REFERENCE TO RELATED APPLICATIONS

This PCT application claims one or more inventions which were disclosed in Provisional Application Number 61/292,188, filed January 5, 2010, entitled

"HYDROCARBON ADDITIVES". The benefit under 35 USC § 119(e) of the United States provisional application is hereby claimed, and the aforementioned application is hereby incorporated herein by reference.

FIELD OF THE INVENTION

The invention pertains to the field of liquid fuel additives. More particularly, the invention pertains to olefin block copolymers that prevent gelling of liquid hydrocarbon compositions at low temperatures.

DESCRIPTION OF RELATED ART

A well-known problem in the fields of transportation and petroleum processing is the undesired gelling of liquid hydrocarbons at low temperatures. This is a particular problem with diesel and biodiesel fuels. Fuel oils contain alkanes that precipitate at low temperature as large crystals or spherulites of wax to form gels. This results in problems with fuel delivery such as filter blockage. Similar problems can arise in the transport of crude, intermediate, and finished petroleum products, especially during the transfer of such materials via pipelines or during pumping from tankers or offshore supplies.

The lowest temperature at which a liquid will flow freely is known as its pour point. Obviously, as the temperature of a hydrocarbon liquid approaches its pour point, difficulties arise in the use or transfer of the liquid. Furthermore, wax crystals can plug screens and filters at temperatures above the pour point, potentially causing failure or damage to engines or other equipment. The temperature at which this occurs is known as the cold filter plugging point. Additives have been developed to lower the pour point or cold filter plugging point of hydrocarbon liquids. These additives act by decreasing the size and/or altering the shape of the wax crystals; for example by creating much smaller crystals that do not lead to gelling and are less likely to clog filters.

A related problem arises with the low-temperature behavior of lubricating oils. The viscosity of oils is carefully controlled to provide the needed lubricity and performance characteristics in specific applications. One challenge is to provide lubricants that can maintain the necessary viscosity over a broad temperature range. As with the fuel oils described above, lubricating oils tend to become more viscous at low temperatures; under low temperature conditions such viscous oils may fail to perform as designed and allow damage to the parts being lubricated. Substitution with oils that provide lower viscosity at reduced temperatures is problematic since such oils tend to be too thin at higher operating temperatures. One solution to this problem is to include additives in the lubricating oil that can phase separate at low temperatures thereby leaving the bulk lubricating oil in a less viscous state suitable for lubrication at low temperatures. Upon warming the phase separated additives redissolve in the bulk lubricant and thereby increase its high temperature viscosity.

Polymeric materials have been used as wax crystal nucleators and viscosity modifiers for the above-described applications. The polymers currently being used are effective, but they require specialized synthesis, and are rather expensive. Materials that have been applied include random copolymers such as poly(ethylene-co-vinylacetate) and (ethylene/butylene copolymers) and diblock polymers such as polyethylene- poly(ethylene-co-propylene) diblocks and polyethylene-poly(ethylene-co-butylene) diblocks. Each of these materials has certain shortcomings, such as high cost, poor performance, or narrow applicability. As such, there remains a need for effective yet inexpensive additives to improve the low temperature characteristics of liquid

hydrocarbon materials.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides liquid hydrocarbon compositions containing olefin block co-polymers as additives to improve their low temperature viscosity characteristics. In certain embodiments, the olefin block copolymer includes one or more blocks including polyethylene and one or more blocks of an ethylene/alpha olefin copolymer of different composition. In certain embodiments, the olefin block copolymer has the structure: where,

a is 0 or 1 ;

b is an integer from 1 to 100;

c is 0 or 1 ;

L _R a I n

A is

where ^a is a C _1-10 alkyl group, x is a fraction from 0 to 1, and n is an integer from 5 to 5,000; and

where R ^b is a C _1-10 alkyl group, y is a fraction from about 1/1000 to 1, and m is an integer from 5 to 5,000,

wherein, at least one of (R ^a and R ^b ), or (JC and y) are different.

In another aspect, the present invention encompasses the recognition that certain commercially-available polyolefin block copolymers have utility as pour point depressants for liquid hydrocarbon compositions. In certain embodiments, the present invention encompasses the recognition that certain commercially-available polyolefin block copolymers have utility as viscosity modifiers for liquid lubricants.

In another aspect, the present invention encompasses methods of modifying a low temperature flow characteristic or viscosity of a liquid hydrocarbon including the step of dissolving an effective amount of one or more olefin block co-polymers described above and herein to the liquid hydrocarbon. DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention encompasses liquid hydrocarbon compositions containing a wax crystal nucleator wherein the wax crystal nucleator comprises an olefin block copolymer. In other embodiments, the present invention encompasses lubricating oils containing a viscosity modifier wherein the viscosity modifier comprises an olefin block copolymer.

In certain embodiments, the olefin block copolymer comprises two or more blocks having different compositions. In certain embodiments, the olefin block copolymer comprises at least three blocks. In certain embodiments, the olefin block copolymers are characterized in that they have alternating segments of different levels of crystallinity.

In certain embodiments, one or more blocks of the olefin block copolymer comprises at least 75% ethylene units. In certain embodiments, one or more blocks of the olefin block copolymer comprises at least 80%, at least 85%, at least 90%, or at least 95% ethylene units. In certain embodiments, the olefin block copolymer contains one or more blocks that are essentially pure polyethylene.

In certain embodiments, one or more blocks of the olefin block copolymers include one or more blocks comprising an ethylene/alpha olefin copolymer. In certain

embodiments, the alpha olefin comprises a C _3-2 o alpha olefin or mixture thereof. In certain embodiments, the alpha olefin comprises a C _4-12 alpha olefin or mixture thereof. In certain embodiments, the alpha olefin comprises a C _5-12 alpha olefin or mixture thereof. In certain embodiments, the alpha olefin comprises a C _6-12 alpha olefin or mixture thereof. In certain embodiments, the alpha olefin comprises a C _6-10 alpha olefin or mixture thereof. In certain embodiments, the alpha olefin comprises a C _6- 8 alpha olefin or mixture thereof. In certain embodiments, an alpha olefin is 1-hexene. In certain embodiments, an alpha olefin is 1- octene.

In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 90% ethylene units and one or more blocks of an ethylene/alpha olefin copolymer of different composition. In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 95% ethylene units and one or more blocks of an ethylene/alpha olefin copolymer of different composition. In certain embodiments the olefin block copolymer includes one or more blocks comprising essentially pure polyethylene and one or more blocks of an ethylene/alpha olefin copolymer of different composition.

In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 90% ethylene units and one or more blocks of an ethylene/ 1-hexene copolymer of different composition. In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 95% ethylene units and one or more blocks of an ethylene/ 1-hexene copolymer of different composition. In certain

embodiments the olefin block copolymer includes one or more blocks comprising essentially pure polyethylene and one or more blocks of an ethylene/ 1-hexene copolymer of different composition.

In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 90% ethylene units and one or more blocks of an ethylene/ 1-octene copolymer of different composition. In certain embodiments the olefin block copolymer includes one or more blocks comprising at least 95% ethylene units and one or more blocks of an ethylene/ 1-octene copolymer of different composition. In certain

embodiments the olefin block copolymer includes one or more blocks comprising essentially pure polyethylene and one or more blocks of an ethylene/ 1-octene copolymer of different composition.

In certain embodiments, liquid hydrocarbon compositions of the present invention, include an olefin block copolymer having a structure:

where, a is 0 or 1 ;

b is an integer from 1 to 100;

c is 0 or 1 ;

where R ^a is a C _1-10 alkyl group, x is a fraction from 0 to 1, and n is an integer from 5 to 5,000; and

where R ^b is a C _1-10 alkyl group, y is a fraction from about 1/1000 to 1, and m is an integer from 5 to 5,000,

wherein, at least one of (R ^a and R ⁶ ) or ( andj), are different.

In certain embodiments, the sum of a, b, and c is greater than 2 (e.g. the block copolymer is not a diblock polymer). In certain embodiments where the sum of a, b, and c is 2 and R ^a is hydrogen, R ^b is other than methyl or ethyl. In certain embodiments, where R ^a is hydrogen, methyl, or ethyl, R ^b is other than methyl or ethyl. In certain embodiments, where R ^a is hydrogen, R ^b is other than methyl or ethyl.

In certain embodiments, R ^a is hydrogen or an «-alkyl group. In certain

embodiments, R ^a is hydrogen. In certain embodiments, R ^a selected from the group consisting of methyl, ethyl, ^-propyl, «-butyl, «-pentyl, «-hexyl, «-octyl, and «-decyl.

In certain embodiments, R ^b is an «-alkyl group. In certain embodiments, R ^b is selected from the group consisting of ethyl, ^-propyl, «-butyl, «-pentyl, «-hexyl, «-octyl, and ft-decyl. In certain embodiments, R ^b is selected from the group consisting of ^-propyl, ft-butyl, ft-pentyl, «-hexyl, «-octyl, and «-decyl. In certain embodiments, R ^b is selected from the group consisting of «-butyl, «-pentyl, «-hexyl, and «-octyl. In certain

embodiments, R ^b is «-butyl, or «-hexyl. In certain embodiments, R ^b is «-butyl, «-hexyl or «-octyl. In certain embodiments, R ^b is «-butyl. In certain embodiments, R ^b is «-hexyl. In certain embodiments, R ^b is other than methyl. In certain embodiments, R ^a is other than ethyl.

In certain embodiments, R ^b is different from R ^a . In certain embodiments, R ^a is hydrogen and R ^b is an «-alkyl group. In certain embodiments, R ^a is hydrogen and R ^b is selected from the group consisting of ethyl, w-propyl, w-butyl, w-pentyl, w-hexyl, w-octyl, and w-decyl. In certain embodiments, R ^a is hydrogen and R ^b is selected from the group consisting of w-propyl, w-butyl, w-pentyl, w-hexyl, w-octyl, and w-decyl. In certain embodiments, R ^a is hydrogen and R ^b is selected from the group consisting of w-butyl, n- pentyl, w-hexyl, and w-octyl. In certain embodiments, R ^a is hydrogen and R ^b is w-butyl, or w-hexyl. In certain embodiments, R ^a is hydrogen and R ^h is w-butyl. In certain

embodiments, R ^a is hydrogen and R ^h is w-hexyl.

In certain embodiments, R ^a and R ^b are each an w-alkyl group. In certain

embodiments, R ^a and R ^b are the same w-alkyl group, and x and y are not the same.

In certain embodiments, the olefin block copolymers are not subjected to hydrogenation. In certain embodiments, the olefin block copolymers contain no residual sites of unsaturation.

In certain embodiments, x is <0.1. In certain embodiments, x is <0.1 and R ^b is selected from the group consisting of w-butyl, w-hexyl, and w-octyl. In certain

embodiments, x is <0.1 and R ^b is w-butyl. In certain embodiments, x is <0.1 and R ^b is n- hexyl. In certain embodiments, x is <0.1 and R ^b is w-octyl.

In certain embodiments, a ratio between n and m is from about 0.01 to about 100. In certain embodiments, a ratio between n and m is from about 0.1 to about 10. In certain embodiments, a ratio between n and m is from about 0.2 to about 5. In certain

embodiments, a ratio between n and m is from about 1 to about 10. In certain

embodiments, a ratio between n and m is from about 10 to about 100. In certain embodiments, a ratio between n and m is from about 0.01 to about 1.

In certain embodiments, a number average molecular weight of the olefin block copolymer is between about 1,000 and about 5,000,000 g/mol. In certain embodiments, a number average molecular weight of the olefin block copolymer is between about 5,000 and about 1,000,000 g/mol. In certain embodiments, a number average molecular weight of the olefin block copolymer is between about 10,000 and about 500,000 g/mol. In certain embodiments, a number average molecular weight of the olefin block copolymer is between about 20,000 and about 250,000 g/mol. In certain embodiments, the olefin block copolymer is a multiblock copolymer comprising between about 2 to about 200 blocks. In certain embodiments, the olefin block copolymer is a multiblock copolymer comprising between 3 to about 200 blocks.

In one aspect, the present invention encompasses the recognition that certain existing block copolymeric polyolefins are useful as additives to stabilize liquid hydrocarbon compositions at low temperatures. In certain embodiments, these polyolefins are produced by the chain shuttling copolymerization of ethylene with a C ₆ -2o alpha olefin.

In certain embodiments, the present invention encompasses liquid hydrocarbon compositions containing a wax crystal nucleator, wherein the wax crystal nucleator comprises an olefin block copolymer of the family marketed by the Dow Chemical Company under the trade name INFUSE™. In certain embodiments, the wax crystal nucleator comprises INFUSE™ Olefin Block Copolymer Grade 9000, Grade 9007, Grade 9100, Grade 9107, Grade 9500, Grade 9507, Grade 9530, Grade 9807, or Grade 9817 have physical properties as listed in an appendix to this patent application.

In another aspect, the present invention encompasses the recognition that certain existing block copolymeric polyolefins are useful as additives to modify the viscosity of lubricating oils. In particular, these block copolymeric polyolefins have the ability to phase separate at low temperatures providing lubricants with good low temperature performance characteristics. In certain embodiments, these polyolefins are produced by the chain shuttling copolymerization of ethylene with a C ₆ -2o alpha olefin.

In certain embodiments, the present invention encompasses lubricant compositions containing a viscosity modifying additive wherein the viscosity modifying additive comprises an olefin block copolymer of the family marketed by the Dow Chemical Company under the trade name INFUSE™.

Olefin block copolymers suitable for the present invention and methods to make them are described in Science 2006, 312, p. 714 and references therein. The entirety of this reference is incorporated herein by reference. Additional details on suitable block copolymers are described in the INFUSE™ Product Selection Guide published by the Dow Chemical Company and included, in part, as an appendix to this patent application. In certain embodiments, the present invention encompasses liquid hydrocarbon compositions containing less than 0.1 weight percent of a polyolefin block copolymer as a wax crystal nucleator. In certain embodiments, the wax crystal nucleator comprises less than 0.01, less than 0.001, or less than 0.0001 weight percent of the liquid hydrocarbon composition.

In certain embodiments, the presence of the olefin block copolymer lowers the cold filter plugging point of the liquid hydrocarbon composition by at least about 20 °C. In certain embodiments, the cold filter plugging point of the liquid hydrocarbon composition containing the wax crystal nucleator is below about 0 °C. In certain embodiments, the cold filter plugging point is below about -10 °C, below about -20 °C, below about -30 °C, or below about -40 °C.

In certain embodiments, the liquid hydrocarbon composition comprises a liquid fuel. In certain embodiments, the liquid fuel is diesel fuel. In certain embodiments, the liquid fuel is jet fuel. In certain embodiments, the liquid fuel is heating oil. In certain embodiments, the liquid fuel is a biofuel. In certain embodiments, the liquid fuel is biodiesel.

In certain embodiments, the present invention encompasses lubricating oils containing less than 1 weight percent of a polyolefin block copolymer as a viscosity modifier. In certain embodiments, the viscosity modifier comprises less than 0.5, less than 0.25, less than 0.1, less than 0.05, less than 0.01, less than 0.001, or less than 0.0001 weight percent of the lubricating oil.

In another aspect, the present invention encompasses methods of modifying the low temperature flow characteristics or viscosity of a liquid hydrocarbon. In certain embodiments, the methods include the step of adding an effective amount of one or more olefin block co-polymers described hereinabove to the liquid hydrocarbon. In certain embodiments, the methods include a step of agitating the liquid hydrocarbon to dissolve the olefin block copolymer. In certain embodiments, the methods include a step of heating the liquid hydrocarbon to dissolve the olefin block copolymer. It is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.

Appendix 11

Typical Properties of INFUSE ^™ Olefin Block Copolymers" ^■ "

INFUSE™ OBC Grades

Test Method 9000 9007 9100

Description / Key Attributes Good Highly flexible, High service elastic excellent elastic temperature recovery recovery performance

Excellent compres ^¬ Excellent General sion set in blends for blends purpose and compounds and compounds elastomer

Talc dusted

Typical Applications Compounding, Compounding, Compounding

Profile TPEs Profile Extrusion Extrusion,

Blown Films

Physical Properties

Melt Index, g/10 min (2.16 kg @ 190°C) ASTM D1238 0.5 0.5 1

Density, g/cm ³ ASTM D792 0.877 0.866 0.877

DSC Melting Point, °F (°C) Dow Method 248 (120) 246 (1 19) 248 (120)

Glass Transition Temperature, °F (°C) Dow Method -80 (-62) -80 (-62) -80 (-62)

Mechanical Properties

Hardness, Shore A ASTM D2240 71 64 75

Tensile Modulus, 100% Secant, psi (MPa) ASTM D638 477 (3.3) 258 (1 .8) 404 (2.8)

Ultimate Tensile Strength, psi (MPa) ASTM D638 91 1 (6.3) 590 (4.1 ) 950 (6.6)

Ultimate Tensile Elongation, % ASTM D638 370 400 480

Ultimate Tensile Strength, psi (MPa) ASTM D412 2,175 (15) 1 ,407 (10) 1 ,885 (13)

Ultimate Tensile Elongation, % ASTM D412 1 ,150 1 ,300 1 ,250

Tear Strength, kN/m ASTM D624 42 29 40

Thermal Properties

TMA @ 1 .0 mm, °F (°C) 1 N, 5°C/min ^|31 219 (104) 190 (88) 237 (1 14)

Compression Set @ 21 °C, % ASTM D395 23 18 19

Compression Set @ 70°C, % ASTM D395 45 57 47 Appendix 12

9107 9500 9507 9530 9807 9817

High service Excellent Excellent Excellent General General temperature flow and flow and flow and purpose purpose performance processability processability processability elastomer elastomer

General Excellent General Excellent compresHigher Reduced purpose haptics purpose sion set at high set-up part elastomer elastomer temperatures temperature weight

Talc dusted Talc dusted Talc dusted Talc dusted

TPEs, Injection Molding, Injection Injection Injection Injection

Elastic Films, Crosslinked (XL) Molding, Molding, Molding Molding

Blown Films Foams, Overmolding Elastic Films XL Foams for TPEs, for TPEs, on PPand PE, Adhesives Adhesives

Cast Films

1 5 5 5 15 15

0.866 0.877 0.866 0.887 0.866 0.877

250(121) 251 (122) 246(119) 246(119) 244(118) 248(120)

-80 (-62) -80 (-62) -80 (-62) -80 (-62) -80 (-62) -80 (-62)

60 69 60 83 55 71

234(1.6) 331 (2.3) 216(1.5) 554 (3.8) 189(1.3) 335 (2.3)

739 (5.1) 723 (5.0) 419(2.9) 1,069 (7.4) 176(1.2) 355 (2.4)

600 1,150 1,210 1,000 1,200 1,540

1,595(11) 1,378(10) 1,015(7) 2,465(17) 435 (3) 1,015(7)

1,550 1,600 1,900 1,300 2,200 1,700

27 35 22 52 17 31

151 (66) 207 (97) 171 (77) 232(111) 140 (60) 203 (95)

16 22 22 20 16 15

49 55 70 45 76 58