Process for the production of an aqueous dispersion of poly(organic-poly-sulfide-silicate) copolymer

An alkali metal hydroxide, sulfur, and an oxidated silicon compound are mixed, then heated to just above the melting point of sulfur while agitating for 10 to 30 minutes, thereby producing an alkali metal polysulfide silicate; then it is added to an aqueous solution containing an emulsifying or dispersing agent and is reacted with a polysubstituted organic compound, thereby producing a poly(organic-polysulfide-silicate) copolymer.

BACKGROUND OF THE INVENTION 
This invention relates to a process for the production of 
poly(organic-polysulfide-silicate) copolymers by reacting alkali metal 
hydroxide, sulfur and an oxidated silicon compound to produce an alkali 
metal-polysulfide-silicate condensation product which is then reacted with 
an organic compound to produce a poly(organic polysulfide silicate) 
copolymer. 
In my U.S. patent application, Ser. No. 921,728, filed by David H. Blount, 
M.D., on July 3, 1978, alkyl dihalides are used as the organic reactant to 
produce a polymer, but not an aqueous dispersion of the copolymer. 
The poly(organic-polysulfide-silicate) copolymer of this invention is 
produced in the form of an aqueous dispersion with particle sizes of about 
a micron to larger-size crumbs or pellets. The size of the particles may 
be varied by using various emulsifying or dispersing agents and by varying 
the concentration of the reactants. The aqueous dispersion of the 
poly(organic-polysulfide-silicate) copolymer is an improvement in the 
formation of the thioplast silicate elastomer as illustrated in U.S. 
patent application, Ser. No. 921,728, filed on July 3, 1978, by David H. 
Blount, M.D. 
Furthermore, by operating in accordance with the present invention, I am 
also able to secure the poly(organic-polysulfide-silicate) copolymers 
referred to above in the form of an aqueous emulsion or latex, which can 
be readily purified, and from which poly(organic-polysulfide-silicate) 
copolymers may be coagulated, either before or after the incorporation 
into the latex of desired compounding ingredients. In addition, by 
securing the plastic material in a dispersed state as a latex, it may be 
used as a coating agent for wood, fabrics, textiles, fibers, paper, 
leather, metal, concrete and others, and may subsequently cause the 
plastic material to coagulate in situ. 
Aqueous dispersions of poly(polysulfide-silicate) copolymers are obtained 
from reacting the following components: 
(a) sulfur; 
(b) an alkali metal hydroxide; 
(c) an oxidated silicon compound; 
(d) an organic compound having at least two carbon atoms, each of which is 
attached to a substituent which will split off during the reaction; 
(e) an emulsifying or dispersion agent; 
(f) water. 
Component (a) 
Sulfur in any of its commonly known forms may be used in this invention. 
The sulfur may also be reacted with an alkali metal compound to produce 
alkali metal sulfides and alkali metal polysulfide, or sulfur may be 
reacted with alkaline earth metal compounds to produce alkaline earth 
metal sulfides and alkaline earth metal polysulfides, and mixtures thereof 
may be used in this process. It is preferred to use sulfur. The alkali 
metal sulfides and alkaline earth metal sulfides may be used with sulfur. 
Ammonium polysulfides and polysulfides of ethanolamines may also be used. 
Component (b) 
Any suitable alkali metal hydroxide may be used in this invention. Alkali 
metal oxides may also be used in this invention. Suitable alkali metal 
hydroxides include sodium hydroxide, potassium hydroxide, lithium 
hydroxide, and mixtures thereof. Sodium hydroxide is the preferred alkali 
metal hydroxide. 
Component (c) 
Any suitable oxidated silicon compound may be used in this invention such 
as silica, e.g., hydrated silica, silicon dioxide, silicoformic acid, 
polysilicoformic acid, silicic acid gel and silica sol, alkali metal 
silicates, alkaline earth metal silicates and natural silicates with free 
silicic acid radicals and mixtures thereof. Silica is the preferred 
oxidated silicon compound. 
Component (d) 
Any suitable organic compound that will react with the 
alkali-polysulfide-silicate may be used. An organic compound is 
preferable, having at least two carbon atoms, of which one is attached to 
a substituent, which are split off during the reaction. These organic 
compounds which are the reactants used in the preparation of poly(organic 
polysulfide silicate) copolymers have the graphical skeleton carbon 
structure of 
##STR1## 
represents two adjacent carbon atoms, or 
##STR2## 
where X and X' represent the substituents which split off during the 
reaction. The R between the pair of reactive carbon atoms is selected from 
the following groups: saturated straight chain carbon atoms, unsaturated 
carbon atoms, ether linkages, aromatic structures, and others, for it is 
to be understood that other intervening structures may be employed. The X 
and X' substituents can be halogen, acid sulfate, nitrate, acid phosphate, 
bicarbonate, formate, acetate, propionate, laurate, oleate, stearate, 
oxalate, acid malonate, acid tartrate, acid citrate and others. Examples 
of these organic compounds include, but are not limited to: 
__________________________________________________________________________ 
CH.sub.3 CHXOCHX'CH.sub.3 
AA' disubstituted ethyl ether; 
XC.sub.2 H.sub.4 OC.sub.2 H.sub.4 X' 
BB' disubstituted ethyl ether; 
XCH.sub.2 OCH.sub.2 X' Disubstituted methyl ether; 
XC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 X' 
Disubstituted ethoxy ethyl ether; 
XCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 X' 
Disubstituted thio ethyl ether; 
##STR3## Disubstituted 1,3 methoxy 2,2,di- methyl 
propane; 
XCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 
Disubstituted dipropyl formal; 
##STR4## Disubstituted para-diethoxy benzene; 
##STR5## Disubstituted dimethoxy ethane; 
##STR6## Disubstituted diethyl carbonate; 
##STR7## Disubstituted glycol diacetate; 
##STR8## pp' Disubstituted dibenzyl ether; 
##STR9## pp' Disubstituted diphenyl ether; 
XCH.sub.2 CH.sub.2 SO.sub.2 CH:CH.sub.2 X' 
Disubstituted diethyl sulphone; 
##STR10## AA' Disubstituted propyl ether; 
##STR11## Para Disubstituted benzene; 
##STR12## Disubstituted para xylene; 
##STR13## pp' Diwubtituted dibenzyl; 
##STR14## Disubstituted para hexyl propyl benzene; 
##STR15## Disubstituted 3 toyl propene 2; 
__________________________________________________________________________ 
and others such as methylene chloride or bromide, ethylene dichloride, 
ethylene dibromide, propylene dichloride or dibromide, halohydrins, 
epihalohydrins, dihalides of unsaturated hydrocarbon gases derived from 
pressure-cracking processes, natural gas-cracking processes as well as 
compounds having more than two substituents such as 1,1,2 trichloroethane; 
1,2,4 trichlorobutane; 1,2,3,4 tetrachlorobutane; trichloromesitylene and 
the like. Mixtures of these compounds may be used in this process. 
Component (e) 
Emulsifying or dispersing agents may be used in this invention to produce 
aqueous emulsions of the poly(organic polysulfide silicate) polymer. Any 
salt-stable compound which is highly hydrophobous in nature and has a 
hydrophobic group as one component and a hydrophilic group as the other 
may be used. The emulsifying or dispersing agent which may be used for the 
formation of lattices of small-particle size are those compounds having 
such groups as SO.sub.3, SO.sub.4, NH.sub.2, etc., as the hydrophilic 
component and a higher molecular weight alkyl, aralkyl, aryl or alkyl 
group as the hydrophobic component. The more hydrophobic the entire 
compound becomes, the smaller the polymer particle size becomes in the 
latex. 
Compounds which are most suitable as emulsifying or dispersing agents for 
latex formation are the lignin sulfonates such as calcium and sodium 
lignin sulfonates, alkyl benzene sulfonates having more than 20 carbon 
atoms in the alkyl group, aryl alkyl sulfonates, sorbitan monolaurates, 
especially those which are oil soluble and slightly water soluble, and 
others. The dominance of the hydrophobic group over the hydrophilic groups 
is one of the important factors in producing a latex of small-particle 
size. The molecular weight of the hydrophobic group alone is not the 
deciding factor, for aryl groups, for example, may be more hydrophobic 
than an alkyl group of like molecular weight. Aryl alkyl groups are more 
hydrophobic than alkyl aryl groups of the same molecular weight. Thus by 
selection of emulsifying or dispersing agents, the particle size of the 
latex can be varied to suit any particular needs. Emulsifiers which can be 
used are sorbitan monolaurates, alkyl aryl sulfonates, alkyl aryl 
sulfates, aryl alkyl sulfonates, aryl alkyl sulfates, lignin sulfonates, 
methyl cellulose, sulfonated petroleum fractions, polymerized alkyl aryl 
sulfonates, polymerized aryl alkyl sulfonates, soybean lecithin, and the 
like. The particle size can be controlled by selecting emulsifying or 
dispersing agents having different molecular-weight hydrophobic groups as 
well as different hydrophobic groups. The particle size will also vary 
with the concentration of the emulsifying or dispersing agents. 
In certain cases, other dispersing agents such as magnesium hydroxide or 
aqueous dispersions of peptized starch, gelatin, glue, blood-albumen, egg 
albumen, or the like, may be used. 
The preferred process to produce poly(organic-polysulfide-silicate) 
copolymers in the form of an aqueous dispersion is to mix 1 to 4 parts by 
weight of Component (a) (sulfur), about 2 parts by weight of Component 
(b) (alkali metal hydroxide) and 1 to 2 parts by weight of Component (c) 
(oxidated silicon compound), then to heat the mixture to just above the 
melting temperature of sulfur while agitating at ambient pressure for 10 
to 30 minutes, thereby producing an alkali metal-sulfur-silicate 
condensation product which is then added to water to produce an aqueous 
solution containing 10% to 70% alkali metal-sulfur-silicate condensation 
product. The solution is then filtered to remove any reactants that are 
not water soluble. A disubstituted and/or polysubstituted organic 
compound, capable of splitting off the substituted radical to react with 
the alkali metal radical, and of reacting the organic radical with the 
sulfur-silicate radical, in the amount wherein the mols of the substituted 
radicals are about equivalent to the mols of the alkali metal radicals, 
and 1% to 5% by weight, based on weight of the water, of an emylsifying or 
dispersing agent are added to the aqueous solution of the alkali 
metal-sulfur-silicate condensation product, then vigorously agitated or 
passed through a homogenizer. The mixture is agitated at ambient 
temperature at a temperature just below the boiling temperature of the 
reactants for 30 minutes to 8 hours, thereby producing an aqueous 
dispersion of poly(organic-polysulfide-silicate) copolymer. 
The proportion of the disubstituted organic compound to alkali 
metal-sulfur-silicate condensation product is not critical; either may be 
in excess, but since the alkali metal-sulfur-silicate condensation product 
is the least expensive, it is preferred that an excess of it be used. The 
chemical reaction between the disubstituted organic compound and the 
metal-sulfur-silicate condensation product is usually not exothermic and 
usually there is very little change in the temperature of the solution. 
The chemical reaction will take place at any suitable temperature and 
pressure, but the chemical reaction is speeded up when the solution is 
heated to just below the boiling temperature of the reactants. 
The components may be mixed in any satisfactory manner, or various 
components may be reacted first, then reacted with the rest of the 
components. Components (a) and (b) may be pre-reacted to produce alkali 
metal polysulfides, then be reacted with Component (c) to produce the 
alkali metal-sulfur-silicate condensation product. Components (a) and (c) 
may be pre-reacted, then reacted with Component (b) to produce alkali 
metal-sulfur-silicate condensation products. Components (b) and (c) may be 
pre-reacted to produce an alkali metal silicate, then reacted with sulfur 
to produce alkali metal-sulfur-silicate condensation products. 
Various water-soluble sulfides and polysulfides may be added with the 
alkali metal-sulfur-silicate condensation product, such as alkali metal 
sulfides, alkaline earth metal sulfides, ammonium sulfides, alkali metal 
polysulfides, alkaline earth metal polysulfides, polysulfides of 
ethanolamines and mixtures thereof in the amount of up to 2 parts by 
weight to 4 to 8 parts by weight of the alkali metal-sulfur-silicate 
condensation product. 
Alkali metal silicate produced by any of the methods known in the arts may 
be used in place of the alkali metal hydroxide and oxidated silicon 
compound. It is used in the amount of 1 to 2 parts by weight with 1 to 4 
parts by weight of sulfur. The alkali metal silicate may also be used as 
the oxidated silicon compound and reacted with the sulfur and alkali metal 
hydroxide to produce alkali metal-sulfur condensation products. About 1 to 
2 parts by weight of granular alkali metal silicate are mixed with 1 to 4 
parts by weight of sulfur, then heated to above the melting point of the 
sulfur while agitating at ambient pressure for 10 to 30 minutes, thereby 
producing a yellow, granular alkali metal silicate-sulfur condensation 
product. Then about 2 parts by weight of the alkali metal hydroxide are 
added to the alkali metal silicate-sulfur condensation product while 
heating to just above the melting point of sulfur while agitating for 10 
to 30 minutes, thereby producing alkali metal-sulfur-silicate condensation 
products. 
The fine granular oxidated silicon compound may be first reacted with 
sulfur by mixing 1 to 4 parts by weight of the sulfur with 1 to 2 parts by 
weight of the oxidated silicon compound. Then the mixture is heated to 
just above the melting temperature of sulfur while agitating for 10 to 30 
minutes, thereby producing a sulfur-silicate condensation product. Then 
about 2 parts by weight of an alkali metal hydroxide, preferably sodium 
hydroxide, are added, and the mixture is heated to just above the melting 
temperature of sulfur while agitating for 10 to 30 minutes, thereby 
producing an alkali metal-sulfur-silicate condensation product. It may be 
necessary to add 1 to 2 parts by weight of the alkali metal hydroxide if 
all the alkali metal hydroxide-sulfur-silicate condensation product does 
not go into solution, then to reheat the solution at 80.degree. C. to 
100.degree. C. for 10 to 30 minutes. 
The particles in the aqueous dispersion of the 
poly(organic-polysulfide-silicate) copolymer may vary in size from about a 
micron in diameter to pellet size. The dispersions are heavy particles and 
settle. The particles may be washed with water to remove the salt and the 
unreacted components by filtering or by decantation. The aqueous 
dispersion may be coagulated on flocculation with aluminum sulfate, 
calcium nitrate, mineral acid, organic acids, inorganic hydrogen 
containing salts and the like. The washed particles may be dried, then 
fused into sheets by raising the temperature to the softening temperature 
of the polymer. This washed and dried polymer may be cured with zinc oxide 
to produce an elastomer when heated to 70.degree. C. to 90.degree. C. To 
vulcanize the elastomer, the washed and dried polymer (100 parts by 
weight), 30 to 60 parts by weight of carbon black, 0.5 part by weight of 
stearic acid, 10 parts by weight of zinc oxide, 0.3 part by weight of 
benzothiozyl disulfide and diphenyl guanidine are thoroughly mixed, then 
heated in a mold until the mixture softens (70.degree. C. to 90.degree. 
C.); then pressure is applied to the elastomer until it cools. 
The coagulated poly(organic-polysulfide-silicate) copolymer forms a 
gray-to-white-colored elastic, spongy mass. It has the characteristics of 
a soft plastic and is pliable. Its characteristics may be improved by 
incorporating into it metallic oxides such as litharge, zinc oxide, 
magnesium oxide or other compounds of the class of sulphur carriers well 
known in the rubber industry. 
Various inert materials such as those of the type used in compounding 
rubber, for example, fibers, wood flour, carbon black, glue, asbestos and 
the like, may be compounded with the latex, either with or without the 
sulphur carrier. These various materials may be incorporated in the 
coagulated latex also. About 1 to 10% by weight of the metallic oxide is 
used. 
The coagulated latex and the vulcanized poly(organic-polysulfide-silicate) 
polymers are stable in organic solvents, resist the action of oils, salt 
water and the like, and do not flow under pressure. The aqueous dispersion 
of poly(organic-polysulfide-silicate) copolymer is stable and may be 
preserved and stored as such. 
The aqueous dispersion of poly(organic-sulfur-silicate) polymer may be used 
to coat or impregnate absorbent materials such as fabrics, textiles, 
fibers, paper, leather and the like, as well as non-absorbent materials 
such as synthetic filaments and fibers, wood, metal, concrete, and others 
and subsequently cause the coagulation in situ of the desired 
poly(organic-polysulifide-silicate) copolymer. 
The coagulated poly(organic-polysulfide-silicate) copolymers formed may be 
vulcanized and used to produce rubber hoses, sheets, rubber rollers, 
tanks, diaphragms, gaskets and wire covering. The aqueous dispersion and 
coagulated polymer may be used for caulking, putties, adhesives, binders, 
coatings for wood and metal, in epoxy resins, as molding material, in 
urethane resins and foams, and may be reacted with acid compounds to 
produce thiol groups in the polymer. The thiol groups will react 
chemically with polyisocyanates to produce useful foams and elastomers. 
The coagulated poly(organic-polysulfide-silicate) copolymer which has been 
washed and dried may be mixed with 1% to 10% by weight of a metal oxide 
such as zinc oxide powder. Optionally, fillers may be added and thoroughly 
mixed. The mixture may be placed in a mold of a useful object such as a 
gasket, then heated to 70.degree. C. to 90.degree. C. wherein the mixture 
becomes soft; then pressure is applied. The mold is then cooled, thereby 
producing a useful, tough, strong gasket. 
The primary object of the present invention is to produce an aqueous 
dispersion of poly(organic-polysulfide-silicate) copolymers. Another 
object is to produce an aqueous dispersion of 
poly(organic-polysulfide-silicate) copolymers that can be used as coating 
agents and be coagulated in situ. Still another object is to produce an 
aqueous dispersion of poly(organic-polysulfide-silicate) copolymers that 
may be coagulated and used as caulking compounds, as molding powder, and 
may be vulcanized to produce useful products such as hoses, tubes, sheets, 
etc.

DESCRIPTION OF PREFERRED EMBODIMENTS 
My invention will be illustrated in greater detail by the specific Examples 
which follow, it being understood that these preferred embodiments are 
illustrative of, but not limited to, procedures which may be used in the 
production of aqueous dispersions of poly(organic-polysulfide-silicate) 
polymers. Parts and percentages are by weight unless otherwise indicated. 
EXAMPLE 1 
About 5 parts by weight of sulfur, 2 parts by weight of fine granular 
hydrated silica and 5 parts by weight of sodium hydroxide flakes are 
mixed, then heated to above the boiling temperature of sulfur for 10 to 30 
minutes, thereby producing a sodium hydroxide-sulfur-silicate condensation 
product. 
EXAMPLE 2 
About 2 parts by weight of fine granular hydrated silica and 3 parts by 
weight of sulfur are mixed, then heated to just above the melting 
temperature of sulfur while agitating for 10 to 30 minutes, thereby 
producing sulfur-silicate condensation product; then 3 parts by weight of 
sodium hydroxide flakes are added while agitating and heating the mixture 
to just above the melting temperature of sulfur for 10 to 30 minutes, 
thereby producing an alkali metal-sulfur-silicate condensation product. 
EXAMPLE 3 
About 2 parts by weight of sulfur, 1 part by weight of fine granular 
hydrated silica and 2 parts by weight of potassium hydroxide pellets are 
mixed, then heated to above the boiling temperature of sulfur while 
agitating for 10 to 30 minutes, thereby producing a 
potassium-sulfur-silicate condensation product. 
EXAMPLE 4 
About 2 parts by weight of sulfur, 1 part by weight of fine granular silica 
and 2 parts by weight of sodium hydroxide flakes are mixed, then heated to 
just above the melting point of the sulfur, while agitating for about 30 
minutes, thereby producing a sodium-sulfur-silicate condensation product. 
EXAMPLE 5 
About 1 part by weight of fine granular hydrated silica, and 2 parts by 
weight of sulfur are mixed, then heated to just above the melting 
temperature of sulfur while agitating for 10 to 30 minutes, thereby 
producing a sulfur-silicate condensation product; the product is then 
added to 15 parts by weight of water containing 2 parts by weight of 
sodium hydroxide and 0.5 part by weight of sodium sulfide. The mixture is 
heated to just below the boiling temperature of the mixture while 
agitating at ambient pressure for 1 to 4 hours, thereby producing an 
aqueous solution of sodium hydroxide-sulfur-silicate condensation product. 
EXAMPLE 6 
About 3 parts by weight of sulfur and 2 parts by weight of granular sodium 
silicate are mixed, then heated to just above the melting temperature of 
sulfur while agitating at ambient pressure for 10 to 30 minutes, thereby 
producing an alkali metal-sulfur-silicate condensation product. 
EXAMPLE 7 
Example 6 is modified wherein 2 parts by weight of sulfur are used. 
EXAMPLE 8 
About 4 parts by weight of sulfur, 1 part by weight of sodium sulfide and 3 
parts by weight of granular potassium silicate are mixed, then heated to 
just above the melting temperature of sulfur while agitating for 10 to 30 
minutes, thereby producing an alkali metal-sulfur-silicate condensation 
product. 
EXAMPLE 9 
About 3 parts by weight of sulfur, 2 parts by weight of potassium sulfide 
and 2 parts by weight of fine granular calcium silicate are mixed, then 
heated to just above the melting temperature of sulfur while agitating at 
ambient pressure for 10 to 30 minutes, thereby producing an 
alkali-sulfur-silicate condensation product. 
EXAMPLE 10 
About 3 parts by weight of sulfur, 1 part by weight of silica, 1 part by 
weight of calcium silicate and 2 parts by weight of sodium hydroxide are 
mixed, then heated to just above the boiling temperature of the sulfur 
while agitating for 10 to 30 minutes, thereby producing an alkali-sulfur 
condensation product. 
EXAMPLE 11 
About 2 parts by weight of sodium hydroxide, 1 part by weight of hydrated 
silica containing Si-H groups (silicoformic acid) and 2 parts by weight of 
sulfur are mixed, then heated to just above the melting temperature of 
sulfur while agitating for 10 to 30 minutes, thereby producing alkali 
metal-sulfur-silicate condensation product. 
EXAMPLE 12 
About 4 parts by weight of sulfur and 3 parts by weight of sodium hydroxide 
flakes are mixed, then heated to just above the melting point of sulfur 
while agitating for 10 to 30 minutes, thereby producing a sodium 
polysulfide. It is then mixed with 1 part by weight of fine granular 
silica, then heated to just above the melting point of the sodium 
polysulfide while agitating for 10 to 30 minutes, thereby producing a 
sodium hydroxide-sulfur-silicate condensation product. 
EXAMPLE 13 
About 6 parts by weight of the alkali metal-sulfur-silicate condensation 
products, as produced in Example 1, are added to 20 parts by weight of 
water containing 2% sodium lignin sulfonate to form an aqueous solution. 
The solution is then filtered to remove any unreacted sulfur or silica. 
Very little is not water-soluble. To the solution is slowly added 
methylene chloride, in the amount containing mols of chloride nearly 
equivalent to the mols of sodium atoms present in the solution, while 
agitating vigorously at a temperature between ambient and a temperature 
just below the boiling temperature of the methylene chloride for 30 
minutes to 8 hours, thereby producing an aqueous dispersion of 
poly(methylene-polysulfide-silicate) elastomer. 
The finely divided particles are dense and slowly settle when the agitation 
is discontinued. The latex-like dispersion is washed with water to remove 
the salt and any unreacted reactants, then the water is filtered off. 
Optionally, fillers, vulcanizing agents, coloring agents, etc., are added. 
The dispersion is then coagulated by adding a dilute aqueous solution of 
aluminum sulfate until coagulation takes place, then is washed with water 
and filtered to remove the salt and unreacted components. 
EXAMPLE 14 
About 5 parts by weight of the alkali metal-sulfur-silicate condensation 
product, as produced in Example 2, are added to 20 parts by weight of 
water containing 4% by weight of calcium lignin sulfonate to form an 
aqueous solution; then ethylene dichloride is slowly added to the 
solution, while vigorously agitating the mixture, in the amount containing 
mols of chloride nearly equivalent to the mols of sodium atoms present in 
the solution. The solution is then heated to just below the boiling 
temperature of ethylene dichloride while vigorously agitating for about 30 
minutes. The reaction is complete in 30 minutes to 8 hours, thereby 
producing an aqueous dispersion of poly(ethylene-polysulfide-silicate) 
elastomer. 
The aqueous dispersion of the copolymer slowly settles and the water, salt 
and unreacted components are removed; then the aqueous dispersion is 
washed several times and decanted to remove any remaining salt. The 
copolymer is then dried, mixed with 1% to 10% of zinc oxide, and fillers 
may be optionally added, then heated to 70.degree. C. to 90.degree. C. 
under pressure and fused into a cured sheet. The washed aqueous dispersion 
may be coagulated with acid compounds, then washed to remove the salt. The 
washed and dried coagulated copolymer may be mixed with curing agents such 
as metal oxide, vulcanizing catalyst, and optionally with fillers, 
reinforcing agents, etc., then heated in a mold to 70.degree. C. to 
90.degree. C. When the copolymer softens, pressure is applied to the 
copolymer to fill in the mold, and it is cooled in the mold, thereby 
producing a useful product. 
EXAMPLE 15 
About 1 part by weight of the alkali metal-sulfur-silicate condensation 
product, as produced in Example 3, is added to 3 parts by weight of water 
containing 3% sodium dodecylbenzene sulphonate to form an aqueous 
solution; then propylene dichloride is added to the solution until the 
mols of the chloride and potassium atoms are about equal. The mixture is 
vigorously agitated, then heated to a temperature just below the boiling 
temperature of propylene dichloride. The mixture is agitated for about 30 
to 60 minutes, thereby producing an aqueous dispersion of 
poly(propylene-polysulfide-silicate) copolymer. 
EXAMPLE 16 
About 4 parts by weight of the alkali metal-sulfur-silicate condensation 
product, as produced in Example 4, are added to 12 parts by weight of 
water containing 5% sodium dinaphthyl methane disulphonate; then ethylene 
dichloride containing 5% 1,2,3-trichloropropane is added in the amount 
wherein the chlorine atoms are about equal to the sodium atoms. The 
mixture is vigorously agitated until it is thoroughly mixed. The mixture 
is then heated to a temperature just below the boiling temperature of 
ethylene dihalide while agitating at ambient pressure for about 30 minutes 
to 1 hour, and the reaction is complete in 30 minutes to 8 hours, thereby 
producing an aqueous dispersion of poly(organic-polysulfide-silicate) 
copolymer. 
EXAMPLE 17 
About 3 parts by weight of the alkali metal-sulfur-silicate condensation 
product, as produced in Example 6, and 1 part by weight of Na.sub.2 
S.sub.x (x=4 to 5) are added to water containing 2% sodium salts of 
ricinoleic sulphonates, thereby producing an aqueous solution. About equal 
parts by weight of ethylene dichloride and bis(2-chloroethyl) ether, in 
the amount wherein the chlorine atoms are about equal to the sodium atoms 
in the mixture, are slowly added to the aqueous solution while vigorously 
agitating and keeping the temperature just below the boiling temperature 
of the reactants for 30 minutes to 8 hours, thereby producing an aqueous 
dispersion of poly(organic-polysulfide-silicate) copolymer. 
EXAMPLE 18 
To an aqueous solution containing 25% alkali metal-sulfur-silicate 
condensation product, as produced in Example 7 and containing 2% sodium 
lignin sulfonate, is slowly added propane, 1,3-dihydrogen phosphate in the 
amount to give about equivalent mols of the alkali metal and the 
dihydrogen phosphate radical while vigorously agitating. The mixture is 
then heated to just below the boiling temperature of the reactants while 
agitating for about 30 to 60 minutes. The reaction is complete in 30 
minutes to 8 hours, thereby producing an aqueous dispersion of 
poly(organic-polysulfide-silicate) copolymer. 
EXAMPLE 19 
1,2-nitropropane, in the amount to obtain about equivalent mols of the 
nitro and alkali metal radicals, is slowly added to an aqueous solution 
containing 30% alkali metal-sulfur-silicate condensation product, as 
produced in Example 8, and 3% sodium lignin sulphonate while agitating 
vigorously. The mixture is then heated to just below the boiling 
temperature of the reactants while agitating for 30 to 60 minutes. The 
reaction is complete in 30 minutes to 8 hours, thereby producing an 
aqueous dispersion of poly(organic-polysulfide-silicate) copolymer. 
EXAMPLE 20 
An amount of para-Dinitrobenzene, wherein the nitro and alkali metal 
radicals are about equal, is slowly added to an aqueous solution 
containing 25% alkali-sulfur-silicate condensation product, as produced in 
Example 8, and 2% sodium lignin sulphonate while vigorously agitating. The 
mixture is then heated to just below the boiling temperature of the 
reactants for 30 to 60 minutes while agitating. The reaction is complete 
in 30 minutes to 8 hours, thereby producing an aqueous dispersion of 
poly(organic-polysulfide-silicate) copolymer. 
Other disubstituted organic compounds may be used in place of 
para-Dinitrobenzene such as para dichlorobenzene; 2,4-dinitrotoluene; 
tolylene diisocyanate; chloroform; 1,3-dichloro-2-propanol; bis(2 
chloroethyl) formal; 1,3-dibromopropane; butane-1,4-di(hydrogen sulfate); 
dichloroethyl ether; methylene chloride; 1,4-dibromo-2-butene; 
1,3-chloromethoxy 2,2,di-methyl propane; dichloroethyl carbonate; 2,4 
dinitrobenzene sulfonic acid and pp'-dichlorobenzyl. 
EXAMPLE 21 
An aqueous solution containing 25% sodium hydroxide-sulfur-silicate 
condensation product, as produced in Example 6, 3% sodium lignin 
sulphonate, and ethylene dichloride, in an amount which contains 
equivalent mols of the chlorine atoms to the mols of sodium atoms in the 
aqueous solution, are mixed, then run through an homogenizer, then heated 
to just below the boiling temperature of the reactants while agitating for 
30 to 60 minutes at ambient pressure. The chemical reaction is complete in 
30 minutes to 8 hours, thereby producing an aqueous dispersion of 
poly(organic-polysulfide-silicate) copolymer. The dispersed particles 
settle and the copolymer is washed several times with water by decantation 
to remove the salt and unreacted reactants. 
Any of the previously listed emulsifiers and types of emulsifiers can be 
substituted in the above Example. 
Any of the other previously described disubstituted organic compounds may 
be used in place of the ethylene dichloride in this Example, such as 
ethylene dibromide, propylene dichloride or dibromide, dihalides of 
unsaturated hydrocarbon gases derived from pressure-cracking processes, 
natural gas-cracking processes, polyhalide alkanes such as 
1,1,2-trichloroethane; 1,2,4-trichlorobutane; trichloromesitylene; 
compounds containing disubstituted halogens; acid sulfates, nitrates, acid 
phosphates, bicarbonates, formates, acetates, propionates, laurate, 
oleate, stearate, oxalate, acid malonate, acid tartrate, acid citrate and 
mixtures thereof such as: AA' disubstituted ethyl ether, BB' disubstituted 
ethyl ether, disubstituted methyl ether, disubstituted ethoxy ethyl ether, 
disubstituted thio ethyl ether, disubstituted 1,3-methoxy 2,2-dimethyl 
propane, disubstituted dipropyl formal, disubstituted para-diethoxy 
benzene, disubstituted dimethoxy ethane, disubstituted diethyl carbonate, 
disubstituted glycol diacetate, pp' disubstituted dibenzyl ether, pp' 
disubstituted diphenyl ether, disubstituted diethyl sulphone, AA' 
disubstituted propyl ether, para-disubstituted benzene, disubstituted 
paraxylene, p,p'-disubstituted dibenzyl, disubstituted para hexyl propyl 
benzene, disubstituted 3-toyl propene-2, and mixtures thereof. 
Although specific materials and conditions were set forth in the above 
Examples, these were merely illustrative of preferred embodiments of my 
invention. Various other compositions, such as the typical materials 
listed above may be used, where suitable. The reactive mixtures and 
products of my invention may have other agents added thereto to enhance or 
otherwise modify the reaction and products. 
Other modifications of my invention will occur to those skilled in the art 
upon reading my disclosure. These are intended to be included as defined 
in the appended claims.