Sulfur cement-aggregate-organosilane compositions and methods for preparing

Sulfur cement-aggregate compositions comprising a sulfur cement and an aggregate containing an expansive clay and processes for preparing such compositions. The processes, and resulting compositions, are characterized by the addition of certain organosilanes in the composition prior to solidifying (cooling) the composition. The resulting solidified composition has improved water stability. The compositions can be used as mortars or concretes depending on the particle size of the principal aggregate component.

BACKGROUND OF THE INVENTION 
1. The Invention 
This invention relates to sulfur cement-aggregate compositions. In a 
further aspect, the invention relates to sulfur mortars and concretes 
containing an aggregate which is contaminated with a water-expandable 
clay. 
2. The Prior Art 
Sulfur mortars and concretes generally refer to a mixture of sulfur and 
aggregate wherein the sulfur functions as the cement or binder. Generally, 
whether a composition is classed as a mortar or concrete is based on the 
particle size of the predominate aggregate. Thus, compositions containing 
larger sized aggregates are generally referred to as concretes whereas 
compositions containing smaller sized aggregate are referred to as 
mortars. In either case, the compositions can also contain very fine 
particle size aggregates, such as fly ash, etc., as fillers. Sulfur 
mortars and concretes are prepared by heating sulfur with an aggregate at 
a sufficient temperature to render the sulfur molten and then allowing the 
mixture to cool to solidify the sulfur. Not infrequently, the sulfur also 
contains a plasticizer which desirably increases the cold plasticity 
crystallization time of the sulfur, probably by reacting with at least a 
portion of the sulfur. Such sulfur is referred to as plasticized sulfur. 
Sulfur mortars and concretes can be broadly classified as sulfur cement 
products. Sulfur cement is similar to Portland cement in forming concretes 
or mortars. In the latter case, a mixture of Portland cement and aggregate 
is solidified into a final solid product by treatment with water. In the 
case of sulfur products, heat is required to render the sulfur cement 
molten, which, upon cooling, solidifies, binding the aggregate. 
Sulfur cement concretes can be used for many of the same purposes as 
conventionally formed concretes. For example, sulfur concretes can be used 
for structural members, roads, slabs, curbings, gutters, and can be 
precast or cast at the job site. Sulfur cement concrete affords a 
significant advantage over Portland cement concrete, especially in the 
case of preformed articles, in that the sulfur cement concrete can be 
remelted and recast. Thus, when defective or surplus articles are 
prepared, the sulfur aggregate composition can be reused by merely melting 
down the article and recasting the composition. Sulfur cement mortars can 
be used for similar purposes as Portland cement mortars, such as, for 
example, bonding structural members together. Sulfur cement mortars and 
concretes also generally have good corrosion resistance to acids and other 
chemicals. 
Sulfur cement mortars and concretes are wellknown to the art and various 
modifications are, for example, described in the patent literature, for 
example, U.S. Pat. Nos. 2,135,747, 3,954,480, 4,025,352, 4,058,500, and 
4,118,230. 
U.S. Pat. No. 4,164,428 discloses that a plasticized sulfur coating 
composition comprising at least 50 wt % sulfur, optionally containing 
aggregate, is strengthened and stabilized by the incorporation therein of 
a finely divided particulate mineral suspending agent and an organosilane 
stabilizing agent. U.S. Pat. Nos. 4,036,661 and 4,038,096 disclose the use 
of certain silanes in bituminous or asphalt surfacing composition to 
promote adhesion of the bitumen or asphalt to aggregate. U.S. Pat. No. 
4,154,619 discloses asphalt-sulfur emulsions containing up to 50% sulfur 
having improved emulsion stability through the incorporation of an 
organosiloxane polymer. 
One of the disadvantages of sulfur cement mortars and concretes is that the 
presence of even small amounts of water-expandable clay (for example, 1% 
by weight or more) in the aggregate causes the solidified sulfur cement 
mortars and concretes to disintegrate when exposed to water. This problem 
is particularly serious since, because of transportation costs, economic 
necessity usually requires the use of aggregate sources close to the 
casting or job site, regardless of the presence of expansive clay. The 
expansive clay can be removed from the aggregate by washing procedures but 
such procedures are also generally inconvenient and uneconomical. Thus, if 
the local sources of aggregate contain expansive clay, the use of sulfur 
cement mortars concretes is pragmatically severely restricted. 
U.S. Pat. No. 4,188,230 teaches that this problem may be obviated by the 
incorporation of petroleum or polyol additives. Such procedures have not, 
in fact, proved entirely satisfactory. The problem of water-expansive 
clays is also considered in an article by Shrive, Gillott, Jordaan and 
Loov, appearing at Page 484 of the Journal of Testing and Evaluation 
(1977). 
In the commonly assigned co-pending application U.S. Ser. No. 237,350, 
filed Feb. 23, 1981, B. S. Albom discloses that the water stability of 
sulfur cement-aggregate products containing aggregate having up to about 
5% weight expandable clay can be substantially improved by treating this 
aggregate with a salt solution prior to admixture with the sulfur cement. 
SUMMARY OF THE INVENTION 
It has now been discovered that the water stability of sulfur 
cement-aggregate compositions containing aggregate containing up to about 
5% expansive clay based on the weight of the aggregate can be very 
substantially improved by the simple incorporation of an effective amount 
of an organosilane having at least one reactive functional group. This 
invention is important to the commercialization of sulfur cement mortars 
and concretes, because the treatment is effective and merely requires the 
addition of a small amount of the organosilane to the aggregate. Further, 
the invention has broad applicability, because most aggregates contain 
less than 5% by weight of expansive clay and generally contain less than 
about 3% by weight. 
In one embodiment, the invention comprises a sulfur cement-aggregate 
composition, comprising sulfur cement and an aggregate, containing up to 
about 5% by weight, and preferably less than 4% by weight, based on the 
aggregate, of an expansive clay and containing in admixture with said 
aggregate an amount of an organosilane effective to substantially reduce 
the water expandability of said expansive clay, and wherein said 
organosilane has at least one reactive functional group. 
In one embodiment, the invention provides a process for preparing a sulfur 
cement-aggregation composition containing an aggregate having up to 5% by 
weight, based on the aggregate, of expansive clay which comprises the 
improvement of admixing with the ingredients of said composition an amount 
of an organosilane effective to substantially reduce the water 
expandability of said expansive clay, and wherein said organosilane has at 
least one reactive functional group. 
The invention will be further described hereinbelow. 
FURTHER DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS 
The present composition can be prepared, in accordance with the present 
process by simply adding the appropriate organosilane to the ingredients 
of the composition. Because of the small amount of organosilane used, it 
is typically mixed with the sulfur cement, though it could also be added 
directly to the aggregate or the molten mixture of the sulfur cement and 
aggregate. The molten mixture is then preferably mixed to distribute the 
aggregate and organosilane throughout the sulfur cement. The organosilane 
can be added as a solid or liquid and generally will be applied in its 
usual commercial form. If desired where the particular organosilane is 
supplied commercially as a solid it can be applied as a liquid (e.g., by 
melt liquefying or dissolution or suspension in a volatile solvent or 
carrier). 
As is conventional, it is preferred to heat the aggregate prior to 
admixture with the molten-sulfur cement to avoid random cold spots, remove 
entrained moisture, and improve bonding of the sulfur cement to the 
aggregate. With the exception that it is preferred to add the organosilane 
to the sulfur cement, the order of addition of the various other 
ingredients is not significant. Although, as is conventional, where 
plasticized sulfur is used as the sulfur cement, it is generally preferred 
to add the plasticizer to the sulfur before adding the aggregate. The 
sulfur cement, aggregate and any other ingredients are mixed together at 
temperatures above the melting point of the sulfur cement (i.e., sulfur or 
plasticized sulfur) and below the decomposition or boiling point of the 
materials. Typically, mixing is effected at temperatures in the range of 
about from 110.degree. to 180.degree. C. and preferably, about from 
125.degree. to 160.degree. C. The molten mixture is then cast into the 
desired shape or form, in the case of concrete, or applied in the case of 
mortar. Upon cooling, the composition solidifies into a final product 
having improved water stability. 
Typically, about from 0.0015 to 0.015 g-mol, preferably about from 0.0038 
to 0.0075 g-mol, of organosilane is used per kilogram of expandable clay 
contaminated aggregate. In terms of a more convenient weight-to-weight 
basis, generally about from 0.25 to 3 parts by weight, preferably about 
from 0.65 to 1.5 of the organosilane are used per 1000 parts by weight of 
expandable clay contaminated aggregate. 
Appropriate organosilanes which can be used in the present invention are 
those organosilanes which have at least one molten-sulfur reactive group 
which reacts with sulfur or which converts in the presence of 
molten-sulfur to such a group and, of course, a boiling point and 
decomposition temperature above the melting point of the particular sulfur 
cement used. The term molten-sulfur reactive group, as used herein, means 
a group which reacts with sulfur or which converts in the presence of 
molten-sulfur to a group which reacts with sulfur. Examples of such 
molten-sulfur reactive groups include, for example, amino, diamino, epoxy, 
carbonyl, methacryloxy, aryl, (e.g., phenyl) mercapto, double bonds, alkyl 
having at least two carbon atoms, and the like. 
Suitable organosilanes which can be used include, for example, those 
organosilanes having the formula: 
##STR1## 
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from the 
group consisting of lower alkoxy, aryloxy, ara-lower alkoxy, and halo; and 
Z is an organic radical attached to Si via a carbon atom and has at least 
one molten-sulfur reactive group, such as, for example, amino, epoxy, 
double bond, triple bond, mercapto, cyano, hydroxy, aryl, substituted 
aryl, aralkyl, substituted aralkyl, carbonyl, alkyl having 2 through 20 
carbon atoms (including the carbon atom of R attached to Si) cycloalkyl, 
and the like. 
Typical Z groups include, for example, aminoalkyl, 
aminoalkylene-aminoalkyl, N-lower alkyl aminoalkyl, epoxyalkyl; 
epoxyalkoxyalkyl; alkenyl, alkynyl, mercaptoalkyl, alkylthioalkyl, 
cyanoalkyl, hydroxyalkyl, aryl, substituted aryl, arylalkyl, substituted 
arylalkyl, alkyl having at least 2 carbon atoms, cycloalkyl, cycloalkenyl, 
arylalkyl, aryloxyalkyl, preferably having 2 through 12 carbon atoms. 
(In the case where Z is hydrocarbyl it is believed that its sulfur 
reactivity is due to a single bond which converts to a double bond in 
presence of molten-sulfur). 
The preferred organosilanes are those wherein R has at least one 
molten-sulfur reactive group selected from the group of amino, epoxy 
(especially glycidoxy), and/or methacryloyloxy mercapto. In terms of the 
R.sup.1, R.sup.2, and R.sup.3 groups the preferred organosilanes are those 
wherein R.sup.1, R.sup.2, and R.sup.3 are lower alkoxy or aryloxy and 
especially lower alkoxy, for example, methoxy and ethoxy. Preferably, 
organosilanes having a combination of at least one preferred molten-sulfur 
reactive group and preferred R.sup.1, R.sup.2 and R.sup.3 groups are used. 
The organosilanes are commercially available as coupling agents and 
adhesion promoters used with various polymeric materials such as epoxy 
resins, polyesters, polycarbonates, nylons, sulfur-cured elastomers, and 
mineral-filled compositions. Suitable organosilanes can thus be purchased 
or prepared via conventional procedures. Suitable organosilanes which can 
be used in the present composition include for example, 
vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, 
beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 
gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane 
and gamma-mercaptopropyltrimethoxysilane, and the like and compatible 
mixtures thereof. 
The preferred organosilanes are those wherein R is mercapto, epoxy, 
methacryl, amino or diamino, and/or R.sup.1, R.sup.2 and R.sup.3 are 
independently selected from the group of alkyl and aryl, and especially 
methyl and ethyl. 
The remaining components of the sulfur cement aggregate compositions are 
not unique to the present invention save that the present invention 
permits the use of aggregate containing an otherwise deleterious amount 
(e.g., about 1% or more) of expandable clay up to about 5% weight, based 
on the aggregate, and preferably up to about 3% by weight in terms of 
producing a product having excellent water resistance. Also in terms of 
the sulfur cement, better results are obtained using plasticized sulfur 
than with pure sulfur. 
The principal sub-genuses of the present composition are sulfur cement 
mortars and sulfur concretes. The two compositions are actually very 
substantially the same with the exception of the size of the principal 
aggregate component. Typically, in the case of the present sulfur cement 
mortars, the mortar contains about from 10 to 50% by weight, preferably 
about from 15 to 25% by weight, of sulfur cement and about from 50 to 90% 
by weight, preferably about from 75 to 85% by weight, fine-size aggregate. 
Typically, fine-size aggregate generally has a particle size less than 
about No. 4 mesh (U.S.A. Standard Testing Sieves), and about 50 to 100, 
preferably less than about No. 16 mesh, (U.S.A. Standard Testing Sieves). 
Suitable fine-size aggregate include, for example, various sands, for 
example, plaster, monterey, Kaiser, and Texas sands, and the like. 
Sulfur cement concretes are similar to the sulfur cement mortars except 
that larger-size aggregate is used along, with, or in place of all or a 
portion of the smaller-size aggregate. Typically, the larger-size 
aggregate has a particle size of about from No. 4 to 11/2, preferably 
about from 3/8" to 3/4". The small sized aggregate generally has a 
particle size below about No. 8 mesh (U.S.A. Standard Testing Sieve) and 
preferably, below 16 mesh and preferably predominantly above 40 mesh. 
Suitable examples of such small-sized aggregate have already been 
illustrated hereinabove with respect to the sulfur cement mortars. 
Typically, the sulfur cement concrete comprises, by weight, about from 10 
to 50% sulfur cement; 20 to 60% large-size aggregate; and 30 to 70% 
fine-size aggregate. 
The sulfur cement can be unaltered sulfur and/or plasticized sulfur and if 
desired can contain minor amounts of various compatible additives (e.g. 
flame retardants, ductilating agents, etc.). The term plasticized sulfur 
refers to the reaction product of sulfur with a plasticizer and/or 
mixtures of sulfur and plasticizers and/or the reaction product of sulfur 
with a plasticizer. Although it is not wholly necessary to use plasticized 
sulfur as the sulfur cement, the compositions of invention using 
plasticized sulfur generally have much superior water stability to the 
corresponding composition using sulfur without a plasticizer. Where a 
plasticizer is used, the amount of the plasticizer(s) will vary with the 
particular plasticizer and the properties desired in the cement. The 
cement can contain about from 0.1 to 10% of the plasticizer and typically 
will contain about from 2 to 7, preferably about 21/2 to 5% by weight, 
based on the total weight of both free and combined (or reacted) sulfur in 
the composition (herein referred to as "total sulfur"). 
The term "sulfur plasticizer" or "plasticizer" refers to materials or 
mixtures of materials which, when added to sulfur, lower its melting point 
and increase its crystallization time. One convenient way to measure the 
rate of crystallization is as follows: the test material (0.040 g) is 
melted on a microscope slide at 130.degree. C. and is then covered with a 
square microscope slide cover slip. The slide is transferred to a hot 
plate and is kept at a temperature of 70.degree..+-.2.degree. C., as 
measured on the glass slide using a surface pyrometer. One corner of the 
melt is seeded with a crystal of test material. The time required for 
complete crystallization is measured. Plasticized sulfur, then, is sulfur 
containing an additive which increases the crystallization time within 
experimental error, i.e., the average crystallization time of the 
plasticized sulfur is greater than the average crystallization time of the 
elemental sulfur feedstock. For the present application, plasticizers are 
those substances which, when added to molten elemental sulfur, cause an 
increase in crystallization time in reference to the elemental sulfur 
itself. 
Inorganic plasticizers include, for example, the sulfide of iron, arsenic 
and phosphorus, etc. Generally, the preferred plasticizers are organic 
compounds which react with sulfur to give sulfur-containing materials. 
Suitable sulfur plasticizers which can be used include, for example, 
aliphatic polysulfides, aromatic polysulfides, styrene, dicyclopentadiene, 
dioctylphthalate, acrylic acid, epoxidized soybean oil, triglycerides, 
tall oil fatty acids, and the like and compatible mixtures thereof. 
One class of preferred plasticizers is the aliphatic polysulfides, 
particularly those that will not form cross-linking. Thus, butadiene is 
not a preferred constituent to form the aliphatic polysulfide, as it may 
form cross-linking sulfur bonds, whereas dicyclopentadiene is a preferred 
compound for forming the aliphatic polysulfide useful as the sulfur 
plasticizer. With molten-sulfur, dicyclopentadiene forms an extremely 
satisfactory aliphatic polysulfide. 
Another class of preferred plasticizers for use in the composition of the 
present invention are aromatic polysulfides formed by reacting one mol of 
an aromatic carbocyclic or heterocyclic compound, substituted by at least 
one functional group of the class --OH or --NHR in which R is H or lower 
alkyl with at least two mols of sulfur. 
Suitable organic compounds of this type include: phenol, aniline, N-methyl 
aniline, 3-hydroxy thiophene, 4-hydroxy pyridine, p-aminophenol, 
hydroquinone, resorcinol, meta-cresol, thymol, 4,4'-dihydroxy biphenyl, 
2,2-di(p-hydroxyphenol) propane, di(p-hydroxyphenyl) methane, etc., 
p-phenylene diamine, methylene dianiline. Phenol is an especially 
preferred aromatic compound to form the aromatic polysulfide. 
The aromatic polysulfides are generally prepared by heating sulfur and the 
aromatic compound at a temperature in the range of 120.degree. to 
170.degree. C. for 1 to 12 hours, usually in the presence of a base 
catalyst such as sodium hydroxide. (See for example, Angew, Chem. Vol. 70, 
No. 12, Pages 351-67 (1958), the polysulfide product made in this way has 
a mol ratio of aromatic compound: sulfur of the 1:2 to 1:10, preferably 
from 1:3 to 1:7. Upon completion of the reaction, the caustic catalyst is 
neutralized with an acid such as phosphoric or sulfuric acid. Organic 
acids may also be used for this purpose. The resulting aromatic 
polysulfide may be used immediately or it may be cooled and stored for 
future use. 
Another type of aliphatic polysulfide useful as a plasticizer for this 
invention are the linear aliphatic polysulfides. Although these 
polysulfides may be used alone as the sulfur plasticizer, it is preferred 
to use them in combination with either (a) dicyclopentadiene or (b) the 
aromatic polysulfides described above, especially with the phenol-sulfur 
adduct. In this connection, the preferred plasticizer mixtures contain 
from 5% to 60% by weight linear aliphatic polysulfide, based on total 
plasticizer, preferably about 20% to 50% by weight. 
These aliphatic polysulfides can have branching indicated as follows: 
##STR2## 
wherein x is an integer of from 2 to 6 and wherein B is H, alkyl, aryl, 
halogen, nitrile, ester or amide group. Thus, in this connection the 
aliphatic polysulfide is preferably a linear polysulfide. The chain with 
the sulfur preferably is linear, but it can have side groups as indicated 
by B above. Also, this side group B may be aromatic. Thus, styrene can be 
used to form a phenyl-substituted linear aliphatic polysulfide. The 
preferred aliphatic polysulfides of this type are both linear and 
nonbranched. 
Unbranched linear aliphatic polysulfides include those such as Thiokol LP-3 
which contains an ether linkage and has the recurring unit: --S.sub.x 
CH.sub.2 CH.sub.2 OCH.sub.2 OCH.sub.2 CH.sub.2 S.sub.x -- wherein x has 
an average value of about 12. The ether constituent of this aliphatic 
polysulfide is relatively inert to reaction. Other suitable aliphatic 
polysulfides have the following recurring units: 
--S.sub.x --(--CH.sub.2 --).sub.y --S.sub.x -- from reaction of alpha, 
omega-dihaloalkanes and sodium polysulfide; 
--S.sub.x --(--CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --).sub.y --S.sub.x 
-- from reaction of alpha, omega-dihalosulfides and sodium polysulfide; 
and 
--S.sub.x --(--CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --).sub.y --S.sub.x 
-- from reaction of alpha, omega-dihaloesters and sodium polysulfide 
wherein x is an integer of 2 to 5; and y is an integer of 2 to 10. 
In some instances, it is preferred to use mixtures of materials having 
different reactivities with sulfur as the plasticizer. For example, very 
good results can be obtained using a mixture of cyclopentadiene and/or 
dicyclopentadiene with oligomers of cyclopentadiene. Various plasticizers 
are also described in the art, for example, see U.S. Pat. Nos. 4,058,500 
and 4,190,460. 
The sulfur cement can also contain very fine particle sized fillers such 
as, for example, fly ash, talc, mica, silicas, graphite, carbon black, 
pumice, insoluble salts (e.g., barium carbonate, barium sulfate, calcium 
carbonate, calcium sulfate, magnesium carbonate, etc.), magnesium oxide, 
and mixtures thereof. Such fillers typically have a particle size less 
than 100 mesh (U.S.A. Standard Testing Sieve) and preferably, less than 
200 mesh. Such fillers generally act as thickening agents and generally 
improve the hardness or strength of the sulfur cement product. Where 
fillers are used, the sulfur cement typically contains about from 1 to 
15%, and more generally, about from 5 to 10% of the filler, based on the 
weight of total sulfur. 
Also, various additives can be added as desired to alter various properties 
of the sulfur cement, as is well-known to the art; see, for example, U.S. 
Pat. Nos. 4,188,230 (durability altered by the addition of certain 
petroleum products); and 4,210,458 (viscosity altered by the addition of 
polyhydric alcohols). 
Definitions 
As used herein the following terms have the following meanings unless 
expressly stated to the contrary. 
All mesh sizes are given in and refer to U.S.A. Standard Testing Sieves 
sometimes also referred to as the U.S. Sieve Series. 
The term "alkyl" refers to both straight- and branched-chain alkyl groups 
and also includes alkylenes. Generally such alkyl groups have 1 through 20 
carbon atoms. The term "lower alkyl" refers to both straight- and 
branched-chain alkyl groups having a total from 1 through 6 carbon atoms 
and includes primary, secondary and tertiary alkyl groups. Typical lower 
alkyls include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 
t-butyl, n-hexyl and the like. 
The term "alkylene" refers to both straight- and branched-chained alkylene 
groups. The term "lower alkylene" refers to alkylene groups having from 1 
through 6 carbon atoms. Typical alkylene groups include, for example, 
methylene, ethylene (i.e., --CH.sub.2 --CH.sub.2 --) 2-methylpropylene 
##STR3## 
and the like. 
The term "cycloalkyl" refers to cycloalkyl groups having 3 through 12 
carbon atoms and includes both monocyclic (e.g., cyclopropyl) and 
polycyclic (e.g., bicyclo[3,2,1]octyl) alkyls. The term "cycloalkenyl" 
refers to cycloalkyl but having at least one degree of unsaturation (i.e., 
at least one ring double bond). 
The term "alkenyl" refers to unsaturated alkyl groups having a double bond 
(e.g., CH.sub.3 CH=CH(CH.sub.2).sub.2 --,) and includes both straight- and 
branched-chain alkenyl groups. 
"Lower alkenyl" groups refer to alkenyl groups having from 2 through 6 
carbon atoms. Typical lower alkenyl groups include, for example, ethylene; 
but-3-enyl; hex-4-enyl; 2-methylpent-4-enyl and the like. 
The term "alkynyl" refers to unsaturated alkyl groups having a triple bond 
(e.g., CH.sub.3 C.dbd.C(CH.sub.2).sub.2 --) and includes both straight- 
and branched-chain alkynyl groups. 
The term "lower alkynyl" refers alkynyl groups having from 2 through 6 
carbon atoms and includes, for example, but-3-ynyl; hex-4-ynyl; 
3-methylpent-4-ynyl and the like. 
The term "halo or halogen atom" refers to the groups fluoro, chloro and 
bromo. 
The term "alkoxy" refers to the group R.sup.1 O-- wherein R.sup.1 is alkyl. 
The term "lower alkoxy" refers to alkoxy groups having from 1 through 6 
carbon atoms and includes, for example, methoxy, ethoxy, t-butoxy, hexoxy 
and the like. 
The term "lower alkoxyalkylene" refers to groups wherein both the alkoxy 
group is a lower alkoxy group and the alkylene group is a lower alkylene 
group. Typical alkoxyalkylene groups include, for example, 
methoxymethylene, pentoxyhexylene and the like. 
The term "aryl" refers to aryl groups having from 6 through 14 carbon atoms 
and includes, for example, phenyl, naphthyl, anthryl, phenanthryl and the 
like. 
The term aralkyl refers to the group Ar--Y-- wherein Ar is aryl and Y is 
alkyl preferably lower alkyl and includes for example, benzyl, phenethyl, 
naphthylethyl and the like. 
The term aryloxy refers to the group having the formula Ar--O-- wherein Ar 
is aryl and the term arylalkoxy refers to the group Ar--Y--O-- wherein 
Ar--Y-- is arylalkyl. 
The term "substituted aryl" refers to the radical having the general 
formula 
##STR4## 
wherein Z is aryl having 6-14 carbon atoms (e.g., phenyl, naphthyl, 
anthryl, phenanthryl, and preferably phenyl) and 
R.sup.5, and R.sup.6 are independently hydrogen, lower alkyl, amino, cyano, 
lower alkyl amino, di(lower alkyl)amino, lower alkylsulfinyl, lower 
alkylsulfonyl, lower alkylthiomercapto or acyloxy; 
R.sup.7 is hydrogen, halo, nitro, C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; 
R.sup.8 and R.sup.9 are independently selected from the group of hydrogen 
and halo, preferably hydrogen; 
and wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 can be at any 
available ring carbon atom and at least one R.sup.5, R.sup.6, R.sup.7, 
R.sup.8, or R.sup.9 is other than hydrogen. 
The term substituted arylakyl refers to the group Ar'Y-- wherein Ar' is 
substituted aryl and Y is alkyl preferably lower alkyl. 
The term "di(lower alkyl)amino" refers to the group having the formula 
##STR5## 
wherein R.sup.10 and R.sup.11 are independently lower alkyl. 
The term "acyl" refers to acyl groups derived from carboxylic acid having 2 
through 12 carbon atoms such as, for example, acetyl, propionyl, butynyl, 
valeryl, isovaleryl, hexanoyl, octanoyl, nonanyl, undecanoyl, lawroyl, 
acryloyl, methacryloyl, maleoyl, oleoyl, benzoyl, phenylacetyl, and the 
like. 
The term "acylalkyl" or "acylalkylene" refer to the group having the 
formula R.sup.12 R.sup.13 -- wherein R.sup.12 is acyl and R.sup.13 is 
alkylene as defined herein. 
The term "epoxyalkyl" refers to alkyl groups (preferably lower alkyl) 
having at least one epoxy moiety. 
The term "epoxyalkoxyalkyl" refers to ethers having the formula R.sup.14 
--O--R.sup.15 -- wherein R.sup.14 is epoxyalkyl and R.sup.15 is alkyl, 
preferably lower alkyl. Such groups include, for example, glycidoxyalkyl.

A further understanding of the invention can be had from the following 
non-limiting examples. 
EXAMPLE 1 
This example illustrates the composition and process of the invention, and 
the improved water stability afforded by the present invention. 
Sulfur cement aggregate compositions illustrating the present invention 
were prepared containing 25% by weight plasticized sulfur (95% by weight 
sulfur, 2.5% by weight dicyclopentadiene and 2.5% by weight 
cyclopentadiene oligomer); 3.0% by weight of the expansive clay, bentonite 
clay (4.0% based on aggregate) and the remainder Kaiser top sand having a 
U.S.A. Standard Testing Sieves size range of 4 mesh to 100 mesh and 
respectively containing 0.1 parts by wt of the organosilane, identified in 
Table 1 hereinbelow, per 100 parts by wt of the sulfur cement-sand-clay 
composition. The test compositions were prepared by mixing the 
organosilane with molten-sulfur cement and then mixing the 
organosilane-sulfur cement mixture with a preheated mixture of sand and 
clay. The molten mixture (125.degree.-135.degree. C.) was then cast into 
three 2".times.4" cylinder molds and aged overnight at room temperature 
(about 20.degree. C.). 
A control composition was prepared and cast into three cylinders in the 
same manner but, without the addition of the organosilane. 
Representative cylinders for the control composition and each of the test 
compositions, of the present invention, were selected and immersed in tap 
water at room temperature (about 20.degree. C.) and visually inspected 
daily for fractures, cracks, crumbling, etc. At the first evidence of any 
of these the cylinder was considered to have failed. The results of these 
trials are reported in Table 1 hereinbelow. 
As can be seen from Table 1, the compositions of the present invention had 
greatly superior water stabilities as compared to the corresponding 
control composition. The control composition containing 4% bentonite clay 
aggregate only had a life of about 4 hours whereas the test compositions 
containing 4% bentonite clay aggregate exhibited lives of 3-28 days. 
TABLE 1 
______________________________________ 
Parts by Reactive Days 
weight* Or- 
Functional 
to 
Organosilane ganosilane Group (Z) Failure 
______________________________________ 
Control None -- about 4 
hours 
N--(2-aminoethyl)-3-amino 
0.1 diamino 26 
propyl trimethoxysilane 
gamma-glycidoxy propyl tri- 
0.1 epoxy 24 
methoxysilane 
gamma-glycidoxy propyl 
0.1 epoxy 25 
trimethoxysilane 
gamma-methacryloxy propyl 
0.1 methacrylic 
28 
trimethoxysilane 
phenyltriethoxysilane 
0.1 phenyl 13 
gamma-amino propyl tri- 
0.1 amino 10 
ethoxysilane 
ethyl triethoxysilane 
0.1 ethyl 3 
vinyl triethoxysilane 
0.1 vinyl 5 
gamma-mercapto propyl 
0.1 mercapto 28 
trimethoxysilane 
______________________________________ 
*Parts by weight organosilane per 100 parts of total composition 
(excluding organosilane). 
EXAMPLE 2 
In this Example the same procedure as described in Example 1 was followed 
using the organosilane-gamma-glycidoxy propyl trimethoxysilane sold under 
the Trademark DC Z6040 by the Dow-Corning Company. A number of test 
compositions were prepared containing different amounts of the 
organosilane. In each case the compositions contained 25% sulfur cement 
(95% by weight sulfur, 2.5% by weight dicyclopentadiene and 2.5% by weight 
cyclopentadiene oligomer); 75 weight % aggregate (72% Kaiser top sand plus 
3% Bentonite clay) and the amount of organosilane indicated in Table 2 
hereinbelow. A control sample was prepared in the same manner but without 
the organosilane. 
In each case three cylinders were cast per composition. A representative 
cylinder was selected for each composition and immersed in tap water and 
observed for failure in the same manner as in Example 1 hereinabove. The 
results of these tests are recorded in Table 2 hereinbelow. 
As can be seen from Table 2 the use of 0.02 to 0.5 parts of the 
organosilane per 100 parts of composition increased the life of the 
composition from about 6 hours to upwards of 7 days. Best results were 
obtained using 0.05 to 0.1 parts of organosilane increasing the life of 
the composition to upwards of 24 days. 
TABLE 2 
______________________________________ 
Parts by Weight 
Days to 
Organosilane* Failure .+-. 
______________________________________ 
0 about 6 hours 
0.02 71/4 
0.05 48 
0.1 24 
0.5 7 
______________________________________ 
*Parts by weight organosilane per 100 parts by weight of sulfur cement 
plus aggregate (sand and clay). 
Obviously, many modifications and variations of the invention described 
hereinabove and below can be made without departing from the essence and 
scope thereof.