Note: Descriptions are shown in the official language in which they were submitted.
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1~6776Z ~i 9476-
,:
BACKGROUND OF THE INVENTION
This invention relates to novel metal silicate
treated minerals which are receptive toward silane coupl-
ing agents. More particularly this invention relates to
metal silicate treated inorganic mineral fillers, to a ;~
process for producing same, and to polymer composite com-
positions containing said treated fillers and silane coupl-
ing agents, as well as to silane modified metal silicate
treated inorganic mineral fillers, and to polymer composite
compositions containing said silane modified metal silicate
treated inorganic mineral fillers.
- The use of finely divided particulate and fibrous
mineral materials, commonly referred to as mineral fillers
or mineral pigments, for compounding into rubbers, resins,
paints, inks, and other substances to form composite com-
positions is well known in the art. For instance, the use
o nonsiliceous mineral fillers, e.g. natural and synthetic
calcium carbonates, and partially siliceous synthetically
coprecipitated mixed structural pigments, e.g. calcium
carbonate-silica and calcium carbonate-metal silicate, as
filler components in polymer-filler composites is well
known as shown e.g. by British Patent 838,903 and U.S.
Patents 2,923,802; 3,152,001 and 3,290,165. Moreover,
certain wholly siliceous fillers, e.g. natural and synthetic
silica fillers and metal siiicate fillers, when used as
2.
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: ~o~776Z 9476-1
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- filler components in polymer-filler composites are
kn~wn to respond to the action of organosilane co~pling
agents with the produ~tion of improved cured composite
properties as seen e.g. by U.S. Patents 2,665,264;
; 2,744,879; 2,831,828; 2,831,829; and 2,897,173. However,
~; natural and synthetic calcium carbonates and other non-
sili~eous mineral fillers do not show any significant
or useful response in the presence of organosilane coupling
agents by way of improved properties in the finished polymer
composites. Since certain non-siliceous mineral fillers,
particularly calcium carbonate, are among th~ most abundant,
economical and widely used particulatefillers employed in
polymer-filler composites, their lack of response to
organosilane coupling agents has constituted a significant
area of technological disadvantage in the development of
; . improved polymer-filler composite compositions.
It has now been discovered that metal silicate
treated inorganic mineral products can be prepared which
, can be employed along with organosilane coupling agents`in.. . .
polymer composites to confer improved properties in the
; finished composites and that said metal silicate treated
mineral products can be further modified with organosilane
i coupling agents to form organosilane modified metal
silicate treated mineral products which can also be
employed as fillers ~n polymer composites to confer improved
properties in the finished composites.
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1~6q76Z ~' 9476
SUMMARY OF THE INVENTION . .
Accordingly it is an object of this invention to
provide metal silicate treated inorganic mineral products
which are responsive to silane coupling agents. It is also
an object of this invention to provide a process for the
manufacture of said treated mineral products. It is another .
object o~f this invention to provide polymer composite com-
. .
positions containing said treated inorganic mineral products.It is a further object of this invention to provide organo-
'silane modified metal silicate treated inorganic mineral
prodùcts. Still another object of this invention is to
provide polymer composite compositions containing said
silane modified metal silicate treated mineral products. :
Other objects and advantages of this invention will become
readily apparent from the following description and appended
.
,~, claims.
' More specifically this invention may be described
,~ ' as a metal silicate treated inorganic mineral product, '` '
said prQduct having been produced by a process which com~
, 20 prises (a) contacting in the presence of water, the surface ,'
~ ~ , of a water-insoluble inorganic mineral selected from the
-; group consisting of metal carbonates, metal sulfates, ''
and mixtures thereof with a precipitated, undried water in- ' '
.",j ,
soluble silicate salt on said water-insoluble mineral.
. . .
:
, DESCRIPTION OF THE PREFERRED EMBODIMENTS
~' l~e water-insoluble inorganic minerals employed in
~ the instant,inven,tion may be selected from a wide variety
- of naturally occur~ing mineral deposits or synthetically
', produced (e.g. precipitated) inorganic salts of similar
.. . .
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~ 9476~
~067 76
mineral c~mposition. Such minerals include water-insoluble
metal carbonates and/or metal sulfates wherein the metal is
selected from the group consisting of barium, beryllium,
calcium, magnesium, strontium, zinc, and mixtures thereof.
Such minerals are commonly identified in industrial usage
and the art by both their chemical names and mineralogical
names and include e.g. barium carbonates (witherites),
barium sulfates (barytes, blanc fixe), beryllium carbonates,
calcium carbonates (whitings, calcites, marbles, limestones~,
calcium sulfates (gypsums, anhydrites, alabasters), calcium
magnesium carbonates (dolomites), magnesium carbonates
(magnesites), strontium carbonates (strontianite), zinc
carbonates (smithsonites), as well as the precipitated salts
of said carbonates and sulfates, e.g. precipitated calcium
carbonates and sulfates~ precipitated barium carbonates
and sulfates, precipitated zinc carbonates, precipitated
magnesium carbonates, and the like. Of course, it is to be
understood that in addition to employing only one water-
~ ,I
insoluble mineral at a time, mixtures of two or more differentwater-insoluble minerals can be employed as desired. More-
over, the particular size and shape of the water-insoluble
inorganic mineral employed is not critical and is dictated
primarily only by the end use of the final treated mineral
product desired (e.g. a slab of marble could be treated with
the water-insoluble metal silicate salt according to the
instant in~ention if one;desired to bond silane coupling
agents to the marble). Since the primary end use of the
metal silicate treated mineral products of this invention
is as fillers or pigments in a polymer-filler composites
it is preferred to employ the initial water-insoluble
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1~ 67 7 62 9476-1
mineral in conventional particulate form~ Numerou~ grades
of the tifferent kinds of particulate water-insoluble in-
organic minersls mentioned above are li~ted in "Materials
and Compounding Ingretients for Rubber", Bill Publications,
New York, New York, 1968. Naturally occurring or synthetical-
ly produced water-in~oluble inorganic minerals can be em-
ployed herein. The preferred minerals are the naturally
occurring and synthetic metal carbonates and mo~t preferably
the natural calcium carbonates. Of course, it i~ clear from
the above description and it is to be understood that the
natural and synthetic water-in~oluble inorganic minerals -
employed in the instant invention are non-siliceou~ minerals
and are not to be confused with partially siliceous synthetic-
ally coprecipitated mixed structural pigments or filler6 mate
up of coprecipitated siliceous and non-siliceous components.
However, it is also to be understood that said mineral~
employed in the instant invention may have small amounts of
.: -,.,
inorganic siliceous substances as~ociated with them as
impurities as distin~uished from deliberately and intentionally
- 20 added lnorganic siliceous substances.
The water-insoluble metal silicate salts employable
:.
in the instant inven~ion include any precip~tated, undried,
water-insoluble metal silicic acid salt and mixtures thereof,
wherein the metal is selected from the group consisting of
alu~inum, barium, beryllium, cadmium, calcium, cobalt,
copper, lron, lead, lithium, magnesium, manganese, mercury,
nickel, silver, strontium, tin, zinc, zirconium, and the
rare earth metals having atomic numbers from 57 to 71 inclusive.
~-
6.
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9476-1
'''' - la67762 ,................. ~,
Said 5ilicic acid salts and methods for their
preparation are well known in the art and are convention-
ally precipitated from an aqueous composition of silicate
ion~ and a water soluble metal salt. The water ~oluble
metal salt used to prepare the silicic acid salts can be
any metal salt having a solubility of at least 0.1 weight
percent in water at 25C. wherein the ~etal is selected
from the group consisting of aluminum, barlum, beryllium,
cadmium, calcium, cobalt, copper, iron, lead, lithium,
magnesium, manganese, mercury, nickel, silver, strontium,
tin, zinc, zirconium and the rare earth metals having
atomic numbers from 57 to 71 inclusive.
, .
Of course.it is to be understood that the
water soluble metal salt includes simple salts, double
8alt~, and mixtures of such salts7 which salts may con-
tain any anion or combination of anions, which will form
a metal salt having the abo~e mentioned solubility, such
as chloride, bromide, iodide, nitrate, nitrite, sulfate,
sulfite, thiosulfate, thiosulfite, carbonate, bicarbonate,
formate, acetate, glycolate, alkylsulfonate, cyanate,
cyanide, thiocyanate, chlorate, bromate9 iodate, hydrox-
ide and the like. The preferred metals are barium,
calcium and zinc while the preferred anions are chloride,
nitrate and sulfate. ~Illustrative of such metal salts
include barium chloride, barium nitrate, calcium chloride,
calcium nitrate, zinc chloride, zinc nitrate and zinc
sulfate.
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. 9476-1
~6776Z `
The water soluble metal salts are normally
u8ed in the form of solutions or dispersions in solvents
consisting of water or mixtures of water and mi~cible
proportions of organic solvents such as for example,
methanol, ethanol, propanol, ethylene.glycol, glycerine,
2-methoxyethanol, 2-ethoxyethanol, ethylene glycol
dimethylether, diethylene glycol dimethylether, tetra- .
hydrofuran, dimethylsulfoxide, acetonë, dimethyl forma-
mide, d~methylacetamide, trimethylamine, hexamethyl-
phosphoramide, and the like. Such metal salts may be
employed alone or if desired the form of mixtures of
two or more different salts. In add~tion such water
801uble solutions or dispersions if desired may contain
acids such as hydrochloric, sulfuric and nitric acids,
.
.. and the like, in amounts necessary to satisfy a desired
8toichiometry in forming the water-insoluble metal silicate :~ .
s salt desired to be employed in the instant invention.
;~ The silicate ions.in the above mentioned aqueous
- compositions used in the preparation of said water- .
insoluble metal silicate salts can include monosilicate :
as well as polysilicate ions and mixtures thereof which .:~
ions can.be derived from any silicate solution, i.e. a
~ liquid mixture of a solvent and one or more compounds of
.. silicon capable of su~plying monosilicate or polysilicate
anions such as for example monomeric and polymeric
silicic acids; alkali metal salts of monomeric and poly-
meric silicic acids, except lithium; organosubstituted
:~ -
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r.9476 1
1~677(~2 ~; -
~mmonium,guanidinium, and hydrazinium salts of monom~ric
and polymeric silicic acids; lower alkyl, alkoxyalkyl,
alkylaminoalkyl and dialkylamino~y e~ters of monomeric
- ~and polymeric silicic acids; acylates of lower alkyl and
:. alkoxyalkyl carboxylic ac~ds and monomeric and polymeric
~ silicic acids; tetrakis (dialkylamino) silanes and par-
`. ~tially hydrolyzed and condensed derivatives thereof; and
the like. The solvent component of such s ilicate solu-
tions consists of water or water-miscible organic solvents
such as mentioned above, or mix~ures thereof. While a
single source of silicate ions may be employed if desired
mdxtures of two or more different sources of silicate
-ions may be used, In addition, such sources of silicate
ions if desired may contain bases such as sodium,
potassium, ammonium, and substituted ammonium hydroxides
. in amour-ts necessary to satis~y a desired stoichiometry
: in form-ng the water-insoluble metal si.licate salt desired to
be employed in the instant invention~
As pointed out above, said water-ins.oluble
metal silicate salts are employed in the instant inven-
tion in the form of precipitated, undried salts, that
i8 to say said salts have not been completely dried
after their initial formation and are used whiie still
at least in their precipitation- ist state. Preferably
it is desired to employ the water-insoluble metal
silicate salts in their freshly precipLtated, highly
hydrated and incompletely condensed form, since
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~ - ~06776Z 9476-1 ~
t.he time interval between formation of the water-insoluble ~
: metal silicate salt and its contact with the water-insoluble
:' mineral has a bearing on achieving the most optimum results
desired. For e~ample, it has been found that when precipitated .: -
metal silicate, which had been kept in dilute aqueous.sus- :
pension for various time intervals, is slurried with a ..
: water-insoluble mineral, the silicate treated mineral product
after work up is found to be responsive to silane coupling
. agents. However, as the time interval between formation.
. 10 of the water-insoluble metal si].icate and its contact ~ :.
with the water-insoluble mineral was increased, the ..
,. .: .
. . response displayed by the sil1cate treated mineral to ~ - .
: . silane coupling agents lessened. In an extreme case where
a previously completely dried~and condensed water-in~
: soluble metal silicate was redispersed in water and . .
slurried with a water-insoluble mineral, the recovered - ..
. ~ treated mineral product failed to show any response . .~
;. to the silane coupling agent. Thus, in order to insure - .~ .
.. . ..
~: ~ the most optimum results, it is most preferred to
prepare the silicate-treated mineral products of this ~:
-
; invention by precipitation of the water-insoluble metal
silicate salt while in the presence of the water-insoluble
mineral to be treated. Less preferably but still within ;~
., .
~` the scope of the invention is to contact the water- ~ :
insoluble mineral with the water-insoluble undried metal
. silicate within a short time, the shorter the better,
.~.. . . . .
after precipitation of said silicate.
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~06776Z q476-
The metal silicate treated inorganic mineral
products of the instant invention ~hich are responsive
to silane coupling agents can be prepared in any manner
involving contact of the surface of the water insoluble
mineral in the presence of water with a precipitated,
undried water-insoluble metal silicate salt and there-
after drying the silicate treated mineral product.
Illustrative of such methods are as follows:
(A). Adding the water-soluble metal salt solu-
tion and the water-soluble silicate solution either con-
currently or consecutively to a stirred aqueous slurry
of the water-insoluble inorganic mineral to be treated
to form the water-insoluble metal silicate salt in the
presence of the.mineral. The silicate treated mineral
product can then be dried and recovered by any conven-
tional method desired.
. . (B). First forming a dilute aqueous slurry of the
water-insoluble metal silicate salt by mixing together
a water-soluble silicate solution and a water soluble
metal salt and then subsequently and within a short
time and without drying the so.formed insoluble metal
silicate salt, bringing the water-insoluble metal silicate
slurry into contact with the surface of the.water-insoluble
~norganic.mineral to.be.treated. The silicate treated
. .
~ mineral product can then be dried and recovered by any
~ conventional method desired.
`. (C). The silicate treated mineral product can
also be prepared by continuously pumping streams of an
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~476 - l :
106776Z
aqueous slurry of the water-insoluble inorganic mineral
to be treated, a water-soluble metal salt solution, and
a water-soluble silicate solution in~o a zone of high
turbulence as in a mixing tee, and removing a slurry of
the silicate treated mineral product which can then be
dried and recovered by any conventional method desired.
(D). Aqueous solutions of the water-soluble metal
salt and water-soluble silicate can be sprayed in an
atomized form either concurrently or consecutively onto
an agitated mass of the water-insoluble inorganic mineral
to be treated. The silicate treated mineral product can
then be dried and recovered by any conventional manner
desired,
Preferably it i~ desired to precipitate the
water-insoluble metal silicate salt while in contact with
the surface of the water-insoluble inorganic mineral to
; be treated, especially by method (A) outlined above. For
example, to a stirred 81Urry of particulate calcium
carbonate in water are added water solutions of sodium
. .:
silicate and calcium chloride in proportions such as to
precipitate a small amount of water-insoluble calcium
silicate, The calcium silicate treated calcium carbonate
mineral product is then washed, filtered, dried and
recovered as desired and can be employed as explained more
fully bel~w.
In formdng the metal silicate treated inorganic
mineral products of this invention by any of the above
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~ 947~1
~067762
.:
described methods the process factors of initial mineral
concentration, temperature, reactant solution concentra-
; tions and addition rates are not critical although
certain practical choices may be made a8 described below.
Initial mineral concentrations are not critical
and at the start of a preparation may range from 100 per
cent by weight, that is undiluted dry inorganic mineral
as in 8pr&y coating methods, downward to any desirable
level as in 81urry method8. In slurry preparations the
inorganic mineral concentrations are usually started at
the highest levels which permit adequate agitation by the
equipment used.
!
The temperature employed during formation of
the meta; 8ilicate treated mineral product8 i8 not known
to be critical and may be held at any point between the
,. .
freezing and boiling point temperatures of the aqueous
.
~ solvent. For convenience and economy, the treating pro-
..... .
cedure is usually carried out under normal ambient room
conditions, i.e. from about 18C. to 30C. While normal
atmospheric pressure i8 also normally used, higher or
lower pressures can be employed if desired.
The concentrations of the water-soluble metal
salt and water-soluble silicate reactants in their solu-
tions are not critical and are merely selected to form
stable solutions or dispersions at levels convenient for
the particular preparation method employed. For example,
!.~'~ : ~
~-; in most slurry preparations, concentrations o~ about
. . ~
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9476 - 1
~L067'762
10 weight per cent are convenient although higher or .
lower levels could be used. On the other hand, in spray
treatment of the mineral, higher reactant concentrations
- are useful to avo~d clotting of the agitated powder.
The rates of reactant solution addition are
also not critical but locallzed overconcentrations in
the reaction mass æhould be avoided. Thus in batch
slurry metlods it is convenient to add one reagent solu-
tion quite rapidly to the slurry (usually, but not
necessarily the silicate solution) and to control the
rate of water-insoluble metal silicate formation by
adding the other reactant solution over a period ranging
from a few minutes to several hours or longer. In con-
trast, where very high agitation rates are used, as in
continuous mixing tees, the entire amounts of reagents
required per unit of mineral may be concurrently added
in a fraction of a second.
As pointed ou~ ab~ve, it is preferred that
the process factor described as contact time, i.e~ that
~i 20 time interval between the formation of the water-
insoluble metal silicate and its contact with the
` water-insoluble inorganic mineral be as short as
possible to achieve the optimum results desired.
The procedures used for drying and recovery
., .
of the metal silicate treated water-insoluble inorganic
mineral are not critical and any conventional method
can be used as desired such as spray drying, leaving
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" 947
106~76Z
it to dry at room tempera~ure, oven drying and the like,
Normally the metal silicate treated mineral is washed
with water and separated from the reaction solution by
filtration, e g. and then oven dried. Of course it is
to be understood that the metal silicate treated mineralPrdUCt
m~y still contain some moisture even after drying but
it is generally preferred to dry the metal silicate
treated mineral to an essentially constant weight at
temperatures above about 100C, or at least to a moisture
; 10 content at which the metal silicate treated mineral
is no longer damp to the touch, It should also be
understood that if the mineral to be treated is employed
in its particulate filler or pigment form, the metal
silicate treated mineral product can easily be returned
to its particulate form by any suitable comminution
method if said product is obtained in cake form.
The chemical compositions of the water-
insoluble metal silicate salts employed herein can also
be conveniently expressed in terms of metal oxide ratios
for example, MxOy/SiO2 wherein M is the metal and x and
y are the normal combining valances of the oxide and
metal ions respectively as explained for instance in
"Dana's Mineralogy", by Dana, 18th Edltion, John Wiley,
New York, New York, 1971, page 202, Thus, the metal
oxide ratio of the water-insoluble metal silicate salts
equal~ the number of moles of MxOy divided by the number
of moles of SiO2 in the salt. The metal oxide ratio of
'' ' :
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10 67 7 6 2 9 4 7 6 1
the water-insoluble metal silicate salts employed in the
instant invention may range from about 0.1 to 4.0 or
higher if desired, while a metal oxide ratio of less than
about 3.1 is preferred.
The amount of water-insoluble metal silicate em-
ployed in the instant invention obviously need only be
that amount sufficient to render the untreated water~in-
soluble inorganic mineral starting ma~erial responsive
or reactive to silane coupling agents which will of course
be largely dependent upon the desired end use of the
silicate treated illineral product. Since it is preferred
to employ the water-insoluble metal silicate treated
inorganic mineral product in particulate form, the water-
insoluble metal silicate salt can generally be precipitated
and used in amounts ranging from about 0.1 to about 20.0
parts by weight per 100 parts by weight of the inorganic
mineral starting material. Of course, lower or higher
amounts may be employed if desired. Preferably the amount
.
of water insoluble metal silicate salt used ranges from
about 0.3 to ahout 10.0 parts by weight per 100 parts
by weight of the inorganic mineral starting material. ~ --
~ The amount of water present need only be sufficient
- to dissolve the water soluble metal salt and silicate
ion reactants as for example when solutions of water
soluble metal salt and solutions of silicate ion are
~ ~ -
~ sprayed onto the surface of the water insoluble inorganic
;~ mineral being treated~ 'However, larger amounts of water
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~ 7 ~476-1
1(~6'7'76Z
may be employed for convenience and ease of treatment when
it is desired that the water insoluble inorganic mineral
be handled in the form of a paste or fluid slurry.
Thus, the instant invention involves the surprising
; discovery that water-insoluble inorganic minerals which
are unresponsive to silane coupling agents can be made
reactive towara silane coupling agents by contact with
small amounts of a precipitated, undried water-insoluble
metal silicate salt. This discovery is demonstrated by
-10 the fact that when employed as fillers or pigments in
polymer composites along with a silane coupling agent
. , ~, .
the untreated water-insoluble inorganic minerals produce
~- no significant changes in finished composite product
properties from those conferred by use of the untreated
. ~ ., .
mineral alone. However, the metal silicate treated
water-insoluble inorganic mineral products of the instant
invention clearly demonstrate their responsiveness and
' D
- activity toward the silane coupling agents in such
j polymer composites by imparting improved physical
properties to the finished composite product. Yet even
the metal silicate treated mineral products of the instant
.... . .
invention by themselves, without silane coupling agents,
.
produce no significant changes in finished composite
properties from those conferred by the untreated mineral.
-- Thus, the significant improvements in finished composite
. ,,~ ~ .
~ properties can only be demonstrated by the use
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~06776% ~ 9476-1-
of a combination of both the metal silicate treated ,~
mineral,products of the instant invention and silane
coupling agents. Although not intending to be bound by
a~y theory or mechanism, this phenomenon leads one to
express the belief that the metal silicate treated water-
insoluble inorganic mineral products of the instant in-
vention consist essentially of said mineral having a
coating of the water-insoluble metal silicate salt associated
with its surface. Thus, unlike any sort of mixed ~rystal
form of coprecipitated mineral fillers or pigm,ents, the
, , metal silicate treated mineral products of the instant
invention which are prepared from already formed minerals
that have been subsequently contacted with a water-in-
,; soluble metal silicate salt as described herein are believed
to be of a layered form.
" While the metal silicate "layer or coating" per se
, on the metal silicate trQated mineral products of the
, . instant invention is not measurable, its presence is
surely confirmed by the display of large easily measur-
, 20 able responses of said silicate treated mineral products to
silane coupling agents in terms of finished polymer composite
, properties as explained above. I ,
, Accordingly the metal silicate"coatings" associated
... .
with the metal silicate treated water-insoluble inorganic
-mineral products of this invention may completely encapsulate
the mineral employed or may only represent a partial
coating of some portion~of th~ surface of the treated
;' ' ' - 18
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~ ~ ~O 677 6 Z ~ 9476 -1
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mineral or may consist of an association of discrete metal
silicate moeities at non-contiguous sites of the mineral
particles. Moreover, said metal silicate "coatings" may
consist of a single metal silicate compound or of two or
more different metal silicate compounds associated with
the treated mineral. When two or more metal silicate
compounds are employed or desired they may be applied in
any selected sequence. For example, ~or a "coating" con-
sisting of water-insoluble metal silicates A and B, "A"
may be applied first and "B" second or the reverse order
may be used. In addition, it is evident that the chemical
compositions of the water-insoluble metal silicate salts
used to form the "coatings" on the silicate treated water-
insoluble inorganic mineral can be varied ind~pendently
of each other if desired. For example, the water-in-
soluble metal silicate salt within a given "coating" may
contain one or more metal ions and with each metal ion a
metal oxide ratio MxOy/SiO2 as explained above can be
associated as an independent compositional parameter and
these may be kept constant or varied according to some pre- ~ -
determined desire by controlling starting ratios, order of -~
addition, and feed rate ratios of the water-soluble metal
salt and silicate solutions. In the simplest case involv-
- ing two metal ions in the silicate "coating" of the treated
- mineral, the average metal-oxide ratio is used and a mixed
structure water-insoluble metal silicate coating is provided.
Of course, it is also~evident that much more complex "coat-
ings" could be prepared within the scope of this invention
by varying both the "coating" structure and composition if
desired as outlined above.
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~ 9476-1
1067'76Z
As pointed out above, a further aspect of the
instant invention is directed to an organosilane modified
metal silicate treated inorganic mineral composition, said
composition having been produced by a process which com-
prises contacting a water-insoluble metal silicate in-
organic mineral product of this invention as hereina~ove
described with an organosilane coupling agent selected from
the group consisting of organo-functional silanes having the
formula
R a
R-Si-(X)
3-a
; 10 wherein R which contains a carb~n atom directly bonded to
the Si a~om of the above form~la represents a functionally
substituted organic radical, R' represents a ~adical selected
from the group consisting of R and monovalent hydrocarbon
radicals, a has a value of 0 or 1 and X represents a hydro-
, .
lyzable group, the hydrolyzates of said silanes, the con-
densates of said silanes, and mixtures thereof.
Said organosilane modified mineral compositions can be
prepared by any method involving intimate contacting one or
more of the water-insoluble metal silicate treated in-
organic mineral products of this invention with one or
more said organosilane coupling agents, singly or in
admixture, consecutively or concurrently as desired.
For example, by way of ilIustration, said organosilane
coupling agents in neat form or optionally liquid solutions
or dLspersions of said organosilane coupling agents in
. . .
20.
'
. ' .
~06776Z `~; 9476-l
- water or inert diluent carriers can be sprayed in a atomized
form onto an agitated mass of the finely divided water- -
insoluble metal silicate treated inorganic mineral products
- to be modified.Alternatively liquid suspensions of the
finely divided water-insoluble metal silicate treated in-
organic mineral products to be modified along with said
organosilane coupling agents in neat form or liquid solutions
or dispers'ions of said coupling agents in water or diluent
carriers can be introduced into a zone of high turbulence,
as in a mi~ing tee or as in the vicinity of a rapidly mov-
ing rotary stirrer. The desired organosilane modified
mineral compositions can ~e recovered by any conventional
metho~ desired, and can be used as is or they can be dried
at ambient or elevated temperatures, e.g. about 100C., by
any conventional method as desired.
The amount of said organosilane coupling agent
that can be employed in forming the silane modified silicate
treated mineral compositions of this invention is not
narrowly critical and can range from about 0.01 to 50
parts by weight and preferably from about 0.10 to 10.0
parts by weight per 100 parts by weight of the water-
insoluble metal silicate treated inorganic mineral product
. . .
to be modified, although higher or lower amounts may be
empLoyed if desired. Likewise said silane coupling agents
and said minerals to be modified can be contacted at any
suitable ~emperature, ambient temperatures generally being
preferred, e.g. about room temperature. The time period
of contact between the silane coupling agent and the mineral
to be modified is also not critical and need only be suf-
ficient to provide intimate contact between the ingredients
-
~a
.. . . .
. . - ::.
9476-1
106776Z
.
involved.
: Moreover, while the organosilane modified water-
insoluble metal silicate treated inorganic mineral com-
positions of this invention can be prepared merely by
- contacting a organosilane in neat form with the dried - ~ -
metal silicate treated mineral product to be modifie~ .
if desired, as pointed out above, an inert diluent and/or
water can be added to facilitate handling of the materials
involved. Any conventional inert diluent which will not
-adversely effect the organosilane coupling agent and water-
insoluble metal silicate treated mincral filler, and the ,~
- desired resultant silane modified silicate treated mineral
composition can be employed. Examples of such inert
diluents include hydroxy-containing compounds e.g. alcohols
such as methanol, ethanol, propanol, butanol, and the like;
hydrocarbons such as hexane, heptane, benzene, toluene,
and the like, ethers such as diethylether, dipropylether
and the like; esters and ketones, such as ethyl acetate, `
acetone, methylethylketone, diethylketone and the like.
Of course, the amount of added water and/or inert diluent~
- employed is not critical since either solutîons or dis-
persions of said silanes and/or mineral products are employ-
~, able herein. Indeed the production of the organosilane
modified metal silicate treated inorganic mineral com-
positions can be carried out in the absence of any added
water and/or added inert diluent.
.. ~ :
~ ~ Of course, it is to be understood that the organo-
; silane coupling agents employed in the production of the
organosilane modified water-insoluble metal silicate treated
.... .
~ inorganic mineral compositions of t~is invention include and
: ~ .
. ~ .
4-"
'~ 1 ' '22
: ', .
,
-
.
~ . ~ 9476-1 ,
~06776Z
.
encompass in addition to the siIane compounds per se,
the hydrolyzates of said silanes, the condensates of said
silanes, and mixtures thereof. Such is completely obvious
to one skilled in the art, e.g. the employment of water
as a diluent can cause hydrolysis and!-or condensation of ~;
the silane compound employed in view of the hydrolyzable
groups on the silane. Indeed if desired the silane
compound can be hydrolyzed and/or condensed prior to its
contact with the silicate treated mineral filler to be
modified. Such hydrolysis and/or condensation may also
be caused by àtmospheric moisture conditions andJor water
moleçuleæ normally found on the surface of the silicate
treated mineral filler employed. Of course, the term~
- "hydrolyzate" and "condensate" used herein are meant to
include cohydrolyzates and cocondensates of more than one of
such organofunctional silanes hereinabove described. Thus,
while the precise structural configuration of the organo-
silane modified water-insoluble metal silicate treated
., . :
inorganic mineral composition products of this invention is
not determinable, it is to be understood that said com-
- position products also include and encompass the hydrolyzates,
condensates, and mixtures thereof. It is to be further
understood that the instant invention also includes the
organosilane modified water-insoluble me~al silicate
-- treated inorganic mineral composition products obtain upon
removal of the inert diluent carrier if such is employed in
; the production process.
The organosilane coupling agents andlor methods
for their preparation are well known in the art and
' . .
23L ~ ~
~.
~; -
- 1067762 9476-1
:"
include e.g. organofunctional silanes having the formula
R~
~ a
R-Si-(X)
3-a
~herein R which contains a carbon atom directly bonded to
the Si atom of the above formula represents a functionally
substituted organic radical, R' represents a radic~l selected~
from the group consisting of R and monovalent hydrocarbon
radicals containing from 1 to 6 carbon atoms, e.g. phenyl
and alkyl radicals, especially methYl,a has a value of 0
, . .
or 1, preferably 0, and X represents a hydrolyzable group
tha hydrolyzates of said silanes, the condensates of said
silanes, and mixtures thereof. Illustrative of the more
preferred functionally substituted organic radicals are
unsaturated organic radicals such as olefinic radicals,
e.g. vinyl, allyl, gamma-methacryloxypropyl, and the like;
aminosubstituted radicals such as aminoalkyl radicals e.g.
beta-aminoethyl, gamma-aminopropyl, N-beta(aminoethyl)
gamma-aminopropyl, and the like; epoxy substi~uted radicals
such as beta-(3,4-epoxycyclohexyl)-ethyl, gamma-glycidoxy-
propyl, and the like; and mercapto substituted radicals,
.. ..
such as beta-mercaptoethyl, gamma-mercaptopropyl, and the
like. Among the more preferred silane coupling agents
that may be mentioned are vinyltrichlorosilane, vinyl-
~ triethoxysilane, vinyltrimethoxysilane, vinyltris(2-
methoxyethoxy) silane,` gamma-methacryloxypropyltrimethoxy-
silane, beta-(3j4-epoxycyclohexyl)-ethyltrimethoxysilane,
` gamma-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane
beta-mercaptoethyltriethoxysilane, gamma-mercaptopropyl-
trimethoxysilane, beta-aminoethyltriethoxysilane, gamma-
aminopropyltriethoxysilane, N-beta-(aminoethyl)-gamma-
aminopropyltrimethoxysilane and the like.
- 24.
' '
1067762 9476-1 ~
Additional silanes which may be used in the practice
. of this invention include the following: :
HOOC(CH ) CHSi(OCH )
: 2 8 3 3
CH CH=CH(CH ) CH Si(OCH )
3 2 2 4 2 3 3
. [~CH CH ~ ~CH CH~ ]
2 2 a 2 b
,C O :'
OH.H N(CH ) Si(OCH CH )
2 2 3 2 3 3 .
[~CH CH~ ~CH CH~]
2I x ' 2
Si(OCH )
3 3
HOOCCH CH Si(OCH CH )
~ 2 2 2 3 3
; NCCH CH Si(OCH CH )
.: 2 2 2 3 3
10H N(CH ) Si(OC H )
.~ 2 2 4 2 5 3
H NCH CH NHCH CH NHCH CH CH Si(OC H )
2 2 2 2 2 2 2 2 2 5 3
. O
' H NCNHCH CH CH Si(OCH )
2 2 2 2 3 3
O
: ., C-NH2
. H NCNHCH CH N(CH ) Si(OCH )
' 2 2 2 2 3 3 3
:1 O H N-C=O
1 ,. 2
.~ H NC-NH(CH )N-(CH ) -NH(CH ) Si(OCH )
1 2 2 2 2 2 3 3 3
-1 polyethyleneimine-(CH ) Si(OCH )
. , .
.
'~ :
25.
.,
1067762 9476 -1
polyethyleneimine-[(CH ) Si(OCH ) ]
2 3 3 3 2
.; .
N(CH ) Si(OC H
\~/ 2 3 2 5 3
~_CH NHCH CH N(CH ) Si(OCH ) ~ :
2 2 2. 2 3 3 3
HCl
: ' ..
. HOCH CH CH Si(OC H )
i 2 2 2 2 5 3
H NCH Si(OC H
2 2 2 5 3
HOCH Si(OCH
2 3 3
H NCHCH Si(OC H
2 ' 2 2 5 3
CH
.l 3
.1 polyazamide----[CH CH CH Si(OCH ) ] (see U.S. Patent No.
s 2 2 2 3 3 1-5
3,746,348, patented July 17, 1973, for a complete description
of silylated polyazamides)
CH =C(CH )COO(CH ) Si(OCH CH OCH )
2 3 2 3 C 2 2 3 3
,~¦ CH =CH~ CH NHCH CH NHCH CH CH Si(OCH )
'` 2 2 2 2 2 2 2 3 3
~, ~ O
" ~
CH =CHC-NCH CH NH(CH ) Si(OCH
2 2 2 2 3 3 3
.. O
CH =CHCNH(CH ) Si(OCH CH )
2 2 3 2 3 3
CH =CHCH Si(OCH CH OCH
2 2 2 2 3 3
26.
.~
, .. . . .. . .
, , :
,: , ,
106776Z 9~76-l :
CH =C-CH Si(OCH )
2 1 2 3 3 ::
CH
. HSCH Si(OCH ) :
2 3 3 :
,
H5CH Si(OCH CH )
2 2 3 3
HS- ~ CH CH Si(OCH CH )
. 2 2 2 3 3
.~ ~H3 ~ .
HS- ~ CH CH Si(OCH CH )
W 2 2 2 3 3
O O
.. - .
: HOCCH=CHC-OCH CH CH Si(OCH ) .
; 2 2 2 3 3 :
O
. HSCH CH CH CNH(CH ) Si(OCH CH )
2 2 2 2 3 2 3 3
: o , .:
.. .. .
HOCH CH CH CH CH CNH(CH ) Si(OC H )
2 2 2 2 2 2 3 2 5 3
., ,
` (CH CH 0) SiCH CH CH S-S-S-CH CH CH Si(OCH CH )
~ 3 2 3 2 2 2 2 2 2 2 3 3
.- -, .
10(CH CH ! si (CH ) -S-S-(CH ) Si(OCH CH )
3 2 3 2 3 2 3 2 3 3
.: :
.~[(CH CH 0) SiCH CH ~ -CH ] [-S-S-S-]
~. 3 2 3 2 2 ~-~\ 3 2
': :
[(CH O) SiCH CH ~ -CH ] lS ]
: 3 3 2 2 ~ 3 2 4
~ .:
~ :
.~ ".
... . .. .. . .. . . . . . .
'' . ; , ' :' ' ' . . `' '
' '' ' ' :
9476-1
1~)6776Z
,~
G-~HSi (OCH )
2 3 3
.~ ~
, o
CH CH OCNH(CH ) Si (OC H )
3 2 2 3 2 5 3
'
CH OH
HO-~ C ~/
I CH
3 CH CH=CH
CH 2 2
CH
CH S 1 (OCH
2 3 3
" ..
and the like.
, Thus, the instant invention involves the further
discovery that preformed organosilane modified water-
insoluble metal silicate treated inorganic mineral
compositions can be prepared and used as fillers in polymer/
filler composites to impart improved physical properties
(e.g. tensile modulus) to the finished composite product
'~ even in the absence of any further additional amount of
organosilane coupling agent ingredients in the formulation
of the polymer/filler composite. The measurable improvement
of the finished polymer composite properties attributable
,'
28 .
:`
; - . .. ; ,~ . ~ .
; . ~ . .
~06776Z 9476-1
..
to the use of the organosilane modified water-insoluble
metal silicate treated inorganic mineral composition ~illers
of this invention clearly demonstrates that a definite :
interaction (i.e. response or reaction~ between the silane
coupling agent and the silicate treated mineral filler
employed) takes place in the production of said composition
fillers.
,~ The metal silicate treated inorganic mineral
products and the organosilane modified metal silicate
treated mineral compositions of the instant invention
have a wide range of utility and may be employed as re-
inforcing filler or pigment agents Ln any conventionally
known polymer composite formulations that generally require
a filler or pigment such as rubbers, thermoplas~ic and
; thermosetting resins, paints, varnishes, inks, and the like,
in t7..e same manner that conventional mineral fillers and
pigments have been employed heretofore. Moreover, improved
physical properties are imparted to the finished polymer `
composite when the organosilane modified metal silicate
treated mineral compositions of the instant invention
are employed even in the absence of additional organosilane :~
coupling agents, or when the metal silicate treated
mineral products of the instant invention are employed
as fillers along with silane coupling agents in conventional
polymer composites, e.g. rubbers, resins, etc. Such
improved properties may be many and varied depending upon
the particular materials employed. However, such effects
.. ..
29.
.':
.
,
106776Z 9476 -1
are usua~ly easily determinable and manif~sted through
. changes in the values of the finished composite properties
away from the values of the same properties displayed at
the absence of any silane coupling agent. For example,
in elastomeric and resinous composites the improved
effects attributable to the instant invention are often
seen in the finished composite product in terms of their
resistance to deforming forces such as commonly expressed
by tensile, compression and shear moduli, in increased
abrasion resistance and in decreased hysteresis losses in
flexure, and other such physical properties.
Still another aspect of the instant invention is
. polymer composite compositions comprising as the essential
ingrèdients (a) a polymer component, (b) an organosilane
coupling agent and (c) as the filler component, a metal
silicate treated inorganic mineral product of the present
invention, or alternatively (a') a polymer component, and
(b') as the filler component, an organosilane modified
metal silicate treated inorganic mineral composition of
the instant invention, and optionally (c') an organosilane
coupling agent.
It is to be understood that while polymer composite
compositions comprising as the essential ingredients either
the above defined components (a), (b) and (c), or alternatively
.' (a') and (b') and optionally (c') can be regarded as
' practically equivalent with respect to the development
: of improved properties in the finished composite state,
~. preference for assembling specific polymer composites from
.,
~ 30.
.
- , ~ . -
.. ~ .. . - , .. .. ~: . . .
.. . . .
106776Z 9476-l
the above defined components ~a), (b) and (c) rather than
from the above defined components (a') and (b') and
optionally (c') and vice versa may arise depending on the
particular finished polymer composite composition desired,
the particular facilities and equipment available for
àssembly of the composite, and requirements of the end use
in which the composite is to be employed. By way of
- illustration, where a specific combination of metal silicate
treated mineral product (c) and organosilane coupling agent
( ~ are to be used in large total amounts among several
polymer composite assembly sites, it may be most efficient
and ecoromical to provide an equivalent organosilane
modified metal silicate treated mineral composition to
the several sites. Thus, preference may be developed on
the basis of efficiency and economy factors. ~urthermore,
preference may arise from technological factors as for
example, when a by-product from interaction of an organo-
silane coupling agent (b~ and a metal silicate treated
mineral filler (c~ is in some way detrimental or undesir-
able, then a technologically based preference may be
developed for the alternative component (b') i.e. an
equivalent organosilane modified metal silicate treated
mineral composition filler. Other examples will be
1 readily envisioned by those skilled in the art.
i The polymer components of the novel composites
'l of this invention as well as methods for their preparation
are well known in the art and may include e.g. either
31.
.' :
1 .
,
' . : , . . ' '
. . ~ , , , .. , . ,. . . : .
~ 106776Z 9476-1
Sing1Y OL in adjuncture any of the synthetic homopolymers
and copolymers of olefinic and diolefinic monomers such as
ethylene, propylene, butylenes, methylpentenes, styrenes,
a~pha-methyl styrene, vinyl chloride, vinyl fluoride,
vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl
alcohol esters, acrylic acid and its esters and amides,
methacrylic acid and its esters and amides, allyl phthalate
esters, butadiene, isoprene, chloroprene, ethylidene
norbornene, 1,5-hexadiene, divinyl benzenes and the like,
as well as synthetic condensation polymers commonly classed
as alkyd resins, polyesters, nylons, phenolics, epoxides,
polyslufones, polysulfides, polysulfonates, polysulfonamides,
polyurethanes, polyureas, and the like, as well as oligomers
and polymers derived from plant and animal sources such as
cellulose esters and ethers, carbon-carbon unsaturated
fatty acid triglycerides, and natural hevea and icus
rubbers, and the like. The preferred polymers are rubber
polymers and thermoplastic and thermosetting resins that
lead to the conventional crosslinked product articles
of same.
~ .:
The organosilane coupling agent components of
the novel compo~ites of this invention as well as methods
for their preparation are well known in the art and include
the hereinabove defined organofunctional silanes as weIl
as the hydrolyza~es and condensates of said silanes,
and mixtures thereof. The function of a silane coupling
agent to provide a strong chemical bridge between a
silane reactive filler and polymer employed is well known
in the art. However, it is indeed surprising that such
is accomplished in polymer/filler composites comprising
the above defined components (a) (b) and (c) when there is
9476-1
~06776Z
so little silicate employed in the entire polymer composite
formulation. It is further surprising that such may be
accomplished in polymer/filler composites comprising the
above defined ccm~onents (a') and (b') which do not require
the presence in the composite formulation of any further
; additional amount of organosilane coupling agent component
(c') although such an optional ingredient (c') may be of
course ernployed if desired. It is of course understood
that for effective coupling action in a particular polymer-
filler composite, it is necessary to select the appropriate
organosilane coupling agent, i.e. one wh~ch is suitably
reactive towards both the polymer component and the
filler component for each particular polymer-filler
composite considered. Thus while there may be more than
one appropriate silane coupling agent for a particular
polymer composite, a given silane coupling agent may
not be appropriate for all polymer composites. The selection
of the most preferred silane coupling agent fox any particular
polymer composite is well within routine experimentation.
Of course, the filler component of the novel polymer
composite compositions of this invention comprise the metal
silicate treated inorganic mineral products(above defined
component (c))of the instant invention as defined herein
` above, and the organosilane modified metal silicate
treated inorganic mineral compositions (above defined
component (b')) of the instant invention as defined herein
above.
33.
, . ' .
' ~ ' .
:, - :' :, . '
.
9476-1
~0677~Z
The particular manner of compounding and finishing
the polymer composite compositions of this invention as well
as the various amounts of ingredients employed is not
critical for such is conventionally known and merely
depends on the particular finished polymer composite
desired along with the ultimate end use for which it is
to be employed, and such conventional steps as compounding,
crosslinking, drying, and the like may be conducted in
the same known manner as heretofore employed for conventional
polymer composites containing siliceous fillers. In
general the amount of organosilane coupling agent component
( ~ employed with a metal silicate treated mineral filler
component (c) will normally range from about 0.1 to 10
parts by weight per 100 parts by we~ght of metal silicate
treated mineral filler employed although higher or lower
amount~ may be employed although higher or lower amounts
may be employed if desirable. Of course the amount of
metal silicate treated mineral filler component (c) or
the amount of organosilane modified metal silicate treated
mineral composition filler component (b') employed in a
given composite may range from as little as 0.1 parts
by weight up to as high as 300 parts by weight or higher
per 100 parts by weight of polymer employed for such
merely depends on the desired end product and use. Of
course the amount of the optional organosilane coupling
agent component (c') employed may range from nothing
up to 10 parts by weight or higher per 100 parts by
:; .
weight of polymer employed.
:
~ 34.
.: '
. .
; 106~76Z 9476-1
It is to be understood that in addition to the
essential components described above, the novel polymer-
filler composite compositions of this invention can also
contain as desired, various other conventional ancillary
ingredients such as softening, plasticizing and peptizing
agents, lubricating agents, conventional particulate
and fibrous fillers, coloring dyes and pigments,
antioxidant and antiozonant agents, ultra-violet protective
agents, odorizing agents, thermal decomposition protective
agents, crosslinking agents, cure rate accelerating
and activating agents and the like. Of course, the
~ multitude of various conventional utility applications
; of the finished composite articles are well known to
anyone skilled in the art.
: The following examples are illustrative of the
:; instant invention and are not to be regarded as limitative.
It is to be understood that all parts, percentages and
proportions referred to herein and in the claims are by
weight unless otherwise indicated. Tensile modulus is
defined as the tensile stress in pounds per square inch
or original cross-sectional area necessary to produce a
given extension in a composite specimen, usually 300%
of the unstressed length.
'~
, 35-
" '~
, .
.1,,~
'' ' ' ' ' ' : ' ' ' ' ` ! ' . . . ..
. '
D-9476-1
106776Z
Exam~
500 par~s of wet ground calcium carbonate
B (calcite mineral~ Atomite~ 2.5 micron, Thomson-Weinman
Co,) were added to 2000 parts of rapidly stirred water
at ambient room temperature (23C.) to form a fluid
slurry. 200 parts of a 10 wt.~/o aqueous solution of
sodium metasilicate nonahydrate (Na2SiO3.9H20) were
then added to the~stirred slurry followed by dropwise
addition over a period of 20 minutes of 78.1 parts of
a 10 wt. % aqueous solutLon of anhydrous calcium
chloride (CaC12) to provide 1.64 parts of calcium
, silicate per 100 parts of the calcium carbonate mineral
as charged. The mixture was then rested until the
~,
'
.,,
,, .
.,. . :
:
' :'
. :
'~ .
~ 36. ~ :
~ .
9476 -
1~6776Z
solids had settled out and the upper water lay~r was
siphoned off. The 601ids were washed twice, each
time by adding 1000 parts o water, stirring, settling
and siphoning off the upper layer. To assist drying,
the solids were then washed by adding 1000 parts of
acetone, stirring, settling and siphoning off the upper
layer. The solids were then filtered out and oven
dried at 150C., 2 mm. Hg. pressure for 4 hours, The
dried solids were then pulverized to produce 492 parts
of the desired water-insoluble calcium silicate
treated calcium carbonate mineral which was identified
and found to contain by analysis, 1.27 parts of calcium
silicate (as CaSiO3) per 100 parts of product,
.
Example 2
,:
This example illustrates the preparation of a
calcium silicate treated carbonate filler wherein a base
. , ,
(NaOH) is used to provide a calcium silicate having a
CaO/SiO2 ratio of 3/1 as charged,
750 parts of wet ground calcium carbonate
(calcite mineral, Atomite, 2,5 micron, Thomson-Weinman
Co.) were added to 3000 parts of water to form a fluid
- slurry, 152,2 parts of a 10 wt.Z aqueous solution of
.. ~ .
sodium metasilicate nonahydrate and 85.8 parts of a
~',
;l 10 wt.70 aqueous solution of sodium hydroxide were
l added to the stirred slurry followed by dropwise addi-~j j
tion over 20 minutes of 178.5 parts of a 10 wt %
; aqueous solution of anhydrous calcium chloride to
37,
.
.. . . ..... . .. . . .. . . .
9476 -1
0 ~77 6 Z
provide 1.63 parts of calcium silicate having a
CaO/SiO2 ratio of 3/1 as charged per 100 parts of
the calcium carbonate mineral. The mixture was then
rested until the solids had settled and the upper
water layer was siphoned off. The solids were filtered
off and washed with water on the filb~. The washed
solids were dried at ambient room temperature for 16
hours then oven dried at 110C. for 24 hours~
Example 3
This example illustrates the preparation of
a calcium silicate treated carbonate filler wherein an
acid (HCl) i~ used to provide a calcium silicate having
a CaO/SiO2 ratio of 1/3 as charged.
750 parts of wet groùnd calcium carbonate
; (calcite mineral, Atomite, 2.5 micron, Thomson-Weinman
Co.) were added to 3000 parts o~ water to form a fluid
~lurry, 441.3 parts of a 10 wt. % aqueous solution of
sodium metasilicate nonahydrate were added to the
stirrea ~lurry followed by dropwise addition over 20
minutes of a mixture of 57.5 parts of a 10 wt. % aqueou8
.
solution of anhydrous calcium chloride with 75.6 parts
of a 10 wt.% aqueous solution of hydrochloric acid to
provide 1.63 parts of calcium silicate having a
CaO/SiO2 ratio of 1/3 as charged per 100 parts of
calcium carbonate mineral. The mixture was then worked
up, washed and dried according to the procedure of
Example 2.
,'
38.
-
.:
,. . .
9476-1
106776Z
Example 4 ~ :
This example demonstrates the effect of
treating calcium carbonate filler with water-insoluble
calcium silicate on action of a silane coupling agent
. ~ in sulfur vulcanized rubber composite.
A series of sulfur vulcanized rubber com-
posites were prepared using the following composite
formulation wherein the particular mineral filler and
a unt of silane employed was varied as shown in
Table I.
Composite Parts By
Formulation Wei~ht
Natural Rubberl 50
Styrene Butadiene Rubber2 50
Mineral Filler 100
Silane Coupling Agent3As 8hown
Stearic Acid
Zinc Oxide 4
Sulfur 2
i. 20! NCBS4
;~ . DPG5 0.3
1 No. 1 Smoked Sheet
2 SBR 1710
3 3-mercaptopropyltrimethoxysilane
4 N~cyclohexylbenzothiazolesulfenamide
5 Diphenylguanidine
. The sulfur vulcanized rubber composites were
all prepared in the same manner as follows:
The vulcanizable rubber polymers were charged
; 30 to a water-cooled 2-roll rubber mill, banded thereon
: and milled until smooth and plastic. The mineral filler
39.
,
9476_1
~ 067762
was added to the polymer band and where employed the
silane coupling agent was added dropwise and con-
currently with the mineral filler. After an intimate
mlxture of the polym~r, filler and silane was obtained,
~-; the curing agents, accelerators and other ancillary
: ingredients employed were ~dded and the mixture milled
~ until an intimate dispersion was obtained. The mixture
; was stored at ambient ro~m condition for a minim~m of
16 hour~, then remilled until smooth and plastic.
Molding preformed sheets were cut from the remilled
. . .
mixture and cured under pressure of about 1000 psi at
an elevated temperature of about 320F. After resting
at ambient room condition for a minimum of 16 hours
,
the physical properties of the sulfur w lcanized rubber
composites were measured and are recorded in Table I
below.
In Table I below Filler A represents the use
of commercial wet ground untreated calcium carbonate
(calcite mineral, Atomite, 2.5 microns, Thomson-Weinman
Co,), Filler B repre~ents the uæe of the same commer-
cial untreated calcium carbonate mineral filler but
after it had been slurried in water, washed and dried
in the manner set forth in Example 1 above. Filler C
represents the use of water-insoluble calcium s~licate
treated calcium carbonate mineral filler that had been
prepared using the same ingredients and method deæ-
cribed in Example 1 above with the exception that the
:,
,. ,
~ 40
-. - . . , . . . . ~
`~
i - 9476-1
~06776Z
parts by weight of precipitated watex-insoluble calcium
. 8ilicate per 100 parts by weight of the calcium carbonate
l~ mlneral a8 charged to the aqueous slurry was varied as
:I given in said Table I below.
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! Run Nos. 1 and 2 show that the untreated
calcium carbonate mineral filler employed is non-
responsive to the silane coupling agent, e.g. there was
I no improvement in the Tensile Mcdulus test. Run Nos. 3
j and 4 ~how that aqueou~ slurrying washing and drying of
, the untreated calcium carbona~e mineral filler employed
; doe~ not affect the fillers response to the silane
coupling agent. Run Nos. 5, 7 and 9 show that the water-
, insoluble calcium silicate treated calcium carbonate
~ 10 mineral filler of this invention when employed alone
¦ without the silane coupling agent has no effect on the
Tensile Modulus propertie~ of the cured composite article.
Run Nos.6,8 a~ 10 demonstrate the instant i~vention and
i show that the water-insoluble calcium silicate treated
~ calcium carbonate mineral filler of t4is invention is
¦ indeed responsive to the silane coupling agent as wit-
' nessed by the signi~icant improvements in the Tensile
j Modulus of the cured composite article when said sili-
cated treated carbonate mineral filler is employed along
with the silane coupling agent.
Similar improved results may be obtained for
I example by compounding in appropriate amounts the water-
`1 insoluble calcium silicate treated calcium carbonate
i mineral filler prepared as in Example 1 along with an
... .
approprlate silane coupling agent into other conventional
type8 of polym~r composites such as thermoplastic resin
composites, e.g. polyethylene, polyvinyl chloride,
ethylene-vinyl acetate, and the like.
43.
,: :
947~ -
106776Z
Example 5
This example demonstrates the respon~e o~
the water-insoluble calcium silica~e treated calcium
carbonate mineral fillers of this invention to silane
-coupling agents as compared to physical mixtures of
calcium silicate and calcium carbonate flllers~
A series of sulfur vulcanized rubber com- ~:
posites were prepared u~ing the same composite formula-
tion and procedure given in Example 4 above and the
followlng form~lation.
Composite Parts By
Formulation Wei~ht
Natural Rubberl 2 50
Styrene Butadiene Rubber 50
; Mineral Filler 50
Silane Coupling Agent As shown
Stearic Acid 1.5
Zinc Oxide 6
Sulfur 2
NCBS 1.1
DPG 0-7
No. 1 Smoked Sheet
2 5BR 1710
3-mercaptopropyltrimethoxysilane
4 N-cyclohexylbenzothiazole~ulfenamide
5 Diphenylguanidine
wherein the particular mineral filler and amount of
silane employed was varied as shown in Table II.
In Table II below in Run Nos. 1-11 the same
composite formulation given in Exampl2 4 was employed
while in Run No8. 12-15 the composite formulation out-
lined above in thi~ Example 5 was employed; Filler A
~.
~ 106776Z 9476-l
represents the u8e of commercial wet ground untreated
; calcium carbonate (calcite mineral, Atomite, ~.5
microns, Thom80n-Weinman Co.); Filler B represents a
i dry blended mixture of Filler A and synthetic precipitated
, B calcium silicate (Silene EF, Pittsburg Plate Glass
~ Industries); Filler C represents an aqueous slurry
-~ of Filler B; Filler D represents the use of water-
insoluble calcium 8ilicate treated calcium carbonate
mineral filler that had been prepared using the same
ingredients and method described in Example 1 above with
the exception that 1.5~ and 3.1 part8 by weight of water-
insoluble calcium silicàte was precipitated and used per
,
100 parts by weight of the calcium carbonate mineral as
charged to t~e aqueous slurry; Filler E represents the
use of a dry blended mixture of 8ynthetic precipitated
calcium carbonate (Multifex~lDX, 0.05 micron, Diamond-
Shamrock Corp.) and synthetic precipitated calcium
silicate (Silene EF, Pittsburgh Plate Glass Ind.); and
;l Filler F represents the use of water-insoluble calcium
silicate treated calcium carbonate mineral filler that
had been prepared using the 8ame ingredients and method
, . .
describ~d in Example 1 above with the exception that
the calcium carbonate mineral, starting material
employed was synthetic precipitatet calcium carbonate
(Multifex IDX, 0.05 micron, Diamond-Shamrock Corp.)
and that 1.5 parts by weight of water-insoluble calcium
silicate was precipitated and used per 100 parts by
.
~, .
9476 -
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weight of the calcium c~rbonate as charged to the :
aqueous 81urry. The part8 by weight o~ the 3-mercapto~
propyltrimethoxysilane coupling agent employed per 100 :
parts by weight of Filler used below as well as the :
parts by weight of calcium silicate employed per 100
parts by weight of the calcium carbonate mineral used
are also gLven in ~able II below,
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~¦ Run No8, l and 2 show that the untreated
.1
calcium carbonate mineral filler employed is non-
responsive to the silane coupling agent and showed no
improvement in the Tensile Modulus test even when
employed with the silane. Run Nos. 3 and 4 and 5 and
6 show that physical mixtures of calcium carbonate
..^:
and calcium silicate made by dry (Run Nos. 3 and 4)
or wet (Run Nos. 5 and 6) methods are also inert to
the silane coupling agent. Run Nos~ 7 and 8 demonstrate
the instant invention and show that the water-insoluble
,l calcium silicate treated calcium carbonate mineral
' filler of this invention when employed along with the
silane coupling agent is indeed silane responsive as
witnessed by the significant improvemen~ of the Tensile
. .
Modulus of the cured composite. A comparison of Run
I Nos. 9-ll again de nstrate that the water-insoluble
i,.,,~
calcium silicate treated calcium carbonate mineral
filler of this invention (Run No. 11) i8 silane res-
I ponsive and that the improvement in tensile modulus is
., ~ .
not due to the mere presence of calcium silicate. Run -
~, Nos. 12-15 also demonstrate the same effects for
fillers of the instant invention (Run Nos, 14 and 15)
i , .
having a base of synthetic calcium carbonate having a
higher surface area~
~.,, ~'''.
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- 48
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9476 -
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Example 6
This example demonstrates the e~fect that :
the time between the formation of a water-insoluble
metal silicate and its contact with an inorganic mineral
filler has on the responsiveness of the water-insoluble
.:
metal silicate treated inorganic mineral to an organo-
- 8 ilane coupling agent.
A series of sulfur vulcanized rubber com-
posites were prepared according to the procedure of
Example 4 using the ~ollowing composite formulation.
:; . Composite Parts by
Formulation Wei~ht
. Natural Rubberl $0
'~ Styrene Butadiene Rubber2 50
: Mineral Filler 100
- Silane Varied
~ . Stearic Acid ~ 1.5
Zinc Oxide 6
Sulfur 2
: ,
~ 20 NCBS4 1.1
.~ .
j DPG5 0.7
,. . .
. ~No. 1 Smoked Sheet
.~ ~ 2SBR 1710
33-mercaptopropyltrimëthoxysilane
.~ N-cyclohexylbenæothiazole 8ulfenamide
,
5Diphenylguanidine
,
49 .
. .
. .
~ .
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- . . . ,` , ;
: .; ,
- 9476-1
106776Z
The cured composite properties of the sulfur
vulcanized Rubber articles are given in TABLE III below.
In said TABLE III, Filler A represents the use of a
water-insoluble calcium silicate treated calcium carbon-
ste filler produced by employing the same ingredients,
amounts and procedure of Example 1 above, i.e. the water
.. .. .
soluble calcium silicate was precipitated in the
presence of the calcium carbonate filler; Filler B
represents the use of a water-insoluble calcium silicate
~reated filler produced by employing the same ingredients,
amounts and procedure of Example 1 above except that the~
calcium carbonate filler was contacted with the water-
insoluble calcium silicate immediately after completion
of the precipitation of said silicate; Filler C repre-
sents t~e use of a water-insoluble calcium silicate
treated calcium carbonate filler produced by employing
the same ingredients, amounts and procedure of Example 1
above, except that the calcium carbonate filler was not
contacted with the water-insoluble calcium silicate
, ;'. ~ . . :.
~` 20 until ten minutes after completion of the precipitation
of said silicate; Filler D represents the use of a water-
insoluble calcium silicate treated calcium carbonate
. . , , . : ~
filler produced by employing the same ingredients,
amounts and procedure;of Example 1, except that the
calcium carbonate filler was not contacted with ~he
water-insoluble calcium silicate until 100 minutes after
completion of the precipitation of said silicate;
.~ ~
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; . ,
. . .
`; 1067762 9476 -1
.
. Filler E represents the ~se of a water-ins.oluble
- calcium silicate-treated calcium carbonate filler pro- - -
duced by employing the same ingredients, amounts and
- -procedure of Example 1 above, except that the calcium
: carbonate filler was not contacted with the water-
insoluble calcium silicate until 1000 minutes after
.completion of the precipitation of said silicate. The
amount of the silane coupling agent used in terms of
4" parts by weight per 100 parts by weight of filler
: - . 10 employed in each composite is also given in TABLE III
below.
TABLE 3
Cured Composite Pr~perties
Run S~lane Tensile Tensile Elonga-
~ No. Filler PPHF Modulus Strength tion at Hardness
- (PSi) ~psi) Break (/O) (Shore A~
: 1. A 0.0 375 1475 575 59
. ' 2. A 1.51125 1575 425 62
20 3. B . 0.0 400 1675 575 59
4. B 1.5 - - 875 175 64 ' ~
5. C 0.0 425 1700 575 59 .:
6. C 1.5 - 1125 ~50 64
7. D 0.0 400 1800 600 60
- -- 8. D 1.5 -- 975 150 64
9. E 0.0 400 1650 575 60
10. E - 1.5 - 1225 325 . 64
. .
- .
.~ 51.
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947~ -
' 106776Z ;
Example 7 -
. ,. - - , . . .
-- This example illustrates the response of
various water-insoluble metal silicate-treated
inorganic mineral fillers of this invention to organo- ~ ,
- silane coupling agents. ;
A variety of water-insoluble m~tal silicate-
treated calcium carbonate mineral fillers were prepared
' employing the same ingredients and pr'ocedure of Example 1 -
' above except, that the following different water-soluble '
1~ salts were employed: Iron (FeC13~, Barium (BaC12), '
Cadmium (CdC12), Cobalt (CoC12.6H20), Copper (Cu~12)~
d (Pb(02C2H3)2~3~120)~ ~ithium (LiCl), Zinc (ZnCl ),
"~ - Beryllium (Be(N03)2.3H20), Magnesium (Mg(No3)~.6H20),
~ Strontium (SrC12,6H20), Manganese (MhC12.4H20),
,, Nicke,l (NiC12.6H20), Silver (AgN03), Mercury (Hg(NO~)2.H20), ''
' ~in (Sn~14,5H20), Cerium (Ce(N03)3.6H20) and Zirconium '
(ZrOCl ,8H20), in place of the calcium chloride salt. ~,
A series of sulfur vulcanized rubber composites were then
, prepared according to the procedure of Example 4 using
the composite formulation in Example 6 and the various
,; different water-insoluble metal silicate treated calcium '
carbonate fillers prepared above along wlth different
~ - amounts of the silane coupling agent. The particular
`, , water-insoluble metal sil~cate treated calcium carbonate
'- filler employed is indicated by the metal given in
, ' TABLE IV ~elow, as is the amount of water-insoluble ~,
metal silicate precipitated and used in terms of parts
52. ::
~ ` ~; i06776Z ` 9476-1
.~,
by weight per 100 parts by weight of untreated calcium
carbonate as charged to the aqueous slurry in the prep-
aration of said silicate treated calcium carbonate
fillers. The amount of the silane coupling agent
employed in terms of parts by weight per 100 parts by
weight of the silicate treated calcium carbonate filler
us~d and the cured composite properties of the sulfur
vulcanized rubber articles are also given in TABL~ IV
below.
. .
.. .
.
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~067762 9476_1
TABLE IV
Cured ComE~osite_roperties~
300~/o Elonga-
Tensile Tensiletion at
Modulus StrengthBreak
( ps i2 ( PS i)( /~)
Metal ~ Silane ~ -~
Run Silicate
No. M~tal (PPHF)0 1.5 O 1.5 0 1.5
1 None ~one425 525 1700 1275 575 450
2 Iron 1,85775 lO00 1325 1150 400 375
3 Barium 3.0 400900 1825 1900 600 550 ; :
4 Cadmium 2. 65 5Q011001950 1850 575 475
Cobalt 1.9 400875 1925 2075 600 575
6 Copper 1. 96 425675 1975 2025 650 575
7 Lead 3.98 375500 1825 1900 600 675
8 Lithium 1.26 425775 1900 1800 600 550
9 Zinc 1.99350 1100 l9D0 2025 625 500
; 10 Beryllium 1.0 400 - 1950 925 625 250
11 Magnesium 1.0 400 - 1650 925 600 200
12 Strontium 1.0 400 825 1825 1250 600 375
13 ~anganese 1.0 400 ~ 1775 1000 625 225
14 Nickel 1.0 400850 1700 1400 575 450
Silver 1.0 425625 1600 1350 550 500
16 Mercury 1.0 400700 1750 1400 600 475
17 Tin 1.0 400775 1550 1450 575 450
18 CeriL~ 1.0 350 - 1450 900 575 300
l9 Zirconium 1.0 425 775 1850 1450 575 425
.
:
54
- - . . - , : . ~ :
.
. - . . 9476 -1
1o67762
'..
Example 8
This example demonstrates the respon8e of
various water-insoluble metal silicate-treated ino~ganic
. mineral fillers of this invention to organosilane
- coupling agents.
A variety of water-insoluble calcium
.` silicate-treated inorganic mineral fillers were
. employed, employing the same ingredients and procedure
of Example 1 above, except that barium carbonate
: 10 (Ba~.~.), magnesium carbonate (MgC03), zinc carbonate
:~ (ZnC03), calcium sulfate (CaS04.2H20) and barium sulfate
(BaSo4) were employed as the inorganic mineral in place
' ~ of the calcium carbonate mineral. A series bf sulfur
vulcanized rubber composites were then prepared accord-
: ing to the procedure of Example 4 using the composite
., .
. formulation in Example 6 and the various different
water-insoluble calcium silicate treated inorganic ..
mineral fillers prepared above, along with different
amounts of the silane coupling agent. The particular
water-insoluble calcium silicate treated inorganic
: .
mineral filler employed is indicated by the inorganic
... . .
mineral given in TABLE V below, as is the amount of .:
water-in801uble calcium silicate precipitated and used
. . in term8 of parts by weight per 100 parts by weight of . .
the untreated inorganic mineral as charged to the :~
~ . . . .:~ ' .
aqueous s~urry in the preparation of said c81cium
. silicate treated inorganic mineral fillers. For ::
. ' ' ,:
: 55.
. - ' ' ' ' ' ''~ . ,:
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9476-1 :
~067762
comparison cured composites were also made in the same ~ :
manner using the untreated inorganic mineral fillers.
The amount of the 8ilane coupling agent employed in
terms of parts by weight per 100 parts by weight of ;~
the filler used in the composite and the cured com-
posite properties of the sulfur vulcanized rubber :
articles are also given in TABLE V below. ~:
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Example 9 - .:
,.
This example illustrates the effect of varying ~-
-. the metal oxide ratio on the responsiveness of the
.
water-insoluble metal silicate treated inorganic mineral ~
fillers of this invention to organosilane coupling :.-
agents,
: Four water-insoluble calcium silicate-treated
calcium carbonate mineral fillers were prepared and used
to make sulfurized rubber composites according~to the .
procedure of Examp~e 4, using the composite formulation
of Example 6, The cured composite properties are given
in TABLE VI below, Filler A represents the use of un-
treated calcium carbonate (Atomite, 2,5 micron, Thompson-
: Weinman Co,); Filler B represents the use of a water-
i in801uble calcium silicate treated calcium carbonate
... mineral filler prepared by using the same ingredients
and procedure given in Example 3 above, Filler C repre- :
:. . . .
sents the use of a water-insol.uble calcium silicate
~ treated calcium carbonate mineral fille~ prepared by
; 20 using the same ingredients and procedure given in Example
1 above; Filler D represents the use of a water-insoluble . :~
.. calcium s~licate treated calcium carbonate mineral
:~ . filler prepared by.using the same ingredients and pro-
cedure given Ln Example 2 above. The amount of water-
insoluble calcium sil~cate precipitated and used in the
. ~ preparation of each of said silicate treated carbonate
fillers was 1,6 parts by weight of calcium carbonate as
, .~
58.
.;
:` .
,
. - :
` .` 9476-1
~ 067762 ~` -
charged in the preparation of said silicate treated
fillers. Each composite formulation employed also
- contained 1.5 parts by weight per 100 parts by weight
of the mineral filler employed in said composite, The
metal oxide ratio (CaO/SiO2) of each filler employed
in said composite is also given in TABLE VI below.
TABLE VI
.
CURED COMPOSITE PROPERTIES
- 300%
Tensile Tens~le
Run -Modulus Stréngth Elongation at
No. Filler CaO/SiO2 (psi) (psi) Break %
1 A 0') 550 j50 450
2 B 0.3 1100 1250 350
3 B 0.5 1000 1500 450
4 C 1.0 950 1~00 45Q `~
D 2.0 800 1350 475 ;
6 D 3.0 800 1j25 450
Example 10
This example illustrates,the effect of water-
insoluble metal silicate treated inorganic mineral `
fillers prepared by consecutively using two different
~ water-in801uble metal silicates. I
A series of water-insoluble metal silicate
treated calcium carbonate mineral fillers were prepared
by employing the same ingredients ~nd procedure of -
Example i above except that in eac~ instance two
!- ~
. . - . ss. I ':
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. ~ .. . . . .
. . .; . . ~
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diEferent water-soluble metal salt solutions were
added to the aqueous slurry of calcium carbonate and
sodium metasilicate solution consecutively and in the
order indicated below The reactants were employed
in amounts calculated to pro~ide equal volumes of
each precipitated metal silicate, i.e., 0.25 ml. of
precipitated metal silicate per 100 parts by weight
of the calcium carbonate as charged. Sulfur vu~can-
ized rubber composites were then prepared using said
prepared water-soluble metal silicate treated calcium
carbon~te mineral fillers by the same procedure given
in Example 4 above while using the came composite
formulation given in Example 6 above. The amount of
3-mercaptopropyltrimethoxysilane coupling agent when
used was 1.5 parts by weight per 100 parts by weight
of the filler employed in the composite. The par-
ticular water~insoluble metal silicate treated calcium
carbonate mineral fillers employed are indicated in
~ABLE VII below as is the cured composite properties
of the sulfur vulcanized rubber articles. In TABLE VII
below, Filler A represents the use of a water-insoluble
calcium silicate, barium silicate treated calcium
carbona~e mineral filler prepared in the above des-
cribed manner by employing consecutive solutions of
water-soluble calcium chloride and barium chloride -
salts so as to precipitate the water-insoluble calcium
: .
and barium silicate salts in the order given; Filler B
: .
6~.
9476 -1
~ 67 ~6 2
represent8 the use of a water-insoluble barium
silicate, calcium silicate treated calcium carbonate
mineral filler prepared in the above described manner
: by employing consecutive solutions of water soluble
barium chloride and calcium chloride salts as to
precipitate the water-insoluble barium and calcium
salts in the order given; Filler C represents the use
of a water insoluble calcium silicate, zinc silicate
treated calcium carbonate mineral filler prepared in
the above deæcribed manner by employing consecutive
solutions of water soluble calcium chloride and zinc
chloride salts so as to precipitate the water-insoluble
... . .
calcium and zinc silicate salts in the order given;
Filler D represents the use of a water-insoluble zinc
silicate, calcium sllicate treated calcium carbonate
. mineral filler prepared in the above described manner
by employing consecutive solutionæ of water soluble
zinc chloride and calcium chloride salts so as to
precipitate the water-insoluble zinc and calcium
silicate salts in the order given; Filler E represents
~ the use of a water-insoluble barium silicate, zinc
.~ilicate treated calcium carbonate mineral filler pre-
pared in the above described mannPr by employing
consecutive solutions of water soluble barium chloride
and zinc chloride salts so as to precipitate the
: water-insoluble barium and zinc silicate salts in the
. order given; and Filler F represents the uæe of a -
: .
61.
~ , .
~ . 9476-1
~067762
water-insoluble zinc silicate, barium silicate treated
calcium carbonate mineral filler prepared in the above
. ~ described manner by employing consecutive ~olutions of
water-soluble zinc chloride and barium chloride salts
: 60 as to precipitate the water-insoluble zinc and
barium silicate salts in the order given.
TABLE VII
300%
Ten8ile Tensile
- 10 Run Silane Modulus Strength Elongation : .
No. Filler (PPHF2 (psi~ (psi~ at Break %
1 A0.0 400 1875 575
, , 2 A1.5 475 1600 525
:~ 3 B0.0 425 1500 525
4 B1.5 825 1875 500
C0.0 425 1675 575
6 C1.5 1175~ 1825 450
7 D0.0 375 1875 600
: 8 D1.5 1075 1650 425
9 E0.0 400 1775 575
E1.5 1200 1625 400
' ' '
11 F0.0 350 1.775 600
!' 12 F1.5 1275 1550 350
~, i .
Example 11
:I This example illustrates the effect of
water-insolùble metal silicate treated inorganic
mineral fillers prepared by consecutively using two
j. different water-insoluble metal silicates.
: . ..
62.
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9476-1
106776Z
A series of water-insoluble metal silicate
treated calcium carbonate mineral fillers were prepared
by employing the same ingredients and procedure of
Example 1 above except that in each instance two differ-
ent water-soluble metal salt solutions were mixed
together before addition to the aqueous slurry of calcium
carbonate and sodium metalsilicate solution. The re-
actants were employed in amounts calculated to provide
equal volumes of the coprecipitated mixed water-insoluble
metal silicate, i.e. 0.5 mil. of coprecipitated mlxed
water-insoluble metal silicate per 100 parts by weight
of the calcium carbonate as charged. Sulfur vulcanized
rubber composites were then prepared using said prepared
water-insoluble mixed metal silicate treated calcium
carbonate mineral fillers by the same procedure given
in Example 4, above, while using the same composite
- formulation given in Example 6 above. The amount of
3-mercaptopropyltrimethoxysilane when used was 1.5
~! parts by weight of the filler employed in the composite.
The particular water-insoluble mixed metal silicate
treated calcium carbonate fillers employed are indi-
cated in TABLE VIII below as is the cured composite
properties o the sulfur vulcanized rubber articles.
In TABLE VIII below, Filler A represents the use of a
water insoluble calcium and barium silicate mixture
, I : . ...
treated calcium carbonate mineral filler prepared in
the above described manner by employing a premixture
,'~
~ 63.
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9476 -1
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solution of water-soluble calcium chloride and barium
: chloride salts so as to coprecipitate the m~xture of
; water-insoluble calcium and barium 9ilicate salts . :~
. , .
together; Filler B represents the use of a water-
in801uble calcium and zinc 8ilicate mixture treated . ~-
~ calcium carbonate mineral filler prepared in the ~
:', , ..: above described manner by employing a premixture
ii~ . .
.~ solution of wat~r-801uble calcium chloride and zinc
~ chloride salts so as to coprecipitate the mixture of
, .
water-insoluble calcium and zinc silicate 8alts to-
gether; and Filler C represents the use of a water-
i,
~1 in~oluble barium and zinc ~ilicate mixture treated
calcium carbonate mineral filler prepared in the above . .
. .
.~ ; described manner by employing a premixture ~olution of
~I water-801uble barium chloride and zinc chloride 8alt8
80 as to coprecipitate the mixture of water-insoluble
barium and zinc silicate salts together.
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TABLE VIII
... .
300%
Ten8ile Tensile
Run Silane Modulus StrengthElgonation
No. Filler(PPHF) (p~i~ (psi) at Break /0 -'
;:
A 0. 0300 1500 600
2 A 1. 51475 1500 300
3 B 0. 0375 1575 575
4 B 1.51125 1625 400
10 5 C 0. 0375 16S0 575
6 C 1.51025 1850 475
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. Example 12
.~ This example illustrates the responsiveness
,~ .
of different water-insoluble metal silicate treated
- inorganic mineral fillers to different organosilane
I coupling agsnt 8 in different composite formulations,
A variety of water insoluble metal silicate
treated calcium carbonate mineral fillers were employed
` by using the same ingredients and procedure in Example 1
above except that different water-soluble metal salts
were employed. The particular water insoluble metal
'~ 8ilicate treated calcium mineral ~iller prepared and
employed in this example is indicated by the metal
given in the following TABIES rx, X and XI as is the
l~ amount of water-insoluble metal silicate precipitated
; and used in terms of parts by weight per 100 parts by
l weight of untreated calcium carbonate as charged to
the aqueous slurry in the preparation of said silicate
. treated calcium carbonate filler. For instance, in .
¦.~ TABLES IX, X and XI below Filler A represents the use
!' 20 of untreated calcium carbonate (Atomite, 2.5 microns,
Thomson-Weinman) as a control comparison, while
Filler B represents the use of a water-insoluble
calcium silicate treated calcium carbonate filler
prepared in the above described manner using a water-
soluble calcium chloride salt, said filler having a
. .
~ metal oxide (CaO/SiO2) ratio of ll3; Filler C
-; 66.
.. . . .
.
; .
9476-l
106776Z ~
represents the use of a water-insoluble barium silicate
treated calcium carbonate filler prepared in the above
described m~nner u8ing a water-soluble barium c~loride
salt, said filler having a metal oxide (BaO/SiO2)
ratio of 1/1; Filler D represents a water-in801uble
zinc silicate treated calcium carbonate treated filler
prepared in the above described manner using a water-
soluble zinc chloride salt, said filler having a metal
oxide (ZnO/SiO2) ratio of 1/1; and Filler E representæ
a water-insoluble calcium silicate treated calcium
carbonate filler prepared in the above described manner
using a water-soluble calcium chloride salt, said
i filler having a metal oxide (CaO/SiO2) ratio ~f 1/1.
The water-insoluble metal silicate treated
calcium carbonate fillers so prepared were then employsd
in various composite formulations and the cured com-
posite properties of the prepared vulcanized articles
are~given in TABTFS rx, X and XI be~ow. The cured
vulcanized composite articles were all prepared in the
same manner by following the procedure of Example 4
above except that different curable composite formula-
tions were employed. For instance in TABLE IX below
the following curable composite formulation was
employed.
67.
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06776Z
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Composite Parts
Formulation B~ Weight
EPDM Rubberl 100
; Mineral Filler2 100
Silane Coupling Agent3 As Shown
~ EGD ~ 4 ,~
i D DCp5 1.6
. lRoyalen ~501, (Uniroyal Corp,) (Ethylene Propylene
Diene Monomer Rubber)
2Varied as shown
3Varied a~ shown
~ thylene glycol dimethacrylate
; 5Dicu~ylperoxide, recrystallized
In TABLE X below the following curable com-
¦' posite formulation was employed~
; Composite Parts
, Formulation By Weiht
.'1 Chloroprene Rubberl 100
. Mineral Filler2 100 . ..
.¦~ 20 Silane Coupling Agent3 As Shown
j~ . Stearic Acid 0.5
: " '
Zinc Oxide 5
~'1 Magnesium Oxide 4
:~ Process Oil4 7.5
TMTU5 0.5
Neopr~n ~ ~ (DuPont Co. ?
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~ 3Varied as shown
.''. 4Circosol~ 240
.` 5Tetramethylthiourea
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In TABLE XI the following curable composite
formulation was employed,
Composite Parts
Formulation By Weight
Nitrile Rubberl 100
Mineral Filler2 100
Silane Coupling Agent As Shown
Stearic Acid 1.5
Zinc Oxide 5
Sulfur 1,75
MBTS4 1 5
TMTD5 0.5
Hyca ~ 1052, (B. P. Goodrich Chem. Co.)
2Varied as shown
Varied as shown
Mercaptobenzothiazyldisulfide
5Tetramethylthiuramdisulfide ~-
~Dibutylphthalate.
~0 The amount of silane coupling agent when
used is expressed in TABLES IX, X and XI below is
expressed in terms of parts by weight per 100 parts
by weight of mineral filler employed in the composite.
In TABLE IX below, Silane A represents the use of a
vinyltriethoxysilane coupling agent; Silane B repre-
sents the use of a isoprenyltrimethoxysilane,
(l-tri~ethoxysilyl,3-methyl-butadiene-1,3) coupling
~..
9476 -1
106776~
agent; and Silane C represents the use of a metha-
cryloxypropyltrimethoxysilane coupling agent. In
TARLE X below Silàne D represents the use of a
3-aminopropyltrimethoxysilane coupling agent. In
TABLES X and XI, below Silane E represents the use
of a 3-mercaptopropyltri=ethoxysilane couplLng agent.
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EXAMPLE 13
2.84 pounds of sodium metasilicate nonahydrate
(Na2SiO39H20) were added to a thirty gallon kettle fitted
with a mechanical stirrer along with five gallons of water
and stirred until the sodium salt had dissolved. Then 10
gallons of a 50 weight percent aqueous slurry of wet
ground calcium carbonate (58 pounds CaC03, calcite mineral,
Atomite, 2.5 micron, Thomson-Weinman Co.) were added and
the mixture stirred for about ten minutes. Then 11.1
pounds of a 10 weight percent aqueous solution of anhydrous
calcium chloride (CaC12) were added in increments of 500
ml. every five minutes. After addition of all the CaC12
the mixture was stirred for two hours. The desired water-
insoluble calcium silicate treated calcium carbonate min-
eral product was then filtered from the reaction mixture
and dried.
EXAMPLE 14
A series of sulfur vulcanized rubber composites
were prepared using the following composite-formulation
wherein the particulate mineral filler employed was the
water-insoluble calcium silicate treated calcium carbonate
mineral product of Example 13 and wherein the amount of
silane employed was varied as shown in Table XII.
;: I
74.
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. . . .. . . . . .. .. .
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: . , . . , , . , . . , . ~ ,
1~67762 9476-l
Composite Amount
Formulation Grams
.
Natural Rubberl 100
Styrene Butadiene Rubber2 100
ineral Filler3 200
Silane Coupling Agent4 As shown
Stearic Acid 3
Zinc Oxide 12
Sulfur 4
NCBS5 2 2
DPG6 1 4
1 :.
No. 1 smoked sheet
SBR 1710
3-Mercaptopropyltrimethoxysilane
Water-insoluble calcium silicate treated calcium carbonate
mineral product of Example 13.
N-cyclohexyl-2-benzothiazolesulfenamide
Diphenylguanidine
The sulfur w lcanized rubber composites were all
prepared in the same manner following the procedure out-
`. lined in Example 4 and press cured at about 320F. The
physical properties of the sulfur vulcanized rubber com-
posites were measured and are recorded in Table XII below.
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Run numbers 2-4 show that the water-insoluble
calcium silicate treated calcium carbonate mineral filler
of this invention when employed along with the silane
coupling agent is indeed silane responsive as witnessed
by the significant improvement of the Tensile Modulus of
the cured composite.
EXAMPLE 15
This example demonstrates the production of an
organosilane modified water-insoluble calcium silicate
treated calcium carbonate mineral filler.
About 2724 grams of the water-insoluble calcium
silicate treated calcium carbonate product of Example 13
were thoroughly mixed with about 27.24 grams of gamma-
methacryloxypropyltrimethoxysilane in the presence of about
120 milliliters of an aqueous-alcohol diluent (90% methanol
and 10% water) in a twin shell blender at room temperature
for about 10-15 minutes. The desired silane modified
silicate treated mineral filler product so formed was then
recovered and dried for one hour at about 110C.
:.
'/ 20 EXAMPLE 16
A series of cross-linked polyethylene composites
. . .
were prepared using the following composite formulation
wherein the particular mineral filler and amount of
silane employed was varied.
. .
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.
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1067~6Z 9476-1
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Composite Parts by
Formulation Weight
Polyethylene Resin 100
Mineral ~iller 120
-~ Silane Coupling Agentl As Shown
Blue Pigmen~2 1.5
Antioxidant 1.1
Crosslinking Agent4 3.9
.,, 1
Gamma-methacryloxypropyltrimethoxysilane
B Blue Pigment F-627 ~(Ferro Corp.)
Age Rit ~ esin D-a polymerized 1,2-dihydro-2,2,4-trimethyl-
:l quinoline (R.T. Vanderbilt Co.)
Dicu ~40KE, Dicu~yl peroxide (Hercules Inc.)
The crosslinked polyethylene composites were all
,~ . prepared in the same manner as follows:
The polyethylene resin was charged to a 2-roll mill
l' (mill temperature-front roll 170F; back-rcll 180F. at 65
; pounds of pressure) and banded thereon and milled until
smooth and plastic. One-half of the mineral filler was
,l 20 added to the polymer band and where employed the silane
; coupling agent was added dropwise and concurrently with
:.. , . :
the mineral filler, and thoroughly mixed. Then the rest of
the filler was added and thoroughly mixed, followed by the
addition of other ingredients (antioxidant, peroxide and
pigment) which were also thoroughly mixed. The composite
formulation was then taken off of the rolls and molded by
crosslinking (curing) the composite formulation for 20
minutes in a compression mold at 320F. The median
physical properties of the crosslinked polyethylene com~
posites were measured and are recorded in Table XIII below.
78.
: .
' '
.. .. ... ,. . .. .. :, ,. . ~ ... .
106776Z 9476-1 ~
; In Table XIII below, Filler A of Run No. 1
represents the use of commercial wet ground untreated
: calcium carbonate (calcite mineral, Atomite, 2.5 microns,
- Thomson-Weinman Co.) and no silane coupling agent was
employed in the composite formulation of said Run No. 1.
Filler B of Run No. 2 represents the use of the water-
.~ insoluble calcium silicate treated calcium carbonate
mineral product of Example 13, but no silane coupling
agent was employed in the composite formulation of said
Run No. 2. Filler C of Run No. 3 represents the use of
the organosilane modified water-insoluble calcium
silicate treated calcium carbonate mineral composition
product of Example 15 and no further silane coupling
: agent was employed in the composite formulation
il of said Run No. 3. Filler D of Run No. 4 represents the
,: use of the water-insoluble calcium silicate treated
calcium carbonate mineral product of Example 13 and
the composite formulation of said Run No. 4 also contained .
1.2 parts by weight of gamma-methacryloxypropyltrimethoxysilane :-
(based on the 100 parts by weight of polyethylene employed). ~:
,,1 .
1 In Run Numbers 1 and 2 of Table XIII below the median
.~ tensile modulus was measured at 300% while for Run Numbers
~,~ 3 and 4 it was measured at 200 percent.
h '~ .
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Comparison Run Numbers 1 and 2 show that low
; Tensile Modulus results were obtained for the crosslinked
composites when either the untreated calcium carbonate
mineral filler or the calcium silicate treated calcium
carbonate mineral filler was employed without a silane
coupling agent. Run Numbers 3 and 4 which demonstrate
the instant invention show that highly improved Tensile
Modulus results were obtained for the cross-linked com-
posites, when the silane modified calcium silicate treated
calcium carbonate mineral filler was employed even without
any addi~ional silane coupling agent, and when the calcium
~ silicate treated calcium carbonate mineral filler was
l employed along with a silane coupling agent. Thus,
; Run Numbers 3 and 4 demonstrate that the calcium
, silicate treated calcium carbonate mineral flller
is responsive to the silane coupling agent both when
modified with the silane coupling agent prior to addition
;~ to the composi~e formulation or when employed separately
along with the silane coupling agent in the composite
formulation.
j~l EXAMPLE 17
This example demonstrates the production of an
I organosilane modified water-insoluble calcium silicate
treated calcium carbonate mineral filler.
About 5 pounds of the water-insoluble calcium
~¦ silicate treated calcium carbonate mineral product of Example 13
'I were thoroughly mixed with about 22.7 grams of vinyl-tris(2-
-~I methoxyethyoxy)silane in the presence of about-120 milliliters
; ' '
.:1
~ 81.
. .
- ~ .
67 7 6 2
9476-1
of an aqueous-alcohol diluent (90% methanol and 10% water)
in a twin shell blender at room temperature for about 10-
15 minutes. The desired silane modified silicate treated
mineral filler product so formed was then recovered and
- dried in an oven for two hours at about 225F. It was
found that the use of said silane modified water-insolubLe
calcium silicate treated calcium carbonate mineral filler
product improved the tensile modulus properties of a gulf~r
vulcanized elastomeric composite over that of the same ~i
composite when an untreated calcium carbonate mineral filler
was employed. Such demonstrates the responsiveness of the
silane coupling agent and the calcium silicate treated
calcium carbonate mineral filler in the production of said
silane modified silicate treated mineral filler.
E~AMPLE 18
' This example demonstrates the production of an
organosilane modified water-insoluble calcium silicate
treated calcium carbonate mineral filler.
About 5 pounds of the water-insoluble calcium
silicate treated calcium carbonate mineral product of Example
13 were thoroughly mixed with about 22.7 grams of gamma-meth-
acryloxypropyltrimethoxysilane in the presence of about 120 -
milliliters of an aqueous-alcohol diluent (90% methanol and
10% water) in a twin shell blender at room temperature for
` about 10-15 minutes. The desired silane modified silicate
` treated mineral filler product so formed was then recovered
and dried in an oven for two hours at about 225F. It was
found that the use of said silane modified water-insoluble
82.
' ~
,
` -
9476-1
1~)6776Z
calcium silicate treated calcium carbonate mineral filler
product improv~_d the tensile modulus properties of a sulfur
w lcanized elastomeric composite over that of the same com-
posite when an untreated calcium carbonate mineral filler
was employed. Such demonstrates the responsiveness of
the silane coupling agent and the calcium silicate treated
calcium carbonate mineral filler in the production of said
silane modified silicate treated mineral filler. -
EY~MPLE 19
This example demonstrates the production of an
organosilane modified water-insoluble calcium silicate
treated calcium carbonate mineral filler.
~ About 5 pounds of the water-insoluble calcium
: silicate treated calcium carbonate mineral product of Example
' 13 were thoroughly mixed with about 22.7 grams of gamma-
aminopropyltriethoxysilane in the presence of about 120
milliliters of an aqueous-alcohol diluent (90% methanol
¦ and 10% water) in a twin shell blender at room temperature
for about 10-15 minutes. The desired silane modified
silicate treated mineral filler product so formed was then
recovered and dried in an oven for two hours at about 225F.
It was found that the use of said silane modified calcium
silicate treated calcium carbonate mineral filler product
improved the tensile modulus properties of a thermoplastic
polyvinyl chloride composite over that of the same composite
when an untreated calcium carbonate mineral filler was
employed. Such demonstrates the responsiveness of the silane
coupling agent and the calcium silicate treated calcium
carbonate mineral filler in the production of said
silane modified silicate treated mineral filler.
:i
~, 83.
. . .
.i.,~ .~. ~ , , ,
-
1~:)6776Z 9476 - 1
Various modific~tions and variations of
this invention will be obvious to a worker skilled
in the art and it is to be understood that such ~;~
modifications and variations are to be included
within the purview of this application and the spirit :~
and scope of the appended claims.
,. ` ' ' ~ .
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