EP4638670A1 - Viscosity index improver additives for lubricating oils and process for their preparation - Google Patents
Viscosity index improver additives for lubricating oils and process for their preparationInfo
- Publication number
- EP4638670A1 EP4638670A1 EP23836587.8A EP23836587A EP4638670A1 EP 4638670 A1 EP4638670 A1 EP 4638670A1 EP 23836587 A EP23836587 A EP 23836587A EP 4638670 A1 EP4638670 A1 EP 4638670A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylene
- weight
- comprised
- equal
- propylene copolymer
- 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.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to viscosity index improver (V.I.I.) additives for lubricating oils.
- the present invention relates to a viscosity index improver (V.I.I.) additive for lubricating oils comprising an ethylene-propylene copolymer, said additive having the specific features reported below.
- V.I.I. viscosity index improver
- the aforesaid viscosity index improver (V.I.I.) additive for lubricating oils is advantageously usable in base oils of mineral origin, or of synthetic origin, or mixtures thereof.
- said base oils of mineral origin or of synthetic origin are selected from the base oils belonging to Group I, or Group II or Group III.
- the present invention also relates to a process for preparing said ethylenepropylene copolymer.
- the present invention also relates to a composition of lubricating oil comprising said viscosity index improver (V.I.I.) additive for lubricating oils and a base oil.
- V.I.I. viscosity index improver
- Ethylene-propylene copolymers are widely used in the sector of the lubricating oil additives [in the sector also known as olefin copolymers (OCP)] as viscosity index improvers (V.I.I.) in order to modulate the viscosity of said lubricating oils at varying temperatures.
- OCP olefin copolymers
- V.I.I. viscosity index improvers
- V.I.I. viscosity index improvers
- the thickening power (TP) increases with the increase in the ethylene content and molecular weight.
- the semicrystalline ethylene-propylene copolymers, characterized by a high content of chain- bonded ethylene, are therefore characterized by ratios between the thickening power (TP) and the shear stability index (SSI) (TP/SSI) higher than those of the amorphous ethylene-propylene copolymers, but have insufficient performance at low temperatures.
- the amorphous ethylene- propylene copolymers characterized by a low content of chain-bonded ethylene and by a low weight average molecular weight (M w ), present problems associated with the stability of physical form (pellets) that make the handling of said ethylene-propylene copolymers particularly critical.
- the balancing of the technological parameters of the lubricating oil cannot be carried out only through the use of the ethylene-propylene copolymers having an intermediate ethylene content since said ethylene-propylene copolymers have ethylenic sequences capable of interfering with the additives capable of lowering the pour point depressant of the lubricating oil in which they are used, compromising the activity thereof and further worsening the rheology of the lubricating oil at low temperature.
- European patent EP 2424939 relates to a polymeric composition comprising:
- a first ethylene copolymer having: i. a weight percentage of EA units derived from ethylene in the range from greater than or equal to 35 to lower than or equal to 60; and ii. a MWA lower than 130000; and
- a second ethylene copolymer having: i. a weight percentage of EB units derived from ethylene in the range from greater than or equal to 35 to lower than or equal to 85; and ii. a MWB lower than 70000; wherein the first ethylene copolymer and/or the second ethylene copolymer have less than 1 pendant branching point with a carbon chain greater than 19 carbon atoms per 200 carbon atoms along the backbone.
- a process for preparing said polymeric composition as well as a composition comprising a lubricating base oil and said polymeric composition.
- the aforesaid polymeric composition is said to be a rheological modifier usable as a viscosity index improver (V.I.I.) having an unexpected thickening power (TP) with respect to the compositions of the known art while maintaining equivalent rheological properties at low temperatures.
- V.I.I. viscosity index improver
- European patent EP 2809689 relates to a polymeric composition comprising:
- the first ethylene-oc-olefin copolymer (a) has an ethylene content comprised between about 60% by weight and about 80% by weight;
- the second ethylene-oc-olefin copolymer (b) has an ethylene content lower than about 60% by weight;
- the first ethylene-oc-olefin copolymer (a) has a “Melt Flow Rate Ratio” (MFRR), defined as the ratio between the “Melt Flow Rate” (MFR) measured at 230 C with a load equal to 21.6 kg and the “Melt Flow Rate” (MFR) measured at 230 C with a load equal to 2.16 kg, greater than 34 and has a “Melt Flow Rate” (MFR) measured in accordance with standard ASTM D 1238, condition L (230 C with a load equal to 2.16 kg), comprised between 2.5 g/10 min and 5.5 g/10 min; and
- MFRR Melt Flow Rate Ratio
- the mixture between the first ethylene-oc-olefin copolymer (a) and the second ethylene- ⁇ -olefin copolymer (b) has a “Melt Flow Rate Ratio” (MFRR), defined as above, comprised between 33 and 37.
- MFRR Melt Flow Rate Ratio
- lubricating compositions comprising the aforesaid polymeric composition and a lubricating base oil which are said to have reduced or even no gel formation.
- European patent EP 2809716 relates to a process for preparing a polymeric composition comprising the steps of: (a) feeding (i) a first ethylenic monomer, (ii) a first ⁇ -olefinic comonomer, (iii) a first solvent, (iv) optionally a first hydrogen, and (v) a first metallocene catalyst, into a first reaction zone to produce a first ethylene-oc-olefin copolymer; (b) feeding (i) a second ethylenic monomer, (ii) a second oc-olefinic comonomer, (iii) a second solvent, (iv) optionally a second hydrogen, and (v) a second metallocene catalyst, into a second reaction zone to produce a second ethylene-oc-olefin copolymer; and (c) combining the first ethylene-oc-olefin copolymer and the second ethylene-
- the polymeric composition obtained is said to be usable as a viscosity index improver (V.I.I.) in lubricating oils that have reduced or even no gel formation at low temperatures.
- V.I.I. viscosity index improver
- European patent EP 1148115 relates to a viscosity index improver (V.I.I.) for lubricating oil, comprising an ethylene-prop ylene copolymer (B) having the following features (bl)-(b5):
- (b2) a weight average molecular weight determined by gel permeation chromatography in the range between 80000 Da and 400000 Da in terms of polystyrene
- a lubricating composition comprising a lubricating oil and the aforesaid viscosity index improver (V.I.I.): said lubricating composition is said to have excellent properties at low temperature.
- European patent EP 1178102 relates to a viscosity index improver (V.I.I.) for lubricating oil, comprising an ethylene/ ⁇ -olefin copolymer which is a copolymer of ethylene with a ⁇ -olefin having from 3 to 20 carbon atoms and has the following properties:
- a lubricating composition comprising a lubricating oil and the aforesaid viscosity index improver (V.I.I.): said lubricating composition is said to have excellent properties at low temperature, oxidation stability, lubrication at high temperatures and fuel economy.
- the viscosity index improvers (V.I.I.) mentioned above may have some drawbacks.
- V.I.I. viscosity index improvers
- the ethylene -propylene copolymers have medium-high weight average molecular weights (M w ) and, consequently, high shear stability index (SSI) values (i.e. > 30).
- M w weight average molecular weights (M w ) lower than 100000 Da); the low molecular weight products tend to exhibit cold flow phenomena that make their handling and storage prohibitive (a very accentuated phenomenon, in particular, in the case of amorphous ethylene-propylene copolymers).
- European patent EP 1013673 relates to a process for reducing the molecular weight of a polymeric material selected from copolymers and terpolymers of ethylene [EP(D)M)] or mixtures thereof, comprising treating the polymeric material with at least one hydroperoxide, said hydroperoxide being present in an amount such as to perform a reduction in the molecular weight, at a temperature comprised between 80°C and 250°C, said copolymers and terpolymers of ethylene [EP(D)M)] having a propylene molar content comprised between 16% and 50%.
- copolymers and terpolymers of the ethylene [EP(D)M)] thus obtained are said to have several applications, including the use as viscosity index improvers (V.I.I.) for lubricating oils and the modification of high fluidity plastic materials.
- the aforesaid process can be carried out in an extruder, preferably in a twin-screw extruder.
- European patent EP 1671982 relates to a process for preparing viscosity index improvers (V.I.I.) having an improved dimensional stability and able to improve the rheology of the lubricating oils at low temperature, said process comprising the treatment of mixtures of linear polyethylene which is a homopolymer or copolymer of the ethylene characterized by a crystalline structure and by a density comprised between 0.88 and 0.94 and by amorphous copolymers and terpolymers of the ethylene [EP(D)M)], optionally in mixture with semi-crystalline copolymers and terpolymers of the ethylene [EP(D)M)], said treatment being carried out in an extruder, said treatment being carried out in the presence of one or more substances of a hydroperoxide nature and, optionally, in the presence of polyfunctional vinyl monomers in an amount comprised between 0% by weight and 2% by weight, said treatment being carried out at a shear value greater than 100 sec 1 and at a temperature comprised between
- European patent EP 1632504 relates to a process for preparing viscosity index improvers (V.I.I.) comprising treating, under high shear conditions, a composition comprising: (i) one or more copolymers or terpolymers of the ethylene [EP(D)M)] and (ii) one or more polyvinylarene/hydrogenated conjugated diene/polyvinylarene block copolymers, the weight ratio (i)/(ii) being comprised between 98/2 and 80/20, said process being carried out at a temperature comprised between 150 C and 400 C, for a time not higher than 150 seconds and at a shear value greater than 75 sec 1 .
- the aforesaid process can be carried out in an extruder, preferably in a twin-screw extruder.
- European patent EP 1984479 relates to a process for preparing viscosity index improvers (V.I.I.) for lubricating oils comprising a mixing treatment under shear conditions greater than 50 sec 1 , of a composition comprising:
- the aforesaid process can be carried out in an extruder, preferably in a twin-screw extruder.
- Canadian patent CA 991792 relates to a continuous process for producing an additive for lubricating oil by thermal degradation in an extruder, under non-oxidizing conditions, of a substantially linear, high molecular weight, amorphous ethylenepropylene hydrocarbon copolymer containing 25%-50% by weight of polymerized propylene, 0%-5% by weight of a polymerized non-conjugated hydrocarbon diene and the remainder, polymerized ethylene, said process comprising: uniformly mixing and heating the copolymer in a first zone at a temperature comprised between about 150°C and 280°C, until when the copolymer is uniformly melted, said temperature being lower than the degradation temperature of the copolymer; passing the melted copolymer to a second zone in which it is uniformly mixed and heated to a temperature comprised between about 300°C and 500 C, until obtaining a degraded copolymer whose inherent viscosity is lower than the inherent viscosity of the starting copolymer and is comprise
- American patent US 6,753,381 relates to a composition of lubricating oil comprising a greater amount of lubricating oil, an additive package appropriate for the quality and performance levels, a pour point lowering element and an oil-soluble polymeric mixture in an amount to improve the viscosity index (V.I.I.), said polymeric mixture comprising an ethylene-propylene polymeric mixture having a weight average molecular weight comprised between about 20000 and about 300000 and a molecular weight distribution comprised between about 1.3 and about 5 prepared by the process comprising mixing or simultaneously mixing and shearing:
- V.I.I. viscosity index improver
- SSI shear stability index
- TP thickening power
- V.I.I. viscosity index improver
- SSI shear stability index
- TP thickening power
- the aforesaid viscosity index improver (V.I.I.) additive for lubricating oils is advantageously usable in base oils of mineral origin, or of synthetic origin, or mixtures thereof.
- said base oils of mineral origin or of synthetic origin are selected from the base oils belonging to Group I, or Group II or Group III.
- an object of the present invention is a viscosity index improver (V.I.I.) additive for lubricating oils comprising an ethylene-propylene copolymer, said additive having the following features: a shear stability index (SSI) comprised between 18% and 30%, preferably comprised between 20% and 28%, measured according to ASTM D7109-12 standard (30 cycles of shearing) in Group I base oil; a thickening power (TP) comprised between 3 cSt and 8 cSt, preferably comprised between 4 cSt and 7.5 cSt, measured according to ASTM D7042-04 standard in Group I base oil; a gelation index defined by the ratio: where ⁇ represents the steady state dynamic viscosity measured in Group III base oil, said gelation index being lower than or equal to 7000, preferably comprised between 30 and 6000, more preferably comprised between 50 and 5000; an incipient gelation temperature, measured in Group III base oil, at a temperature lower than or equal to 10 C, preferably
- the gelation index, the incipient gelation temperature, and the shape stability have been determined as reported below in the analysis and characterization methodologies.
- base oils means base oils according to API 1509 standard “Engine Oil Licensing and Certification System”, version of November 2004, 15th Ed., appendix E, in which said base oils are divided into five groups as reported in the following Table:
- said ethylene-prop ylene copolymer has the following features: from 61% by weight to 67% by weight, preferably from 62% by weight to 66% by weight, with respect to the total weight of said ethylene-propylene copolymer, of ethylene; from 33% by weight to 39% by weight, preferably from 34% by weight to 38% by weight, with respect to the total weight of said ethylene-propylene copolymer, of propylene; a weight average molecular weight (M w ) comprised between 60000 Da and 120000 Da, preferably comprised between 65000 Da and 100000 Da; a polydispersity index (PDI), i.e.
- M w weight average molecular weight
- PDI polydispersity index
- DSC differential scanning calorimetry
- the Applicant has also posed the problem of finding a process for preparing the aforesaid ethylene-propylene copolymer capable of overcoming the above drawbacks.
- the Applicant has now found a continuous process for reducing the molecular weight of ethylene-propylene copolymers comprising the use of a single screw extruder provided with a reciprocating single screw, three conveying and mixing zones, a gear pump, an underwater die-face cutter, said three conveying and mixing zones and said gear pump operating at specific temperature ranges.
- the Applicant has found that the use of said single screw extruder allows to obtain ethylene-propylene copolymers having molecular weights suitable for use as viscosity index improvers (V.I.I.) in the absence of hydroperoxides, operating at lower temperatures than the known art so as to be able to avoid both operating in an inert atmosphere and the formation of gel and of branchings in the final product. Furthermore, said process does not require the use of polyvinylarene/hydrogenated conjugated diene/polyvinylarene block copolymers or of polyfunctional vinyl monomers in order to improve the dimensional stability of the final product.
- V.I.I. viscosity index improvers
- a further object of the present invention is a continuous process for reducing the molecular weight of ethylene-propylene copolymers comprising the following steps: (a) providing at least one single screw extruder comprising a chamber, a reciprocating single screw mounted in said chamber, said reciprocating single screw being capable of rotating and oscillating within said chamber, said chamber having at least one feeding opening and at least one discharging opening, said extruder comprising three conveying and mixing zones, a gear pump, an underwater dieface cutter;
- a single screw extruder provided with a reciprocating single screw, three conveying and mixing zones, a gear pump, an underwater die-face cutter, which also has the following features, can be used: compared to a traditional single screw extruder in which the screw has the shape of a continuous spiral, the reciprocating single screw has threads interrupted at radial intervals of 120° and pins or teeth coordinated with the aforesaid threads are inserted in the barrel; compared to a traditional single screw extruder in which the movement of the screw consists solely of rotation, the movement of the reciprocating single screw consists of rotation and oscillation, in fact, the rotation of the reciprocating single screw is superimposed by an oscillation (or axial stroke) that leads to an improved mixing and degradation capacity inside the extruder; the frequency of oscillation of the axial motion (“reciprocating action”) is the same as the rotational speed and a gear system ensures that for each rotation of the reciprocating single screw a complete forward and backward stroke is made; the oscillation
- said single screw extruder operates at a screw rotation speed comprised between 220 rpm and 300 rpm, preferably comprised between 230 rpm and 290 rpm.
- said single screw extruder operates at a flow rate comprised between 300 kg/h and 700 kg/h, preferably comprised between 400 kg/h and 600 kg/h.
- the totally degraded ethylenepropylene copolymer is in the form of pellets that are separated from the water, for example by centrifugation, and subsequently sent, by pneumatic transport, to the drying and packaging section.
- said at least one ethylene-propylene copolymer has the following features: from 61% by weight to 67% by weight, preferably from 62% by weight to 66% by weight, with respect to the total weight of said ethylene-propylene copolymer, of ethylene; from 33% by weight to 39% by weight, preferably from 34% by weight to 38% by weight, with respect to the total weight of said ethylene-propylene copolymer, of propylene; a weight average molecular weight (M w ) comprised between 120000 Da and 200000 Da, preferably comprised between 140000 Da and 170000 Da; a polydispersity index (PDI), i.e.
- M w weight average molecular weight
- PDI polydispersity index
- DSC differential scanning calorimetry
- Ethylene -propylene copolymers useful in the process object of the present invention can be obtained in accordance with the process described in American patent US 9,701,764 in the name of the Applicant and incorporated herein by reference.
- Figure 1 reported below shows an embodiment of the process object of the present invention as well as a block diagram of the plant and of the single screw extruder used in said process, for the sole purpose of illustration and not limitation thereof.
- the ethylene-prop ylene copolymer (1) is fed, through the feed hopper to the single screw extruder provided with three conveying and mixing zones, gear pump and underwater die-face cutter, said three conveying and mixing zones and said gear pump operating at specific temperature ranges.
- the ethylenepropylene copolymer through the first conveying and mixing zone is uniformly mixed and heated and uniformly softened thereby obtaining the ethylene-propylene copolymer (2) which is conveyed to the second conveying and mixing zone where it is further mixed and heated and partially degraded thereby obtaining the partially degraded ethylenepropylene copolymer (3) which is conveyed to the third conveying and mixing zone where it is further mixed and heated and further degraded thereby obtaining the further degraded ethylene-propylene copolymer (4) which is conveyed to the gear pump thereby obtaining a further degraded ethylene-propylene copolymer (5) which is recovered at the exit of the underwater die-face cutter in the form of pellets which are separated from water, for example by centrifugation, and subsequently sent by pneumatic transport to the drying and packaging section.
- the present invention also relates to a composition of lubricating oil comprising the aforesaid viscosity index improver (V.I.I.) additive for lubricating oils and a base oil.
- V.I.I. viscosity index improver
- the present invention also relates to a composition of lubricating oil comprising: from 1% by weight to 30% by weight, preferably from 2% by weight to 20% by weight, with respect to the total weight of said composition of lubricating oil of the above viscosity index improver (V.I.I.) additive for lubricating oils; a base oil of mineral origin, or of synthetic origin, or a mixture thereof, said base oil of mineral origin or of synthetic origin being preferably selected from the base oils belonging to Group I, or to Group II or to Group III.
- V.I.I. viscosity index improver
- the viscosity index improver (V.I.I.) additive for lubricating oils object of the present invention is advantageously usable in base oils of mineral origin, or of synthetic origin, or mixtures thereof.
- said base oils of mineral origin or of synthetic origin are selected from the base oils belonging to Group I, or Group II or Group III.
- the present invention also concerns the use of the aforesaid viscosity index improver (V.I.I.) additive for lubricating oils in base oils of mineral origin, or of synthetic origin, or mixtures thereof, said base oils of mineral origin or of synthetic origin preferably selected from the base oils belonging to Group I, or Group II or Group III.
- V.I.I. viscosity index improver
- C2D2CI4 deuterated tetrachloroethane
- TMS tetramethylsilane
- ethylene (%), propylene (%) content was determined through the analysis of the aforesaid spectra based on what is reported in the literature by Di Martino S., Kelchterrmans M., in "Journal of Applied Polymer Science” (1995), Vol. 56, Issue 13, pg. 1781-1787 (method No. 3, pg. 1784).
- the incipient gelation temperature for the purpose of the present invention was deemed to be the one in which the value of the normalized ( ⁇ norm.) steady state dynamic viscosity was found to be at least 75% higher than the datum calculated as reported in Figure 4 [Example 7 (invention)] and in Figure 5 [Example 8 (comparative)] [the abscissa reports the temperature (T) in centigrade degrees; the ordinate reports the normalized ( ⁇ norm.) steady state dynamic viscosity in logarithmic scale.
- the “spaghetti” were obtained by feeding the aforesaid ethylenepropylene copolymers to a capillary rheometer operating at a temperature equal to 140 C, at a shear rate equal to 1 s’ 1 , and relaxation of 16 hours.
- AL% [(L/L0)-l)]*100 wherein L is the length after 24 hours and L0 is the initial length equal to 10 cm.
- PL-SP-260 automatic dissolver from Agilent Technologies; column injection temperature: 135°C; temperature of columns and detection lines: 135 C; solvent/eluent: 1,2-dichlorobenzene (99+% for HPLC - Acros OrganicsTM); flow: 1 mL/min; calculation of the molecular mass by universal calibration curve.
- the calibration was carried out as follows.
- the calibration curve was calculated through a personal computer provided with the aforesaid Agilent GPC/SEC software from Agilent Technologies, using a 3rd order polynomial function.
- Differential Scanning Calorimetry DSC
- DSC Differential Scanning Calorimetry
- AH melting enthalpy
- AH residual melting enthalpy
- Samples weighing equal to 15+1 mg were collected from the aforesaid ethylene- propylene copolymers: the samples were as flat as possible so as to ensure the greatest contact surface with the aluminium crucible.
- the crucible was closed with an aluminium lid previously perforated with a punch so as to allow the steam emitted by the sample to exit.
- the crucible was closed with the lid by means of a special press.
- the crucibles containing the different samples to be analysed and the empty reference crucible were placed in the numbered self-sampling positions (each position was associated with the name of the sample) and, subsequently, the computer, the differential scanning calorimetry (DSC) and the refrigerated cooling system (RCS) were switched on in sequence and the heat treatment to be carried out was selected.
- the Thermal Advantage” software Version 5.1.2, was used for the analysis.
- thermograms obtained were processed using the “Universal Analysis” software Version 4.7A.
- the heat treatment to which the samples were subjected was as follows: 1st step: scanning cooling from +25 C to -90°C, at 20 C/min;
- 3rd step scanning heating from -90 C to +170°C, at 20°C/min (1st heating);
- 5th step scanning cooling from +170 C to -90°C, at 20°C/min;
- the degraded ethylene-propylene copolymers obtained as reported in the following examples were dissolved in an amount equal to 1% by weight in the reference base oil SN 150 Group I (Eni S.p.A.).
- the thickening power (TP) was determined according to ASTM D7042-04 standard and calculated according to the following formula:
- TP KV100 C (oil + polymer 1 % weight) - KV 100 C (oil) wherein KV is the kinematic viscosity.
- the degraded ethylene-propylene copolymers (EPR) obtained as reported in the following examples were dissolved in an amount equal to 1% by weight in the reference base oil SN 150 Group I (Eni S.p.A.).
- the shear stability index (SSI) was determined according to ASTM D7109-12 standard (30 “cycles of shearing”).
- Table 1 reports the operating conditions used: feeding the compounds to the reactor, temperature and pressure.
- the average residence time of the compounds in the reactor was about 1 hour.
- the ethylene-propylene copolymer suspension obtained was discharged from the bottom of the reactor and sent, continuously, to the strippers filled with water at 120 C, to which steam was also sent, so as to obtain the stripping of hydrogen, of propane and of the unreacted monomers (propylene and ethylene).
- (11) gas phase in which the measurements are performed to determine the concentration of the monomers in the reactor expressed in % by volume (%/v).
- the ethylene-propylene copolymer was fed to a single screw extruder (BUSS MDK 140 from Aaron Equipment) with reciprocating screw, provided with three conveying and mixing zones, a gear pump and an underwater die-face cutter, having a diameter equal to 140 mm and a ratio between the length (L) and the diameter (D) (L/D) equal to 11, at a flow rate equal to 500 kg/h, said extruder operating under the following conditions: screw rotation speed: 280 rpm; temperature profile 1 st zone: 180°C - 240°C; temperature profile 2 nd zone: 250 C - 300°C; temperature profile 3 rd zone: 190 C - 300°C; gear pump temperature: 190 C - 300°C.
- BUSS MDK 140 from Aaron Equipment
- the degraded and cooled ethylene-propylene copolymer was recovered in the form of pellets which were subjected to centrifugation to separate them from the water and subsequently sent by pneumatic transport to the drying and packaging section.
- the degraded ethylene-propylene copolymer obtained was subjected to the above reported characterizations and the results obtained are reported in Table 7.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT102022000025956A IT202200025956A1 (en) | 2022-12-19 | 2022-12-19 | ADDITIVES FOR IMPROVING THE VISCOSITY INDEX OF LUBRICATING OILS AND PROCEDURE FOR THEIR PREPARATION. |
| PCT/IB2023/062659 WO2024134391A1 (en) | 2022-12-19 | 2023-12-14 | Viscosity index improver additives for lubricating oils and process for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4638670A1 true EP4638670A1 (en) | 2025-10-29 |
Family
ID=85462083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23836587.8A Pending EP4638670A1 (en) | 2022-12-19 | 2023-12-14 | Viscosity index improver additives for lubricating oils and process for their preparation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP4638670A1 (en) |
| JP (1) | JP2025539946A (en) |
| KR (1) | KR20250125944A (en) |
| CN (1) | CN120380117A (en) |
| CA (1) | CA3268131A1 (en) |
| IT (1) | IT202200025956A1 (en) |
| MX (1) | MX2025006910A (en) |
| TW (1) | TW202432809A (en) |
| WO (1) | WO2024134391A1 (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA992529A (en) * | 1971-12-06 | 1976-07-06 | Exxon Research And Engineering Company | Degraded olefin polymer useful as a viscosity index improving additive for lubricating oil |
| CA991792A (en) | 1971-12-22 | 1976-06-22 | Thomas E. Johnston | Continuous process for the manufacture of oil soluble ethylene-propylene copolymers for use in petroleum products |
| DE69926015T2 (en) | 1998-12-09 | 2006-05-18 | Mitsui Chemicals, Inc. | VIKOSITY CHANGERS FOR LUBRICATING OILS AND LUBRICATING OIL COMPOSITION |
| IT1304499B1 (en) | 1998-12-22 | 2001-03-19 | Enichem Spa | PROCEDURE FOR REDUCING THE MOLECULAR WEIGHT OF ETHYLENE ETHERPOLYMIC COPOLYMERS. |
| WO2000060032A1 (en) | 1999-03-30 | 2000-10-12 | Mitsui Chemicals, Inc. | Viscosity regulator for lubricating oil and lubricating oil composition |
| US6753381B2 (en) | 2002-03-15 | 2004-06-22 | Ethyl Corporation | Polymer blends and their application as viscosity index improvers |
| ITMI20041672A1 (en) | 2004-08-27 | 2004-11-27 | Polimeri Europa Spa | ETHYLENE-PROPYLENE COPOLYMERS WITH IMPROVED STABILITY OF FORM SUITABLE FOR THE MODIFICATION OF LUBRICANT OILS AND PROCEDURE FOR THEIR PREPARATION |
| ITMI20042399A1 (en) | 2004-12-16 | 2005-03-16 | Polimeri Europa Spa | ADDITIVES FOR LUBRICATING OILS WITH IMPROVED SHAPE STABILITY AND IMPROVED LOW TEMPERATURE PERFORMANCE AND PROCEDURE FOR THEIR PREPARATION |
| ITMI20060286A1 (en) | 2006-02-16 | 2007-08-17 | Polimeri Europa Spa | ETHYLENE-PROPYLENE COPOLYMERS SUITABLE FOR THE MODIFICATION OF LUBRICATING OILS AND PROCEDURE FOR THEIR PREPARATION |
| US8378042B2 (en) | 2009-04-28 | 2013-02-19 | Exxonmobil Chemical Patents Inc. | Finishing process for amorphous polymers |
| EP2809716B1 (en) | 2012-02-03 | 2018-01-24 | ExxonMobil Chemical Patents Inc. | Process for the production of polymeric compositions useful as oil modifiers |
| US20240218282A1 (en) * | 2021-05-14 | 2024-07-04 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene branched copolymers used as viscosity modifiers |
-
2022
- 2022-12-19 IT IT102022000025956A patent/IT202200025956A1/en unknown
-
2023
- 2023-12-11 TW TW112148079A patent/TW202432809A/en unknown
- 2023-12-14 WO PCT/IB2023/062659 patent/WO2024134391A1/en not_active Ceased
- 2023-12-14 JP JP2025534918A patent/JP2025539946A/en active Pending
- 2023-12-14 CA CA3268131A patent/CA3268131A1/en active Pending
- 2023-12-14 KR KR1020257012546A patent/KR20250125944A/en active Pending
- 2023-12-14 EP EP23836587.8A patent/EP4638670A1/en active Pending
- 2023-12-14 CN CN202380087018.7A patent/CN120380117A/en active Pending
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2025
- 2025-06-12 MX MX2025006910A patent/MX2025006910A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024134391A1 (en) | 2024-06-27 |
| IT202200025956A1 (en) | 2024-06-19 |
| JP2025539946A (en) | 2025-12-10 |
| CA3268131A1 (en) | 2024-06-27 |
| TW202432809A (en) | 2024-08-16 |
| KR20250125944A (en) | 2025-08-22 |
| CN120380117A (en) | 2025-07-25 |
| MX2025006910A (en) | 2025-07-01 |
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