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Патент USA US3036055

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Uite States
3,636,045
Patented May 22, 1962
1
2
3,036,045
tively stable reaction products. We have now found that
because of the reactivity of these reaction products with
hydroxy groups these reaction products may be advan
tageously employed in the vulcanization of hydroxy-con
taining polymers not only for the purpose of yielding
POLYMER COMPOSITIONS AND IMPROVED
PROCESS FOR VULCANIZATION OF RUB
BERY HYDROXY-CONTAINING POLYMERS
WITH POLYISOCYANATES
James N. Short, Borger, and Paul W. Solomon, Phillips,
Tex., assignors to Phillips Petroleum Company, a cor
poration of Delaware
No Drawing. Filed July 5, 1955, Ser. No. 526,116
2 Claims. (Cl. 260--77.5)
This invention relates to the production of polymers.
In one aspect it relates to a process for vulcanizing or
curing hydroxy-containing polymers and to the vulcanized
polymers produced thereby. In another aspect it relates
to a novel vulcanizing agent or curative which decreases
the occurrence of premature vulcanization. In another
aspect it relates to a millable and vulcanizable polymeric
composition.
By the vulcanization or curing of synthetic polymers
polymeric products having desirable physical characteris
tics but also to prevent premature vulcanization of the
polymeric composition. In the practice of this invention,
the reaction products to be employed as vulcanizing agents
or curatives can be prepared by the well known reaction
of an isocyanate with ‘a compound containing active hy
drogen. In particular, we have found it advantageous
to use at least a stoichiometric amount, and, if desired,
an excess, of the active hydrogen-containing compounds
per mol of the polyisocyanate. The polyisocyanate is
caused to react with the active hydrogen-containing com—
pound at an appropriate temperature. The temperature
and the time of reaction will be dependent upon the ac
tivity of the reactants. The reaction products so obtained
and natural rubber, the physical characteristics, such as
are stable at room temperature and may be handled with
tensile strength, abrasion resistance, and heat build-up,
out di?iculty.
may be greatly in?uenced, as is well known in the art.
Various vulcanizing agents or curatives and other addi
tives are mixed with the polymeric compositions prior
to the actual step of vulcanization in order to influence
ing compounds can be aliphatic, cycloaliphatic, or aro
matic, and they may contain other reactive groups. While
we have found that organic polyisocyanates in general
these physical characteristics. The vulcanizing agents
chemically react with the polymeric composition during
The polyisocyanates and the active hydrogen-contain
may be used in the practice of this invention, the di
isocyanates are to be preferred because of their availabil
ity and ease of preparation. Representative polyisocyan
ates useful in the practice of this invention include: m
vulcanization, and the nature of some of the reactions
is known while the nature of other reactions is uncertain.
In the past, polyisocyanates have been employed in the 30 phenylene diisocyanate; p-phenylene diisocyanate; hexa
vulcanization or curing of hydroxy-containing polymers.
However, when these vulcanizing agents or curatives are
employed per se the vulcanization or curing occurs rapid
methylene diisocyanate; m-tolylene diisocyanate; p-tolyl
ene diisocyanate; p,p'-diphenylmethane diisocyanate; p,p'
diphenyl diisocyanate; diphenyl~3,3'-dimethyl-4,4’diisocy
anate; 2-chloropropane diisocyanate-1,3; diphenyl-3,3'-di
methoxy-4,4'-diisocyanate; 2,2'-diisocyan-ate diethyl ether;
ly and at relatively low temperatures. Such procedure
often results in premature vulcanization, or “scorching,” 35
of the compounded stock prior to the period in the proces
3 - ( diethylamine) -pentane-diisocyanate-l,5; 1,5 -naphthy
sing cycle when vulcanization is desired. This scorching
lene diisocyanate; pentamethylene diisocyanate; tetram
prevents (in many instances) the further milling or Work
ethylene diisocyanate; octamethylene diisocyanate; ethy
ing of the polymeric composition.
lene diisocyanate; propylene-1,Z-diisocyanate; cyclohexyl
We have now found that vulcanization of hyd-roxy 40
containing polymers can be effected without scorching
by employing as a novel vulcanizing agent or curative
the reaction product of a polyisocyanate with an active
ene-l,2-diisocyanate; xylylene-l,4-diisocyanate; benzene
l,2,4-triisocyanate; and the like.
,
Representative active hydrogen-containing compounds
useful in the practice of this invention include: phenol;
0-, m-, and p-cresol; di-n-butylamine; diphenylamine;
Accordingly, an object of this invention is to provide 45 piperidine; morpholine; phenyl-beta-naphthylamine; N
a process for vulcanizing hydroxy-containing polymeric
methyl-acetamide; N-ethylvaleramide; N-rnethyl-Z-naph
hydrogen-containing compound.
materials and to provide novel polymeric materials pro
duced thereby.
Another object is to provide a novel vulcanizing agent
comprising the reaction product of a polyisocyanate with
an active hydrogen-containing compound without the ten
dency for a polymeric composition containing said agent
thamide; diacetamide; acetanilide; N-phenylbenzamide;
succinimide; phthalimide; malonimide; and the like.
The polymeric compositions which can'be vulcanized
or cured by the practice of this invention can be prepared
by Well known procedures from mixtures of conjugated
dienes and hydroxy-conta-ining monomers or from mix
tures of hydroxy-containing monomers and certain other
to exhibit that premature vulcanization or scorching
which occurs when polyisocyanates are employed per so 55 copolymerizable monomers having an active vinylidene
group, e.g., CHFC<. Representative hydroxy-contain
as the vulcanizing agent.
ing monomers include: 2-phenyl-4-hydroxy-l-butene;
A further object is to produce a millable and vulcaniz
able hydroxy-containing polymeric composition.
2-(4 - chlorophenyl) - 4 - hydroxy-l-butene; 2-(2-brorno
A still further object is to produce novel polymeric
materials of desirable physical characteristics.
Further objects and advantages of our invention will
phenyl) - 4-hydroxy-l-butene; 2-(2,4,6-trimethylphenyl)
become apparent, to one skilled in the art, from the ac
companying discussion and disclosure.
4-methylphenyl) - 4 - hydroxy - 1 - butene; Z-(Z-methoxy
4-hydroxy-l-butene; and the like. Other hydroxy-contaiu
ing monomers include: dimethylethynylcarbinol; hy
droxyethyl arcylates and methacrylates; hydroxyethylsty
rene; Z-hydroxyethyl - 5 - vinylpyridine; N~hydroxyethyl
It is known that certain compounds which contain ac
iaorylamide; N-methylolacrylarnide and the like.
'
tive hydrogen react with polyisocyanates to form rela 65
Representative conjugated dienes copolymerizable with
3,036,045
3
4
the hydroxy-containing monomers generally include those
ucts having good physical properties can be obtained in
containing from 4 to 8 carbon atoms per molecule ‘as
the absence of sulfur in the compounding recipe. 'The
polymeric materials obtained by the practice of this in
exempli?ed by: 1,3-butadiene; isoprene; 2,3dimethyl
1,3-butadiene; piperylene; 2-methyl-1,3-pentadiene; ch1o—
vention are non-corrosive to metals and, therefore, have
advantages over sulfur-containing polymers for many ap
plications. It is to be understood, however, that the use
of sulfur and other additives such as plasticizers, anti
roprene; 2-methoxy-l,3~butadiene; 2-ethoxy-1,3-butadiene;
2-cyano-l,3-but-adiene; 2-methyl - 3 - cyano-1,3-butadiene;
and the like.
.
Other representative copolymerizable monomers con
t-aining ‘an active vinylidene group include the aryl ole?ns,
oxidants, reinforcing agents, vulcanization accelerators,
para-methoxystyrene; methyl acrylate; ethyl acrylate;
methyl methacrylate; ethyl methacrylate; butyl methacry
late; acrylonitrile; methacryloninile; methacrylamide;
methyl isopropenyl ketone; methyl vinyl ketone; methyl
and the other speci?c ingredients of the recipes are pre
sented as being typical and should not be construed to
limit the invention unduly.
vinyl ether; vinyl acetate; vinyl chloride; vinylidene chlo
ride; vinylfurane; vinyloarbozole; vinylacetylene; Z-rneth
EXAMPLE I
etc., can be employed in the compounding recipe. How
esters. of acrylic and substituted acrylic acids, nitriles, 10 ever, these ingredients are not necessary and in some re
spects it is advantageous if they are omitted.
amides, ketones, ethers, and halides. Speci?c examples
Advantages of this invention are illustrated by the fol
useful in the practice of this invention include: styrene;
lowing examples. The reactants and their proportions
nuclear substituted alkyl styrenes; para-chlorostyrene;
yl-S-vinylpyridine; and the like.
20
While we have found ‘that practice of this invention is
A 75/25 butadienel2-phenyl-4-hydroxy-l-butene rub
ber having a Mooney value (ML-4) of 56 was obtained
by blending several butadiene/2-phenyl-4-hydroxy-l-bu
particularly applicable to the processing of a 2-pheny1-.
tene copolymers which had been prepared by emulsion
4-ihydroxy-1-butene/ 1,3-butadiene rubbery copolymer, it is
polymerization at 41° F. The combined 2-phenyl-4-hy
obviously not limited thereto and other polymeric mate
rials herein disclosed are within the scope of this inven 25 droXy-l-butene in the rubber was approximately 10.7
weight percent (0.072 mols per 100 grams rubber).
tion.
Reaction products of hexamethylene diisocyanate and
In the preparation of rubbery copolymers of hydroxy- '
m-t-olylene diisocyanate each with phenol and diphenyl
containing monomers and conjugated dienes, from 50 to
98 parts by weight of conjugated diene is employed per
100 parts by weight of monomeric material. Such hy
amine were used as curatives in the above-described rub
Synthesis of these reaction products was accom
30 ber.
plished by heating one mol of the diisocyanate ‘with two
droxy~containing monomer is employed in an amount
_ suflicient vto yield a polymer containing at least 0.009 mol,
mols of the phenol or amine in the presence of a few
drops of triethylamine catalyst for 8 hours at 150° C.
and more preferably, at least 0.025 mol of hydroxy group
(302° F.). Nitrogen analyses are shown in Table I
per 100 grams of rubbery copolymer. It is necessary that
at least ‘0.009 mol of hydroxy group be present in order 35 together with theoretical values:
that-the desired vulcanization with the reaction products
of polyisocyanates with active hydrogen-containing com
pounds be obtained. As long as the requisite amounts
of the hydroxy-cont-aining monomer and the conjugated
diene are present in the initial charge, as hereinbefore de
Table I
Nitrogen, weight
40
.
Ourative
scribed, the various amounts of the other aforementioned
'copolymerizable materials containing an active vinylidene
group can also be present.
Diisoeyanate
percent
Other compound
number
Found
'
Theoret
ical
The amount of the vulcanizing agent employed in the
practice of this invention is dependent upon the particular 45
compounding recipe, .the particular reaction product em
ployed, the extent of, vulcanization or curing desired, and
‘other considerations which will be evident to those in the
'art and may be readily determined according to the par
7.8
7.9
2 ___________________________ _.
Diphenylamine...
10.9
11.1
‘1
1 _________ __
Hexamethylene.
Phenol
l0. 9
7. 7
m-Tolylene
4 ___________________________ __
Phenol __________ -_
Diphenylamine-.- ________ __
10.9
ticular polymeric product desired. Generally, however,
50
The butadienel2-phenyl-4-hydroxy-1-butene rubber was
in most instances, the amount of vulcanizing agent is in
compounded in black and gum recipes using the formula
the range between 0.13 and 5,.mols, preferably in the range
tions in Table II.
between 0.35 and 3 mols, per mol of hydroxy group in
the polymer. The vulcanizing agent useful in the practice
Table II
of this invention may be incorporated into the polymeric 55
composition along with other additives such as ?llers,
.
Gum recipe
so?teners, plasticizers, etc., by any suitable mixing pro
Rubber
cedure such as during milling.
Curative
V
.
e vuloanizing or curing temperature employed in the
practice of this invention is generally that which is re 60
garded in the range for rubber processing. Ordinarily,
this can be in ‘the range between 200° and 400°. F. By
‘varyirigthe composition ofthe vulcanizing agent, curing
grams" 100
__
agent employed. Generally this time will be at least 10
vminutes and may be ,48 hours or longer. The curing is
continuedluntil the vulcanizate has the desired physical 70
properties.
.
Sulfur is frequently regarded ,as having a deleterious
e?e'ct on a rubber vulcanizate, particularly as regards
aging characteristics. The present invention makes avail
:able to'theart a process whereby ?nished polymeric prod 75
1 0.05
Black recipe
Rubber _..__
grams__ 100
Carbon black (Philb'lack O) ____________ __d0..-__
50
Circe-Para 2 ________________________ __do____
10
"conditions may be varied according to known procedures
Curative:
to obtain the desirable physical properties in the ?nished 65
Mols __________________ .._ 0.03,
polymeric product. The curing time will depend upon
Mols per moi hydroxy group in
'the curing temperature and ‘the particular vulcanizing
mols
0.05, 0.07 0.09
copolymer ____________ __ 0.42, 0.69, 0.97 1.25
10.69 mol per mol hydroxy group in copolymer.
.
3A blend containing equal parts of Circosol-2XH with
Para Flux Circosol-2XH: Petroleum hydrocarbon softener
containing hydrocarbons of high molecular weight, in the
form of a heavy, viscous, transparent pale green, odorless
liquid of low volatility; sp. gr. 0.940; aybolt Universal vis
cosity at 100° F., about 2,000 seconds. Para Flux: Saturated
polymerized hydrocarbonv
The stocks were milled, cured for different lengths of
.12.
3,036,045
tirne, and physical properties determine(1. Stocks in which
taneously when the materials are milled. Snch stocks are,
dusocyanates alone are used as curatives instead of the
therefore, not processable. Physical properties of the
reaction products herein described scorch almost instan
cured rubbers are shown in Tables III and IV.
Table III .—Stress-Strain Properties (Original)
Gum Recipe (No Black)
2
0
Compression set,
percent
Curative
2
90’ cure 2
_e
Elon
No.1 Mols
30'
60’
90’
120’
sile,
60.52H7m89 lE“rgv(459m3812w W"o4u5s6.7.05421.
7._8‘62M031 m)%we=0c7i82.m9 “msluq016 2Mn/8r
321m_,1P
"6W85O21HS.0“ 501_t
,01T,2so1,.
Ten
Ius,
p.s.i.
p.s.i.
sile,
tion,
cent
S.
Ce7
on.050e
modu
per
m
n
82.J
_
_
300%
ga
tion,
101,11pT.
190
1,000
_______ _______
170
0.
_
3
_
_
.
.00_00.50
03579 5620497 0&.L4~An5316978 idn?Auomalv.479123605
1
Black Recipe
_.11,1,$3
132 .L26374~5
50.
1 No. 1. Hexamethylene diisocyanate— phenol reaction product, No. 2. Hexarnethylene diisocyanate-diphenylamine reaction product, No. 3.
m-Tolylene diisocyanate—phen0l reaction product, No. 4. m Tolylene diisocyenate-diphenylamine reaction product
2 Cured at 307° F.
3 Poor slab.
Table IV
Gum Recipe (No black)
r
P
m
Curative
G
“my
w.
e
0
m
m
0s
T, F,
S
mm
80
w,
_W
m
A
N 0.1
Mols
S(
R
T
w_
_
n
8
7
4
0
1
3
2
6
.
“
v
l
?
m
w
u
4
3
2
5
0%W~.wm/2)4e5 1.695283
O
B
n
A
0.
(r1
%0$ %0
3579
O
A1935248 0“g30\/8)3014. "15802593
KZL_Q73d.Q&
e
I
a<
.
~..
-~
¢
0MWa:mZQ/D1m3»kA54186350
1!r\(I.
a
n
__
g
m
n
u
pA
m7570 42.50
W“WW“%eH67 6 mm
.6d5.2 .,&5.
4.7.“05.&7..&Qm
6nMmM?Uhe%ld/una%bie_15Q7289021
u
U./\tI\g
.7d
6”
.L
U67.60.5.
Mm%6"5H43@7mW6 .n094627w381.
_
e
n
c D.A
mmwW5e47?./BH86“7-%m
e
t
t..
,
.
.
.
,
M.m983145026
71.69450
W%.63
.052.4~5 M.56
(
.51e3d076_O.
.7.om&01d23,96.& 4
2.L7.17L.0.530.5
1.v0491 .58.
See footnotes at end of table.
w
5
0
7
1
8
2
4
6
A29518 W4%3e5 ? .M%65m47 wNWH7e6548
7m32180u549
w
..A
H
u
eF.m
N
u
1___________
MW’
Q, _
.SC
O
‘70.2691.42:0L
2563148
3,036,045
Table lV-Con'tinued
Gum Recipe (No black)—Cont_inued
Hysteresis properties—Gontinued
Shore hardness
120' core
Cure time
Curative
.
A TF
Mols
Orig.
1
0.05
2___..
3
0.05
0. 05
4
0. 05
Comp.
7
MS 11/4
Resilience, percent
30'
No.1
Scorch at 280° F.
Aged
Orig.
60'
.
90'
Minimum
Minutes
Mooney
to scorch
120’
Aged
___
39. 5
________ __
_____
--
“___
21
51
________ __
___
__________ ._
40
Black Recipe—0ontinued
0. 03
0.05
0.07
0. 09
O. 03
V0. 05
0.07
0. 09
0. 03
0.07
0.09
0. 03
0. 05
0.07
0.09
52. l
40. 5
33. 8
34. 1
62. 5
53. 7
50.0
51. 7
32. 5
31. 8
33. 8
33. 8
35. 1
35. 1
34. 4
42. 6
37. 5
33. 8
33. 8
53. 4
48.3
42. 6
43. 9
32. 8
32. 5
43. 3
34. 8
33. 8
38. 1
45. 9
1 Ouratives as in preceding table.
68. 3
73.1
75. 0
70. 1
61.3
61.6
59. 7
54. 3
82. 0
79. 7
73. 9
80.0
78. 8
76. 2
72. 4
2 Too soft.
73. 3
75.3
76.1
71. 6
66. 2
63. 9
59. 2
51. 2
80. 8
74. 1
67. 5
79. 9
77. 7
72. 6
66. 9
51
61
63
67
38
37
35
34
65
67
65
56
57
61
63
3 Poor pellet.
52
58
61 5
66
42
41 5
39
37
69
70
67
64
66
66
67
54
56
60
64
46
46
42
40
71
71
68
68
70
69
69
57
58
58
63
49
48
46
44
72
72
69
70
71
71
70
31. 5
34
36
37. 5
29. 5
26. 5
26
23
34. 5
38. 5
39
36
37
41
42
28
26
23. 5
19
30
26. 5
27
22
41
44
40
34
31. 5
30
27. 5
20
16. 5
11.5
10
'19
14
15. 5
16
5
5
4. 5
12
12
13. 5
14
4 No pellet.
When diisocyanates are used as curatives instead of the
reaction products described above, they cause almost im
Reaction products of p,p’-diphenylmethane diisocyanate
mediate scorch when milled into the butadiene/Z-phenyl
with phenol, diphenylamine, and acetanilide, and of hexa 35 4e11ydroXy-1-butene rubber.
methylene diisocyanate and m-tolylene diisocyanate with
EXAMPLE 1H
acetanilide were prepared by, heating one mol of the di
isocyanate with two mols of the phenol, amine, or ace
7 The reaction product of one mol of p-p'-diphenylmeth
tanilide in the presence of a few drops ‘of triethylamine
ane diisocyanate with two mols of p,-p'-dimethoxydiphenyl
Nitrogen
‘catalyst for 8 hours at 150° C. (302° R).
' amine was. used as a curative for a 75/25 butadiene/2
analyses are shown in Table V together with theoretical 40 phenyl-4-hydroxy-1-butene rubber similar to that described
values:
in Example I. The compounding recipe was as follows:
Table V'
EXAMPLE II
Rubbery copolymer _________________ __grams__ 100
Philblack O _________________________ ....do-...._ 50
Nitrogen, weight
percent
Dilsocyanate
Found
p’-Di henylmethane _____ __
p’
45 Curative
Other compound
6.4
Diphenylamine-.-
9. 3
9. 5
'
Acetanilide_-._ __
Hexarnethylene _____________ __ ___do _____________ __
-10.4
13. 3
10.8
12. 8
10. 3
12. 9
m-Tolylene
do
Compression set ______________ __.-____percent__
9.3
60 300% modulus ______________________ __p.s.i_.. 1400
Tensile
'
Elongation
A 75/25 butadienel2-pheny1-4-hydroxy-l-butene rub
‘Rubbery copolymer ____..>_;_; ____ _._‘__-__..grams__ 100'
Philblack 0
'
'
,
'
~
dn
'
so,
mnls
0.05
psi
______ ___.______________ ___-percent“
Permanent set ____________________ __percent__
do
3.8
60.6
-
60
EXAMPLE IV
60 mate with two mols each of various compounds containing
active jhydrogen were prepared and used as ouratives for
in all cases. Results are shown in Table VI.
the 75/25 butadiene/2-phenyl-4-hydroxy-1~butene rubber
described in Example I. The compounding recipe was the
same as that given in the preceding example. The stocks
Table VI
.
pm
Other compound
'
’-Di hen 1methane_--_____ Phenol ______________ __
p
y
Dipheynlamine-_
'Hex
meth lane
m-Tilylenz
1 Poor slab.
A216tanmde"""""" "
___rn
___do
2 Too soft.
Compres- Tensile,
sion set, ' p.s.i.
~percent
Elongation,
percent
10.5
6.5
(1)
1, 730
(1)
222
.
51,260
,
(1)140
11. 0
420
89.6
Reaction products of one mol of m-tolylene diisocya
The stocks were milled, cured 60 minutes at 307° F,
and physical properties determined. Milling was easy
Diisocyanate
2200
ATP
’
bery copolymer similar to that described in Example‘l was 55 Resilience
Shore hardness
compounded in the following manner using the above
described reaction products as. curatives:
'Curative
0.05
The stock was milled, cured 60 minutes at 307° F., and
physical properties determined. Results were as follows:
Theoret
ical
Phenol ____________________ ._
p
mols
2, 080
100
280
Perme-
ATF
52.4
36.5
'
115.0
nent set,
percent
0.2
0.1
(a)
34. 4
_Resilience,
percent
Shore
hardness
71.3
75.4
71
70
2%:
.
23
55. 7
61
Jim‘A.
3,036,045
8
10
were milled, cured 60 minutes at 307° F., and physical
properties determined. No odor or handling problems
were encountered during milling or curing of the stocks.
tion into the unvulcanized or uncured polymeric composi
Results were as follows:
tion, without the tendency for premature vulcanization to
essence of which is that the processing of hydroxy-contain
ing polymeric materials can be improved by the incorpora
Table VII
Compound reacted with m-tolylene
diisocyanate
Comp.
300% Tensile,
set,
modulus
p.s.i.
percent
p.s.i.
Elongation
percent
Permapercent
ATF
nent set,
Di-n-butylamine __________________________ ._
Piperidine _________________________________ __
6. 3
12. 6
1, 020
780
2, 800
1, 240
510
500
77. 7
169. 6
h/Iornhnl me
16. 4
390
580
590
(1)
Phenyl-beta-naphthylamine _______________ __
Phthalimirle
8.0
40. 2
(1)
ResilShore
ience, hardness
percent
56. 6
47. 4
46. 1
50
63
58
6. 7
2, 400
2, 900
360
57. 5
0. 8
64. 1
64
13. 6
______ __
2, 450
120
55.8
0.7
66. 9
76
1 Pellet split.
The reaction product of m-tolylene diisocyanate with
occur, a novel vulcanizing agent comprising the reaction
lauryl alcohol was tried as a curative using the procedure 20 product of p-olyisocyanates with active hydrogen-contain
described above. Very little, if any, curing was obtained
ing compounds.
after 60 minutes at 307 ° F. as evidenced by a compression
Having described our invention we claim:
set value of 46.7 percent.
1. In a method for producing a synthetic copolymer,
wherein said copolymer is prepared by polymerizing from
EXAMPLE V
' 50 to 98 parts by weight per 100 parts by weight of mono
The reaction product of m-tolylene diisocyanate with
phthalimide, described in Example IV, was employed as
a curative for the 75/25 butadiene/2-phenyl-4-hydroxy-l~
butene rubber of Example I using the following conven
tional compounding recipe containing sulfur:
Parts by weight
Copolymer
30
100
Philblack 0 (carbon black) __________________ _._
50
meric material of 1,3-butadiene and 2-phenyl-4-hydroxy
butene, the latter monomer being employed in an amount
su?icient to yield a copolymer containing at least 0.009
mol of hydroxy group per 100* grams of copolymer, and
said copolymer is subjected to milling and subsequent
vulcanization, said copolymer being reactive with a poly
isocyanate, the improvement which comprises adding to
said composition during said milling a reaction product of
m-tolylene diisocyanate with at least a stoichiometric
10
1.75 35 amount ‘of diphenylarnine per mol of said diisocyana-te,
Circo-Para 1
Sulfur
Zinc oxide
3
said reaction product being employed in an amount in
Stearic acid _
1
the range of 0.13 to 5 mols per mol of hydroxy group in
Flexamine 2 _
Santocure 3
' Curative 4
1
1
23
_
1 As in Exam le I.
said copolymer.
_
2. A milla‘blle and vulcanizable rubber mix comprising
40 a copolymer prepared by polymerizing from 50 to 98 parts
by weight per 100 parts by weight of monomeric material
of a conjugated diene having 4 to 8 carbon atoms per
molecule with a hydroxy-containing monomer having a
2‘Physical mlxture containing 65 percent of a complex di
arylamineketone reaction product and 35 percent of N,N’-di—
pheny1—p-phenylenediamine.
CH2=C< group, said hydroxy-containing monomer being
3 N<cyclohexy1-2~benzothiazylsulfenamlde.
4 0.05 mol per 100 grams rubber.
45 employed in an amount sufficient to yield a copolymer
having at least 0.009 mol of hydroxy group per 100 grams
The rubber was milled, cured at 307° F., and physical
of copolymer, said copolymer being reactive with a poly
isocyanate, and a vulcanizing agent comprising the reac
Cure time, minutes 50 tion product of m-tolylene diisocyanate with at least a
stoichiometric amount of diphenylamine per mol of said
properties determined. Results were as follows:
30
diisocyanate, said reaction product being employed in an
60
- amount in the range of 0.13 to 5 mols per mol of hydroxy
Compression set, percent ________________________ __
Tensile, p.s.i., original _______________ ._
_.-_
19. 7
1, 400
8. 8
1, 600
____
110
140
Tensile, p.s.i., oven aged 24 hrs. at 212° F______..__
Elongation, percent. oven aged 24 hrs. at 212° F.--
1900
110
A TF
58.8
Resilience, percent ______________________________ __
65. 9
68. 1
72
73. 5
Elongation, percent, original _____________ _-
200° F. maximum hot tensile, p s i
Shore hardness
850
_ _ __
__ __
group in the copolymer.
55
References Cited in the ?le of this patent
_ _ __
_ _ __
UNITED STATES PATENTS
50.
60
2,381,063
2,683,727
2,683,728
Kung ________________ __ Aug. 7, 1945
Masten ______________ __ July 13, 1954
Masten ______________ __ July 13, 1954
574,901
150,416
Great Britain __________ .._ Jan. 25, 1946
Australia ______________ __ May 3, 1951
The corresponding run with the same curative in a sul—
FOREIGN PATENTS
fur-free curing system is given in Example IV.
Variations and modi?cations are possible Within the
scope of the foregoing disclosure and discussion, the
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