KR102059973B1 - Lubricant spray polymer - Google Patents

Abstract

The invention disclosed in the present invention is a copolymer of an alkyl methacrylate monomer, wherein the alkyl methacrylate monomer is at least
a. Monomer (A) selected from C6-C10 alkyl methacrylate monomers, and
b. Monomer (B) selected from C10-C18 alkyl methacrylate monomers
Including,
The mass ratio of monomer (B): monomer (A) in the copolymer is 99: 1 to 60:40 by weight. In some embodiments, the copolymer is a copolymer of lauryl methacrylate and C8 alkyl methacrylate. Also disclosed is a method of preparing the copolymer.

Description

Lubricant spray polymer

The present invention relates to copolymers, synthesis of copolymers and methods of using copolymers.

The main function of lubricants is to reduce friction. However, lubricants often require additional properties to be effective. For example, lubricants used in crankcases of large diesel engines, such as marine diesel engines, are often used in operating conditions that require special consideration.

Marine diesel engines can generally be classified as low speed, medium speed or high speed engines, the type of low speed being used in accordance with the largest deep shaft marine vessels and certain industries. Low speed diesel engines are unique in size and operation. Larger units can weigh up to 200 tons and can be more than 10 feet wide and 45 feet high. The engine's power can be up to 100,000 horsepower at 60 to about 200 engine revolutions per minute. They typically operate in two stroke cycles in a crosshead design.

In large diesel engines of the crosshead type used in marine and solid stationary applications, the piston cylinder is lubricated separately from other engine components. The cylinders are lubricated on a total loss basis with cylinder oil sprayed separately into each cylinder by a lubricator disposed around the cylinder liner. The oil is distributed to the lubricator via a pump, and modern engine designs reduce oil consumption by applying oil directly to the oil ring.

The unique design of these engines creates the need for lubricants with improved rheological properties. Low speed engines are prone to corrosion because they operate at lower temperatures than medium or high speed engines. Therefore, lubricants used in ship engines must protect engine parts from corrosion, especially rust. Molten ferrous metal engine parts are generally produced when in contact with water produced by internal combustion processes or external sources. Regardless of the source, rust and corrosion reduce engine efficiency and lifespan.

In addition, fuels commonly used in these diesel engines typically contain significant amounts of sulfur. In the process of combustion, sulfur can combine with water to form sulfuric acid, the presence of which can lead to corrosion wear. Especially for marine two-stroke engines, the area around the cylinder liner and piston ring can be corroded and worn by acids. Therefore, diesel engines must be properly lubricated to withstand corrosion and wear.

To prevent corrosion, lubricants should typically be applied to the cylinder wall by spraying lubricant onto the cylinder wall by a pulse lubrication system or via an injector. In marine engines, lubricant is injected or sprayed into the cylinder liner, spread horizontally by an atomizer or injector, and vertically spread by the piston ring as the piston moves upwards. Lubricants are not used in circulation systems; If excess lubricant comes to the bottom of the cylinder, it is discarded. Typically fresh lubricant is injected every 4 to 8 strokes depending on engine speed.

Thus, there is a need for lubricant additives that will provide effective oxidation and corrosion resistance without incurring the environmental risks and costs of other oxidation and corrosion inhibitors. In addition, since no lubricating oil is circulated in the marine engine, any rheological improvements that increase lubrication or reduce oil usage can significantly improve engine life and reduce costs.

We have discovered new copolymers that can alter the rheology of marine lubricants to provide improved lubrication properties. In particular, marine engine lubricating oil comprising the copolymer of the present invention as an additive covers the marine engine piston cylinder wall more completely than with prior art oils (with or without additional additives) to provide better lubrication and less engine cylinders. Induces wear and corrosion.

The inventors also recognized that the method by which the copolymer is prepared can control the properties of the copolymer.

In a first embodiment, the invention is a copolymer of an alkyl methacrylate monomer, wherein said alkyl methacrylate monomer is at least:

a. Monomer (A) selected from C6-C10 alkyl methacrylate monomers, and

b. Monomer (B) selected from C10-C18 alkyl methacrylate monomers

It provides a copolymer comprising a. The ratio of monomer (B): monomer (A) in the copolymer is from about 99: 1 to about 10:90 by weight. In one embodiment, A is selected from C6-C9 alkyl methacrylate monomers. In other embodiments, B is selected from C11-C18 alkyl methacrylate monomers. In another embodiment, the ratio of monomer (B): monomer (A) in the copolymer is from about 99: 1 to about 60:40 by weight.

In a second embodiment, the present invention provides a copolymer obtained by combining at least monomer (A) and monomer (B) in a mixture and copolymerizing the monomers, wherein the monomers are from about 99: 1 to Present in a mass ratio of monomer (B): monomer (A) of about 10:90, preferably about 99: 1 to about 60:40, wherein monomer (A) and monomer (B) are distinguished from one another.

In a third embodiment, the present invention provides a method of preparing a copolymer as described above.

All publications referenced herein are incorporated by reference in their entirety unless they contradict the teachings presented herein.

In a first embodiment, the invention is a non-crosslinked copolymer of an alkyl methacrylate monomer, wherein the alkyl methacrylate monomer is

a. Monomer (A) selected from C6-C10 alkyl methacrylate monomers, and

b. Monomer (B) selected from C10-C18 alkyl methacrylate monomers

Including,

The mass ratio of monomer (B): monomer (A) in the copolymer is from about 99: 1 to about 10:90, preferably 99: 1 to 60:40, by weight.

In all embodiments of the invention the ratio of monomers can be adjusted to manipulate the properties of the copolymer as desired. For example, the monomer may have a ratio of monomer (B): monomer (A) of 10:90, 15; 85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50 : 50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95: 5, and 99: 1. In one embodiment the monomer has a ratio of monomer (B): monomer (A) 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95: 5, and It exists at 99: 1.

In some embodiments of all embodiments of the invention, monomer (A) is linear or branched C ₈ alkyl. In some embodiments, monomer (A) is 2-ethylhexyl methacrylate.

In some embodiments of all embodiments of the invention, the copolymers used in the lubricant composition according to the invention are composed of monomers comprising at least two monomers of one monomer (A) and one monomer (B) which are distinguished from one another. It is prepared from the mixture. The monomer is preferably selected from monomers which, when polymerized, form copolymers that are soluble in liquids, preferably oils, more preferably marine diesel engine oil lubricants.

In other embodiments of all embodiments of the invention, the copolymer is a copolymer of a mixture of monomers comprising at least C8 alkyl methacrylate, C12 alkyl methacrylate, C14 alkyl methacrylate and C16 alkyl methacrylate, They are present in the mixture in the following weight ratios:

Based on the total weight of the mixture

5 wt% to 30 wt% C8 alkyl methacrylate,

40% to 70% by weight of C12 alkyl methacrylate,

12 to 35 weight percent C14 alkyl methacrylate,

From 1% to 12% by weight of C16 alkyl methacrylate,

0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight of other methacrylates.

In other embodiments of all embodiments of the invention, the copolymer is substantially free of monomers other than monomers (A) and (B), in particular including methyl methacrylate having a C1-C5 alkyl group It is substantially free of methacrylate. Monomers such as methyl methacrylate reduce the solubility in the oil of the resulting copolymers and the presence of such monomers is limited or omitted.

In other embodiments of all embodiments of the invention, the copolymer is free of monomers other than monomers (A) and (B), in particular methacryl including for example methyl methacrylate having a C1-C5 alkyl group There is no rate.

Typically, the copolymers according to the invention are about 100 to about 200 (nm) Rg, about 120 to about 190, as measured by hydrodynamic column chromatography-multi-angle light scattering (HCC-MALS). (nm), about 130 to 180, or about 140 to about 170 (nm) Rg, with an average root mean square rotation radius (Rg).

In a second embodiment, the copolymer is obtained by combining at least monomer (B) and monomer (A) in a mixture and copolymerizing monomers, the monomer being from about 99: 1 to about 10:90 monomer (B): monomer It exists in the mass ratio of (A).

Copolymers can be synthesized by conventional methods of vinyl addition polymerization known to those skilled in the art, such as but not limited to solution polymerization, precipitation polymerization, and dispersion polymerization including suspension polymerization and emulsion polymerization.

In some embodiments, the polymer is formed by suspension polymerization in which monomers that are insoluble in water or poorly soluble are suspended as drops in water. The monomer droplet suspension is maintained by mechanical stirring and the addition of stabilizers. Alkali metal salt containing polymers of cellulose ethers, poly (vinyl alcohol-co-vinyl acetate), poly (vinyl pyrrolidone) and (meth) acrylic acid and colloidal (water insoluble) inorganic powders such as tricalcium phosphate, hydroxy apatite, Active polymers such as barium sulphate, kaolin, and magnesium silicate can be used as stabilizers. In addition, small amounts of surfactants such as sodium dodecylbenzene sulfonate may be used with the stabilizer. The polymerization is initiated using an oil soluble initiator. Suitable initiators include peroxides such as benzoyl peroxide, peroxy esters such as tert-butylperoxy-2-ethylhexanoate and azo compounds such as 2,2'-azobis (2-methylbutyronitrile). do. Upon completion of the polymerization, the solid polymer product can be separated from the reaction medium by filtration and washed with water, acid, base or solvent to remove unreacted monomer or glass stabilizer.

In another embodiment, the polymer is formed by emulsion polymerization, one or more monomers are dispersed in the aqueous phase and the polymerization is initiated using a water soluble initiator. The monomers are typically water insoluble or very poorly soluble in water and surfactants or soaps are used to stabilize the monomer droplets in the aqueous phase. The polymerization takes place in the expanded micelles and latex particles. Other components that may be present in the emulsion polymerization include chain transfer agents such as mercaptans to control molecular weight (e.g. dodecyl mercaptan), electrolytes to adjust pH, and small amounts of organic solvents to control the polarity of the aqueous phase, Preferably, water-soluble organic solvents include, but are not limited to, acetone, b-butanone, methanol, ethanol and isopropanol. Suitable initiators include alkali metal or ammonium salts of persulfate, water soluble azo compounds such as 2,2'-azobis (2-aminopropane) dihydrochloride, and Fe (II) and cumene hydroperoxides, and tert-butylhydro Redox systems such as loperoxide-Fe (II) -sodium ascorbate. Suitable surfactants are anions such as fatty acid soaps (e.g. sodium or potassium stearate), sulfates and sulfonates (e.g. sodium dodecyl 20 benzene sulfonate), sulfosuccinates (e.g. dioctyl sodium sulfosuccinate) Surfactants; Nonionic surfactants such as octyl phenol ethoxylate, and linear and branched alcohol ethoxylates; Cationic surfactants such as cetyl trimethyl ammonium chloride; And amphoteric surfactants. Anionic surfactants and combinations of anionic and nonionic surfactants are most commonly used. Polymeric stabilizers such as poly (vinyl alcohol-co-vinyl acetate) can also be used as surfactants. Solid polymer products free of aqueous media can be obtained by a number of methods including destabilization / solidification of the final emulsion followed by filtration, solvent precipitation of the polymer from the latex, or spray drying of the latex.

The polymer may be separated by conventional methods known to those skilled in the art such as solvent exchange, evaporation of solvent, spray drying and freeze drying, but are not limited thereto.

The properties of the copolymer obtained by combining at least monomer (A) and monomer (B) in the mixture and copolymerizing can be manipulated by adjusting further reagents added to the polymerization mixture. These reagents include, but are not limited to, initiator systems and surfactants.

The type and amount of initiator system used in the polymerization mixture can affect the properties of the resulting copolymer. The initiator system can be a single initiator compound (eg persulfate salt) or a mixture of two or more components (eg hydrogen peroxide and sodium ascorbate). In some embodiments, the initiator system may include an oxidizing agent, a reducing agent and optionally a metal salt. The oxidant may be, for example, a persulfate such as ammonium persulfate, or a peroxide such as, for example, hydrogen peroxide (H ₂ O ₂ ) or tert-butyl hydroperoxide (TBHP). Preferred copolymers can be obtained, for example, when the polymerization mixture comprises from about 0.01 to about 0.06 mass% tert-butyl hydroperoxide of all monomers in the mixture. In another embodiment, the mixture may include from about 0.01 to about 0.03 mass% tert-butyl hydroperoxide of the monomers in the mixture. In some examples, the mixture further comprises about 0.013 mass% tert-butyl hydroperoxide of the monomers in the mixture. Useful initiators for the copolymers of the present invention include any conventional initiator, including any conventional redox initiators.

In some embodiments, the reducing agent of the redox initiator system can be ascorbic acid or a salt thereof. For example, the polymerization mixture may comprise about 0.04 to about 0.1 mass% of sodium ascorbate of the monomers in the mixture. In another embodiment, sodium ascorbate may be present in about 0.08 to about 0.1 mass% of the monomers in the mixture. In some embodiments, the polymerization mixture comprises about 0.098 mass% of sodium ascorbate of the monomers in the mixture.

The initiator system may also include metal salts. The metal can be any suitable transition metal, for example iron. In some embodiments, the metal salt of the initiator system can be iron sulfate (FeSO ₄ ). In some embodiments, the metal salt is present in the polymerization mixture at about 0.0005 to about 0.1 mass% of the monomers in the mixture. In some embodiments, the metal salt is added to the polymerization mixture as a solution.

Copolymers can also be obtained for polymerization mixtures further comprising a surfactant. In some embodiments, the surfactant may contain sulfonate groups. For example, the surfactant may include a dialkyl sulfosuccinate, for example dioctyl sulfosuccinate sodium salt. In some embodiments, the surfactant may be Aerosol® OT.

The copolymer may be a random copolymer, a block copolymer or a mixture thereof. In some embodiments, the copolymer is substantially random copolymer (eg, greater than 90, 95, 98, or 99 mass%). In another embodiment, the copolymer is partly random copolymer and partly block copolymer. In this embodiment, the weight percent ratio of random copolymer: block copolymer is generally 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70; 20:80 or 10:90. The copolymer may also be substantially block copolymer (eg greater than 90, 95, 98 or 99 weight percent). In other embodiments, the copolymer may contain additional monomers in addition to the monomers (A) and (B) described. These additional monomers may be present in amounts less than 10% by weight. In some embodiments, the additional monomer is present in an amount of about 0.5 to 10 weight percent, or about 1 to 10 weight percent or about 1 to 5 weight percent or about 5 to 10 weight percent. In other embodiments, the additional monomer is present in an amount of less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or about 0.5 weight percent. Additional monomers may include, for example, crosslinking monomers, acrylates, styrenes, C ₁ -C ₃ alkyl methacrylates and other similar monomers.

The copolymer may also be crosslinked. That is, the copolymer may contain monomer units that link one or more backbone chains of the polymer. In some embodiments, the copolymer contains crosslinked monomer units present in up to about 5% by weight of the copolymer. In other embodiments, the copolymer is not crosslinked or noncrosslinked and is substantially free of monomers that act as crosslinkers. In another embodiment, the monomer mixture for preparing the copolymer is substantially free of crosslinkers.

Crosslinked copolymers can be obtained when the polymerization mixture comprises a crosslinking agent. In some embodiments, the crosslinker is a diacrylate or dimethacrylate crosslinker such as, for example, 1,6-hexanediol dimethacrylate. In some examples, the mixture comprises at least about 0.005 mass% of the monomers in the mixture to contain a crosslinking agent.

Exemplary copolymers are shown in Tables 1 and 2. For each example, Table 1 shows the ratio of monomer (B): monomer (A) used (e.g. 2-ethylhexyl methacrylate), and the amount of acetone, redox initiator system and components of the surfactant. To show. Table 2 shows the molecular weight, Rg and viscosity of the copolymers of each example.

In a third embodiment, a method of preparing a copolymer as described above is disclosed. The process involves the polymerization of monomers (A) and (B), wherein the mass ratio of monomers (B): monomers (A) in the copolymer is from about 99: 1 to about 10:90 (eg , 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70 : 30, 75:25, 80:20, 85:15, 90:10, 95: 5, 99: 1).

In some embodiments, the process comprises the steps of adding monomer (B) and monomer (A) at about 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55 , 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95: 5, 99: 1 And initiating the polymerization of the monomers to provide a copolymer.

In some embodiments, the ratio of monomer and initiator, or initiator system, can be selected as described above. This method may include additional components to provide copolymers with desirable properties. For example, the process may comprise a surfactant such as, for example, Aerosol® OT, or a crosslinker such as, for example, 1,6-hexanediol dimethacrylate.

The polymerization can be produced in an aqueous mixture or in a mixture comprising both aqueous and organic solvents. For example, the polymerization mixture may comprise a mixture of water and acetone. In some embodiments, the polymerization mixture may require an organic solvent. It will often be desirable to include organic solvents when lauryl methacrylate is present in the polymerization mixture. Organic solvents for use in such polymerization reactions are known and may be generally selected by those skilled in the art of polymer synthesis. Suitable organic solvents include, but are not limited to, for example, acetone, 2-butanone, methanol, ethanol and isopropanol.

The copolymer of the first or second embodiment may be present in an oil in an amount of about 0.5% to about 25% by weight. Depending on the oil used, the copolymer may be present in the oil in an amount of about 1% to about 25% by weight.

The oil may be selected from those known in the art and may be selected from mineral oils, ie oils obtained from crude oil processing, or artificially prepared oils containing synthetic oils, ie polyglycols or esters, or semisynthetic oils, ie It may be a blend of mineral and synthetic oils. In some embodiments, the oil is a mineral base oil, ie a complex mixture of paraffins, naphthenes and aromatic compounds. In some embodiments, the oil may be a paraffinic base oil such as 150 neutral solvent, 600 solvent neutral or bright stock. The oil composition may comprise further components, in particular components used in marine diesel engine oil lubricants.

Tests to determine the enhanced lubricant properties and utility of oils containing the copolymers of the first or second embodiments were conducted under the following conditions. The oil / polymer composition was investigated for performance / compatibility as a lubricant by a finger pull test performed by pipetting a droplet of sample fluid (about 65 μl) into the thumb of a gloved hand. Gently squeeze the thumb and forefinger to ensure contact between the two fingers and the droplet, then move the finger away, observing the time the composition provides a fluid connection between the thumb and forefinger. Pull vertically for about 1 second over a distance. All finger drawing tests were performed at ambient temperature, about 21 ° C. The performance of the sample was characterized as "very short", "short", "normal", "long" or "very long" depending on how long the sample maintains a fluid connection between the thumb and index finger. In finger drawing tests, compositions with "very short" performance are less than 1 second, "short" is 1-4 seconds, "normal" is 4-7 seconds, "kim" is 7-60 seconds, "very long" is composition It means a situation in which the two fingers are connected indefinitely. Compositions with "very short" and "very lame" configurations do not exhibit improved suitability or performance as lubricants. Compositions having a "short", "moderate" or "kim" configuration exhibit improved suitability to varying degrees because, for example, the ability to effectively spread over the cylinder wall of the engine being lubricated is improved. Compositions having a "kim" configuration have particularly good suitability as lubricants. The results of the finger drawing test are shown in Table 2.

One advantage of the copolymers disclosed herein is that they can be used to improve the performance of oils as lubricating oils while at the same time maintaining the ability to handle oils in the way needed for field use. For example, because many lubricants are pumped through a fluid pump, the lubricant must have a suitable viscosity so that it can be pumped without mechanical complexity or pumping equipment damage. Lubricants with inadequate viscosity (especially very high viscosities) may require much higher power to prevent the lubricant from pumping properly or otherwise to pump the lubricant. The polymers disclosed herein strike a balance between maintaining lubricating oil performance while maintaining a sufficient level of viscosity to enable efficient handling in the field. It was unexpectedly found that the combination of monomer (B) homopolymer and oil provides improved lubrication performance in viscosity that allows for efficient handling. The combination of oil and copolymer having a monomer (B): monomer (A) ratio of 5:95 results in a material having a viscosity and a material with other physical handling properties that prevents the composition from being handled efficiently in the field. do.

In one embodiment, the polymer has a molecular weight greater than 20000 D.

In one embodiment, the polymer has a bimodal molecular weight distribution.

A copolymer having a specific range of molecular weight (Mw), root mean square rotation radius (Rg) and viscosity correlation is an oil additive that improves oil performance as a lubricant while maintaining the ability to handle and pump oil. It is particularly suitable as. Preferred correlations of bimodal Mw, Rg and viscosity values for one embodiment of the copolymers disclosed herein are represented by the following formula:

Performance X = 1139.69418+ (2.54756 * Peak 1 Mw)-(0.91396 * Peak 1 Rg)-(66.18535 * Peak 2 Mw)-(0.23020 * Viscosity + 1.18947E-003 * Peak 1 Rg) * (Viscosity),

Here, as shown in Table 2, the unit for Mw is 10 ⁶ g / mol, the unit for Rg is nm and the unit for viscosity is mPa.s. Performance X values of 500 to 900, more preferably 550 to 800, most preferably 600 and 750 represent copolymers having properties that are particularly suitable for improving the performance of oils as lubricants.

Justice

As used herein, lauryl methacrylate is a mixture of C _14-16 alkyl methacrylates including dodecyl methacrylate (C ₁₂ ; CAS 142-90-5) or dodecyl methacrylate. That is, lauryl methacrylate may include a mixture in which dodecyl methacrylate is a component, but tetradecyl methacrylate (C ₁₄ ; CAS 2549-53-3) and hexadecyl methacrylate (C ₁₆ ; CAS) Mixtures comprising one or more other C _14-16 alkyl methacrylates, such as 2495-27-4). For example, lauryl methacrylate is about 40-70% by weight of dodecyl methacrylate, 15-, such as commercially available methacrylic ester 13.0 (Evonik trade name: VISIOMER® Terra C13,0-MA). 40% by weight of tetradecyl methacrylate and 4-10% by weight of hexadecyl methacrylate.

The term "about" as used herein refers to a value of ± 10% of a given value.

As used herein, the term "C ₈ alkyl" refers to a group of eight saturated carbon atoms linked in a linear or branched configuration. Examples of linear C ₈ alkyl groups include n-octyl. Examples of branched C ₈ alkyl groups include, but are not limited to, 2-ethylhexyl.

As used herein, the term "alkyl methacrylate" refers to a compound of methacrylol radicals bonded to linear or branched, saturated or unsaturated alkyl groups.

As used herein, the term "substantially free of monomers" means that up to 3.0% by weight of the copolymer, preferably up to 1.0% by weight and more preferably up to 0.5% by weight of monomer are present in the copolymer.

As used herein, the term "substantially free of crosslinker" means that the monomer units linking the backbone chains of two or more polymers are present at 1.0 wt% or less, preferably 0.5 wt% or less of the copolymer.

Any embodiment disclosed herein can be combined with any other embodiment, the results of which are subject to the claims according to the invention.

Unless otherwise used, "%" means weight percent.

Example

The lauryl methacrylate used in Examples 1-8 was provided as methacrylic ester 13.0, commercially available as VISIOMER Terra C13,0-MA from Evonik Industries.

Example  One

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 270.0 g of lauryl methacrylate, 30.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  2

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 240.0 g of lauryl methacrylate, 60.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  3

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 210.0 g of lauryl methacrylate, 90.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  4

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 180.0 g of lauryl methacrylate, 120.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  5

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 120.0 g of lauryl methacrylate, 180.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  6

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. 60.0 g of lauryl methacrylate, 240.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were then added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  7

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. 30.0 g of lauryl methacrylate, 270.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were then added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Example  8

To a 4-neck 2000 mL flask equipped with an overhead stirrer, condenser, thermocouple and nitrogen purge below the surface was added 645.5 g of water and 8.7 g of Aerosol® OT. Agitation was turned to 200 rpm and a nitrogen purge below the surface was started. Then 15.0 g of lauryl methacrylate, 285.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 ° C using a thermostat batch set at 45 ° C. When the reaction reached 43 ° C., 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, a solution of 0.29 g sodium ascorbate and 0.60 g 0.25% iron sulfate hexahydrate dissolved in 7.5 g water was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held for an additional 5 hours, cooled to room temperature and separated.

Among oils Copolymer 5%  Solid Solution Preparation

Emulsion of one of Examples 1-8 was added to a 4-neck 1000 mL flask equipped with a Barrett distillation trap with an overhead stirrer, condenser and thermocouple to yield 20.0 g of polymer. It was. Subsequently, neutral solvent 600 was added and the sum total was 400.0g, and 150.0g of toluene was then added. Stirring was turned to 200 rpm and the mixture was refluxed. Water condensed out of the Barrett trap. When the water did not overflow, the contents of the reactor were raised to 130 ° C. to distill most of the toluene. The remaining material was transferred to a 1000 mL one-neck round bottom flask and concentrated in vacuo with a 60 ° C. bath until the material reached a constant weight.

Molecular weight and rotation radius determination method

The molecular weight and rotation radius of the polymer sample fed at 5% solids in the base oil were determined by the following procedure:

Eluent: HPLC grade tetrahydrofuran stabilized with 0.01% butylated hydroxytoluene

Column: Phenogel Column 100A 10um 300mm x 7.8mm.

Flow rate: 0.50 ml / min.

Detector: Wyatt Dawn Heleos-II Multi-Angle Light Scattering (MALS) at 663 nm and room temperature, and Wyatt Optilab T-rEX refractive index detector at 658 nm and 40 ° C

Pumps / Autosamplers: Agilent 1100 Isocratic HPLC Pumps and Autosamplers

Column compartment: 40 ° C.

Standards: No standard was directly related to the analysis, but the Heleos-II MALS calibration constants were set to toluene and the Optilab T-rEX calibration constants were set to NaCl in water. The 17 angles in Heleos-II were standardized to a narrow range of polystyrene standards of 28,500 molecular weight and the detector retardation volume was adjusted to the same standard.

Sample Preparation: A sample was prepared by diluting about 8.0 mg of sample by gravimetrically with about 5.0 g of tetrahydrofuran. The actual concentration of the polymer in mg / ml was calculated based on the density of tetrahydrofuran (0.889 g / ml) and the percentage of solids in the sample solution (5.0 wt.%).

Injection: 50 μl.

Run time: 20 minutes.

Software: Wyatt Astra version 6.1.4.25.

Calculation: Astra software offers several choices of format and exponential order suitable for your data. All samples were suitable for the secondary Berry. The angle used was adjusted to the optimum value, using a minimum of 13 angles and a maximum of 17 angles. dn / dc was calculated from the refractive index data assuming 100% recovery. The software reported the average molecular weight in Mw and the Root Mean Square Radius of Gyration in Rg. The results are shown in Table 2.

Viscosity Determination Method

The shear viscosity of the polymer sample fed at 5% solids in the base oil was determined by the stress-controlled rheometer MCR 302 manufactured by Anton Paar GmbH, Anton Paar Strasse 20, 8054, Graz, Austria. Double Gap System of Measurement was used for excellent accuracy (Instruction Manual, MCR Series, Modular Compact Rheometer MCR 52/102/302/502, page 50, Anton Parr, Graz, Austria, 2011). The temperature was set to 22 ° C with an accuracy of 0.1 ° C. Shear rate gradually increased from 1 / second to 100 / second with a viscosity reading of 10 points per decade. At each of these points, an equilibrium time of 10 seconds was given before reading and lasted for 3 seconds. The viscosity at 10 / sec shear rate is shown in Table 2. The instrument control and data acquisition software is RheoCompassTM, version 1.13.445.

TABLE 1

¹ percent by mass of total amount of monomer, percent of monomer

² Weight percent based on total amount of monomer

LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate

TABLE 2- Hydraulics (Hydrodynamic) Chromatography / MALS

¹ percent by mass of total amount of monomer, percent of monomer

LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate;

² vs = very short, s = short, m = normal, l = long, vl = very long

³ Two duplicate samples for Example 7 were prepared using the preparation method described in Example 7

Claims (13)

As a non-crosslinked copolymer of alkyl methacrylate monomers,
The alkyl methacrylate monomer is
a. Monomer (A) selected from C6-C10 alkyl methacrylate monomers, and
b. Monomer (B) selected from C10-C18 alkyl methacrylate monomers
Including,
The mass ratio of monomer (B): monomer (A) in the copolymer is 99: 1 to 60:40 by weight,
Monomer (A) and monomer (B) are different from each other,
The copolymer comprises up to 3.0 wt%, up to 1.0 wt%, or up to 0.5 wt% methyl methacrylate, the copolymer being subjected to hydrodynamic column chromatography-multi-angle light scattering where tetrahydrofuran is used as solvent. A non-crosslinked copolymer as measured by having an average root mean square radius of gyration of 100 to 200 nm. As a non-crosslinked copolymer,
The non-crosslinked copolymer is
At least a. Monomer (A) selected from C6-C10 alkyl methacrylate monomers, and b. Combining a monomer (B) selected from C10-C18 alkyl methacrylate monomers in the mixture, and
Copolymerizing monomers
Obtained from,
The monomers are present in a mass ratio of monomer (B): monomer (A) of 99: 1 to 60:40,
Monomer (A) and monomer (B) are different from each other,
The copolymer comprises up to 3.0 wt%, up to 1.0 wt%, or up to 0.5 wt% methyl methacrylate, the copolymer being subjected to hydrodynamic column chromatography-multi-angle light scattering where tetrahydrofuran is used as solvent. A non-crosslinked copolymer, as measured by having a mean root mean square radius of rotation of 100 to 200 nm. The method according to claim 1 or 2,
The non-crosslinked copolymer wherein the mass ratio of monomers is 80:20 monomer (B): monomer (A). The method according to claim 1 or 2,
The non-crosslinked copolymer, wherein the mass ratio of monomers is 90:10 monomer (B): monomer (A). The method according to claim 1 or 2,
The monomer (B) is lauryl methacrylate, non-crosslinked copolymer. The method according to claim 1 or 2,
Non-crosslinked copolymer wherein monomer (A) is C8 alkyl methacrylate. The method of claim 6,
Wherein said C8 alkyl methacrylate is 2-ethyl hexyl methacrylate. The method according to claim 1 or 2,
The copolymer is a non-crosslinked copolymer wherein more than 90 mass% is a random copolymer. The method according to claim 1 or 2,
The copolymer is a partially random copolymer and a partially block copolymer, a non-crosslinked copolymer. The method according to claim 1 or 2,
The monomers (A) and (B) are non-crosslinked, based on the total weight of the monomers used to make the copolymer, of at least 75 wt%, at least 90 wt%, at least 95 wt%, or 99 wt%. Copolymer. The method according to claim 1 or 2,
Monomer (B) in the copolymer is a mixture of C12 alkyl methacrylate, C14 alkyl methacrylate, C16 alkyl methacrylate, and C18 alkyl methacrylate,
The non-crosslinked copolymer wherein monomer (A) in the copolymer is C8 alkyl methacrylate. C ₈ alkyl methacrylate and lauryl ratio of the methacrylate - as a cross-linked copolymer of a copolymer of lauryl methacrylate monomer: as C ₈ alkyl meth basis weight ratio of the acrylate monomer is the weight of 99: 1 to 60 : 40, wherein the copolymer is a non-crosslinked copolymer having an average mean root rotation radius of 100 nm to 200 nm, as measured by hydrodynamic column chromatography-multi-angle light scattering in which tetrahydrofuran is used as a solvent. . delete