic acid
1
‘
Curing mixture H:
Brominated copolymer ___________________ __ 100
Carbon black
50
Zinc oxide _____________________________ __
Stearic acid _____________ _'_‘_'_ ___________ __
10
1
together with the tensile strengths and elongations of the
Curing mixture I:
corresponding brominated and unbrominated copolymers
Brominated copolymer ___________________ __
for comparison purposes.
75
Carbon black ___________________________ __
100
50
3,034,143
Curing mixture J :
Parts
Curing mixture P:
Parts
Bromlnated copolymer ___________________ .._ 100
Brominated copolymer ___________________ .... 100
Zinc _OX1de ----------------------------- _-
5
Carbon black.._..___- ____ _-_ _____________ __
50
_Stear_1° acld --------------------------- --_
1
Magnesium oxide...._______________________
10
Curing nuxture K:
5 Curing mixture Q:
Bf'ommafed copolymer ------------------- —- 100
Brominated copolymers __________________ __ 100
Zmc _0X1d¢_-
Carbon black ___________________________ __
50
PbaQ1
10
-
-
10
Steanc acid
1
Curing mixture L:
Brominated cgpolymer ___________________ __ 100 10
Carbon b1ack_____ _____________________ ___
Cadmium sul?de________________________ __
50
10
Curing mixture M;
_
It (I311 175 Seen fI'Om the above table that marked 1m
provement in tensile strength compared to both the un
brominated and the brominated copolymers can be ob
tained by treating the brominated copolymers with as
Brominated eopolymer___________________ __ 100
little as 5 parts of zinc oxide for very short curing times,
Carbon black ___________________________ __ 50 15 It was found that a relationship existed between desirable
Zlnc ox1de _____________________________ ___ 10
mechanical properties for the cured brominated copoly
Table V
Xv
'1‘.s.,1
p.s.i.
XVI
per13.,1
p.s.i.
T3,
perE_,
cent
Unbromiuatetl copolymeru
123
660
XVII
p.s.i
01.3,
cent
XVIII
per-
p.s.i.
T.S.,
cent
145
444
230 ____________ __
123
000
perE.,
p.s.i.
’1‘.S.,
cent
XX
per13.,
p.s.i.
12s.,
cent
XXI
pcr-
11.3.1.
'I‘.S.,
ccut
XXII
per12.,
p.s.i.
cent
per
cent
123
000
235
30
235
30
235
30
235
30
232
130
223
116
251
103
420
130
230
220
30’at308“ F ____ __
00'at303° F ____ __
543
520
1,474
1,429
90'3t30S°F .......... __
515
1,515
120' at 308° F _________ .-
484
1,520
Bromlnnted copolymer _________________ ..
230
XIX
Curing mixture G:
15’nt308°F __________ .-
1, 750
136
_____ __
Curing mixture H:
30’ at 303° F
_____ ._
60'31", 303° F
90' at 303° F
440
2,000
120’33 303° F
390
503
1,249
972
1,017
472
510
1,324
1,549
..... .. 1,213
536
1,503
734
390
390
Curing mixture I:
30' at 303° F-.__
60' at 303° F
_____ __
90' at 303° F
_____ _
120' at 303° F
Curing mixture J:
30' at 303° F
_____ ..
_
60’ at 303° F .................................................... -.
631
90’et308°
043
372
315
304
F
... . .__
_ _ _ _ . _.
120' at 303° F
Curing mixture K:
30’ at 303° F__
760
_____ __
00' at 303° F
90' at 303° F
120' at 303°
.
_
F.
_ _ ... _ _
_ _ _ _ _ _.
Curing mixture L:
30’11330
--
_
00' at 303° F
. _ . _ . _ .
_ _ _ _ . ..
. _____ _.
90' at 303° F
120' at303° F
_____ __
Curing mixture M:
00'
30' at 303° F
..... ._
-
30' at 303° F
_____ ..
_
Curing
120'mixture
at 303° N:
30'
at 303°
. ... . _ .
_ . . . _ ..
-
30' at 303° F
90' at 303° F
..... _
120' at 303° F
Curing mixture 0:
30' at 303° F
30' at 303°
F
90m: 303°
F
_____ .
._ . _ _ _ _
_ _ . . . _.
. __ . . _ .
120' at 303° F
__ ._.-
..... _.
Curing mixture P:
30' at 303° F
30' at 303° F
90' at 303° F
120' at 303° F
_____ _.
omigigglslgg’rg‘gl . . . _ . _ 1 . _
_ . . . . _ .
__ . _ ._ .
. . _. .. .
. . . . . _ .
00' at 303° F
90' at 303° F
1 T.S.—-Te11sile strength.
............ ..
_ _ _ _ _ -_
1,070
300
1,300
300
1,900
240
1 E.——Elongatlon.
‘Curing mixture N:
mers and the inter-relation between the bromine content
Brominated eopolymer _______ __>__________ __ 100
of the copolymer and the curing time. In general, the
Carbon black _____ __.. _______________ ____.._. 50 70 higher the bromine content the shorter the curing time
Ferric oxide___.._._______.._______ _______ ..__ 10
Curing mixture 0:
V
Brominated copolymer__._.______ ____ ___..__.__ 100
Carbon black ____________________ __
Zinc
-_
sul?de-,___,,__,_- __________________ __
‘50
required to produce cured copolyrners with excellent
mechanical properties. It is to be noted that the data
given in all Of the above tables where carbon black is
a component of the curing mixture is given for semi
10 75 reinforcing furnace carbon black.
Other carbon blacks
3,084,145
9
10
such as medium thermal carbon black and high modulus
It is to be understood that this invention is not limited
polymers with excellent physical characteristics. It can
to the speci?c examples which have been presented for
illustration purposes only. Moreover, modi?cations of
be seen from the above table that a large variety of
metal oxides and metal salts can be used as eiiective
the invention can be made by those skilled in the art
without departing from the scope and spirit of the in
furnace carbon black were also used and gave cured co
curing agents for the brominated copolymers.
vention.
What is claimed is:
A brominated ethylene-butene-l copolymer was also
1.
process for producing a synthetic rubber which
prepared by the above bromination process. This co_
comprises:
polymer can be cured to give a superior synthetic rubber
(1) reacting a copolymer of 5 to 95 mol percent
in accordance with the invention.
10
ethylene and 95 to 5 mol percent of a ‘C3—C6 alpha
EXAMPLE XXIII
ole?n in an inert solvent selected from the group
The brominated copolymer of Example XXI cured
consisting of aliphatic and aromatic hydrocarbons
by curing mixture H was formed into two 6" x 6" pads
and their halogenated derivatives, said solvent capable
using a 60 minute curing time at a 308° F. curing tem
of at least partially dissolving the copolymer, with
perature. The cured pads had the following properties.
Tensile strength ______________ __
a brominating agent at a temperature in the range
of 20°—130° C. to form a brominated copolymer
1200 p.s.i.
having from 1 to 10 weight percent bromine;
(2) isolating and drying said copolymer; and
Elongation, percent ___________ __ 430.
Modulus/300% ______________ __ 740 p.s.i.
20
Oven aged for 72 hours at 300° F.:
perature in the range of 225 °—350° F. with an aro
Tensile strength __________ __ 900 p.s.i.
Elongation _______________ _.
300%.
Shore hardness ___________ __
65.
matic polyfunctional compound containing at least
one primary amine group as one of the functional
groups.
2. A process according to claim 1 wherein the aromatic
Ozone resistance __________ _. After 6 hours expo
sure to ozone, the
pads ’ Were
still
smooth
un
and
cracked.
Dynamic modulus tests:
Percent relative damping____. 35.8.
polyfunctional compound is Z-aminopyridine.
3. The process of claim 1 wherein the aromatic poly
functional compound is p-phenylene diamine.
4. The process of claim 1 wherein the aromatic poly
30
functional compound is m-phenylene diamine.
Internal viscosity (17f) _____ __ 1.315><105 poises
6. The rubbery product of claim 5.
cycles/sec.
References Cited in the ?le of this patent
UNITED STATES PATENTS
As can be seen from the above example the cured co
polymers of the invention unlike natural rubber have
excellent high temperature properties and ozone resist
2,183,556
2,200,429
ance due to the absence of any functional groups re
active to ozone. Additionally, they have the unusual
combination of high dynamic sti?iness and low percent
relative damping. In these properties they resemble
GR~S and natural rubber. Accordingly, the cured co
polymer of the invention are ideal for use in tire treads
where resilience and stiffness characteristics are particu
functional compound is 2,6-diarnino pyridine.
5. The process of claim 1 wherein the aromatic poly
Dynamic stiitness (K) _____ _. 447x105dynes/cm.2.
larly desirable.
(3) curing the dried brominated copolymer at a tem
2,364,410
Fawcett ______________ __ Dec. 19, 1939
Perrin et al. __________ __ May 14, 1940
Wittaker ______________ __ Dec. 5, 1944
2,405,971
2,850,490
2,920,064
McAlevy ____________ _.. Aug. 20, 1956
Canterino et al. ________ __ Sept. 2, 1958
Baptiss et a1 _____________ __ Jan. 5, 1960
478,513
Canada ______________ __ Nov. 13, 1951
FOREIGN PATENTS
45
Документ
Категория
Без категории
Просмотров
0
Размер файла
702 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа