United States Patent 0 "ice

2,903,430
Patented Sept. 8, 1959
2

1 7

Siliceous reinforcing pigments which may be used in

accordance with the present invention are ?nely divided

2,903,439
SYNTHETIC RUBBERS REINFORCED WITH
SILICEOUS PIGMENTS

pulverulent materials containing in excess of about 55

to 60 percent SiO2 by weight on the waterfree basis and
having an average ultimate particle size below 0.1 -mi

Ralph F. Wolf, Akron, Ohio, assignor to Columbia

Typical pigments of this character are ?nely divided

Southern Chemical Corporation, Allegheny County,

Pa., a corporation of Delaware

No Drawing. Application January 5, 1956

. -

Serial No. 557,437

10 Claims. (Cl. 26023.7)

cron, preferably in the range of 0.01 to 0.05 micron.

silica, calcium silicate, magnesium silicate, sodium alu

minum silicate, sodium calcium aluminum silicate, alu
10 minum silicate, and the like.
Siliceous pigments particularly suitable for the present
invention may be prepared in several ways. Thus, ?nely

divided silica in pigmentary form having a surface area

in the range of 25 to 250 square meters per gram and
This invention relates to the production of rubber 15 an average ultimate particle size below 0.1 micron may

compositions having improved physical properties. In

be prepared by a precipitation method which involves

particular, the present invention is concerned with im

reacting an aqueous solution of an alkali metal silicate

such as sodium silicate with an acid. By carefully con

provement of rubber compounds having relatively high

permanent set.

It has been the bane of rubber com

trolling the concentration of the reactants, the tempera
pounders that Butyl rubbers containing siliceous ?llers 20 ture conditions, rate of addition of acid, etc., as herein
0r pigments as reinforcing agents manifest a very unde~
contemplated, it is possible to precipitate a product hav
sirable high permanent set. This characteristic is particu
ing ?nely-divided, discrete particles as compared to the
larly annoying to automobile manufacturers employing
gel resulting, from processes commonly known in the

Butyl rubber stock in various automotive items, since

\ art.

once the rubber has been stretched in any direction it 25

This precipitation method consists, more particularly,
does not rebound to its original state. Obviously, a
in adding an acid to alkali metal silicate having a pre
gasket of this rubber is very poor after undergoing
determined concentration. It is at times advantageous
physical stresses.
that the alkali metal silicate contain a certain concen
Also, it has been known that the permanent set of
tration of sodium chloride or other alkali metal salt
Butyl rubber reinforced with siliceous pigments is mani 30 admixed therewith. The acid is added to the silicate
festly higher than that of Butyl rubber reinforced with
solution since the rate of neutralization of the alkali

vcarbon black pigments.

metal silicate is important.

For instance, were the

The term Butyl rubber is intended to include poly

silicate solution to be added to an excess of acid, the
mers of isobutylene and copolymers of isobutylene and
former would be neutralized too' rapidly and the con
a diole?n of the group consisting of butadiene, isoprene, 35 ventional gel would be produced. The rate of admixing
dimethyl butadiene, pentadiene, cyclopentadiene and
the acid with the silicate solution is determined by several
piperylene, such as are described in US. Patent No.

- factors.

2,442,068. Such polymers normally contain 70 to 99

Thus, where a solution of Na2O(SiO2)3.3 containing
percent by weight of the isobutylene and 30 to 1 percent
28 grams of SiOz per liter and 20.7 grams per liter of
by weight of the diole?n. The'copolymers are produced 40 NaCl is treated with carbon dioxide at 25 C., the
'by a low temperature polymerization, for example, at a

product has a surface area of 344 square meters per gram

temperature of substantially minus 95 C.

when the slurry is carbonated to a pH of 7 in 20 minutes.
According to the present invention it has been found
On the other hand, when this time of acidi?cation is in
that the high permanent set of Butyl rubber reinforced
creased to 1440 minutes, the surface area falls to 166, a
with siliceous pigments may be reduced substantially,
more desirable surface area. Moreover, by increasing the
usually at least one-third. A vulcanizate of a syntheticv 45 NaCl content to 53.9 grams per liter, a pigment having
rubber-like polymer of isobutylene has been prepared,
a surface area of 112.5 square meters per gram can be
" according to the present invention, comprising a siliceous
'obtained with only 20 minutes of acidi?cation'at 25 C.
reinforcing pigment and sulfurized tall oil. Tall oil is
Thus, the rate of acidi?cation may range from 5 to 2880
a by-product of the manufacture of paper pulp; it is an 50 minutes or longer, so long as 'the other conditions are

acidic material chie?y comprised of rosin acids and

properly

fatty acids, roughly in equal proportions. From about

1 percent to about 25 percent of sulfur may be added

to the tall oil and the mixture heated between about
120 C. and 250 C., preferably between 140 C. and

the Brunauer-Emmett-Teller (B.E.T.)' method which is

described in the Journal of the American Chemical

'

Society, volume 60, page 309 (1938).

When the alkali metal silicate used in preparing a ?nely

i 180 C. or 200 C.

Sulfurized tall oil products may be prepared from

crude tall oil by heating the tall oil with 10 percent of
sulfur at a temperature of 160 C. for 4 hours.

adjusted.

The surface areas mentioned herein are measured by

As

another example, re?ned tall oil may be used to prepare

the sulfurized product. Tall oil re?ned by distillation

and separation of the crystallizable part of the rosin
constituents, the liquid portion then being treated. with

divided pigment is sodium silicate, it should normally

have the composition Na2O(SiO2)x, where x is at least
2, usually 2 to 4, including fractional numbers, preferably
in the range of 3 to 4. The silicate solution'generally
contains 10 to 100 grams of Si02 per liter.
The rate of acid addition is important, as previously
stated, and is dependent upon the concentration of the

.5 percent sulfur at a temperature of 140 C. for one

other reactants. Precipitation usually begins after about

and one-half hours, may be used.
. 30 percent of the acid required to react with the Na2O
Sulfurization of tall oil according to the procedures 65 content of the alkali metal silicate and produce the so
referred to above yields a product which is more or
dium salt has been added and is usually complete after
50 to 70 percent of the theoretical amount of acid has
_.less viscous and of sticky character.
A particularly good sulfurized tall oil for use in the
been added. Any convenient rate may be employed, to

..Present invention is 'a viscous brown, non-toxic liquid

neutralize thev remaining acidic material when precipita

;1-ical Company, Trenton, New Jersey.

to conduct the acidi?cation of the silicate using carbon

.sold under the trade name Fortex by Thermoid Chem 70 tion'has ceased. Although it has been found preferable

2,903,439

accomplished, but the character of the resulting calcium

silicate is improved.

dioxide or an acid salt thereof, such as sodium bicar

bonate, other acids which may be used include: hydro

To insure production of the calcium silicate in a highly

?nely divided state, alkali metal silicate having the com

chloric acid, sulfuric acid, phosphoric acid, sulfurous

acid, nitric acid, as well as the acid or partially neu
tralized alkali metal salts of such acids, such as sodium

position Na20(SiO2),,, where x is a number not less

than 2 nor more than 4, is preferably used. This results

bicarbonate, ammonium bicarbonate, sodium acid ,sul

in the production of a calcium silicate having a com

fate, disodium acid phosphate, and the like.

Precipitated silica having the properties set forth above

position CaO(,SiO2),, where x is as de?ned above. How
ever, other calcium silicates wherein x is higher or lower
may be prepared by still another method. Thus, by re
acting a ?nely divided alkaline earth metal_silicate,..such 10 may be used in certain cases. When calcium silicate

prepared in the fashion just described is treated with a

mineral acid, in the manner disclosed above, a dry, pow
dered silica in extremely ?ne state of division is produced.

as calcium silicate, having an average ultimate particle

size :below 0.1 micron, with an acid having an anion
which forms a water soluble salt with the alkaline earth

This silica normally contains about 75 percent SiOZ, the

metal, a siliceous pigment particularly useful for the pres.

ent invention is prepared.

'

15 usual range being about 78 to 88 percent SiO2.

Inthe preparation of this pigment, calcium silicate in

The siliceous pigments produced by the methods here

an aqueous medium is treated with sufficient acid to de

inabove described contain bound water and free water.

composeit, leaving a maximum of opercent calcium=in

the silica pigment, the calcium being computed as CaO.

The term free water denotes water which may be re

Proper concentrations of CaO in the resulting product

.maybe achieved by reducing the pH of the aqueous cal

a temperature of 105 C. for a period of 24 hours iin a

laboratory oven. The term bound water is intended to
mean the amount of water which is driven off from a

moved from the .silica pigment by heating the pigment at

cium silicate solution to'below about 5, usually in the

range of 3 to 5. Inasmuch as the silica produced by
the process just described is presentin a slurry and is

siliceous pigment by heating the pigment at ignition tem

perature, for example, 1000 C. to 1200 C., untilno

or ?lter rapidly, it has been found expedient to increase

free water inthe pigment. '

The amount of bound and free water in thesilica herein

~dit?cultto recover therefrom becauseit does not settle 25 further water can be removed, minus the amount of

the pH of the slurry above 5, usually in the 7 to 8.5

contemplated is determined by the temperature of drying.

range. The increase in pH affords a twofold bene?t in

that it facilitates separation and recovery by settling
and/ or ?ltration of the silica and it. decreases the surface

low'temperature, forexarnple, 100 to 150 C., the silica

um chloride with alkali metal silicate in aqueous medium

containing sodium chloride or like alkali metal chloride.

tion, the following examples are given. Unless otherwise

speci?ed, percentages are given by weight in these

Where the precipitated silica has been dried at a relatively

contains bound wateryin the proportion of about 3 to 8

area to a more practical and desirable surface area.
moles (normally about 6 moles) of SiOz per mole of
The pH may be increased by adding an alkali, such as
bound water, and from about 2 to 10_percent of free Water
sodium hydroxide or other like alkali metal hydroxide,
based upon the weight of the pigment.

'
to the resultant slurry.
In order to illustrate several methods of preparing
Calcium silicates having an average ultimate particle 35
silica having the required properties for use in this inven
size below 0.1 micron are best prepared by reacting calci

The sodium chloride conveniently may be in the cal~

cium chloride solution although it may also be inlthe 40
sodium silicate solution. Thus, it is found most desir~

examples.

'

'

"

EXAMPLE I

.Streams of aqueous sodium silicate solutioncontaining

100 grams per liter SiOz as Na2O(SiO2)3,36 and calcium
chloride solution containing 100 grams per liter of CaClz
calcium chloride solution containing sodium chloride,
and 30 to 40 grams per liter of sodium chloride were fed
preferably in the proportion of at least 01 pound, and .usu
ally in the range of 0.2 to 0.5 pound, of sodiumchloride 45 directly into the central area of a centrifugal ,purnpvat
150 F.
.per pound of calcium chloride. It has been found that
The rates of ?ow wereadjusted so that calcium chloride
the presence of sodium chloride materially improvesthe
was approximately 10 percent in excess over the stoichio
character of the pigment. Although a wide range ofcon
metric quantity required for reaction, and so that the
.centrations of the alkali metal silicate and the calcium
amount of liquid, supplied to the pump was about 25 per
chloride solutions may be employed, excellent pigments
cent below the output capacity of the pump. In conse
result when a sodium silicate solution containing, in ex~
quence, the solutions were subjected to turbulent inter
_cess of 20 grams of SiOz per liter, usually in the range
mixing in the pump.
of 50 to 150 grams of SiO2, and a calcium chloride
The slurry of calcium silicate thus prepared was intro
solution containing at least 20 grams of calcium chloride
per liter, usually in the range of 50 to 150 grams per 55 duced into a tank and su?icient hydrochloricacid solution
containing 28 percent by weight HCl was added, with
liter, are used.
stirring, to reduce the pH of the slurry to 2. Thereupon,
The amount of calcium chloride is generally in stoichi~
su?icient sodium hydroxide solution containing 40 percent
ometric excess of the sodium silicate. Although a slight
by weight of NaOH was added to raise the pH of the
excess of sodium silicate is tolerable, it is best to have at
-.least a stoichiometric amount of calcium chloride present 60 slurry to 7.5. The precipitated silica was recovered by
decantation and ?ltration and was dried in an oven at a
during the reaction.
drying temperature of 120 to 140 C. for 12 hours. The
Another important factor in this reaction is the mode
free water content of the product was within the range
of mixing the reactants, since it is very desirable that
able to react aqueous sodium silicate with an aqueous

- the reactants be thoroughly intermixed.

An e?icient

of 3 to 8 percent by weight of the. pigment.

method for accomplishing this high degree of intermixing 65

is to introduce the aqueous streams into a centrifugal

pump, thereby creating an excellent turbulence atthe

EXAMPLE II
Seventeen thousand gallons of a sodium silicate solu

point of mixing. Better agitation is realized if the pump

tion is placed in a 50,000-gallon tank. This solution con
is not operated to capacity. If, for instance, the'pump 70 tains the sodium silicate Na2O(SiO2)3_3 in amount su?i
is capable of discharging 100 gallons per minute with
cient to establish an NaZO concentration of 20.3 grams
unlimited ?ow of liquid to the pump, the amount of

per liter. This solution contains no sodium chloride ex

reacting solution supplied to the pump is heldat least

ceptpthat minor amount (less than 0.08 percent) usually

present in commercial sodium silicate. The solution is
held at. a tcmp?riiture Of 167 F .,Plus or minus-5." Car

percent below, and usually 35 percentonmore" below,

amount. By so doing,_ not only is better

5,563,456

'

'

divided silica of the type hereinbefore described and S111

hon dioxide gas containing 10.0 to 10.8 percent COQ, the

balance being nitrogen and air, is, introduced into the

furized tall oil:

Example A

solution at a gas temperature of 115 to 145 F. at a rate

sufficient to provide 1250ycubic feet of the carbon dioxide

Compound

gas per minute (measured at 760 millimeters pressure and

0 C.). Thisgas is introduced directly under a turbo
agitator iii a manner to achieve uniform distribution of
gas, and the mixture is vigorously agitated. Carbon diox!
ide introduction is continued at this rate for 81/2 hours, at

I Butyl 268 (Butyl rubber)1 ________________________ ._

amount of CO2 has been introduced. After this period

of 81/2 hours, the rate of introduction of carbon dioxide
is reduced to 400 cubic feet per minute and the solution
is boiled for 11/2 hours. The slurry is then treated with
su?icient HCl to lower the pH to 7, after which the slurry 15
is ?ltered and washed. The resulting silica has a surface

100

100

100

..

40

40

40

Zinc Oxide _______________________________________ __

Methyl Tuads (tetramethyl thiuramdisul?de) .... -_

Sulfur ________________________________ _'. __________ __

Silica prepared as in Example II.

which time about 120 to 140 percent of the theoretical

Sulfasan R (4,4'-dithlomorpholine)-

l. 5

1. 5

1. 5

Diethylene glycol ___________________ _.

2. 5

2. 5

2. 5

BxDC (butoxyethyl diglyeol oarbonat

Para?'ln ____________________________ ._

0. 75

0. 75

0. 75

2.5

5.0

"FOR/TEX 2 _________________________ __

1 Non-staining form of GR-I-18 sold under name of "Butyl 268" by

area of 140 to 150 square meters per gram.

Enjay Company, New York, New York.

' While speci?c methods of preparing desirable siliceous

materials have been described, it is not intended that the

1 Described in the January 1953 issue of Chemical Processing, page 27.

20

invention be restricted thereto since other silica pigments

having a surface area above 25 square meters per gram,

Compounds A, B and C, when tested according to stand

ard physical tests for rubber exhibited the following

properties:

such as silica produced by burning ethyl silicate or silicon

TABLE I

Minutes

Compound

A.-. ......... -_

B .............. _-

C ______________ _.

Cure

Tensile

500%

320 F.

Modulus

(Pounds

Hardness

Elongation

Per Square (Percent)

Inch)

0"

30

7. 5
10

570
580

2, 350
2, 320

800
790

53
54

15

670

2, 280

2, 350
2, 290
2, 150
2, 270
2, 250

750

740
710
680
820
800

54

590

2, 270

770

20
30
45
7. 5
10
15

20
30
45
7. 5
10
15

20
80
45

tetrachloride in air or oxygen, may be used in the present

invention.
The amount of siliceous pigment used in the rubber
compound normally ranges from 10 to 80 parts by weight

per 100 parts by weight of rubber.

700
750
770
530
550
620
660
680
430
440
500

530
550
580

2, 250
2, 260
2, 150
2, 320
2, 360
2, 280

2, 260
2, 370
2, 160

Set at 75%

40

56
53
59
5B
56

42
42
43
42
40

56
56
56
57
56

56

42

790

56

42

56
56
56

Permanent

39
40

760
740
740
860
850
780
760
740

Tear

(Pounds

Per Inch) otUltlmate

Elongation

42
44
45
39
40
42
42
42

It can be noted from the above table that the practice

of the present invention yields a Butyl stock having a

55 substantially improved permanent set without impairment.

of other properties.
Although the present invention has been described with.

reference to the speci?c details of certain embodiments,.

The amount of sulfurized tall oil employed, such as
Fortex, may vary considerably, but usually 1.5 to about 60 it is not intended that such embodiment shall be regardedv
as limitations upon the scope of the invention except:
8 parts by weight per 100 parts by weight of rubber is
insofar as included in the accompanying claims.
advantageous. Of course, these proportions of siliceous
I claim:
pigment and tall oil will vary considerably depending
1. A vulcanizate of a rubbery copolymer of 70 to 99
upon the type of resulting rubber composition desired.
In the practice of the present invention, the rubber, 65 percent by weight of isobutylene and 30 to 1 percent by
weight of diole?n, a ?nely divided precipitated siliceous:
pigment, and sulfurized tall oil are milled together in a
reinforcing pigment having an average ultimate particle;
manner conventional for milling rubber stock. Other

conventional components normally incorporated in Butyl

rubber stocks, such as accelerators, softeners, plasticizers

size of less than 0.1 micron and a sulfurized tall oil of?
sticky viscous consistency in an amount of up to 8 parts:

by weight per 100 parts by weight of the copolymer.

and the like, may be milled into the stock at the same time
or subsequently. Thereafter, the milled composition is 70 2. The composition of claim 1 wherein the copolymer
is a rubbery copolymer of about 97.5 parts by weight of?
sheeted out and used in accordance with standard accepted
isobutylene and 2.5 parts by weight of isoprene.
procedures. Vulcanization of the product is effected at
3. The method of preparing a synthetic rubber which
conventional temperatures, for example, 300 to 350 F.
comprises combining together a rubbery copolymer of
The following example is illustrative of the rubber
recipes contemplated in the present invention using ?nely 75 70 to 99 percent by weight isobutylene and 30 to 1 percent.

2,903,439
8

by Weight of a diole?n, a precipitated ?nely divided sili

ceousreinforcing pigment having an average ultimate par

10. .A vulcanizate of a rubbery copolymer of 70-to 99

percent by weight of isobutylene and 30 to lpercent by

weight of a diole?n, a precipitated ?nely dividedsiliceous
reinforcing pigment having an average ultimate particle

ticle size of less than 0.1 micron and a sulfurized tall oil of

sticky viscous consistency in aniamount up to 8 parts by

weight per 100 parts by weight of the eopolymer. "
4: The method of claim 3 wherein the copolymer is a

si_z_e_ below 0.1 micron in the proportion ranging from

about 10 to 80 parts by weight per 100 parts by weight
of the .copolymer, and a sulfurized tall oil of sticky viscous

rubbery copolymer of about 97.5 parts by weight of iso

bntylene and'2.5 parts by weight of isoprene.

consistency in an amount from about 1.5 to about 8 parts

5. The vulcanizate of claim 1 wherein the siliceous

reinforcing pigment is ?nely-divided silica.

6. The vulcaniz'ate of claim 1 wherein the siliceous

by weight per 100 parts by weight of the copolymer.

10

reinforcing pigment is ?nely-divided calcium silicate.

-7. The vulcanizate of claim 1 wherein the siliceous

reinforcing pigment is ?nely-divided sodium aluminum

silicate.

1.5.

The. vulcanizate of claim 1 wherein the silicequs

References Cited in the ?le of this patent

UNITED STATES PATENTS
TM581,651

____________________ __ Dec. 27, 1953'

2,480,478

Kalman ______________ "Aug. 30, 1949

2,702,286

Iknayan et a1 __________ __ Feb. 15, 1955

reinforcing pigment is ?nely-divided sodium calcium

OTHER REFERENCES

aluminum silicate.
'
' 9. The vulcanizate of claim 1 wherein the siliceous rein
forcing pigment is ?nely-divided. aluminum silicate.
'

-Chernical Processing, p. 27, vol. 16, No. 1, January

2.0

1953, Tall Oil Dig.

'

McPherson, Engineering Uses in Rubber, pp. 50-51,

Reinholdl(l956)l.