CA1271895A - The use of ethylene terpolymers as additives in mineral oil and miniral oil distillates - Google Patents
The use of ethylene terpolymers as additives in mineral oil and miniral oil distillatesInfo
- Publication number
- CA1271895A CA1271895A CA000510298A CA510298A CA1271895A CA 1271895 A CA1271895 A CA 1271895A CA 000510298 A CA000510298 A CA 000510298A CA 510298 A CA510298 A CA 510298A CA 1271895 A CA1271895 A CA 1271895A
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- CA
- Canada
- Prior art keywords
- weight
- terpolymer
- additive
- mineral oil
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
Abstract of Disclosure An additive for mineral oils and/or mineral oil fractions comprising a terpolymer containing 0.5 to 20% by weight diisobutylene, 20-35% by weight vinyl acetate, both based on total terpolymer, and ethylene, said terpolymer having an average molecular weight of 500 to 10,000.
Compositions containing the additive and methods of reducing both the pour point and the cold filter plug point of the oils and fractions, as well as a method of preparation of the terpolymers, are also disclosed.
Compositions containing the additive and methods of reducing both the pour point and the cold filter plug point of the oils and fractions, as well as a method of preparation of the terpolymers, are also disclosed.
Description
-` ~2~895 Ethylene Terpolymer Additives for Mineral Oil and Mineral Oil Distillates The present invention relates to the use of terpolymers of ethylene, diisobutylene and vinylacetate to improve the flowability and the low temperature behaviour of mineral oil and mineral oil distillates.
Mineral oils such as crude oil, diesel fuel or fuel oil contain varying amounts of long-chain paraffins (waxes) dissolved in them which crystallize out at low temperatures. This leads to solid deposits which often cause breakdowns during the recovery, transportation and use of such oils. Thus, the operability of crude oil conveyance and transportation facilities can be impaired to such a degree that they fail completely. With diesel engines and firing plants the filter can become blocked, preventing accurate dosage of the fuels and finally resulting in a complete breakdown of the equipment.
This undesirable formation of solid deposits is counteracted by additives which prevent the paraffin crystals from forming and stop the viscosity of the oils from increasing.
lZ71895 The flow and low temperature behaviour of mineral oils and mineral oil distillates is measured by the pour point and the cold filter plugging point (CFP point). The pour point (determined in accordance with DIN 51 597) is the lowest temperature at which a mineral oil or mineral oil distillate can still just flow. The cold filter plugging point (determined in accordance with DIN 51 428) represents the limit of filterability. For economic reasons it is of interest to find one single additive which favorably influences both the pour point and the cold filter plugging point.
Typical pour point reducers and flow improvers for crude oils and middle distillates are ethylene copolymers with carboxylic acid esters of vinyl alcohol. Of these copolymers ethylene/vinylacetate has proved to be particularly successful.
Such copolymers and their applications are described, for example, in DE-PS 1 914 756. They are generally produced by copolymerization of the corresponding monomers in autoclaves at temperatures of 80 to 150 C and pressures of 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as reaction media.
A disadvantage of the ethylene/vinylacetate copolymers is that, although they improve the CFP point of middle distillates, they only slightly reduce the pour point.
i;27~895 The task therefore consisted in preparing additives for mineral oils which appreciably reduce both the CFP point and the pour point.
The invention consists in the use of terpolymers which not only contain ethylene but also 0.5 to 20% by weight diisobutylene and 20 to 35% by weight vinylacetate and which have an average molecular weight of 500 to lo,oOo as additives in mineral oils and mineral oil distillates.
Surprisingly, the problem is solved by the use of the particular terpolymers of the present invention. It was impossible to fore6ee that terpolymers of ethylene, diisobutylene and vinylacetate would appreciably reduce kQ~h the CFP point and the pour point of mineral oils and mineral oil distillates.
It is recognized that terpolymers of ethylene, isoolefins (in particular isobutene), and vinylacetate as such are known as flow improvers from the EP 0 099 646 Al. However, these products nave little effect as both pour point and CFP
point reducer6. The ethylene terpolymers employed in accordance with the invention contain 0.5 to 20% by weight diisobutylene.
Terpolymers wherein the proportion of Co-olefins is l to 15% by weight (based on the terpolymer) have proven to be particularly successful.
12~18g5 In the terpolymer employed in accordance with the invention, the proportion of vinylacetate is 20 to 35% by weight, a proportion of 22 to 30% by weight is preferred, based on the terpolymer.
The average molecular weight of the terpolymers of the invention, measured in a steam phase osmometer with toluene as a solvent, is 500 to 10,000; polymers with a molecular weight of 1,000 to 5,000 are preferred.
In another preferred embodiment of the invention terpolymerisates are used whose melt viscosity (measured at 140C) is 100 to 1,OOo mPa x sec. The melt viscosity is determined in a rotation viscosimeter in accordance with the German Standard DIN 53019.
The ethylene/diisobutylene(vinylacetate terpolymers contain branchings which are due to the incorporation of diisobutylene and ethylene in the macromolecule. For every lOo CH2 groups, the terpolymers carry 6 to 20 CH3 groups in the side chains and which do not originate from the vinylacetate. In accordance with the invention, the terpolymers preferably contain 7 to 15 C%3 groups in the side chains per 100 CH2 groups.
The terpolymers which are employed in accordance with the invention are prepared from mixtures of ethylene, diisobutylene, and vinylacetate which are polymerized in the presence of radical-forming initiators (such as peroxides) X
at pressures above 50 mPa and at temperatures of 150 to 350~c in the absence of organic solvents. The molecular weights of the terpolymers are preferably determined by the diisobutylene.
Other molecular weight controllers such as hydrocarbons, aldehydes and ketones can also be used; however, they should be present in amounts of 1 to 5% by weight based on the monomer mixture. Propionaldehyde is particularly suitable as a molecular weight controller. Monomer mix~ures containing 79 to 20% by weight ethylene, 1 to 40% by weight diisobutylene and 20 to 40%
by weight vinylacetate are among those suitable for polymerization.
Generally speaking, the terpolymer is added to the mineral oils or mineral oil fractions in the form of a 40 to 60%
by weight solution in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture. Kerosene has, for example, proven to be very suitable as a solvent. The amount of polymer based on the mineral oil or mineral oil fraction should be 0.001 to 2%, preferably 0.005 to 0.5%, by weight. The terpolymer can be used alone or together with other additives; for example, with dewaxing agents, corrosion inhibitors, antioxidants or sediment inhibitors.
The use of ethylene/diisobutylene/vinylacetate terpolymers according to the invention as additives for mineral oils and mineral oil distillates is explained in detail in the following examples: -`~ 127~89~;
Examples A - C relate to the manufacture and properties of ethylene/diisobutylene/vinylacetate terpolymers. Examples D -F describe the manufacture and properties of polymers which are cited as comparative substances. Data on the efficiency of the terpolymers employed as additives in mineral oil and mineral oil distillates in accordance with the invention are compiled in examples 1 - 3. The data are compared with the figures obtained for the comparative substances in examples 4 - 6.
0 Examples A - C: Manufacture of Ethylene/diisobutylene Vinylacetate Ter~olymers.
Ethylene, diisobutylene (technical diisobutylene with about 75% by weight 2,4,4-trimethylenpentene-1) and vinylacetate are continuously polymerized in an autoclave. The monomer mixture is fed into the autoclave at the reaction pressure after the amount of peroxide required to maintain polymerization has been added as a solution in a petrol fraction. The residence period is about 80 seconds. The manufacture of the terpolymers listed in examples D - F takes place in the same manner. The polymerization conditions used and the characteristic properties of the polymers obtained are listed in Table 1.
X
1~1895 The vinylacetate content of the polymers is determined by the pyrolysis method. This involves taking 200 mg of the polymer and heating it with 300 mg of pure polyethylene in a pyrolysis flask for 5 minutes to a temperature of 450~C. The cracked gases are collected in a 250ml round flask. The acetic acid formed is reacted with a NaI/KIO3 solution and the iodine thus released is titrated with a Na2S2O3 solution.
The degree of branching of the polymers is determined by means of H-NMR spectroscopy. In the following examples, the degree of branching is understood to be the number of CH3 groups per 100 CH2 groups, except for those CH3 groups which originate with the acetate group. The viscosity is measured with a Rotovisco System MV II (manufacturer: Haake, Karlsruhe) at a temperature of 140C. The diisobutylene content in the polymer is determined by means of 13 C-NMR spectroscopy.
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~2~895 ~xamples 1 - 6 In the following examples 1 - 6, the ef~iciencies of the use of various ethylene/diisobutylene/vinylacetate and ethylene/isobutylene/vinylacetate terpolymers are described as additives in mineral oils and mineral oil distillates. The CFPP
test (cold filter plugging point) and determination of the pour points, measure this characteristic. Examples 1 - 3 are terpolymers in accordance with the invention; examples 4 - 6 relate to terpolymers which are not covered by the invention and serve as a comparison. The test is performed in accordance with DIN 51428 and is also published in the Journal of the Institute of Petroleum, volume 52, June 1966, pages 173 to 185. The pour point is measured in accordance with DIN 51597.
Three middle distillates M1, M2 and M3 were tested and their properties compiled in Table 2.
~9s Characteristic data of the middle distillates analysis by boiling (C) boiling begin 180 209 182 5% 202 281 213 50% 297 289 281 90% 357 356 3~9 boiling end 357 368 370 pour point (C) - 6 - 9 CFPP point (~C) + 1 - 1 - 6 ~2718g5 ~ ~ ~_ ~ ~ ~
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U~-v ~_ ~_ ~ ~ ~ ~o i ~ I _ -` ~27~895 The results compiled in Table 3 show that only waxy terpolymers which contain diisobutylene qualitatively as a termonomer and 20 to 35% by weight vinylacetate quantitatively reduce both the pour point and the CFP
point to the extent desired in practice.
Mineral oils such as crude oil, diesel fuel or fuel oil contain varying amounts of long-chain paraffins (waxes) dissolved in them which crystallize out at low temperatures. This leads to solid deposits which often cause breakdowns during the recovery, transportation and use of such oils. Thus, the operability of crude oil conveyance and transportation facilities can be impaired to such a degree that they fail completely. With diesel engines and firing plants the filter can become blocked, preventing accurate dosage of the fuels and finally resulting in a complete breakdown of the equipment.
This undesirable formation of solid deposits is counteracted by additives which prevent the paraffin crystals from forming and stop the viscosity of the oils from increasing.
lZ71895 The flow and low temperature behaviour of mineral oils and mineral oil distillates is measured by the pour point and the cold filter plugging point (CFP point). The pour point (determined in accordance with DIN 51 597) is the lowest temperature at which a mineral oil or mineral oil distillate can still just flow. The cold filter plugging point (determined in accordance with DIN 51 428) represents the limit of filterability. For economic reasons it is of interest to find one single additive which favorably influences both the pour point and the cold filter plugging point.
Typical pour point reducers and flow improvers for crude oils and middle distillates are ethylene copolymers with carboxylic acid esters of vinyl alcohol. Of these copolymers ethylene/vinylacetate has proved to be particularly successful.
Such copolymers and their applications are described, for example, in DE-PS 1 914 756. They are generally produced by copolymerization of the corresponding monomers in autoclaves at temperatures of 80 to 150 C and pressures of 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as reaction media.
A disadvantage of the ethylene/vinylacetate copolymers is that, although they improve the CFP point of middle distillates, they only slightly reduce the pour point.
i;27~895 The task therefore consisted in preparing additives for mineral oils which appreciably reduce both the CFP point and the pour point.
The invention consists in the use of terpolymers which not only contain ethylene but also 0.5 to 20% by weight diisobutylene and 20 to 35% by weight vinylacetate and which have an average molecular weight of 500 to lo,oOo as additives in mineral oils and mineral oil distillates.
Surprisingly, the problem is solved by the use of the particular terpolymers of the present invention. It was impossible to fore6ee that terpolymers of ethylene, diisobutylene and vinylacetate would appreciably reduce kQ~h the CFP point and the pour point of mineral oils and mineral oil distillates.
It is recognized that terpolymers of ethylene, isoolefins (in particular isobutene), and vinylacetate as such are known as flow improvers from the EP 0 099 646 Al. However, these products nave little effect as both pour point and CFP
point reducer6. The ethylene terpolymers employed in accordance with the invention contain 0.5 to 20% by weight diisobutylene.
Terpolymers wherein the proportion of Co-olefins is l to 15% by weight (based on the terpolymer) have proven to be particularly successful.
12~18g5 In the terpolymer employed in accordance with the invention, the proportion of vinylacetate is 20 to 35% by weight, a proportion of 22 to 30% by weight is preferred, based on the terpolymer.
The average molecular weight of the terpolymers of the invention, measured in a steam phase osmometer with toluene as a solvent, is 500 to 10,000; polymers with a molecular weight of 1,000 to 5,000 are preferred.
In another preferred embodiment of the invention terpolymerisates are used whose melt viscosity (measured at 140C) is 100 to 1,OOo mPa x sec. The melt viscosity is determined in a rotation viscosimeter in accordance with the German Standard DIN 53019.
The ethylene/diisobutylene(vinylacetate terpolymers contain branchings which are due to the incorporation of diisobutylene and ethylene in the macromolecule. For every lOo CH2 groups, the terpolymers carry 6 to 20 CH3 groups in the side chains and which do not originate from the vinylacetate. In accordance with the invention, the terpolymers preferably contain 7 to 15 C%3 groups in the side chains per 100 CH2 groups.
The terpolymers which are employed in accordance with the invention are prepared from mixtures of ethylene, diisobutylene, and vinylacetate which are polymerized in the presence of radical-forming initiators (such as peroxides) X
at pressures above 50 mPa and at temperatures of 150 to 350~c in the absence of organic solvents. The molecular weights of the terpolymers are preferably determined by the diisobutylene.
Other molecular weight controllers such as hydrocarbons, aldehydes and ketones can also be used; however, they should be present in amounts of 1 to 5% by weight based on the monomer mixture. Propionaldehyde is particularly suitable as a molecular weight controller. Monomer mix~ures containing 79 to 20% by weight ethylene, 1 to 40% by weight diisobutylene and 20 to 40%
by weight vinylacetate are among those suitable for polymerization.
Generally speaking, the terpolymer is added to the mineral oils or mineral oil fractions in the form of a 40 to 60%
by weight solution in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture. Kerosene has, for example, proven to be very suitable as a solvent. The amount of polymer based on the mineral oil or mineral oil fraction should be 0.001 to 2%, preferably 0.005 to 0.5%, by weight. The terpolymer can be used alone or together with other additives; for example, with dewaxing agents, corrosion inhibitors, antioxidants or sediment inhibitors.
The use of ethylene/diisobutylene/vinylacetate terpolymers according to the invention as additives for mineral oils and mineral oil distillates is explained in detail in the following examples: -`~ 127~89~;
Examples A - C relate to the manufacture and properties of ethylene/diisobutylene/vinylacetate terpolymers. Examples D -F describe the manufacture and properties of polymers which are cited as comparative substances. Data on the efficiency of the terpolymers employed as additives in mineral oil and mineral oil distillates in accordance with the invention are compiled in examples 1 - 3. The data are compared with the figures obtained for the comparative substances in examples 4 - 6.
0 Examples A - C: Manufacture of Ethylene/diisobutylene Vinylacetate Ter~olymers.
Ethylene, diisobutylene (technical diisobutylene with about 75% by weight 2,4,4-trimethylenpentene-1) and vinylacetate are continuously polymerized in an autoclave. The monomer mixture is fed into the autoclave at the reaction pressure after the amount of peroxide required to maintain polymerization has been added as a solution in a petrol fraction. The residence period is about 80 seconds. The manufacture of the terpolymers listed in examples D - F takes place in the same manner. The polymerization conditions used and the characteristic properties of the polymers obtained are listed in Table 1.
X
1~1895 The vinylacetate content of the polymers is determined by the pyrolysis method. This involves taking 200 mg of the polymer and heating it with 300 mg of pure polyethylene in a pyrolysis flask for 5 minutes to a temperature of 450~C. The cracked gases are collected in a 250ml round flask. The acetic acid formed is reacted with a NaI/KIO3 solution and the iodine thus released is titrated with a Na2S2O3 solution.
The degree of branching of the polymers is determined by means of H-NMR spectroscopy. In the following examples, the degree of branching is understood to be the number of CH3 groups per 100 CH2 groups, except for those CH3 groups which originate with the acetate group. The viscosity is measured with a Rotovisco System MV II (manufacturer: Haake, Karlsruhe) at a temperature of 140C. The diisobutylene content in the polymer is determined by means of 13 C-NMR spectroscopy.
~ -1'- 1' 1' ~O ~ p~ ~ ~ (D tD
n ~ U~ x O 1-- 0 ~ O 1' 1' ~ 1' 0 ~ ~ ~ ~ ~ (D
U~ O pJ ~ ~ I' .~
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(D
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rt (D
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X ~ _ ~ ~
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.
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t~ Vl ~ 1::
0~ ~ I uto ~O~On ~ ~D
O P ~n I ~ o ~ ~.n U~ o o t~
_ Z~
~2~895 ~xamples 1 - 6 In the following examples 1 - 6, the ef~iciencies of the use of various ethylene/diisobutylene/vinylacetate and ethylene/isobutylene/vinylacetate terpolymers are described as additives in mineral oils and mineral oil distillates. The CFPP
test (cold filter plugging point) and determination of the pour points, measure this characteristic. Examples 1 - 3 are terpolymers in accordance with the invention; examples 4 - 6 relate to terpolymers which are not covered by the invention and serve as a comparison. The test is performed in accordance with DIN 51428 and is also published in the Journal of the Institute of Petroleum, volume 52, June 1966, pages 173 to 185. The pour point is measured in accordance with DIN 51597.
Three middle distillates M1, M2 and M3 were tested and their properties compiled in Table 2.
~9s Characteristic data of the middle distillates analysis by boiling (C) boiling begin 180 209 182 5% 202 281 213 50% 297 289 281 90% 357 356 3~9 boiling end 357 368 370 pour point (C) - 6 - 9 CFPP point (~C) + 1 - 1 - 6 ~2718g5 ~ ~ ~_ ~ ~ ~
. i ~
X H
. 3o u~
~ ~ ~ ~ b~ ~
l ~0~ H~IOHl ~i 3 P' _ ~;
~ ~ ~s ~o~
~1- ~ ~ ,_ ~ ~ ,_ ~ ~ ,_ ~ w 1-~ ~ )~ ,& nn ~
o oo ooo ooo ooo ooo ooo ~ ~ o 1~-o oo ooo ooo ooo ooo ooo3 r~
o (D ~
O, + ,,, l l l l l l l l l l l l æ rt ~ (D
1- ~ O ~ 1- CO I- ~D IJ ~I 1-~ :J' tD
_ __ ~ (D ~-l l l l ll l ll ll l l l l l l l ~ rtl'~
~1- ~ ~n w co ~n ~ ~o ~D Ul~1~ ~ O ~ ~.......... ~ ~ ~
~_ ~ ~3~0Pr~t lll lll lll lll lll llo ~0 l~
~ ~D O ~ I_ _ p,~a~
l l l l l l l l l ~ ~ o ~ X ~1l ~_ I_ ~I _o~ ,~
U~-v ~_ ~_ ~ ~ ~ ~o i ~ I _ -` ~27~895 The results compiled in Table 3 show that only waxy terpolymers which contain diisobutylene qualitatively as a termonomer and 20 to 35% by weight vinylacetate quantitatively reduce both the pour point and the CFP
point to the extent desired in practice.
Claims (10)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An additive for mineral oils and/or mineral oil fractions comprising a terpolymer containing 0.5 to 20% by weight diisobutylene, 20-35% by weight vinyl acetate, both based on total terpolymer, and ethylene, said terpolymer having an average molecular weight of 500 to 10,000.
2. The additive of Claim 1 wherein there is a 1 to 15% by weight of said diisobutylene based on said terpolymer.
3. The additive of Claim 1 wherein said terpolymer has an average molecular weight of 1,000 to 5,000.
4. The additive of Claim 1 wherein said terpolymer has a viscosity of 100 to 1,000 mPa's at 140°C.
5. The additive of Claim 1 wherein there is 22 to 30% by weight of said vinyl acetate based on said terpolymer.
6. The additive of Claim 1 wherein there are 7 to 15 CH3 groups in side chains per 100 Ch2 groups.
7. A method of preparation of the terpolymers of Claim 1 comprising polymerizing 35 to 75% by weight of said ethylene, 5 to 30 by weight of said diisobutylene, and 20 to 35% by weight of said vinyl acetate, all based on said terpolymer.
8. The method of Claim 7 wherein said polymerizing takes place under a pressure of at least 50 mPa and a temperature of 150 to 350°C in the absence of an organic solvent.
9. A composition comprising at least one said mineral oil and/or at least one said mineral oil fraction and 0.001 to 2.0% by weight of the additive of Claim 1.
10. The composition of Claim 9 wherein there is present 0.005 to 0.5% by weight of said additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3519196 | 1985-05-29 | ||
| DEP3519196.1 | 1985-05-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1271895A true CA1271895A (en) | 1990-07-17 |
Family
ID=6271886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000510298A Expired - Fee Related CA1271895A (en) | 1985-05-29 | 1986-05-29 | The use of ethylene terpolymers as additives in mineral oil and miniral oil distillates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1271895A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789510A (en) * | 1996-05-18 | 1998-08-04 | Hoechst Aktiengesellschaft | Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates |
| US6281292B1 (en) | 1998-05-27 | 2001-08-28 | Clariant Gmbh | Mixtures of copolymers having an improved lubricating action |
| US6495495B1 (en) | 1999-08-20 | 2002-12-17 | The Lubrizol Corporation | Filterability improver |
| US6509424B1 (en) | 1997-12-09 | 2003-01-21 | Clariant Gmbh | Process for the preparation of ethylene copolymers, and their use as additives to mineral oil and mineral oil distillates |
| US7323019B2 (en) | 2001-11-14 | 2008-01-29 | Clariant Produkte (Deutschland) Gmbh | Additives for low-sulphur mineral oil distillates containing an ester of an alkoxylated polyol and a polar nitrogenous paraffin dispersant |
| US7347881B2 (en) | 2001-11-14 | 2008-03-25 | Clariant Produkte (Deutschland) Gmbh | Low-sulphur mineral oil distillates with improved cold properties, containing an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters |
| US7377949B2 (en) | 2001-11-14 | 2008-05-27 | Clariant Produkte (Deutschland) Gmbh | Additives for sulphur-poor mineral oil distillates comprising an ester of an alkoxylated polyol and an alkylphenol-aldehye resin |
| US7815696B2 (en) | 2002-07-09 | 2010-10-19 | Clariant Produkte (Deutschland) Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
-
1986
- 1986-05-29 CA CA000510298A patent/CA1271895A/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789510A (en) * | 1996-05-18 | 1998-08-04 | Hoechst Aktiengesellschaft | Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates |
| US6509424B1 (en) | 1997-12-09 | 2003-01-21 | Clariant Gmbh | Process for the preparation of ethylene copolymers, and their use as additives to mineral oil and mineral oil distillates |
| US6762253B2 (en) | 1997-12-09 | 2004-07-13 | Clariant Gmbh | Process for the preparation of ethylene copolymers, and their use as additives to mineral oil and mineral oil distillates |
| US6969746B2 (en) * | 1997-12-09 | 2005-11-29 | Clariant Gmbh | Process for the preparation of ethylene copolymers, and their use as additives to mineral oil and mineral oil distillates |
| US6281292B1 (en) | 1998-05-27 | 2001-08-28 | Clariant Gmbh | Mixtures of copolymers having an improved lubricating action |
| US6495495B1 (en) | 1999-08-20 | 2002-12-17 | The Lubrizol Corporation | Filterability improver |
| US7323019B2 (en) | 2001-11-14 | 2008-01-29 | Clariant Produkte (Deutschland) Gmbh | Additives for low-sulphur mineral oil distillates containing an ester of an alkoxylated polyol and a polar nitrogenous paraffin dispersant |
| US7347881B2 (en) | 2001-11-14 | 2008-03-25 | Clariant Produkte (Deutschland) Gmbh | Low-sulphur mineral oil distillates with improved cold properties, containing an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters |
| US7377949B2 (en) | 2001-11-14 | 2008-05-27 | Clariant Produkte (Deutschland) Gmbh | Additives for sulphur-poor mineral oil distillates comprising an ester of an alkoxylated polyol and an alkylphenol-aldehye resin |
| US7815696B2 (en) | 2002-07-09 | 2010-10-19 | Clariant Produkte (Deutschland) Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
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