WO2021133583A1 - Procédé et appareil de production en continu de graisse à base de polyurée - Google Patents

Procédé et appareil de production en continu de graisse à base de polyurée Download PDF

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Publication number
WO2021133583A1
WO2021133583A1 PCT/US2020/064879 US2020064879W WO2021133583A1 WO 2021133583 A1 WO2021133583 A1 WO 2021133583A1 US 2020064879 W US2020064879 W US 2020064879W WO 2021133583 A1 WO2021133583 A1 WO 2021133583A1
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Prior art keywords
diisocyanate
stirred tank
continuously stirred
polyurea grease
producing
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PCT/US2020/064879
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English (en)
Inventor
Matthew J. CAMPBELL
Alvin LE VUONG
Todd Timothy Nadasdi
Trevor D. WOOD
David J. AM ENDE
Michael P. McCORMACK
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Exxonmobil Research And Engineering Company
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Publication of WO2021133583A1 publication Critical patent/WO2021133583A1/fr

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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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • 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
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • 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 disclosure provides a process for the continuous production of polyurea grease.
  • the process involves: (1) reaction of a diisocyanate and an amine compound in at least one continuously stirred tank reactor; (2) milling of the reacted product; and (3) hot curing the milled product, thereby forming a polyurea grease product.
  • the disclosure also provides an apparatus for the continuous production of polyurea grease.
  • the apparatus includes involves: (1) at least one of a diisocyanate feed and an amine feed; (2) at least one continuously stirred tank reactor;
  • Polyurea grease is a non-soap thickened lubricating grease that is widely used in applications such as electric motor bearings and automotive applications.
  • low noise greases have been increasingly popular in bearing applications, for example, for vehicle constant- velocity joints, ball joints, wheel bearings, alternators, cooling fans, ball screws, linear guides of machine tools, a wide variety of sliding areas of construction equipment, and bearings and gears in steel equipment and various other industrial mechanical facilities.
  • manufacturing greases with low noise characteristics has proven time consuming and expensive compared to more conventional greases.
  • Polyurea greases are typically prepared by reacting a diisocyanate with a diurea compound. These compounds are capable of forming robust networks by forming intermolecular hydrogen bonds with other diurea molecules, particularly in non-polar solvent like common base oils. As a result, these compounds are effective thickeners to prepare greases.
  • Typical diisocyanates that are used in the industry are 4,4 ’-methylene diphenyldiisocyanate (MDI) and toluene-2, 4-diisocyanate (TDI), because they are inexpensive and readily available.
  • MDI 4,4 ’-methylene diphenyldiisocyanate
  • TDI 4-diisocyanate
  • Three general classes of amines are typically used in the industry: aliphatic amines, alicyclic amines and aromatic
  • the disclosure provides a continuous method of producing a polyurea grease.
  • the polyurea grease is a low noise polyurea grease.
  • the method for producing polyurea grease can include a reaction step wherein a diisocyanate and an amine compound are reacted in one or more continuously stirred tank reactors to form a reaction mixture, a milling step wherein the reaction mixture is milled to form a milled product, and a curing step wherein the milled product is heat cured to form a polyurea grease.
  • the method can be performed continuously.
  • the reaction step can utilize two or more continuously stirred tank reactors.
  • the reaction step can utilize two continuously stirred tank reactors.
  • the diisocyanate compound is diphenylmethane diisocyanate, phenylene diisocyanate, diphenyl diisocyanate, phenyl diisocyanate, napththylene diisocyanate, tolylene orthodiisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate isocyanurate trimer, isophorone diisocyanate, or a combination thereof.
  • the amine compound is a monoamine compound, a diamine compound, or a mixture thereof.
  • the monoamine compound is a compound having the formula: wherein: R is C 6 -C 26 alkyl, C 6 -C 26 alkenyl, C 3 -C 8 cycloalkyl, 5- to 6-membered heteroaryl, phenyl, or C8-C12 bicycloaryl, each of which is unsubstituted or substituted with one or more R 1 groups; and each R1 group is independently F, Cl, Br, CF3, cyano, hydroxy, carboxyl, C1-C6 alkoxycarbonyl, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkoxy, a 5- to 6-membered heteroaryl, phenyl or C8-C12 bicycloaryl.
  • the diamine compound is ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylmethylbenzenediamine, diphenylmethane amine, diphenylmethane di-sec-butylamine, polyoxymethylene diamine, polyoxyethylene diamine, polyoxypropylene diamine, polyoxyisopropylene diamine, polyetheramine, triethylene glycol diamine, or a combination thereof.
  • the reaction step utilizes an alcohol or a combination thereof.
  • the alcohol is 1-decanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, cis-9-octadecen-1-ol, 9-octadecadien-1-ol, 12-octadecadien-1-ol, or a combination thereof.
  • the reaction step further utilizes a catalyst.
  • the catalyst is triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, bis-(2-dimethylaminoethyl)ether, N- methylmorpholine, N-methylimidazole, dibutyltin dilaurate, stannous octoate, or a combination thereof.
  • the diisocyanate can be used with a base oil.
  • the diisocyanate, the amine compound and/or the catalyst can be used with a base oil.
  • the diisocyanate, the amine compound, and/or the catalyst is dissolved or dispersed within a base oil.
  • an average residence time for the reaction step between about 20 minutes and about 90 minutes.
  • two or more continuously stirred tank reactors can be used in the reaction step and an average residence time for each continuously stirred tank reactor individually is between about 20 minutes and about 60 minutes.
  • the reaction step can be performed at a temperature below about 40°C.
  • the continuously stirred tank reactor can be stirred with a stirring device which provides a shear of about 1 to about 30 s -1 .
  • the milling step can be performed at a temperature of about 40°C to about 180°C.
  • the curing step can be performed at a temperature of about 120°C to about 200°C.
  • the curing step can be performed in a hot curing zone comprising one or more heat exchangers.
  • the method can further include a step of pre-reacting the diisocyanate and the amine compound in one or more plug flow reactors.
  • the pre-reacting curing step can be performed at a temperature of about 10°C to about 100°C.
  • the disclosure provides an apparatus for the continuous production of a polyurea grease can include: one or more continuously stirred tank reactors configured to continuously stir contents therein and to form a reaction mixture therein; and one or more diisocyanate feed lines in fluid communication with the one or more continuously stirred tank reactors to provide diisocyanate to the one or more continuously stirred tank reactors; one or more amine compound feed lines in fluid communication with the one or more continuously stirred tank reactors to provide amine to the one or more continuously stirred tank reactors; and a milling device operatively connected to the one or more continuously stirred tank reactors to receive the reaction mixture therefrom and configured to mill the reaction mixture to output a milled product.
  • the apparatus can include a a hot curing device connected to an output of the milling device and configured to receive the milled product from the milling device and to heat cure the milled product to form the polyurea grease.
  • the apparatus can further include one or more plug flow reactors connected to an input of a first continuously stirred tank reactor in between the one or more diisocyanate feed line and the one or more amine feed line to provide pre-reacting of diisocyante and amine.
  • the apparatus can have two or more continuously stirred tank reactors connected in series.
  • the apparatus can have a first continuously stirred tank reactor having an inlet and an outlet and a second continuously stirred tank reactor having an inlet and an outlet.
  • the outlet of the first continuously stirred tank reactor can be connected to the inlet of the second continuously stirred tank reactor, and the outlet of the second continuously stirred tank reactor can be connected to an inlet of the milling device.
  • the one or more continuously stirred tank reactors can be each equipped with an impeller device.
  • FIG.1 is a schematic of an embodiment of a continuous low-noise grease production unit in accordance with this disclosure.
  • DETAILED DESCRIPTION [0023] The following is a detailed description provided to aid those skilled in the art in practicing the present disclosure. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present disclosure. All publications, patent applications, patents, figures and other references mentioned herein are expressly incorporated by reference in their entirety. [0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
  • At least one of A and B can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
  • CSTR continuous stirred- tank reactor
  • MFR mixed flow reactor
  • CFSTR continuous-flow stirred-tank reactor
  • MFR mixed flow reactor
  • CFSTR continuous-flow stirred-tank reactor
  • the apparatus is capable of continuous production of grease products. In certain embodiments, the apparatus is capable of producing a low noise polyurea grease.
  • the apparatus for the production of polyurea grease utilizes a combination of plug flow reactors and tank reactors. In certain embodiments, the apparatus comprises a diisocyanate feed line, an amine feed line, a continuously stirred tank reactor, and a milling device, and a hot curing device. [0037]
  • the diisocyanate feed is not particularly limited. In certain embodiments, the diisocyanate feed line is capable of providing a diisocyanate feed to the reaction vessels or reactors with or without a base oil.
  • the diisocyanate feed is a solution of diisocyanate in a solvent. In another particular embodiment, the diisocyanate feed is a dispersed mixture of diisocyanate in a base oil. In particular embodiments, the apparatus provides for two or more diisocyanate feed lines; including but not limited to two, three, four or five diisocyanate feed lines.
  • the amine feed is not particularly limited. In certain embodiments, the amine feed line is capable of providing an amine feed to the reaction vessels or reactors with or without a base oil. In a particular embodiment, the amine feed is a solution of amine in a solvent. In another particular embodiment, the amine feed is a dispersed mixture of amine in a base oil.
  • the apparatus provides for two or more amine feed lines; including but not limited to two, three, four or five amine feed lines.
  • the apparatus is equipped with one or more solvent feed lines.
  • the apparatus is equipped with one or more alcohol feed lines.
  • the apparatus is equipped with one or more catalyst feed lines.
  • the diisocyanate feed lines and the amine feed lines direct the reaction materials into a continuously stirred tank reactor (CSTR). In embodiments having one or more alcohol, and/or catalyst feed lines, these feed lines also direct the reaction materials into the continuously stirred tank reactor (CSTR).
  • the apparatus provides two or more CSTRs in series; including, but not limited to, two, three, four or five CSTRs. In a particular embodiment, the apparatus provides two CSTRs in series. In certain embodiments, the CSTRs are connected to recirculation pumps to allow for the recirculation of reaction materials within each individual CSTR and to allow for additional mixing. [0042]
  • the average residence time for the materials in each individual CSTR is not particularly limited. In certain embodiments, the average residence time for each CSTR is between about 20 minutes and about 90 minutes. In some embodiments, the average residence time for each CSTR is between about 20 minutes and about 60 minutes, between about 30 minutes and about 60 minutes, or between about 30 minutes and about 45 minutes.
  • the average residence time for each CSTR is between about 60 minutes and about 70 minutes.
  • the average residence time for the first CSTR is the same as or shorter than the residence time for the second and subsequence CSTRS. That is, the average residence time for the first CSTR is about 20 to about 30 minutes and the average residence time for the second and subsequent CSTRs is about 30 to about 60 minutes, or, in some embodiments, about 30 to about 45 minutes. In certain embodiments the average residence time in the first CSTR and the second and subsequent CSTR is about the same.
  • Each CSTR is independently capable of being maintained at a constant temperature. In particular embodiments, each CSTR is held at a low temperature to avoid premature thickening of the grease product.
  • each CSTR is independently held below about 40°C. In particular embodiments, each CSTR is independently held between about 20°C and about 35°C. In some embodiments, each CSTR is held at about 25°C.
  • Each CSTR is equipped with a stirring device, such as an impeller or an agitator. In particular embodiments, each CSTR utilizes an impeller device. In particular embodiments, each CSTRs is capable of providing a low shear. In particular embodiments, the shear is provided without the use of shear valves. In certain embodiments, each CSTR independently provides a shear of about 1 to about 30 s -1 . In some embodiments, each CSTR independently provides a shear of about 1.5 to about 25 s -1 .
  • each CSTR independently provides a shear of about 2 to about 20 s -1 .
  • the milling device is not particularly limited.
  • the milling device can be, without limitation, a colloid mill; for example, a cone rotor/stator colloid mill, including, but not limited to smooth surface rotors, peripheral line rotors, axial serration rotors, or a combination thereof.
  • the milling device is capable of being heated or cooled to and held at a constant temperature. In certain embodiments, the milling device is held between about 40°C and about 180°C.
  • the milling device is held between about 80°C and about 130°C. In still other embodiments, the milling device is held between about 120°C and about 180°C
  • the average residence time in the milling device is typically less than 5 minutes. In certain embodiments, the average residence time in the milling device is less than about 2.5 minutes, less than about 1 minute, less than about 30 seconds, or less than about 15 seconds.
  • the milled product is passed through a hot curing zone or a hot curing device.
  • the hot curing zone comprises one or more heat exchangers.
  • the type of heat exchanger is not particularly limited. In certain embodiments, the heat exchanger is a tube and shell exchanger or a votator exchanger.
  • the hot curing zone comprises two or more heat exchangers in series.
  • the hot curing zone is utilized to cure the milled products to form the ultimate grease product.
  • the hot curing zone is held between about 120°C and about 200°C.
  • the hot curing zone is held between about 140°C and about 180°C.
  • the hot curing zone is held between about 150°C and about 170°C.
  • the average residence time in the hot curing zone is less than about 20 minutes, less than about 15 minutes, less than about 10 minutes, less than about 5 minutes, or less than about 2 minutes.
  • the average residence time in the hot curing zone is between about 0.5 minutes and about 15 minutes, between about 0.5 minutes and about 5 minutes, or between about 0.5 minutes and about 3 minutes. In certain embodiments, the average curing time is between about 0.75 minutes and about 1.5 minutes, or between about 1.5 minutes and about 3 minutes.
  • the apparatus for the production of polyurea grease may optionally include one or more plug flow reactors.
  • the plug flow reactors if utilized, can be incorporated before, between or after the CSTRs.
  • the number and type of plug flow reactors are not particularly limited. In certain embodiments, one plug flow reactor is utilized before the first CSTR.
  • FIG. 1 depicts a schematic of an apparatus for the continuous production of grease products (1) .
  • a diisocyanate feed line (2) and a first amine feed line (3a) are fed into a plug flow reactor (4).
  • the initial reaction mixture then passes into a first continuously stirred tank reactor (5) along with a second amine feed line (3b), followed by a second continuously stirred tank reactor (6).
  • the continuously stirred tank reactors are each equipped with an impeller device (5a and 6a, respectively) to stir the reaction materials and provide the desired shear rate.
  • the reaction product is then passed through a colloid mill (7).
  • the milled product is then passed to a hot curing zone (8).
  • the hot curing zone comprises two heat exchangers (8a) and (8b).
  • pumps to recirculate the reaction mixture within the continuously stirred tank reactors or to pass the milled mixture to the hot curing zone are shown (9a, 9b, and 9c, respectively).
  • diaphragm pumps are used to introduce the reaction components into the respective feed lines. These pumps are all indicated as (10). Although a particular embodiment is shown in Figure 1, the number of feed lines, CSTRs, plug flow reactors, pumps, and heat exchangers can be varied to modify the properties of the ultimate grease product.
  • Method For Production Polyurea Grease [0049] In one aspect, the disclosure provides a method for the continuous production of polyurea grease. In certain embodiments, the disclosure provides a method for the production of a low noise polyurea grease. [0050] Polyurea greases are typically prepared by reacting a diisocyanate with 2 equivalents of an amine to form a diurea compound.
  • the diisocyanate compound is not particularly limited. Typical diisocyanates that are used in the industry include, but are not limited to 4,4’- methylene diphenyldiisocyanate (MDI) and toluene-2,4-diisocyanate (TDI).
  • MDI 4,4’- methylene diphenyldiisocyanate
  • TDI toluene-2,4-diisocyanate
  • the diisocyanate compound is diphenylmethane diisocyanate, phenylene diisocyanate, diphenyl diisocyanate, phenyl diisocyanate, napththylene diisocyanate, tolylene orthodiisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate isocyanurate trimer, isophorone diisocyanate, or a combination thereof.
  • the diisocyanates can be utilized in isomerically pure form or as a mixture of isomers.
  • the amine compound is not particularly limited. There are three general classes of amines that are typically used: aliphatic amines, alicyclic amines and aromatic amines. Non-limiting examples of these amines is shown in Scheme 1 Scheme 1
  • Combinations of amines may also be used.
  • two different amines in combination there are three different diureas that can be formed.
  • Two are symmetrical diureas where both isocyanate groups on a diisocyanate react with two molecules of the same amine (amine-1 or amine-2) and one is an unsymmetrical diurea where one isocyanate reacts with amine-1 and the other reacts with amine-2.
  • Non-limiting examples of these diurea compounds are shown in Scheme 2.
  • the amine compound is a monoamine compound, a diamine compound, or a mixture thereof.
  • the monoamine compound is a compound having the formula: wherein: R is C6-C26 alkyl, C6-C26 alkenyl, C3-C8 cycloalkyl, 5- to 6-membered heteroaryl, phenyl, or C 8 -C 12 bicycloaryl, each of which is unsubstituted or substituted with one or more R 1 groups; and each R 1 group is independently F, Cl, Br, CF 3 , cyano, hydroxy, carboxyl, C 1 -C 6 alkoxycarbonyl, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, a 5- to 6-membered heteroaryl, phenyl or C 8 -C 12 bicycloaryl.
  • the diamine compound is ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylmethylbenzenediamine, diphenylmethane amine, diphenylmethane di-sec-butylamine, polyoxymethylene diamine, polyoxyethylene diamine, polyoxypropylene diamine, polyoxyisopropylene diamine, polyetheramine, triethylene glycol diamine, or a combination thereof.
  • the amount of diisocyanate and amine compound utilized in the reaction is not particularly limited.
  • the ratio of diisocyanate used as a starting material to the amount of amine compound used is in the range of 1:99 to 99:1 molar equivalents. In particular embodiments, the ratio of diisocyanate used as a starting material to the amount of amine compound used is in the range of 1:10 to 10:1 molar equivalents; 1:5 to 5:1 molar equivalents; 1:3 to 3:1 molar equivalents; or 1:2 to 2:1 molar equivalents. In certain embodiments, the ratio of diisocyanate used as a starting material to the amount of amine compound used is 1:1 in terms of molar equivalents. [0059] In some embodiments, the reaction step further utilizes an alcohol or a combination thereof.
  • the alcohol is 1-decanol, 1-tetradecanol, 1-hexadecanol, 1- octadecanol, cis-9-octadecen-1-ol, 9-octadecadien-1-ol, 12-octadecadien-1-ol, or a combination thereof.
  • the reaction step further utilizes a catalyst.
  • the catalyst is triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, bis-(2-dimethylaminoethyl)ether, N- methylmorpholine, N-methylimidazole, dibutyltin dilaurate, stannous octoate, or a combination thereof.
  • Particular starting materials including suitable solvents and base greases can be found, for example, in WO2015/020001, WO2008/073773, US4392967, WO99/42541, and US6498130 each of which are incorporated herein by reference.
  • the diisocyanate and the amine compounds can be reacted in one or more continuously stirred tank reactors (CSTR) to form a reaction mixture.
  • CSTR continuously stirred tank reactors
  • the reaction mixture is milled by a milling device to form a milled product.
  • the milled product is cured to form a grease product.
  • the diisocyanate compound and the amine compound are reacted in a plug flow reactor prior to reaction in the CSTR.
  • the reaction mixture is allowed to react in two or more CSTRs prior to the milling step.
  • the diisocyanate is fed into the CSTR, or, if used, into the plug flow reactor, with or without a base oil. In particular embodiments, the diisocyanate is fed into the reactor as a dispersed mixture of amine in a base oil. In some embodiments, the diisocyanate, the amine compound, and/or the catalyst is provided such that it is dissolved or dispersed within a base oil. [0065] In certain embodiments, the amine compound is fed into the CSTR, or, if used, into the plug flow reactor, with or without a base oil. In particular embodiments, the amine is fed into the reactor as a dispersed mixture of amine in a base oil.
  • the average residence time for the materials in the CSTR, or in each individual CSTR if more than one is used is not particularly limited. In certain embodiments, the average residence time for each CSTR is between about 20 minutes and about 90 minutes. In some embodiments, the average residence time for each CSTR is between about 20 minutes and about 60 minutes, between about 30 minutes and about 60 minutes, or between about 30 minutes and about 45 minutes. In some embodiments, the average residence time for each CSTR is between about 60 minutes and about 70 minutes. In particular embodiments, the average residence time for the first CSTR is the same as or shorter than the residence time for the second and subsequent CSTRs.
  • each CSTR is independently capable of being maintained at a constant temperature.
  • each CSTR is held at a low temperature to avoid premature thickening of the grease product.
  • each CSTR is independently held below about 40°C.
  • each CSTR is independently held between about 20°C and about 35°C.
  • each CSTR is held at about 25°C.
  • each CSTR is subject to stirring with a stirring device, such as an impeller or an agitator.
  • the reaction step utilizes an impeller device to stir the reaction in each CSTR.
  • the stirring is provided during the reaction step at a low shear.
  • each CSTR independently provides a shear of about 1 to about 30 s -1 .
  • each CSTR independently provides a shear of about 1.5 to about 25 s- 1.
  • each CSTR independently provides a shear of about 2 to about 20 s -1 .
  • the reaction product is passed to a milling device for the milling step.
  • the milling step occurs in a colloid mill.
  • the milling step is performed at a constant temperature of about 40°C and about 180°C.
  • the milling step is performed at a constant temperature of about 40°C and about 160°C.
  • the milling step is performed at a constant temperature of about 80°C and about 130°C.
  • the milling step is performed at a constant temperature of about 120°C and about 180°C.
  • the average residence time for the milling step is typically less than 5 minutes.
  • the average residence time for the milling step device is less than about 2.5 minutes, less than about 1 minute, less than about 30 seconds, or less than about 15 seconds.
  • the milled product is cured in a hot curing zone or a hot curing device.
  • the hot curing zone comprises one or more heat exchangers.
  • the type of heat exchanger is not particularly limited.
  • the heat exchanger is a tube and shell exchanger or a votator exchanger.
  • the hot curing zone comprises two or more heat exchangers in series.
  • the hot curing zone is utilized to cure the milled products to form the ultimate grease product. In some embodiments, curing is performed between about 120°C and about 200°C.
  • the curing is performed between about 140°C and about 180°C. In still other embodiments, the curing is performed between about 150°C and about 170°C. In certain embodiments, the average curing time is less than about 20 minutes, less than about 15 minutes, less than about 10 minutes, less than about 5 minutes, or less than about 2 minutes. In certain embodiments, the average curing time is between about 0.5 minutes and about 15 minutes, between about 0.5 minutes and about 5 minutes, or between about 0.5 minutes and about 3 minutes. In certain embodiments, the average curing time is between about 0.75 minutes and about 1.5 minutes, or between about 1.5 minutes and about 3 minutes.
  • the reaction components are reacted in the plug flow reactor before the reaction step in the first CSTR.
  • the reaction in the plug flow reactor is performed at between about 10°C and about 100°C, between about 10°C and about 80°C, or between about 20°C and about 80°C.
  • the average residence time in the plug flow reactor curing zone is less than about 15 minutes, less than about 10 minutes, less than about 5 minutes, or less than about 2 minutes. In certain embodiments, the average residence time in the plug flow reactor is about 5 minutes.
  • the polyurea greases produced according to method described above have significantly lower noise levels associated with it as measured by a lower peak average noise value.
  • inventive polyurea greases have an average noise level peak as measured with a BeQuiet grease noise tester of less than 30/sec, or less than 25/sec, of less than 20/sec, or less than 15/sec, or less than 10/sec, or less than 5/sec.
  • inventive polyurea greases produced according to method described above have a greater percentage of peaks (BQ1, BQ2, BQ3, BQ4) in the lower numbered categories.
  • the inventive polyurea greases produced according to method described above have BeQuiet grease noise tester BQ4 values of less than or equal to 100%, or less than or equal to 98%; BQ3 values of less than or equal to 92%, or less than or equal to 90%; BQ2 values of less than or equal to 52%, or less than or equal to 14%; and BQ1 values of less than or equal to 5%, or less than or equal to 3%.
  • Base Oils [0073]
  • the reaction materials diisocyanate, amine compound, catalyst, etc) are provided to the method or apparatus of the disclosure in a base oil.
  • a wide range of lubricating base oils are known in the art.
  • Lubricating base oils that are useful in the present disclosure are natural oils, mineral oils, and synthetic oils, and unconventional oils (or mixtures thereof) are used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process.
  • Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • One skilled in the art is familiar with many purification processes.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils.
  • Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic- naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
  • Synthetic oils include hydrocarbon oils such as olefin oligomers (including polyalphaolefin base oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), alkyl naphthalenes, and dewaxed waxy isomerates.
  • PAOs polyalphaolefin base oils
  • PAGs polyalkylene glycols
  • alkyl naphthalenes alkyl naphthalenes
  • dewaxed waxy isomerates dewaxed waxy isomerates.
  • Groups I, II, III, IV, and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks have a viscosity index of 80 to less than 120 and contain greater than 0.03% sulfur and/or less than 90% saturates.
  • Group II base stocks have a viscosity index of about 80 to less than 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stocks have a viscosity index greater than 120 and contain less than or equal to 0.03 % sulfur and greater than 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
  • Base Oil Properties [0077] Hydroprocessed or hydrocracked Group II and/or Group III base stocks, as well as synthetic oils such as alkyl aromatics and synthetic esters are also well known base stock oils. [0078] Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins, for example, polypropylenes, polybutylenes, propylene-butylene copolymers, propylene-isobutylene copolymers, ethylene-olefin copolymers, ethylene-alphaolefin copolymers, propylene-olefin copolymers, propylene-alphaolefin copolymers, butylene-olefin copolymers, butylene-alphaolefin copolymers, and the like.
  • Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
  • PAO base oils that may be used in the lubricating compositions may be derived from linear C2 to C32 alpha olefins, and mixtures thereof.
  • PAOs may derive preferably from C6, C8, C10, C12, C14, C16 alpha olefins, or mixtures thereof. See U.S. Patents 4,956,122; 4,827,064; and 4,827,073.
  • Particularly preferred feedstocks for said polyalphaolefins are 1- octene, 1-decene, 1-dodecene and 1-tetradecene.
  • PAOs have number average molecular weights that typically vary from 250 to 3,000, and PAO’s are available in viscosities at 100°C of 1.5 cSt to 150 cSt.
  • PAOs are typically comprised of relatively low molecular weight hydrogenated oligomers or polymers of alphaolefins which include, but are not limited to, C 2 to C 32 alphaolefins, preferrably C 8 to C 16 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like.
  • Preferred polyalphaolefins are poly-1-octene, poly-1-decene, poly-1-dodecene, mixed olefin-derived polyolefins, and mixtures thereof.
  • dimers of higher olefins in the range of C14 to C18 provide low viscosity base stocks of acceptably low volatility.
  • PAOs contain predominantly trimers and tetramers of the starting olefins, with minor amounts of higher oligomers, having a viscosity range of 1.5 to 12 cSt.
  • PAO fluids of particular use may include those having KV100 of 3 cSt, 3.4 cSt, and/or 3.6 cSt, and combinations thereof. Mixtures of PAO fluids having KV100 viscosity of 1.5 to 150 cSt or more are also useful.
  • PAO fluids are conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron tri
  • PAOs useful in the present disclosure may have a kinematic viscosity at 100°C of from 1.5 to 5,000 cSt.
  • PAOs preferably have a kinematic viscosity at 100°C of from 2 to 25 cSt, from 2 to 20 cSt, or from 2 to 15 cSt.
  • PAOs have a kinematic viscosity at 100°C of from 2 to 300 cSt, from 2 to 150 cSt, from 2 to 60 cSt, or from 2 to 40 cSt.
  • Other PAOs useful in the present disclosure are made by metallocene catalysis.
  • Metallocene-catalyzed PAO may be a homo-polymer made from a single alphaolefin feed, or may be a copolymer made from two or more different alphaolefins, each by employing a suitable metallocene catalyst system.
  • Metallocene catalysts are for example simple metallocenes, substituted metallocenes or bridged metallocene catalysts activated or promoted by, for instance, methylaluminoxane (MAO) or a non-coordinating anion, such as N,N-dimethylanilinium tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anions.
  • MAO methylaluminoxane
  • a non-coordinating anion such as N,N-dimethylanilinium tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anions.
  • Homopolymer mPAO compositions are made from single alphaolefins chosen from alphaolefins in the C2 to C30 range, preferably C2 to C16, most preferably C3 to C14 or C3 to C12.
  • the homopolymers are isotactic, atactic, syndiotactic or of any other appropriate tacticity.
  • the tacticity is tailored by the choices of polymerization catalyst, polymerization reaction conditions, hydrogenation conditions, or combinations thereof.
  • Copolymer mPAO compositions are made from at least two alphaolefins of C2 to C30 range, and typically have monomers randomly distributed in the finished copolymers. It is preferred that the average carbon number is at least 4.1.
  • Copolymer mPAO compositions are also made from mixed feed linear alpha olefins (LAOs) comprising from two to 26 different linear alphaolefins selected from C2 to C30 linear alphaolefins.
  • LAOs mixed feed linear alpha olefins
  • Such mixed feed LAO are obtained, for example, from an ethylene growth process using an aluminum catalyst or a metallocene catalyst.
  • the growth olefins comprise mostly C6 to C 18 LAO.
  • LAOs from other processes are also used.
  • Useful alphaolefins may be obtained from a conventional LAO production facility, from a refinery, from a chemical plant, and even from Fischer-Tropsch synthesis processes (as reported in U.S. Patent 5,382,739).
  • Alphaolefins include propylene, 1-butene, 1-pentene, 1- hexene, 1-octene, other C 2 to C 16 alphaolefins, C 16+ alphaolefins, LAOs, and the like.
  • C2 to C16 alphaolefins, more preferably linear alphaolefins are suitable to make homopolymers.
  • alphaolefin plus LAO such as for example, C4 and C14-LAO, C6- and C16-LAO, C8-, C10-, C12-LAO, or C8- and C14-LAO, C6-, C10-, C14-LAO, C4 and C12-LAO, etc., are suitable to make copolymers.
  • a feed comprising a mixture of LAOs selected from C2 to C30 LAOs or a single LAO selected from C2 to C16 LAO, is contacted with an activated metallocene catalyst under oligomerization conditions to provide a liquid product suitable for use as a component in lubricants or functional fluids.
  • copolymer compositions made from two or more alphaolefins of C2 to C30 range, with monomers randomly incorporated into the copolymer, as liquid products suitable for use as a component in lubricants or functional fluids.
  • PAOs useful in this disclosure are described, for example, in U.S. patent application 2013/0005633.
  • Useful base oils include Gas-to-Liquids (GTL) base stocks derived from GTL materials, as well as isomerate base stocks derived from waxes or waxy feed stocks.
  • GTL Gas-to-Liquids
  • Such feed stocks include: natural wax or waxy materials from bio-based sources, and sustainable sources; mineral and/or non-mineral waxes and waxy materials such as slack waxes, waxy gas oils, waxy fuels hydrocracker bottoms, waxy raffinates, waxy hydrocrackates, waxy thermal crackates, and even non-petroleum oil derived waxy materials such as from coal liquefaction, shale oil, sustainable oil sources.
  • GTL materials may derive from hydrogen-containing and carbon-containing compounds as feed stocks, from one or more transformation steps including, for example, synthesis, combination, transformation, rearrangement, or degradation/deconstructive processes.
  • Gaseous feed stocks include, for example, hydrogen, water, carbon monoxide, carbon dioxide, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks are GTL materials of lubricating viscosity that are derived for example from hydrocarbons, particularly waxy synthesized hydrocarbons, and oxygenate analogues, produced from gaseous feed stocks, as discussed herein.
  • GTL base stocks include oils boiling in the lube oil boiling range, having reduced pour point, that may be produced from (1) synthesized wax or waxy hydrocarbons, (2) synthesized GTL materials, (3) synthesized Fischer-Tropsch (F-T) materials (i.e., hydrocarbons, waxy hydrocarbons, waxes, and analogous oxygenates), using one or more of processes that include, for example, fractionation, distillation, catalytic dewaxing, solvent dewaxing, catalytic hydrocracking/hydroisomerization, and hydrofinishing.
  • GTL materials, more particularly GTL base stocks are preferably derived from F-T materials.
  • Synthetic oils may be produced from waxy hydrocarbons.
  • Useful lubricant oil base stocks include, for example, wax isomerate base stocks, hydroisomerized waxy stocks (e.g. waxy gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch (F-T) waxes, Gas-to-Liquids (GTL) base oils, and other wax isomerate hydroisomerized base oils.
  • base oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure, as well as other gas-to-liquid synthetic procedures. Fischer-Tropsch waxes, the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • Hydroprocessing (hydrocracking/hydroisomerization) procedures for converting waxy feedstocks to base stocks may use amorphous catalysts, specialized lube hydrocracking (LHDC) catalysts, or even crystalline, preferably zeolitic, catalysts.
  • LHDC lube hydrocracking
  • Processes for making hydrocracked/hydroisomerized distillates and waxes are described, for example, in U.S. Patents 2,817,693; 4,975,177; 4,921,594; and 4,897,178.
  • Processes using Fischer-Tropsch wax feeds are further described in U.S. Patents 4,594,172 and 4,943,672.
  • Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax isomerate base oils may be advantageously used in the present disclosure, and may have useful kinematic viscosities at 100°C (ASTM D445) of 2.5 or 3 cSt to 50 cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt.
  • Gas-to-Liquids (GTL) base oils, Fischer- Tropsch wax derived base oils, and other wax isomerate base oils may also have useful pour points (ASTM D97) of -10°C or lower, or -20°C or lower, or -25°C or lower, or even pour points of -30°C to -40°C or lower. These are also characterized typically as having viscosity indices of 80 to 140 or higher (ASTM D2270).
  • Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax isomerate base oils are recited for example in U.S. Patents 6,080,301; 6,090,989, and 6,165,949.
  • GTL base stocks are typically highly paraffinic (>90% saturates), and may contain low-to-trace concentrations of cycloparaffins, in combination with mostly non-cyclic isoparaffins.
  • the cycloparaffin (i.e. naphthenic) content in such compositions varies with choice of catalyst and process temperature.
  • GTL base stocks typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, more typically less than 5 ppm of each.
  • the sulfur and nitrogen content of GTL base stocks obtained from F-T material, especially F-T wax, is essentially nil. The absence of phosphorous and aromatics make these materials especially suitable for the preparation of low SAP (i.e.
  • GTL base stock and wax isomerate base stock are to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such individual fractions, as well as binary mixtures of one or more low viscosity fractions with one or more higher viscosity fractions to produce a bi-modal blend having a target kinematic viscosity.
  • Other useful fluids of lubricating viscosity include non-conventional or unconventional base oils and base stocks that are processed and/or synthesized to provide high performance lubrication characteristics.
  • unconventional base oils may include for example, hydrocarbyl derivatives of cylcoalkyl hydrocarbons, bridged hydrocarbons, bicyclo hydrocarbons, tricyclo hydrocarbons, fused cycloalkyl-aromatics, diamondoids, other single-ring and/or multi-ring hydrocarbons, oligomeric/polymeric hydrocarbons, liquid crystal materials, or their heteroatom containing analogues, and the like.
  • Unconventional base oils and base stocks derive from processes comprising, for example, one or more of: separation, distillation, fractionation, purification, filtration, extraction, partitioning, crystallization, deposition, exchange; thermal cracking, catalytic cracking, steam cracking, hydrocracking, liquefaction; catalytic dewaxing, solvent dewaxing, catalytic hydrocracking/hydroisomerization, hydrofinishing, hydrogenation; bio-catalytic processes, biological processes (enzymatic, viral, microbial, cellular, genetic), enzymatic digestion, enzymatic conversion, fermentation; oligomerization, polymerization, co(oligomer/polymer)ization, condensation (oligomer/polymer)ization, ring opening (oligomer/polymer)ization, olefin metathesis (oligomer/polymer)ization, chain growth (radical, cationic, anionic, catalytic, living), Fischer- Tropsch synthesis; esterification, transesterification, ether
  • useful base oils have a urea adduct value of not greater than 4% by mass
  • base oils comprise, for example, hydrocarbyl base oils, paraffinic base oils, isoparaffinic base oils, and wax isomerate base oils, that may suitably derive from natural, mineral, synthetic, bio-derived, conventional, or unconventional sources.
  • the urea adduct value of such useful base oils is not greater than 4% by mass, preferably not greater than 3.5% by mass, more preferably not greater than 3% by mass, and even more preferably not greater than 2.5% by mass.
  • the urea adduct value of the useful base oils may even be 0% by mass.
  • the urea adduct value of the base oils is preferably 0.1% by mass or greater, more preferably 0.5% by mass or greater, and even more preferably 0.8% by mass or greater.
  • the viscosity index of the base oil is 105 or greater, preferably 110 or greater, more preferably 120 or greater, even more preferably 130 or greater, and in certain instances preferably 140 or greater. Measurement of the urea adduct value is described for example in U.S. Patent 9163195.
  • useful base oils have an iodine number of 2 or less
  • such base oils comprise, for example, hydrocarbyl base oils, paraffinic base oils, isoparaffinic base oils, and wax isomerate base oils, that may suitably derive from natural, mineral, synthetic, bio-derived, conventional, or unconventional sources.
  • the iodine number of such base oils is 2 or less, preferably 1 or less, more preferably 0.7 or less, further more preferably 0.5 or less, and particularly preferably 0.1 or less.
  • the iodine number of the such base oils may even be less than 0.001.
  • the iodine number of such base oils is preferably 0.001 or more, and more preferably 0.01 or more. Iodine number is determined in accordance with an indicator titration method described in JIS K 0070.
  • useful base oils have a bromine number of 2 or less, and such base oils comprise, for example, hydrocarbyl base oils, paraffinic base oils, isoparaffinic base oils, polyolefins, polyalphaolefins, and wax isomerate base oils, that may suitably derive from natural, mineral, synthetic, bio-derived, conventional, or unconventional sources.
  • Such base oils preferably have a bromine number of 1.8 or less, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less.
  • the base stock is polyalphaolefin.
  • Hydrocarbyl aromatics are used as a base oil or base oil component and are any hydrocarbyl molecule that contains at least 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives.
  • These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like.
  • the aromatic is suitably mono-alkylated, dialkylated, polyalkylated, and the like.
  • the aromatic is suitably mono- or poly-functionalized.
  • the hydrocarbyl groups is also suitably comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups.
  • the hydrocarbyl groups range from C6 to C60 with a range of C 8 to C 20 often being preferred.
  • a mixture of hydrocarbyl groups is often preferred, and up to three such substituents are suitably present.
  • the hydrocarbyl group optionally contains sulfur, oxygen, and/or nitrogen containing substituents.
  • the aromatic group is also suitably derived from natural (petroleum) sources, provided at least 5% of the molecule is comprised of an above- type aromatic moiety. Viscosities at 100 o C of 2.5 or 3 cSt to 50 cSt are preferred, with viscosities of 3.4 cSt to 20 cSt often being more preferred for the hydrocarbyl aromatic component.
  • an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used.
  • Other alkylates of aromatics are advantageously used.
  • Naphthalene or methyl naphthalene for example, is suitably alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
  • Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition are 2% to 25%, preferably 4% to 20%, and more preferably 4% to 15%, depending on the application.
  • Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure are produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A.
  • an aromatic compound such as benzene or naphthalene
  • an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964.
  • Friedel-Crafts and Related Reactions Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964.
  • Many homogeneous or heterogeneous, solid catalysts are known to one skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and product quality requirements. For example, strong acids such as AlCl 3 , BF 3 , or HF are used.
  • Esters are useful base stocks. Additive solvency and seal compatibility characteristics are often obtained by use of esters in lubricating fluid compositions. Suitable esters derive from the reaction of monocarboxylic acids with monoalkanols, dibasic acids with monoalkanols, and monocarboxylic acids with polyols.
  • Suitable monoesters derive from the reaction of monocarboxylic acids such as linear or branched C6 to C16 acids, and even C>16 acids, with a variety of alcohols such as linear or branched C 4 to C 12 alcohols, and even C >12 alcohols, and the like.
  • monoesters include octyl octanoate, iso-amyl dodecanoate, and 2- ethylhexyl dodecanoate.
  • Suitable diesters derive from the reaction of dicarboxylic acids such as phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, the hydrocarbyl-substituted versions of these same diacids, and the like, with a variety of alcohols such as linear or branched C4 to C12 alcohols, and even C >12 alcohols, and the like.
  • dicarboxylic acids such as phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, the hydrocarbyl-substituted versions of these same diacids, and the like
  • alcohols such as linear or branched C4 to C12 alcohols, and even C >12 alcohols, and the like.
  • diesters include dibutyl adipate, di(2- ethylhexyl) sebacate, di-n-hexyl fumarate, diisooctyl sebacate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, and the like.
  • polyhydric alcohols preferably hindered polyols (e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3
  • esters examples include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol, reacted with one or more monocarboxylic acids containing from 5 to 10 carbon atoms.
  • Useful esters also derive from renewable sourced materials such as coconut, palm, rapeseed, soy, and sunflower oils, and the like. Such esters are monoesters, diesters, polyol esters, complex esters, or mixtures thereof.
  • Other lubricating oils useful in the present disclosure are oil soluble polyalkylene glycols (PAGs).
  • Polyalkylene glycols are also known as polyglycols, or as polyethers.
  • Oil soluble PAGs are selected from alcohol-initiated butylene oxide homopolymers, and alcohol- initiated copolymers of butylene oxide and propylene oxide.
  • the oil soluble PAG is a polyether copolymer derived by ring-opening reactions of butylene oxide and propylene oxide, initiated by one or more alcohols.
  • the copolymer may be a random copolymer or a block copolymer.
  • the oil soluble PAG is an alcohol-initiated propylene oxide/butylene oxide random copolymer.
  • the amount of butylene oxide incorporated into the copolymer is desirably 40 wt% or more, 50 wt% or more, 60 wt% or more, 65 wt% or more, or even 70 wt% or more, and at the same time is typically 80 wt% or less, or 70 wt% or less, based on the total weight of propylene oxide and butylene oxide.
  • the oil soluble PAG derives from 50 wt% propylene oxide and 50 wt% butylene oxide (that is, the oxide monomers are copolymerized at a 50/50 weight ratio).
  • Oil soluble PAGs are desirably prepared from an alcohol initiator having 8 carbons or more, 10 carbons or more, 12 carbons or more, 14 carbons or more, 16 carbons or more, and even 18 carbons or more, while at the same time typically having 20 carbons or fewer.
  • the alcohol initiator for oil soluble PAGs may be for example a mono-ol, diol or triol.
  • the initiator is desirably linear, and preferably a primary alcohol, a mono-ol.
  • One particularly desirable alcohol initiator for preparing the oil soluble PAGs is dodecanol.
  • Alkylene oxide polymers and interpolymers and derivatives thereof, constitute a class of known synthetic oils that may be used as base oils in the present disclosure.
  • Oil soluble PAGs generally have a kinematic viscosity at 40°C (ASTM D445) of 15 cSt or higher, 18 cSt or higher, 32 cSt or higher, 68 cSt or higher, 80 cSt or higher, 100 cSt or higher, 150 cSt or higher, and even 220 cSt or higher, while at the same time is generally 250 cSt or lower.
  • Oil soluble PAGs generally have an average molecular weight of 500 g/mol or more, 750 g/mol or more, 1000 g/mol or more, 1250 g/mol or more, 1500 g/mol or more, 1900 g/mol or more, or even 2400 g/mol or more, and at the same time are generally 3600 g/mol or less.
  • molecular weight refers to number average molecular weight (Mn), and is determined by gel permeation chromatography.
  • Useful concentrations of oil soluble PAGs in lubricating fluids are 2 wt% or more, 5 wt% or more, 10 wt% or more, 15 wt% or more, and even 20 wt% or more, while at the same time are typically 30 wt% or less, generally 25 wt% or less, based on total lubricant weight.
  • Illustrative oil soluble PAGs useful in this disclosure are described, for example, in U.S. Application Publication No.2017/0073611.
  • Other lubricating oils useful in the present disclosure are polytetrahydrofuran, polytetrahydrofuran copolymers, and monoesters or diesters of these polymers.
  • Ionic liquids are so-called salt melts which are preferably liquid at room temperature and/or by definition have a melting point ⁇ 100°C. Ionic liquids are salts consisting of a cation and anion pair. Because of unique fluidity and physical properties, ionic liquids may be useful in lubricant or working fluid compositions, either as base stock components or as additive components.
  • Suitable cations for ionic liquids include for example quaternary ammonium, phosphonium, imidazolium, pyridinium, pyrazolium, oxazolium, pyrrolidinium, piperidinium, thiazolium, guanidinium, morpholinium, trialkylsulfonium, and triazolium cations.
  • Suitable anions include for example, [PF6]-, [BF4] 31 , [CF3CO2] 31 , [CF3SO3]- and higher homologs, [C 4 F 9 --SO 3 ] 31 or [C 8 F 17 --SO 3 ]- and higher perfluoroalkylsulfonates, [(CF 3 SO 2 ) 2 N]-, [(CF3SO2)(CF3COO)N]-, [R 1 --SO3]-, [R 1 --O--SO3] 31 , [R 1 --COO]-, Cr-, Br-, [NO3]-, [N(CN)2]-, [HSO4]-, PF(6-x)R 3 x or [R 1 R 2 PO4]-.
  • groups R 1 and R 2 may be independently selected from hydrogen; linear or branched, saturated or unsaturated, aliphatic or alicyclic hydrocarbyl groups; heteroaryl groups; heteroaryl-C1-C6-alkyl groups; aryl-aryl C1- C6 alkyl groups.
  • Group R 3 may be for example a perfluoroethyl group or a higher perfluoroalkyl group.
  • suitable anions may also include organic anions such as sulfonates, imides, methides, and the like, as well as inorganic anions such as halides, phosphates, and the like, in combinations with cations such that low melting points are achieved.
  • lubricant oil compositions comprising an ionic liquid are achieved through a suitable choice of cation and anion for the ionic liquid.
  • An appropriate choice of cation and anion for the ionic liquid may provide a lubricating oil composition with increased service lifetime and improved lubricating performances.
  • suitable choice of ionic liquid may provide a lubrication oil composition with improved flexibility to adjust electric conductivity, which may be advantageously used in electrified equipment having electric charge buildup, e.g., in electric vehicle powertrains.
  • ionic liquids have other properties that are desirable in lubricating and working fluids, for example: extremely low vapor pressure, virtually no cavitation properties, low or no flammability, high thermal stability to 260°C or more.
  • suitable cations for ionic liquids are proven to be phosphonium, imidazolium, pyridinium, or pyrrolidinium cations which are combined with anions containing fluorine and selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroalkylsulfonyl)imide, perfluoroalkyl sulfonate, tris(perfluoroalkyl)methidenes, bis(perfluoroalkyl)imidenes, bis(perfluoroaryl)imides, perfluoroarylperfluoroalkylsulfonylimides, and tris(perfluoro-alkyl) trifluoro
  • Ionic liquids with highly fluorinated anions are especially preferred because they typically have high thermal stability. Further, water uptake ability of such ionic liquids is significantly reduced by such anions, e.g., as in the case of the bis(trifluoromethylsulfonyl)imide anion.
  • Ionic liquids of the present disclosure may be useful as oil-soluble components in hydrocarbon fluids, hydrophobic-type fluids, and suitable lubricating and working fluids. Ionic liquids of the present disclosure may also be useful as soluble components in polar fluids, hydrophilic-type fluids, amphiphilic-type fluids, ester or ether containing fluids, and suitable lubricating and working fluids.
  • ionic liquids as disclosed herein are useful in solid or semi-solid lubricants, such as e.g. greases.
  • such ionic liquids are suitably used as base stocks and cobase stocks, typically as minor components of a lubricant or working fluid composition.
  • such ionic liquids are suitably used as additives, typically at lower concentrations in a lubricant or working fluid composition.
  • such ionic liquids are used in an amount of 0.1 to 10 wt%, 0.5 to 7.5 wt%, or 0.75 to 5 wt%.
  • Base oils for use in the lubricating oil compositions of the present disclosure are any of the oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, more preferably Group III, Group IV, and Group V base oils, and mixtures thereof.
  • Highly paraffinic base oils are used to advantage in the lubricating oil compositions useful in the present disclosure.
  • the base oil constitutes the major component of the engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from 50 to 99 weight percent, preferably from 70 to 95 weight percent, and more preferably from 85 to 95 weight percent.
  • the base oil is selected from any of the synthetic or natural oils typically used as crankcase lubricating oils for spark-ignited and compression-ignited engines.
  • the base oil conveniently has a kinematic viscosity at 100°C, according to ASTM standards, of 2.5 cSt to 12 cSt (or mm 2 /s) and preferably of 2.5 cSt to 9 cSt (or mm 2 /s). Mixtures of synthetic and natural base oils are used if desired. Bi-modal mixtures of Group I, II, III, IV, and/or V base stocks are also used if desired.
  • the lubricant composition of the present disclosure comprises an oil of lubricating viscosity.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt% the sum of the amounts of all additives.
  • the lubricating oils of the instant disclosure may utilize a bimodal base stock mixture or blend that includes a low viscosity base stock and a high viscosity co-base stock.
  • the base stock is selected from the group consisting of a Group I, a Group II, a Group III, a Group IV, a Group V, and combinations thereof.
  • the cobase stock is selected from the group consisting of a Group I, a Group IV, a Group V, and combinations thereof.
  • a lubricating oil comprising from 15 to 95 wt % of a low viscosity base stock having a KV100 of 2 to 12 cSt, 3 to 12 cSt, 4 to 12 cSt, and from 0.5 to 55 wt % of cobase stock having a KV100 of 29 to 1000 cSt.
  • oil-soluble or “dispersible” used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions.
  • KV100 Kinematic viscosity at 100°C (KV100) is measured according to ASTM D445. Conductivity is measured according to the D2624 method at room temperature. Efficiency gain is assessed by measuring the coefficient of traction at 80°C, and 1.25 GPa load, using the MTM (Mini Traction Machine).
  • This test is performed using the MTM instrument supplied by PCS- Instruments) using a 3/4" (19.05 mm) diameter steel ball (AISI 52100) which is loaded and rotated against the flat surface of a rotating disk (AISI 52100).
  • the disk is held in a bath containing the test lubricant so that the contact between the ball and flat is fully immersed.
  • the ball shaft is aligned with respect to the disk so as to prevent spin in the contact and the slide to roll ratio is controlled independently by driving both the ball and disk with separate motors.
  • Each candidate is tested varying the temperature between 40°C and 140°C, while changing the Slide to Roll Ratio (SRR) between 0 and 100. Under particular circumstances, the SRR value may vary to greater than 100.
  • Grease noise performance was evaluated using the BeQuiet grease noise tester manufactured by SKF Bearing Company. This tester was able to distinguish subtle differences in noise quality among grease batches. Results were reported in terms of vibrational amplitude in microns/second and in terms of the percentage of measured noise peaks, which fall in to defined noise categories. The noise to categories were designated BQ1, BQ2, BQ3, BQ4, etc. Quieter greases will have a greater percentage of peaks in the lower numbered categories and a lower peak average value. Specifically, a BQ4 value corresponds to the percentage of measured noise peaks less than or equal to 40 microns/second. A BQ3 value corresponds to the percentage of measured noise peaks less than or equal to 20 microns/second.
  • a BQ2 value corresponds to the percentage of measured noise peaks less than or equal to 10 microns/second.
  • a BQ1 value corresponds to the percentage of measured noise peaks less than or equal to 5 microns/second.
  • PCT/EP CLAUSES [00140] Clause 1. A method for producing polyurea grease comprising: a reaction step wherein a diisocyanate and an amine compound are reacted in one or more continuously stirred tank reactors to form a reaction mixture; a milling step wherein the reaction mixture is milled to form a milled product; and a curing step wherein the milled product is heat cured to form a polyurea grease, wherein the method is performed continuously. [00141] Clause 2.
  • the diisocyanate compound is diphenylmethane diisocyanate, phenylene diisocyanate, diphenyl diisocyanate, phenyl diisocyanate, napththylene diisocyanate, tolylene orthodiisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate isocyanurate trimer, isophorone diisocyanate, or a combination thereof, and wherein the diisocyanate is optionally dissolved or dispersed within a base oil.
  • the amine compound is a monoamine compound, a diamine compound, or a mixture thereof, wherein the monoamine compound is a compound having the formula: wherein: R is C 6 -C 26 alkyl, C 6 -C 26 alkenyl, C 3 -C 8 cycloalkyl, 5- to 6-membered heteroaryl, phenyl, or C 8 - C12 bicycloaryl, each of which is unsubstituted or substituted with one or more R 1 groups; and each R 1 group is independently F, Cl, Br, CF 3 , cyano, hydroxy, carboxyl, C 1 -C 6 alkoxycarbonyl, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, a 5- to 6-membered heteroaryl, phenyl or C8-C12 bicycloaryl; and wherein the diamine compound is
  • Clause 4 The method for producing a polyurea grease according to any one of clauses 1-3, wherein the reaction step utilizes 1-decanol, 1-tetradecanol, 1-hexadecanol, 1- octadecanol, cis-9-octadecen-1-ol, 9-octadecadien-1-ol, 12-octadecadien-1-ol, or a combination thereof. [00144] Clause 5.
  • the reaction step further utilizes a catalyst, wherein the catalyst is triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, bis-(2-dimethylaminoethyl)ether, N-methylmorpholine, N- methylimidazole, dibutyltin dilaurate, stannous octoate, or a combination thereof, and wherein the catalyst is optionally dissolved or dispersed within a base oil.
  • the catalyst is triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, bis-(2-dimethylaminoethyl)ether, N-methylmorpholine, N- methylimidazole, dibutyltin dilaurate, stannous octoate, or a combination thereof, and wherein the catalyst is optionally dissolved or dispersed
  • An apparatus for producing a polyurea grease comprising: one or more continuously stirred tank reactors configured to continuously stir contents therein and to form a reaction mixture therein; and one or more diisocyanate feed lines in fluid communication with the one or more continuously stirred tank reactors to provide diisocyanate to the one or more continuously stirred tank reactors; one or more amine compound feed lines in fluid communication with the one or more continuously stirred tank reactors to provide amine to the one or more continuously stirred tank reactors; and a milling device operatively connected to the one or more continuously stirred tank reactors to receive the reaction mixture therefrom and configured to mill the reaction mixture to output a milled product.
  • a hot curing device connected to an output of the milling device and configured to receive the milled product from the milling device and to heat cure the milled product to form the polyurea grease.
  • An apparatus for producing a polyurea grease according to any one of clauses 12-14 wherein the one or more continuously stirred tank reactors include a first continuously stirred tank reactor having an inlet and an outlet and a second continuously stirred tank reactor having an inlet and an outlet, wherein the outlet of the first continuously stirred tank reactor is connected to the inlet of the second continuously stirred tank reactor, and the outlet of the second continuously stirred tank reactor is connected to an inlet of the milling device.
  • Clause 16 The method for producing a polyurea grease according to any one of clauses 1-11 wherein the polyurea grease has an average noise level peak of less than 20/sec as measured with a BeQuiet grease noise tester.

Abstract

L'invention concerne un procédé de production en continu de graisse à base de polyurée. Le procédé selon l'invention comprend : (1) La réaction d'un diisocyanate et d'un composé amine dans au moins un réacteur à cuve agitée en continu ; (2) le broyage du produit ayant réagi ; et (3) le durcissement à chaud du produit broyé, ce qui permet de former un produit de graisse à base de polyurée. L'invention concerne également un appareil de production en continu de graisse à base de polyurée. L'appareil selon l'invention comprend : (1) Au moins l'une d'une charge de diisocyanate et d'une charge d'amine ; (2) au moins un réacteur à cuve agitée en continu ; (3) un dispositif de broyage ; et (3) un dispositif de durcissement.
PCT/US2020/064879 2019-12-23 2020-12-14 Procédé et appareil de production en continu de graisse à base de polyurée WO2021133583A1 (fr)

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