International Bureau

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
(19) World Intellectual Property

Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2015/112490 Al
30 July 2015 (30.07.2015) W PO PCT
(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every
C01B 17/02 (2006.01) C08K 3/06 (2006.01) kind of national protection available): AE, AG, AL, AM,
C05G 3/00 (2006.01) EOIC 7/26 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
C04B 28/36 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
(21) International Application Number:
HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
PCT/US2015/012023 KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG,
(22) International Filing Date: MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM,
20 January 2015 (20.01 .2015) PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC,
SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
(25) Filing Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
(26) Publication Language: English
(84) Designated States (unless otherwise indicated, for every
(30) Priority Data: kind of regional protection available): ARIPO (BW, GH,
61/929,664 2 1 January 2014 (21.01.2014) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ,
TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,
(71) Applicant: AGRIUM ADVANCED TECHNOLOGIES TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,
[US/US]; 2915 Rocky Mountain Avenue, Suite 400, Love- DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
land, Colorado 80538 (US). LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
(72) Inventors: HARGROVE, Garrard Lee; 5032 Wagon
GW, KM, ML, MR, NE, SN, TD, TG).
Trace, Birmingham, Alabama 35242 (US). WILSON,
Robert Scott; 2366 Forest Lakes Lanes, Sterrett, Alabama Published:
35 147 (US).
— with international search report (Art. 21(3))
(74) Agents: BUSSE, Paul, W. et al; Kagan Binder, PLLC,
Suite 200, Maple Island Building, 221 Main Street North,
Stillwater, Minnesota 55082 (US).
(54) Title: IMPACT RESISTANT SULFUR

o (57) Abstract: Described herein is a modified sulfur formulations having a carbon black material (e.g., lampblack) and a naturally
derived oil, such as vegetable oil, or its derivative. The modified sulfur has an impact resistance greatly improved over other sulfur
¾ formulations. The modified sulfur can be used, for example, in sulfur coated controlled release fertilizer products. The sulfur can ad-
ditionally or alternately be used in any application that would benefit from an increased impact resistance.
IMPACT RESISTANT SULFUR
PRIORITY CLAIM
[0001] This application claims priority to U.S. Provisional Application Serial No.
61/929,664, filed January 21, 2014, entitled "IMPACT RESISTANT SULFUR,"
which is herein incorporated by reference in its entirety.
FIELD OF THE DISCLOSURE
[0002] This invention relates to modified sulfur, particularly, with increased impact
resistance.
BACKGROUND
[0003] Sulfur is a by-product of petroleum oil refining and, being a by-product, is relatively
inexpensive. Because of this, sulfur is used in many applications where a relatively
low melting material (melting point of approximately 10°C - 11 °C) can be
sprayed or molded. Some common applications for sulfur include: as a component
in marking paint for roads and other high wear applications, as a protective coating
for concrete block walls and tank walls, as a component in encapsulates for toxic
contaminants, as an additive in asphalt or bituminous binders, and as a major
constituent in the coating of many urea controlled release products (e.g., fertilizers).
[0004] Molten sulfur however, once solidified, tends to be brittle, so that applications that
utilize sulfur are subject to impact damage. The likelihood of possible damage from
impact reduces the viability of sulfur in the applications described above and in
other applications.
[0005] Many attempts have been made to modify sulfur in order to improve its physical
properties, including increased resistance to impact damage. For example, attempts
have been made to react the sulfur with various dienes (which can be highly
flammable), with mineral fillers, or both. Attempts have also been made to react
sulfur with organosulfur compounds (which can be highly toxic). Other attempts
have been with the use of carbon, like carbon black, to plasticize the sulfur, but the
results have been lacking.
SUMMARY
[0006] The present disclosure provides sulfur formulations having a carbon black material
(e.g., lampblack) and a naturally derived oil, such as vegetable oil, or its derivative.
The modified sulfur has an impact resistance greatly improved over other sulfur
formulations. T e modified sulfur can be used, for example, in sulfur coating
controlled release fertilizer products. The sulfur can additionally or alternately be
used in any application that would benefit from an increased impact resistance.
DISCUSSION OF THE INVENTION
[0007] The present invention relates to modification of sulfur by the addition of lampblack
or other carbon black and a naturally derived oil, such as vegetable oil, or its
derivatives. The addition of these two ingredients to sulfur substantially increases
the resistance of the modified sulfur to impact damage. The combination of carbon
black plus inexpensive oils, like vegetable oil, constitutes a much more effective,
less dangerous and less expensive system for sulfur modification than the prior art.
[0008] The sulfur, prior to being modified, may be elemental sulfur, which can be
commercial grade, crystalline or amorphous. Sources that provide sulfur including
primary sulfur sources and recovered (recycled) sulfur sources.
[0009] The modified sulfur includes at least 0. 1 wt % of carbon black. Carbon black is a
generic term for a family of products that is used principally for the reinforcement of
rubber, as a black pigment and because of its electrically conductive properties. It
has Chemical Abstracts Service (CAS) Registry # 1333-86-4. It is an extremely
fluffy fine powder with a large surface area and is composed essentially of elemental
carbon. Carbon black is one of the most stable chemical products. In general, it is
the most widely used nano-material and its aggregate dimension ranges from tens to
a few hundred nanometers (nm). Depending on the primary particle size and the
particle size distribution, the carbon black materials is often referred to by different
names, including lampblack, furnace black or oil furnace black, acetylene black,
channel black, and thermal black. Furnace black, or oil furnace black, represents the
major volume of carbon black production. Although lampblack is the preferred
carbon black for the modified sulfur formulations of this disclosure, the other
examples of carbon blacks (e.g., furnace black or oil furnace black, acetylene black,
channel black, and thermal black) are also suitable.
[0010] Lampblack, typically, has an average primary particle size of 50-100 nm, a BET
surface area of 20-95 m /g, a dibutyl phthalate absorption value of 105-165 ml/ 100
g, a pH of about 3-7, solvent extractables (benzene) of 0.00-1.4, and a volatile
content at 950°C of 0.4-9%.
[0011] One particular lampblack, available from Degussa under the designation "Flamruss
101," has an average primary particle size of 95 nm, a BET surface area of20 /g,
a dibutyl phthalate absorption value of 1 17 ml/100 g, a pH of about 7.5, solvent
extractables (toluene) of 0.10 maximum, and a volatile content at 950°C of 1%.
[0012] As indicated, the modified sulfur includes at least 0. 1 wt % of carbon black (e.g.,
lampblack), and no more than 10 wt %. n some embodiments, the modified sulfur
includes 0.25 to 7 wt % carbon black, 0.5 to 5 wt % carbon black, or 0.5 to 2 wt %
carbon black. Non-limiting examples of the amount of carbon black (e.g.,
lampblack) include 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, , 2.0, 3, 3.0,
4, 4.0, 5 and 5.0 wt %.
[0013] The modified sulfur includes at least 0.5 wt % of a naturally derived oil or its
derivative(s). A naturally derived oil, broadly, is a triglyceride extracted from a
plant or seed of a plant. general, the oil is at least partially unsaturated and in
some embodiments may be fully unsaturated. Examples of naturally derived oils
that are suitable for the modified sulfur formulation include vegetable oil (e.g.,
soybean oil, canola oil, corn oil), sunflower oil, safflower oil, rapeseed oil, castor
oil, cottonseed oil, peanut oil, castor oil, linseed oil, and nut oil (e.g., tung oil,
walnut oil). Epoxidized oils, such as castor oil, epoxidized sunflower oil,
epoxidized linseed oil, etc. may also be suitable. Oil derivatives include mono- and
di-glycerides, and can be obtained from generally any oil, including soybean oil.
The glycerides may be used as pure mono-glycerides or pure di-glycerides, or may
be used as a blend, such as a 55/45 blend of mono-/di-glycerides.
[0014] Oil, in general, is not soluble in molten sulfur, and thus floats on the sulfur surface
when no agitation is present (e.g., when the stirrer is turned off). One can observe
the gradual disappearance of the oil layer over time as the oil reacts with the sulfur
via the double bonds present in the oil.
[001S] As indicated, the modified sulfur includes at least 0.5 wt % of a naturally derived oil
or its derivative(s), and no more than 25 wt %. n some embodiments, the modified
sulfur includes 1 to 10 wt % oil or derivative(s), or 1 to 5 wt %. Non-limiting
specific examples of the amount of naturally derived oil or its derivative(s) include
0.5, 1, 1.0, 1.5, , 2.0, 3, 3.0, 4, 4.0, 5, 5.0, 6, 7, 8, and 10 wt %.
[0016] In some embodiments, a catalyst or catalyst system may be added to the modified
sulfur formulation, separate from or together with the oil or its derivative(s). The
presence of the catalyst increases the rate of sulfur modification through reaction
with the oil, in some embodiments by about a factor of four. The presence of the
catalyst system does not yield much, if any, additional resistance to impact over a
sulfur formulation having the same amount of oil and no catalyst.
[0017] The level of catalyst or catalyst system, if present, is no more than 1.8 wt % of the
modified sulfur formulation, typically no more than 0.5 wt %. Suitable catalysts or
catalyst systems include components that will catalyze the vulcanization of rubber
with sulfur. A non-limiting example of a suitable catalyst system comprises steric
acid, zinc oxide, tetramethyl thiuram disulfide (TMTD, or THIRAM), and
mercaptobenzthiazole disulfide (MBTS).
[0018] The modified sulfur formulation, having the carbon black and the oil or oil
derivative(s), with or without catalyst, has an impact resistance at least twice (2x)
that of sulfur without carbon black and oil or oil derivative(s). In some
embodiments, the impact resistance is increased at least three times (3x) over the
impact resistance of sulfur without carbon black and oil or oil derivative(s), and in
other embodiments at least four times (4x). This impact resistance increase remains
constant over time, for example, months and years, after formation of the modified
sulfur.
[0019] The resistance to impact may be quantified by various tests that measure the samples
resistance to cracking or breaking due to an impact (force) on the sample; ASTM D
2444 is one suitable test.
[0020] EXPERIMENTAL
[0021] Examples of the modified sulfur formulation can be made by the following general
procedure: Lampblack (e.g., FLAMRUSS 101 from DEGUSSA) or other carbon
black is stirred into molten sulfur (140°C-150°C), for example with a magnetic
stirring bar set at a stirring speed that develops a vortex in the sulfur. After 60
minutes, a naturally derived oil, such as vegetable oil, derivatives of the oil, or oil
and catalyst(s), is slowly added to the stirring sulfur/lampblack mixture. After the
addition of the oil component is complete, the modified sulfur mixture is stirred for
an additional 2 hours at 140°C-1 50°C with the stirrer still set at a speed that
develops a vortex. The resulting sulfur/lampblack/oil blend is preferably
homogeneous with no lumps.
[0022] It is important to note that attempts to modify sulfur directly with oil, oil with
catalysts, or oil derived glycerides, without the presence of lampblack, resulted in
the generation of large amounts of solids that floated on the surface of the molten
sulfur.
[0023] A sulfur test coupon, for the test below, is produced by pouring molten sulfiir, or
modified sulfur, into a mold and allowing the molten material to solidify before
removing the test coupon.
[0024] To test and measure the resistance of impact of the sulfur formulation, the following
test can be used: A metal sphere (4.47 mm in diameter, weighing 0.34 grams) is
dropped through a 6.35 mm (1/4 inch) inside diameter polyethylene tube of varying
lengths held directly and vertically over a 17 mm x 25 mm x 2 mm thick sulfur test
coupon placed on 4 layers of paper towels. The height that a test coupon survives
after one impact, but not a second impact, is defined as the "impact distance
survived" for the test coupon.
[0025] Example 1: SULFUR ONLY fCOMPARATIVE EXAMPLE) : 250.00 grams of

sulfur were melted in a 250 ml beaker suspended in an oil bath maintained at 145°C
+ 5°C by a hot plate/magnetic stirrer. A Teflon-coated magnetic stirring bar was
added to the beaker, and the molten sulfur was stirred with the stirring bar at
sufficient rpms to generate a deep vortex. The beaker containing the molten sulfur
was removed from the oil bath and the molten sulfur was poured into a silicone mold
and allowed to solidify to form 17 mm x 25 mm x 2 mm test specimens.
[0026] Example 2: SULFUR + 2.0% LAMPBLACK (COMPARATIVE EXAMPLE) :

This example is similar to that taught in U.S. Patent Nos. 6,824,600 and 6,863,724.
250.00 grams of sulfur were melted and stirred as in Example 1, and 5.13 grams of
Flamruss 101 lampblack were slowly added to the well-stirred sulfur. The
sulfur/lampblack mixture was stirred for a total of 60 minutes while being
maintained at 145°C + 5°C. The beaker containing the sulfur/lampblack dispersion
was then removed from the oil bat and the dispersion was poured into a silicone
mold and allowed to solidify to form 17 mm x 25 mm x 2 mm test specimens.
[0027] Example 3 : SULFUR + 4.0% LAMPBLACK fCOMPARATIVE EXAMPLE) :

This example is similar to that taught in U.S. Patent Nos. 6,824,600 and 6,863,724.
Flamruss 101 lampblack were slowly added to the well-stirred sulfur. The
sulfur/lampblack mixture was stirred for a total of 60 minutes while being
maintained at 145°C + 5°C. The beaker containing the sulfur/lampblack dispersion
was then removed from the oil bath and the dispersion was poured into a silicone
[0028] Example 4: SULFUR + 2.0% MICA fCOMPARATIVE EXAMPLE): This

example is similar to that taught in U.S. Patent No. 4,026,719. 150.0 grams of sulfur
were melted and stirred as in Example 1, and 3.06 grams of Alsibronz 06 (mica)
were slowly added to the well-stirred sulfur. The sulfur/Alsibronz 06 mixture was
stirred for a total of 60 minutes while maintained at 145°C + 5°C. . The beaker
containing the sulfur/Alsibronz 06 dispersion was then removed from the oil bath
and the dispersion was poured into a silicone mold and allowed to solidify to form
7 mm x 25 mm x 2 mm test specimens.
[0029] Example 5: SULFUR + 2.0% LAMPBLACK + 2.0% MICA

(COMPARATIVE EXAMPLE): T his example is similar to that taught in U.S.
Patent No. 4,026,719. 150.20 grams of sulfur were melted and stirred as in Example
1, and 3.13 grams of Alsibronz 06 (Mica) and 3.13 grams of Flamruss 101
lampblack were slowly added, one after the other, to the well-stirred sulfur. The
sulfur/Alsibronz 06/Flamruss 101 dispersion was stirred for a total of 60 minutes
while maintained at 145°C + 5°C. The beaker containing the sulfur/Alsibronz
06/Flamruss 101 dispersion was then removed from the oil bath and the dispersion
was poured into a silicone mold and allowed to solidify to form 17 mm x 25 mm x 2
mm test specimens.
[0030] Example 6 : SULFUR + 2.0% LAMPBLACK + 2.0%

DICYCLOPENTADIENE (COMPARATIVE EXAMPLE): This example is
similar to that taught in U.S. Patent Nos. 4,190,460 and US 4,31 1,826. 150.0 grams
of sulfur were melted and stirred as in Example 1, except the initial temperature was
held at 130°C + 5°C and 3.13 grams of Flamruss 101 lampblack and 3.13 grams of
DCPD were slowly added and stirred for 105 minutes. The temperature was then
increased to 164°C + 5°C and the reaction mixture was stirred for an additional 40
minutes. The reaction mixture was then poured into a silicone mold and allowed to
solidify to form 17 mm x 25 mm x 2 mm test specimens.
[0031] Example 7 : SULFUR + 1.0% LAMPBLACK + 1.89% SOYBEAN OIL: 150.00

grams of sulfur were melted and stirred as in Example 1, and 1.54 grams of
Flamruss 101 lampblack were added. Stirring was continued for 60 minutes while
the dispersion of lampblack in sulfur was maintained at 145°C + 5°C. 2.92 grams of
soybean oil were then slowly added to the stirred dispersion of lampblack in sulfur
and stirring was continued for 120 minutes with the sulfur/lampblack/soybean oil
dispersion being maintained at temperature. At the end of 1 0 minutes, the stirrer
was turned off and no soybean oil, or solids, was visible on the surface of the static,
hot liquid. The reaction mixture was then poured into a silicone mold and allowed
to solidify to form 17 mm x 25 mm x 2 mm test specimens.
[0032] Example 8: SULFUR + 1.0% LAMPBLACK + 2.82% SOYBEAN OIL: 150.00

soybean oil were then slowly added to stirred dispersion of lampblack in sulfur and
stirring was continued for 120 minutes with the sulfur/lampblack/soybean oil
dispersion being maintained at temperature. At the end of 120 minutes, the stirrer
was turned off and no soybean oil, or solids, was visible on the surface of the static,
[0033] Example 9: SULFUR + .0% LAMPBLACK + 4.66% SOYBEAN OIL: 150.00

soybean oil were then slowly added to stirred dispersion of lampblack in sulfur and
stirring was continued for 120 minutes with the sulfur/lampblack/soybean oil
dispersion being maintained at temperature. The stirrer was turned off briefly at 10
minutes, 20 minutes, 30 minutes, and 60 minutes to check for the presence of
soybean oil on the surface of the sulfur/lampblack dispersion. Soybean oil was
visible until the full 120 minute reaction period had been reached. At the end of 120
minutes, the stirrer was turned off and no soybean oil, or solids, was visible on the
surface of the static, hot liquid. The reaction mixture was then poured into a silicone
[0034] Example 10: SULFUR + 1.0% LAMPBLACK + 9.31% SOYBEAN OIL:

the dispersion of lampblack in sulfur was maintained at 145°C + 5°C. 15.57 grams
of soybean oil were then slowly added to stirred dispersion of lampblack in sulfur
and stirring was continued for 120 minutes with the sulfur/lampblack/soybean oil
dispersion being maintained at temperature. At the end of 120 minutes, the stirrer
was turned off and no soybean oil or solids were visible on the surface of the static,
[0035] Example 11: SULFUR + 1.0% LAMPBLACK + 4.66% CASTOR OIL: 300.00
of castor oil were then slowly added to stirred dispersion of lampblack in sulfur and
stirring was continued for 120 minutes with the sulfur/lampblack/castor oil
was turned off and no castor oil, or solids, was visible on the surface of the static,
[0036] Example 12: SULFUR + 1.0% LAMPBLACK + 4.66% LINSEED OIL:

of linseed oil were then slowly added to stirred dispersion of lampblack in sulfur and
stirring was continued for 120 minutes with the sulfur/lampblack/linseed oil
was turned off and no linseed oil, or solids, was visible on the surface of the static,
[00371 Example 13: SULFUR + 1.0% LAMPBLACK + 4.66% 55/54 MONO/DI

SOYBEAN OIL GLYCERTOES: 250.00 grams of sulfur were melted and stirred
as in Example 1, and 2.65 grams of Flamruss 101 lampblack were added. Stirring
was continued for 60 minutes while the dispersion of lampblack in sulfur was
maintained at 145°C + 5°C. 12.35 grams of 55/45 mono/di soybean oil glycerides
were then slowly added to stirred dispersion of lampblack in sulfur and stirring was
continued for 120 minutes with the sulfur/lampblack/55/45 mono/di soybean oil
glycerides dispersion being maintained at temperature. At the end of 1 0 minutes,
the stirrer was turned off and no 55/45 mono/di soybean oil glycerides, or solids,
were visible on the surface of the static, hot liquid. The reaction mixture was then
poured into a silicone mold and allowed to solidify to form 17 mm x 25 mm x 2 mm
test specimens.
[0038] Example 14: SULFUR + 1.0% LAMPBLACK + 2.0% SOYBEAN

OIL/CATALYST SYSTEM: The following components were combined and
mixed and heated at 100°C for 60 minutes to form an oil/catalyst system (SBOCAT)
blend.
COMPONENT WEIGHT %
SOYBEAN OIL 93.10
STERIC ACID 2.00
ZINC OXIDE 4.00
TETRAMETHYL TfflURAM DISULFIDE 0.60
MERCAPTOBENZTHIAZOLE DISULFIDE 0.30
150 grams of sulfur was then melted and stirred as in Example 1, and 1.55 grams of
Flamruss 101 lampblack were added and stirring was continued at temperature for
60 minutes. 3.09 grams of the above SBOCAT blend (i.e., blend of soybean oil and
catalyst system) were then slowly added to the sulfur/lampblack dispersion and
stirring was continued at temperature for 120 minutes. At the end of 120 minutes,
the stirrer was turned off, and no soybean oil, or solids, was visible on the surface of
the static, hot liquid. The reaction mixture was then poured into a silicone mold and
allowed to solidify to form 17 mm x 25 mm x 2 mm test specimens.

OIL/CATALYST SYSTEM: 150 grams of sulfur was melted and stirred as in
Example 1, and 1.56 grams of Flamruss 101 lampblack were added and stirring was
continued at temperature for 60 minutes. 4.69 grams of the SBOCAT blend as
prepared in Example 14 were then slowly added to the sulfur/lampblack dispersion
and stirring was continued at temperature for 120 minutes. At the end of 120
minutes, the stirrer was turned off, and no soybean oil, or solids, was visible on the

and stirring was continued at temperature for 120 minutes. At the end of 120

and stirring was continued at temperature for 30 minutes, with the stirrer being
turned off briefly at 10 minutes and 20 minutes. At the end of 30 minutes, the stirrer
was turned off, and no soybean oil, or solids, was visible on the surface of the static,

and stirring was continued at temperature for 1 0 minutes. At the end of 120
[0043] Example 19: SULFUR + Q.5% LAMPBLACK + 5.0% SOYBEAN
OIL/CATALYST SYSTEM: A sample was made by the process generally
described above, resulting in a modified sulfur having 0.5% lampblack
(FLAMRUSS 101) and 5% SBOCAT blend. The formulation yielded large amounts
of solids floating on the surface of the molten modified sulfur.
[0044] Example 20: SULFUR + 2% LAMPBLACK + 12% SOYBEAN

OIL/CATALYST SYSTEM: A sample was made by the process generally
described above, resulting in a modified sulfur having 2% lampblack (FLAMRUSS
101) and 12% SBOCAT blend. The formulation yielded large amounts of solids
floating on the surface of the molten modified sulfur.
[0045] TABLE 1 below summarizes the level of carbon black (i.e., lampblack) and oil or oil
derivative(s) in the above-described inventive examples.
TABLE 1
[00461 IMPACT TESTING
[0047] Examples 1-18 were subject to the following Impact Test: 6.35 mm (1/4 inch) inside
diameter polyethylene pipes of varying length were attached to 15.9 mm by 15.9
mm (5/8 inch by 5/8 inch) wooden back supports, and held vertically by a heavy
duty ring stand. The bottom of the pipe was positioned 2 centimeters directly above
the test specimen, which was placed on 4 sheets of paper towels inside a
crystallization dish. A metal sphere 4.47 mm in diameter, weighing 0.34 grams, was
then dropped from the top of the pipe onto the test specimen. The specimen was
said to survive a particular distance drop, in centimeters, if the first drop did not
break the specimen, but a second drop of the same distance did break the specimen.
The results of this test applied at various times since casting to Examples 1-18 are
contained in Table 2 below.
TABLE 2
IMPACT TEST RESULTS
Ex. 8 68 80
22714 (2.6 years) 90
Ex. 9 360 100
Ex. 10 336 150

24090 (2.75 years) 150
Ex. 1 1 384 60
Ex. 12 240 62
22714 (2.6 years) 60
Ex. 13 192 100
Ex. 14 168 60
Ex. 15 168 90
24816 (2.8 years) 90
Ex. 16 168 105

936 100
Ex. 17 168 100

1296 100
Ex. 18 120 55
168 120
480 150
1272 150
25579 (2.9 years) 150
The data in TABLE 2, some of which is reproduced in TABLE 3 below, show that
the presence of the catalyst system does not yield much, if any, additional resistance
to impact over the sample produced with the same amount of oil, but with no
catalyst. The presence of the catalyst, however, increases the rate of sulfur
modification through reaction with the oil by about a factor of four. For example,
compare Example 9 (without catalyst) to Example 7 (with catalyst).
TABL 3
INFLUENCE OF CATALYST ON IMPACT RESISTANCE
[0049] The data in TABLE 2 also shows that the sulfur modification benefits remain in
force for years. Several of the data are reported again below in TABLE 4.
TABLE 4
STABILITY OF IMPACT RESISTANCE OF MODIFIED SULFURS OVER
TIME
[0050] Clearly, sulfur, modified with lampblack and vegetable oils, or vegetable oil
derivatives, shows much higher resistance to impact in the test than does sulfur
alone, or sulfur modified only with lampblack. In fact, some of the modified sulfurs
display as much as lOx the resistance to impact that sulfur itself does. In addition,
this resistance to impact damage continues over a period of years.
[0051] Thus, various embodiments of the IMPACT RESISTANT SULFUR are disclosed.
The implementations described above and other implementations are within the
scope of the following claims. One skilled in the art will appreciate that the present
invention can be practiced with embodiments other than those disclosed. The
disclosed embodiments are presented for purposes of illustration and not limitation,
and the present invention is limited only by the claims that follow.
What is claimed is:
1. A modified sulfur comprising sulfur, carbon black, and a naturally derived

oil or derivative(s).
2. The modified sulfur of claim 1, wherein the carbon black is lamp black.
3. The modified sulfur of claim 1, wherein the carbon black has an average
particle size of 50 to 100 nm.
4. The modified sulfur of any one of claims 1-3 comprising 0.1 to 0 wt %

carbon black and 0.5 to 25 wt % oil or derivative(s).

carbon black and 1 to 9 wt % oil or derivative(s).

carbon black and 1 to 5 wt % oil or derivative(s).
7. The modified sulfur of any one of claims 1-6, wherein the naturally derived
oil comprises vegetable oil, sunflower oil, safflower oil, rapeseed oil, castor oil,
cottonseed oil, peanut oil, castor oil, linseed oil, or nut oil.
8. The modified sulfur of claim 7, wherein the vegetable oil comprises soybean
oil, canola oil, or corn oil.
9. The modified sulfur of claim 7, wherein the nut oil comprises tung oil or
walnut oil.
10. The modified sulfur of any one of claims 1-9, wherein the derivative(s)
comprises mono-glyceride and/or di-glyceride.
11. The modified sulfur of any one of claims 1-10 further comprising a catalyst
or catalyst system.
12. A method of making a modified sulfur by combining molten sulfur with

carbon black and with a naturally derived oil or derivative(s).
13. The method of claim 12 further comprising combining a catalyst or catalyst

system with the molten sulfur with carbon black and with a naturally derived oil or
derivative(s).
14. The method of claim 13, wherein the catalyst or catalyst system is combined
with the naturally derived oil or derivative(s) prior to combining with the molten
sulfur and carbon black.
15. The method of any one of claims 12-14, wherein the carbon black is lamp
black.
16. The method of any one of claims 12-14, wherein the carbon black has an
average particle size of 50 to 100 ran,
17. The method of any one of claims 12-16 comprising combining sufficient
carbon black and oil or derivative(s) to provide the modified sulfur with 0.1 to 10 wt
% carbon black and 0.5 to 25 wt % oil or derivative(s).
% carbon black and 1 to 9 wt % oil or derivative(s).
% carbon black and 1 to 5 wt % oil or derivative(s).
20. The method of any one of claims 12-19, wherein the naturally derived oil
comprises vegetable oil, sunflower oil, safflower oil, rapeseed oil, castor oil,
cottonseed oil, peanut oil, castor oil, linseed oil, or nut oil.
2 1. The method of claim 20, wherein the vegetable oil comprises soybean oil,
canola oil, or corn oil.
22. The method of claim 20, wherein the nut oil comprises tung oil or wabut oil.
23. The method of any one of claims 12-22, wherein the derivative(s) comprises
mono-glyceride and/or di-glyceride.
A . CLASSIFICATION O F SUBJECT MATTER
INV. C01B17/02 C05G3/00 C04B28/36 C08K3/06 E01C7/26
ADD.
According to International Patent Classification (IPC) o r t o both national classification and IPC
B . FIELDS SEARCHED
Minimum documentation searched (classification system followed b y classification symbols)
C01B C05G C04B C08K EOIC
Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
EPO-Internal , WPI Data
C . DOCUMENTS CONSIDERED T O B E RELEVANT
Category* Citation o f document, with indication, where appropriate, of the relevant passages Relevant to claim No.
US 3 674 525 A ( LOUTHAN RECTOR P) 1-23

4 July 1972 (1972-07-04)
c l aims 1-6
col umn 1, l i nes 43-48
col umn 2 , l i nes 53-64
col umn 2 , l i ne 65 - col umn 3
US 2013/164625 Al (MANTHI RAM ARUMUGAM [US] 1-23

ET AL) 27 June 2013 (2013-06-27)
c l aims 1, 7
DE 16 67 697 Al (RATHJEN CLAUS DR) 1-23

22 July 1971 (1971-07-22)
c l aims 1-4
exampl e s 1, 2
□ Further documents are listed in the continuation of Box C . See patent family annex.
* Special categories of cited documents :

"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to b e of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot b e
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot b e
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family
Date of the actual completion of the international search Date of mailing of the international search report
22 Apri l 2015 29/04/2015

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016
Gerwann , Jochen
Patent document Publication Patent family Publication
cited in search report date member(s) date
US 3674525 04-07-1972 NONE
US 2013164625 Al 27-06-2013 CN 104254936 A 31-12-2014

EP 2795698 Al 29-10-2014
JP 2015503498 A 02-02-2015
KR 20140107582 A 04-09-2014
US 2013164625 Al 27-06-2013
0 2013096747 Al 27-06-2013
DE 1667697 Al 22-07-1971 NONE

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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

(54) Title: IMPACT RESISTANT SULFUR

FIELD OF THE DISCLOSURE

DISCUSSION OF THE INVENTION

[0025] Example 1: SULFUR ONLY fCOMPARATIVE EXAMPLE) : 250.00 grams of

[0026] Example 2: SULFUR + 2.0% LAMPBLACK (COMPARATIVE EXAMPLE) :

[0027] Example 3 : SULFUR + 4.0% LAMPBLACK fCOMPARATIVE EXAMPLE) :

[0028] Example 4: SULFUR + 2.0% MICA fCOMPARATIVE EXAMPLE): This

[0029] Example 5: SULFUR + 2.0% LAMPBLACK + 2.0% MICA

[0030] Example 6 : SULFUR + 2.0% LAMPBLACK + 2.0%

[0031] Example 7 : SULFUR + 1.0% LAMPBLACK + 1.89% SOYBEAN OIL: 150.00

[0032] Example 8: SULFUR + 1.0% LAMPBLACK + 2.82% SOYBEAN OIL: 150.00

[0033] Example 9: SULFUR + .0% LAMPBLACK + 4.66% SOYBEAN OIL: 150.00

[0034] Example 10: SULFUR + 1.0% LAMPBLACK + 9.31% SOYBEAN OIL:

[0036] Example 12: SULFUR + 1.0% LAMPBLACK + 4.66% LINSEED OIL:

[00371 Example 13: SULFUR + 1.0% LAMPBLACK + 4.66% 55/54 MONO/DI

[0038] Example 14: SULFUR + 1.0% LAMPBLACK + 2.0% SOYBEAN

[0039] Example 15: SULFUR + 1.0% LAMPBLACK + 3.0% SOYBEAN

[0040] Example 16: SULFUR + 1.0% LAMPBLACK + 4.0% SOYBEAN

[0041] Example 17: SULFUR + 1.0% LAMPBLACK + 5.0% SOYBEAN

[0042] Example 18: SULFUR + 2.0% LAMPBLACK + 5.0% SOYBEAN

[0044] Example 20: SULFUR + 2% LAMPBLACK + 12% SOYBEAN

[00461 IMPACT TESTING

Ex. 9 360 100

Ex. 10 336 150

Ex. 13 192 100

Ex. 16 168 105

Ex. 17 168 100

1. A modified sulfur comprising sulfur, carbon black, and a naturally derived

4. The modified sulfur of any one of claims 1-3 comprising 0.1 to 0 wt %

5. The modified sulfur of any one of claims 1-3 comprising 0.5 to 5 wt %

6. The modified sulfur of any one of claims 1-3 comprising 0.5 to 2 wt %

12. A method of making a modified sulfur by combining molten sulfur with

13. The method of claim 12 further comprising combining a catalyst or catalyst

EPO-Internal , WPI Data

C . DOCUMENTS CONSIDERED T O B E RELEVANT

US 3 674 525 A ( LOUTHAN RECTOR P) 1-23

US 2013/164625 Al (MANTHI RAM ARUMUGAM [US] 1-23

DE 16 67 697 Al (RATHJEN CLAUS DR) 1-23

* Special categories of cited documents :

22 Apri l 2015 29/04/2015

US 3674525 04-07-1972 NONE

US 2013164625 Al 27-06-2013 CN 104254936 A 31-12-2014

DE 1667697 Al 22-07-1971 NONE

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