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Патент USA US3033842

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United States Patent Office
1
3,033,832
v 3,033,832
Patented may a, 1962
2
-
HALOGENATIGN CF RUBBERY COPOLYIWERS
George E. Serniuk, Roselle, and Irving Knntz, Rosalie
about 0.2 to 5.0, parts by weight based on total reacting
comonomers of such monoole?nic compounds as styrene,
p-methylstyrene, lalpha-methylstyrene, indene, dihydro
Park, N.J., assignors to Esso Research and Engineering
naphthalene, dichlorostyrene, p-chlorostyrene, mixtures
No Drawing. Filed Mar. 7, 1958, Ser. No. 719,725
thereof, etc. Such a copolymer has a Staudinger molec
ular weight between about 20,000 and 300,000, or a viscos
Company, a corporation of Delaware
'
9 Claims.
(Cl. 260-—78.4)
This invention relates to the preparation of high‘mo
lecular weight, halogen and oxygen-containing rubbery
copolymers of isoole?ns and multiole?ns, and particularly
halogenated isoole?n-multiole?n, copolymers of high hal
ogen content produced by halogenation in the presence
of halogen containing compounds and in the presence of
ity average molecular Weightof about250,000 to 2,000,
000 and an iodine number between about 0.5 and 50.
Suitable halogenating'agents which may be employed
10 are gaseous chlorine, liquid bromine, alkali metal hypo- '
chlorites or hypobromites, C4 to C10 tertiary alkyl hypo
chlorites or hypobromites, sulfur bromides or chlorides
(particularly sulfu-ryl bromide 0r chloride), N-chloro~
succinimide, N-bromosuccinimide, alpha-bromo‘or chlo
certain organic acid anhydrides.
15 ~ro acetanilide, N,N’-dibromo-5,S-dimethylhydantoin, tri
Heretofore, it has been impossible to produce butyl
bromophenol bromide, N-chloro-acetamide,_ N-bromo
rubber copolymers, with or without chemical modi?ca
phthalimide, iodine monochloride, etc.
>
tion, which are of high halogen content without, at the
. The modi?cation reaction may be accomplished pref
same time, degrading the molecular weight. The desir~
erably by preparing a 1 to 80 weight percent solution of
ability of such high molecular weight butyl rubber co 20 such copolymers as'above in a C1 to C10 halogenated
polymers of high halogen content is apparent inasmuch
liquid organic solvent such ‘as chloroform, bromo-tri
as they would be readily vulcanizable or covulcanizable
chloro methane, chloro-tribromo methane, carbon tetra
with other highly unsaturated rubbery polymers such as
chloride, dichloro dibromo methane, mixtures thereof,
natural rubber or rubbery diene-styrene copolymers into
etc., and adding thereto the organic acid anhydride and
materials exhibiting a combination of high extension mod
the halogenating agent, which may optionally be in solu
ulus and improved electrical resistivity.
tion, such as dissolved in a halogenated liquid organic
» In accordance with the present invention, it has now
solvent.
r
'
been discovered that isoole?n-multiole?n rubbery copoly
It is preferred to employ as the acid anhydride a C4
mers such as butyl rubber may be halogenated to a high
to C20 unsaturatedpolybasic acid anhydride and especial
halogen content without molecular weight degradation 30 1y a C4 to C16 unsaturated monoole?nic dibasic acid an
provided the halogenation is conducted while the rubbery
hydride. Suitable acid anhydrides, for the purposes of
copoymer is dissolved in a halogenated solvent and in the
the present invention, include among others; maleic acid
presence of about 0.1 to 20, preferably about 0.5 to 5.0
anhydride; chloromaleic acid.v anhydride; citraconic acid
moles of a C3 to C30 unsaturated organic acid anhydride
anhydride; itaconic acid anhydride; dihydro phthalic acid
per mole of added halogen. The ratio of halogenation 35 anhydride; 3,6-endo methylene-delta4-tetrahydro phthalic
agent to total halogenated solvent is normally about 2:1
acid :anhydride; mesaconic acid anhydride, isopropyl ita
to 1:1,000 and preferably about 1:1 to 1:500, the halo
conic acid anhydride, dimethylr maleic acid anhydride,
genation conditions being regulated to combine with the
glutaconic acid anhydride, muconic acid anhydride, etc.
butyl rubber copolymer about 0.1 to 30 weight percent,
The resulting modi?ed Visoole?namultiole?n-containing
advantageously about 2.0 to 15 weight percent, and pref 40 copolymer, maybe recovered .byrrecipitatiou with oxy
erably about 3.0 to 10.0 Weightpercent of halogen.
genated hydrocarbons, particularly alcohols or ketones
In order to halogenate the rubber copolymer to the
such aswacetone or any other known non-solvent for the
extent above-mentioned, the halogenating temperatures
rubbery copolymer and dried under about?OJ to 760
are generally about —50° C. to +200° C., preferably
millimeters or higher of mercury pressure absolute at
about 0° C. to +150° C. for a few minutes to several 45 aboutO“v to1180° 0., preferably about 50° to 150° C.
hours or more (e.g. 3 minutes to 10 days) depending
(e.g., 60° C.). Other methods of recovering the modi-p
upon the particular halogen, copolymer molecular weight,
?ed
polymer are by conventional spray or
drying
type and amount of organic acid anhydride, temperature,
techniques. Alternatively, the solution of modi?ed butyl
pressure, etc. ‘Suitable pressures are about 0.1 to 500
rubber may be injected into a vessel containing steam
p.s.i.a., although this is not particularly critical, atmos 50 and/or agitated water heated to a temperature sut?cient
phen'c pressure being satisfactory. The preferred halo
to volatilize the solvent and form an aqueous slurry of
gens are chlorine or bromine. ,
the modi?ed butyl rubber. This modi?ed butyl rubber’
_Butyl rubber copolymers comprise a major proportion
may then be separated from the slurry by ?ltration and
(preferably about 85.0 to 99.5 Weight percent) of a C4
drying and recovered as a “crumb” or as a dense sheet
to C8 isoole?n such as isobutylene, Z-methyl-l-butene or 55 or slab by conventional hot milling and/or extruding
S-methYI-d-butene, etc., with a minor proportion (pref
erably about 15 to 0.5 weight percent) of a multiole?n
of about 4 to 14, preferably of about 4 to 6 carbon atoms
procedures.
As so produced the modi?ed rubbery co- '
polymer has a Staudinger molecular weight within the
range of approximately 20,000 to ‘300,000, preferably
and are commonly referred to in patents and technical
about 25,000 to 200,000, and an iodine number of about
literature as “butyl rubber,” or GR~I rubber (Govern 60 0.5 to 5.0 The unvulcam'zed modi?ed reaction products
ment Rubber-Isobutylene), for example in textbook
formed are then vulcanized advantageously in the pres
“Synthetic Rubber” by G. S. Whitby. The preparation
ence of about 0.5 to 5 parts by weight of sulfur and about
of butyl rubber is described in US. Patent 2,356,128 to
1 to 10 parts by weight of zinc oxide per ‘100 parts by
Thomas et al. The multiole?nic component of the co
weight of modi?ed rubbery copolymer under vulcaniza
polymer is preferably a conjugated diole?n such as iso~ 65 tion temperatures of between about 250° and 450° F.
prene, ‘butadiene, dimethylbutadiene, piperylene, or such
for several minutes up 1105 hours or more depending
multiole?ns, as cyclopentadiene, myrcene, dimethallyl,
upon the“ state of cure desired. Alternatively, the re
allo-ocimene, vinyl fulvenes, etc. The copolymer com
prising isobutylene and isoprene is preferred, although
sulting halogenated copolymer may be vulcanized by
means of‘conventional quantities of such materials as
the copolymer may contain about 0.05 to 20.0, preferably 70
polyvalent metal oxides, organic amines, zinc oxide in
3,083,832
3
conjunction with amines,rdiisothiocyanates, quinone di—
.
»
[I14
following composition:
'
oxime and its derivatives with the'optional' presence of . I
a such accelerators as benzothiazyl disul?de, mercaptoben
zothiazole or in'the. presence 'of added ultra type accel
Oxygen
erators such as’tetrar'alkylithiuram sul?des, metalpoly
Carbon
____ __
__
0.24
p
4.50
__; ____________ __“_ _______________ _._ 81.60
, Hydrogen
for about ?ve minutes torthree hours ‘at temperatures of‘
.
Weight percent
7.-
Chlorine
alkylthiocarbamates,‘etc. . Normally-the cure is effected
_______________________________ __ 13.60
between about 270° and 350° 1F.‘ The resulting modi
?ed reaction products formed have ‘utility asrubber in
sulation, in air springs, hosing, curing bladders, belting,
.
2 hours at 75° C. The puri?ed product showed the
Example IV _
Example 111 was repeated in all respects except that
10
11.15 grams of maleic anhydride were used. The prod
proofed goods, tire treads and tire bead areas, etc.
In order to more fully illustrate the present invention,
not analyzed as follows:
p .
the following experimentaldata are given.
Oxygen
Example I i
100 grams of a'butyl rubber copolymer. having a vis
'
Chlorine
15
cosity average molecular weight of 340,000, a Mooney
viscosity (212° F. for 8 minutes) of .43 and an iodine
Carbon
..__
___
'_»..
'_
I
-Weight percent
,
_
0.79
___
,
V
. Hydrogen '____ ‘1
number of ‘15.4 corresponding to'a'mole percent unsatu;
4.75
80.70
13.75
The_ products
V V from'Examples
‘1' ' Erumlplerill
Ifand H. were compound
ration of 2.26 was dissolved in‘ 1,000 milliliters of car-1
bon tetrachloride. This solution Was'heated to 40° C.‘v 20 ‘ed as follows:
Component:
and 30 grams of diatornaceous earth (Hy-Flo) were
Parts by weight
Maleic anhydride modi?ed halogenated butyl
added thereto. Stirring was continued for 15 minutes at
' 40° C., the solution being subsequently ?ltered to re
4‘
rubber
100
move the diatomaceous earth and adsorbed impurities
SRF carbon black (Pelletex) _____________ _...
50
thereon. The'resulting ?ltered solution was charged to a
3-liter 3—neck round bottom flask ?tted with a mechan
Zinc oxide ____________________________ ._..
Stearic acid ___________________________ ..
5
0.5
_ ical stirrer, re?ux condenser and thermometer. . To this
Benzothiazyl disul?de ___________________ __
1.0
'
solution were added 4.0 grams of maleic anhydride ‘dis
Sulfur
_____
2.0
solved in 50 ml. of carbon tetrachloride, the solution 30
Diortho tolyl guanidine __________________ .._ 0.1
formed being stirred at 28° C. for 30 minutes; Fol
The resulting compounded stocks were cured for 60
lowing this, a solution of 2.64 grams of chlorine in 200
minutes at 300° F. and their physical properties com
milliliters ofcold carbon tetrachloride was injected into
pared with those of unmodi?ed Butyl rubberrcopolymcrs
the polymer solution dropwise at 25°‘ C. over a period
a Butyl rubber copolymer halogenated in. the absence
of 1/2 hour, the reaction mixture being continuously stirred 35 and
of
maleic
anhydride under the same general conditions
throughout and for one hour after all the chlorine was
as given above, all compositions being similarly com
added. The modi?ed product formed was then isolated
pounded and cured. The results‘were as follows:
by a multiple solution-precipitation technique using ben
zone as the solvent and acetone as the anti-solvent for
Property
three, times; Residual solvents were then stripped from 40
s the modi?ed product by heating for 16 hours at 60° C.
Sample
under 240 millimeters of mercury" pressure absolute. The
resulting modi?ed product showed the rrfollowing anal?
ysis:
Y
‘
,
>
‘
,7
7
(psi)
'
‘
Modulus
at 300%
Elong
(9st.)
Weight percent
Oxygen
0.39 45
Chlorine‘,
2.15
Carbon
Tensile
Strength
’
83.40
. 7 Hydrogen
14.15
From Example I (2.15% 01).---
1,925
1, 250
From Example II (1.75% Cl) _'__
_.__
Unmodi?ed Polymer (0.00% 01)
__
Halogenated Polymer (1.3% 01) ............. ._
1, 935
1, 645
2, 000
1, 100
550
550
The above data show that butyl rubber halogenated in
the presence of an unsaturated organic acid anhydride
andemploying a halogenated solvent results in higher
?nal chlorine content of the modi?ed rubbery copolymer
formed and that the modulus of such modi?ed copoly
mer, upon subsequent vulcanization, is approximately
; The halogen content of the reaction product after halo
genation in the absence of maleic anhydride was found
to be only. 1.3 weight percent chlorine using the fore
going reaction conditions. This proves that higher con
centrations ioi combined halogen are permissible when
halogenating in the presence of organic acid anhydrides 55 twice as high as that for an unmodi?ed butyl rubber co
in accordance with the present invention.
polyrner or a ‘butyl rubber copolymer halogenated in the
Example II
absence of an unsaturated organic acid anhydride plus a.
halogenated solvent. It will also be noted that the ?nal
repeated except that at the end of the chlorination step, 60 polymer contains oxygen in addition to halogen, carbon
and hydrogen.
the reaction mixture was contacted with '100 milliliters
Example VI
of water for V2 hour before isolation of the product.
The same7 general procedure as in Example 'I was
The modi?ed product formed showed the following anal
YSlSi.
~
' 7 ~
Weight percent
Oxygen , Chlorine
~ Carbon
Hydrogen
The same general procedure as in Example I was re~
peated and the product compounded as follows:
'
0.23
1.75
__
65
84.51
14.07
70
Example III
Example I was repeated in all respects except that
Component:
Parts by weight.
Unsaturated anhydride modi?ed halogenated
butyl rubber _________________________ __ 100
SRF carbon black (Pelletex) _____________ .._ a 50
Zinc oxide
Stearic acid
_
.
5.0
0.5
Tetramethyl thiuram disul?de ___! __________ __t 1.0
the chlorine solution was added to. the polymer solution
The resulting compounded stock was cured at 300° F.
at.45°‘ C., during 40 minutes, and after allof the chlo
for 60 minutes and compared to both a non-modi?ed
rine was delivered the'reaction mixture was. heatedfor 75
butyl rubber copolymer andja butyl rubber copolymer
3,033,832“
.
.
.
.
,
V.
.
.
5
,
,
>
halogenated in the absence of an unsaturated anhydride.
All polymers were similarly compounded and cured under
the conditions given above with the following results:
Tensile
-
Component:
Parts by weight
Polymer ____ __~_=_» ____________________ __'__ 100
Elong.
(p.s.i.)
MPC carbon black (Kosmobile 66) ________ __
50
Stearic acid -1. _________ _._,_..__‘__Y_'__V _____ __
Zinc oxide
'
‘
l
5
'
From Example VI (2.15% 01) _______________ __
Unmodi?ed Polymer (0.00% 01) _____________ -Halogenated Polymer (1.3% 01) _____________ _.
Y
The product was compounded as follows:
Modulus
at 100%
Strength
(p.s.i.)
6
C. at 180 Torr.
Property
Sample
I
stripped from the polymer by heating for 16 hours at 60°
Q
__
2
Tellurium diethyl dithiocarbamate (Tellurac) __
1 I
. The compound was cured for 60 minutes at 307° F.
1, 645
N o cure
1, 720
“The vulcanizate properties of this product are compared
with an unmodi?ed butyl rubber similarly compounded
and cured in the table of data which follows:
Example VII
The products from Examples ‘III and IV as well as an
unmodi?ed polymer and a polymer halogenated in the
Physical Properties
absence of an'unsaturated anhydride and a halogen con
taining compound'were compounded as follows:
Vulcanizate'
20.
Component:
",Rubber
3
>
_
SRF' carbon black (Pelletex) ______________ __
Stearic acid
>
Zinc oxide
Sulfur
'
"
_
~
>
Benzothiazyl-disul?de
_
Extension
(p.s.i.)
100
50
1.0
Tensile .
Strength
ohm-cm.
Unmodi?ed polymerz; _________ __ '
1,050
2,850
4.S)5><102a
Product of Example VIII.-. ____ __
2, 000
2, 895
l.53>_<1013
substantial improvement shown by the product in elec
trical resistivity‘indicates that this type of modi?cation
yields 'a-product which shows a better interaction with
All compounds were cured for 60 minutes at 300° F.
with the following evaluation:
carbon blacks.
‘
Property
1
'
Example
IX
' Example .VIII was repeated
Tensile
Strength
(p.s.i.)
the exception that
romaleic anhydride. The puri?ed product analyzed as
follows :
Weight percent
Oxygen
40
1, 992
' 1
.
~ citraconic anhydride (14.6‘g.) vwas used in place of chlo
Modulus
Unmodi?ed polymer (0.00% Cl)"
Halogenated polymer (1.3% Ol)__
From Example III (4.50% Ol)__
From Example IV (4.75% Cl) _______________ __
tivity,
.
The‘ product of Exam'pleVIIIshowed a substantial
increase in modulus over the unmodi?ed polymer. The
1.0
Dior-tho tolyl guanidine,__________________ __ 0.1
Sample
Electrical
Resis
(p.s.i.)
5.0
2.0
___________________ __
Modulus
at 300%
'
Parts by weight
*
1, 696
0.25
Chlorine
1.62
This product, after being compounded and cured ac
cording to the recipe given in Example VIII, showed the
The above data show that by effecting the halogenation
following properties:
of butyl rubber in the presence of an acid anhydride in a
halogenated solvent, a product can be obtained which 45
contains oxygen and chlorine in addition to carbon and
hydrogen. It is also indicated that by halogenating butyl
in this manner more halogen can be incorporated into the
'
Physical Properties
Vulcanizate ‘
Modulus
Tensile
at 300%
Strength
Extension
polymer Without polymer breakdown than can be incor
porated when the polymer is halogenated directly. The 50
data also show that polymers containing the elements
oxygen and halogen give vulcanizates with high moduli
.
(p.s.i.)
(p.s.i.) .
_
.
Electrical
Resis
,tivity,
ohm—crn
Unmodi?ed polymer ___________ __
1, 050
2, 850
4 95><l0a
Product 01‘ Example IX ________ __
2,000
2,730
2 5l><l0l2
and tensile values.
Example VIII
The same general comments apply to therresults ob
tained in Example IX above as were given in Example
One hundred grams of the unmodi?ed butyl rubber 55 VIII.
copolymer used in Example I were dissolved in 1,000
Resort may be had to modi?cations and variations of
milliliters of carbon tetrachloride and the solution treated
the disclosed embodiments without departing .from the
with 30 grams of Hy-Flo and ?ltered as in Example I.
To the resulting clear polymer solution was then added 60 . spirit of the invention or the scope of the appended claims.
What is claimed is:
16.05 grams of chloromaleic anhydride and the resulting .
1. A composition formed by reacting at a temperature
admixture charged to a 2-liter 4-Way reaction ?ask
of —50° C. to +200‘? C. a copolymer of 85 to 99.5 wt.
equipped with a mechanical stirrer, thermometer, re?ux
percent of a C4 to C8 isoole?n and 0.5 to 15 wt. per
condenser, and delivery funnel. Chlorine, 2.87 g. dis
solved in 250 ml. of carbon tetrachloride, was added to 65 cent of a C4 to C14 multiole?n; with a halogenating agent
capable by itself of incorporating halogen only, within
the dropping funnel, and the solution was delivered to the
reaction mixture, which was heated to 40-45° C., over a
period of one hour. The reaction temperature was then
raised to the re?ux temperature of the solvent and the
reaction mixture was contacted at this temperature for 70
two hours. The reaction mixture, after standing at room
temperature overnight, was isolated by a multiple solu
tion-precipitation technique using benzene as the solvent
and acetone as an anti-solvent. Three solutions and pre- ‘
cipitations were effected.
said copolymer, said halogenating agent being present in
an amount sufficient to combine about 0.1 to 30 wt. per~
cent (based on copolymer) of halogen in said copolymer;
in the presence of a C4 to C20 ethylenically unsaturated
organic dicarboxylic acid anhydride in the amount of
about 0.1 to 20 moles of halogen‘per mole of said acid
anhydride; and about 0.05 to 20,000 moles per mole of
added halogen of a halogen-substituted-hydrocarbon sol
vent for said copolymer which is incapable by itself of in
The residual solvents were 75 corporating halogen only, within said copolymer, said ‘
3,033,832
of about 0.1 to 20 moles per mole .of added chlorine of
maleic acid anhydride and about 0.05 to 20,000 moles
per mole 0t added chlorine of carbon tetrachloride.
8. A composition according to claim 5 which contains
solvent containing a halogen selected from the group 7
consisting of chlorine and bromine.
.
2. A process for modifying a copolymer of 85 to 99.5
wt. percent of‘ a C4, to C8 :isoole?n and 0.5 ‘to 15 wt.
2.0 to 15 wt. percent chlorine.
percentof [a C4 to C14 multiole?n which comprises: dis
solving said popolymer in a halogen-substitutedwhydro
‘carbon sclventpwhich isincapableby itself of incorporat
inc halogen onlynwithinusaidcopolvmer. and halogenat
ing the copolymer while dissolved inihe solvent in the
‘ C. a copolymer of 85 to 99.5. wt. percent of: a C4, to C3
isoole?n and 0.5 to '15 wt; percent of a C4 to C14 multi
ole?n with chlorine in the presence of about 0.1 to 20
moles per mole of added chlorine of maleic acid anhy
dride and about 0.05 to 20,000 moles per mole of added
presence of a C4 to C20 ethyleuically unsaturated organic
dicarboxylic acid ,anhydride at a temperature of between
’ anon-T50“ c. and +200)’ so. for b‘euveen about 3 min
chlorine of carbon tetrachloride until said copolymercon
utes-and’ 510 days withahalogenating ‘agent capable by
itself of incorporating halogen'only,
said copoly
rner,'-said’halogenatiug agent ‘being present inan amount
tains 0.1 to 30 wt. percent halogen.
15
su?icient to combine about ‘0.1 to' 30 wt. percent (based
on copolymer) of halogen in-said copolymer, said solvent
being present in an amount of about 0.05 to 20,000 moles
per mole of added (halogen, said solvent containing'a
halogen selected from the group consisting of chlorine and
'UNITED STATES PATENTS
bromine, and said carboxylic acid anhydride being pres
‘
" '
'
. , 3. A composition according?’ to claim 1, containing
' ‘about 0.1 to 20 wt. percent of combined‘ chlorine.
janhydridercomprisest-maleic acid anhydride andthe sol
tetrachloride;
-
.
,
'
‘
~
. , '5. A composition ‘according to claim 1 in which the
anhydride comprises chloromaleic' acid ‘anhydride.
.116; ~A'icompos'ition according to claim 1. in which the’
anhydride comprises citraconic acid anhydride. ,
' 7,.‘ Acomposition formed by reacting at a temperature
~ of ?—50° C. to '+200° C. a copolymer of 85 to 99.5 wt.
percent of all), to C8 isoole'?n and 0.;5qto 15 wt. percent
of a C4 to Cu multiole?n with chlorine in the presence
30
Huijser _______________ _.'._ Jan. 3, 1939
2,230,005
Moser _________ -2 ____ __ Ian. 28, 1941
2,404,411
Stephens'et a'l __________ .._ July 23, 1946
2,623,256
2,757,218
Sparks et al. ., __________ -_ Apr. 7, 1953
Dazzi ________________ .._ July 31, 1956
2,825,723
' - Ballauf et al. .- _________ __ Mar. 4, 1958
_ 2,831,839
Canterino et al, _, ______ __ Apr. 22, 1.958
2,844,502 ‘
4. A composition according to claim 1,in which the
vent iscarbon
References Cited in the ?le of this patient
2,142,980
ent in an amount‘ ofabout 0.1 to 20 vmoles per mole of
added halogen.
:
9. A process for modifying rubbery copolymers which
comprises reacting at a temperature of —-50° C. to +200”
Paxton __.. ____ __, _____ “July 22, 1958
2,844,567 7
’ Dazzi _____________ _v_‘__,_ July 22, 1958
2,845,403 1
'Gunberg _________ _,_~____ July, 29, 1958
2,948,709 '
vKuntz ____‘____ __~...' ____ __ Aug. 9, 1960
»
FOREIGN ‘PATENTS
602,843
_
'
Great Britain __._‘_'_' _____ _._;; June 3, 1948 -
.OTI-IER nannnaricns
VSchildknecht: Polymer’ Processes, Interscience (1956),
pp. 23-27.
,
‘
-~
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