KR20190007501A - 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 has at least
a. A monomer (A) selected from C6-C10 alkyl methacrylate monomers, and
b. A monomer (B) selected from C10-C18 alkylmethacrylate monomers,
Lt; / RTI >
The weight 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 process for preparing the copolymer.

Description

Lubricant spray polymer

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

The main function of the lubricant is to reduce friction. However, lubricating oils often require additional properties for effective use. For example, lubricating oils used in the crankcase of large diesel engines such as marine diesel engines are often used in operating conditions that require special considerations.

Marine diesel engines can be generally classified as low speed, medium speed or high speed engines, and low speed types are used for maximum deep shaft marine vessels and specific industries. Low speed diesel engines are unique in size and operation. Larger units weigh up to 200 tons, can be 10 feet wide and over 45 feet high. The output of this engine can be up to 100,000 horsepower at 60 revolutions per minute with an engine rotation of about 200 revolutions. They typically operate in a two-stroke cycle with a crosshead design.

In a crosshead type large diesel engine used for marine and rigid fixed applications, the piston cylinder is lubricated separately from other engine components. The cylinders are lubricated on a total loss basis with the cylinder oil being individually injected into each cylinder by a lubricator disposed around the cylinder liners. Oil is distributed to the lubricator through the pump, and in modern engine designs, oil is applied directly to the oil ring to reduce oil consumption.

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

In addition, fuels commonly used in these diesel engines typically contain significant amounts of sulfur. In the combustion process, sulfur can form sulfuric acid in combination with water, and its presence can cause corrosion wear. Particularly in a marine two-stroke engine, the area around the cylinder liner and the piston ring can be corroded and abraded by the acid. Therefore, diesel engines must be able to withstand corrosion and abrasion with proper lubrication.

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

There is therefore a need for a lubricant additive that will provide resistance to effective oxidation and corrosion without incurring the environmental risk and expense of other oxidation and corrosion inhibitors. In addition, since the lubricant is not circulated in the marine engine, all rheological improvements that increase lubrication or reduce oil usage can significantly improve engine life and reduce costs.

The present inventors have found new copolymers that can alter the rheology of marine lubricants to provide improved lubrication properties. In particular, marine engine lubricating oils comprising the copolymer of the present invention as an additive cover the marine engine piston cylinder wall completely (compared to with or without additional additives) prior art oils to provide better lubrication and fewer engine cylinders Wear and corrosion.

The inventors have also recognized that the manner in which the copolymers are made can control the properties of the copolymers.

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

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

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

≪ / RTI > 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 another embodiment, 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 a monomer (A) and a monomer (B) in a mixture and co-polymerizing the monomers, wherein the monomers are present in a ratio of from about 99: The monomer (A) and the monomer (B) are present in a mass ratio of the monomer (A) to the monomer (B) of about 10:90, preferably about 99: 1 to about 60:40.

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

All publications referred to in this specification are herein incorporated by reference in their entirety, unless the context clearly dictates otherwise.

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

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

b. A monomer (B) selected from C10-C18 alkylmethacrylate monomers,

Lt; / RTI >

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

In all embodiments of the present 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) of 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95: 5, and 99: 1.

In some embodiments of all embodiments of the present 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 present invention, the copolymer used in the lubricant composition according to the present invention comprises a monomer (A) comprising at least two monomers (A) and one monomer (B) Lt; / RTI > The monomers are preferably selected from monomers which, when polymerized, form a copolymer which is soluble in a liquid, preferably an oil, more preferably a marine diesel engine oil lubricant.

In another embodiment of all embodiments of the present 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, These are present in the mixture in the following weight ratio:

Based on the total weight of the mixture

- 5% to 30% by weight of C8 alkyl methacrylate,

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

- 12% to 35% by weight of C14 alkyl methacrylate,

- 1 wt% to 12 wt% 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 another embodiment of all embodiments of the present invention, the copolymer is substantially free of monomers other than the monomer (A) and the monomer (B), and particularly includes methyl methacrylate having a C1-C5 alkyl group There is substantially no methacrylate. Monomers such as methyl methacrylate reduce the solubility of the resulting copolymer in oil, and the presence of such monomers is limited or omitted.

In another embodiment of all embodiments of the present invention, the copolymer is a monomer having no monomer other than the monomer (A) and the monomer (B), particularly methacrylic acid having a C1-C5 alkyl group such as methyl methacrylate There is no rate.

Typically, the copolymers according to the present invention have an Rg of from about 100 to about 200 (nm) Rg, from about 120 to about 190 (nm) Rg, as measured by hydrodynamic column chromatography- (nm), about 130 to 180, or about 140 to about 170 (nm) Rg.

In a second embodiment, the copolymer is obtained by combining at least a monomer (B) and a monomer (A) in a mixture and copolymerizing the monomers, wherein the monomers are from about 99: 1 to about 10: (A).

The copolymer may 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 water-insoluble or poorly soluble monomers are suspended as droplets in water. The monomer droplet suspension is maintained by mechanical stirring and addition of a stabilizer. (Water insoluble) inorganic powders such as cellulose ethers, poly (vinyl alcohol-co-vinyl acetate), poly (vinylpyrrolidone) and (meth) acrylic acid such as tricalcium phosphate, hydroxyapatite, Active polymers such as barium sulfate, kaolin, and magnesium silicate may be used as stabilizers. Small amounts of surfactants, such as sodium dodecylbenzenesulfonate, may also be used with the stabilizing agent. The polymerization is initiated using an oil soluble initiator. Suitable initiators include peroxides such as benzoyl peroxide, peroxy esters such as tert-butyl peroxy-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 monomers or glass stabilizers.

In another embodiment, the polymer is formed by emulsion polymerization, the at least one monomer is dispersed in an aqueous phase, and the polymerization is initiated using a water-soluble initiator. The monomers are typically insoluble in water or are not very soluble in water, and surfactants or soaps are used to stabilize the monomer droplets in the aqueous phase. Polymerization occurs in expanded micelles and latex particles. Other components that may be present in emulsion polymerization include chain transfer agents such as mercaptans (e.g., dodecyl mercaptan) for controlling molecular weight, electrolytes for controlling pH, and small amounts of organic solvents for controlling the polarity of the aqueous phase, Preferably water-soluble organic solvents, including, but not limited to, acetone, b-butanone, methanol, ethanol and isopropanol. Suitable initiators include alkali metal or ammonium salts of persulfates, water soluble azo compounds such as 2,2'-azobis (2-aminopropane) dihydrochloride, and Fe (II) and cumene hydroperoxide, and tert- And redox oxide-Fe (II) -sodium ascorbate. Suitable surfactants include anions such as fatty acid soaps such as sodium or potassium stearate, sulfates and sulfonates such as sodium dodecyl 20 benzenesulfonate, sulfosuccinates such as dioctyl sodium sulfosuccinate, Surfactant; Nonionic surfactants such as octylphenol ethoxylate, and linear and branched alcohol ethoxylates; Cationic surfactants such as cetyltrimethylammonium chloride; And amphoteric surfactants. Anionic surfactants, and combinations of anionic surfactants and nonionic surfactants, are most commonly used. Polymer stabilization systems such as poly (vinyl alcohol-co-vinyl acetate) can be used as surfactants. Solid polymer product without aqueous medium can be obtained by a number of methods including destabilization / coagulation 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 means known to those skilled in the art such as, but not limited to, solvent exchange, evaporation of solvent, spray drying and freeze drying.

The properties of the copolymer obtained by combining at least monomer (A) and monomer (B) in a mixture and copolymerizing can be manipulated by controlling additional 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 may be a single initiator compound (e.g. persulfate salt) or a mixture of two or more components (e.g., 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 oxidizing agent may be a peroxide such as, for example, 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 about 0.01 to about 0.06 mass% tert-butyl hydroperoxide of all monomers in the mixture. In another embodiment, the mixture may comprise from about 0.01 to about 0.03 mass% tert-butyl hydroperoxide of the monomers in the mixture. In some embodiments, the mixture further comprises about 0.013% by weight of tert-butyl hydroperoxide of the monomer in the mixture. Useful initiators for the copolymers of the present invention include any conventional initiators including any conventional redox initiator.

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 from about 0.04% to about 0.1% by weight of sodium ascorbate of the monomers in the mixture. In other embodiments, sodium ascorbate can be present at about 0.08% to about 0.1% by weight of the monomers in the mixture. In some embodiments, the polymerization mixture comprises about 0.098% by mass of sodium ascorbate of the monomer in the mixture.

The initiator system may also include a metal salt. The metal may be any suitable transition metal, for example, iron. In some embodiments, the metal salt of the initiator system may be a ferrous sulfate (FeSO _4). In some embodiments, the metal salt is present in the polymerization mixture at about 0.0005 to about 0.1 percent by weight of the monomer in the mixture. In some embodiments, the metal salt is added to the polymerization mixture as a solution.

The copolymer may 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 dialkyl sulfosuccinates, such as dioctyl sulfosuccinate sodium salt. In some embodiments, the surfactant may be Aerosol® OT.

The copolymers may be random copolymers, block copolymers, or mixtures thereof. In some embodiments, the copolymer is substantially a random copolymer (e.g., 90, 95, 98, or 99 mass%). In another embodiment, the copolymer is a partially random copolymer and, in part, a block copolymer. In this embodiment, the weight% 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 copolymers (e.g., greater than 90, 95, 98, or 99 weight percent). In another embodiment, the copolymer may contain additional monomers in addition to the monomers (A) and monomers (B) described. These additional monomers may be present in an amount of less than 10% by weight. In some embodiments, the additional monomer is present in an amount of about 0.5 to 10 wt%, or about 1 to 10 wt%, or about 1 to 5 wt%, or about 5 to 10 wt%. In other embodiments, the additional monomer is present in an amount of about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or less than about 0.5 weight percent. Additional monomers may include, for example, crosslinking monomers, acrylates, styrene, C ₁ -C ₃ alkyl methacrylates, and other similar monomers.

Copolymers can also be cross-linked. That is, the copolymer may contain monomeric units linking one or more backbone chains of the polymer. In some embodiments, the copolymer contains crosslinked monomer units present at about 5% by weight or less of the copolymer. In other embodiments, the copolymer is not crosslinked, or is non-crosslinked, and is substantially free of monomers that act as a crosslinking agent. In another embodiment, the monomer mixture for preparing the copolymer does not substantially contain a cross-linking agent.

The crosslinked copolymer can be obtained when the polymerization mixture comprises a crosslinking agent. In some embodiments, the cross-linking agent is a diacrylate or dimethacrylate cross-linker such as, for example, 1,6-hexanediol dimethacrylate. In some embodiments, the blend comprises a crosslinking agent at about 0.005% by weight or less of the monomer in the blend.

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

In a third embodiment, a method of making a copolymer as described above is disclosed. The method comprises the polymerization of monomers (A) and (B), wherein the weight ratio of monomers (B): monomer (A) in the copolymer is from about 99: 1 to about 10:90 , 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 contacting the monomer (B) and the monomer (A) at about 10: 90, 15: 85, 20: 80, 25: 75, 30: 70, 35: 65, 40: 60, , 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95: 5, 99: And initiating polymerization of the monomer to provide the copolymer.

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

The polymerization can be carried out 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 an organic solvent when lauryl methacrylate is present in the polymerization mixture. Organic solvents for use in such polymerization reactions are well known and can be generally selected by those skilled in the art of polymer synthesis. Suitable organic solvents include, but are not limited to, acetone, 2-butanone, methanol, ethanol and isopropanol.

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

The oils may be selected from those known in the art and may be mineral oils, i.e. oils obtained from crude processing, or synthetic oils, i.e. artificially produced oils typically containing polyglycols or esters, or semi-synthetic oils, Minerals, and blends of synthetic oils. In some embodiments, the oil is a mineral base oil, i.e. a complex mixture of paraffin, naphthene and aromatic compounds. In some embodiments, the oil may be a paraffinic base oil such as a 150 neutral solvent, 600 solvent neutral or brightstock. The oil composition may comprise additional components, especially those used in marine diesel engine oil lubricants.

A test to determine the enhanced lubricant properties and availability of an oil containing a copolymer of the first or second embodiment was conducted under the following conditions. The oil / polymer composition was tested for performance / suitability as a lubricant by a finger pull test performed by pipetting a droplet of sample fluid (about 65 [mu] l) to the thumb of a gloved hand. The thumb and forefinger were gently squeezed to secure contact between the two fingers and the droplet, and the fingers were tilted at a distance of about 7.5 cm between the thumb and forefinger while observing the time the composition provided fluid connection Pull vertically for approximately one second across the distance. All finger pull tests were performed at ambient temperature, about 21 ° C. The performance of the sample was characterized by "very short", "short", "normal", "steaming" or "very steaming" depending on the duration that the sample maintains the fluid connection between the thumb and forefinger. The composition with "very short" performance in the finger pull test is less than 1 second, "short" is 1 to 4 seconds, "normal" is 4 to 7 seconds, "steaming" is 7 to 60 seconds, This means that the two fingers are connected indefinitely. Compositions having a "very short" and "very high" composition do not exhibit improved fit or performance as a lubricant. Compositions having a "short", "normal" or "steaming" composition exhibit improved fit to varying degrees, for example, because their ability to effectively spread to the cylinder wall of a lubricated engine is improved. Compositions having a "Kim" configuration have particularly good fitness as lubricants. The results of the finger pull test are shown in Table 2.

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

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

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

Copolymers having a specific range of molecular weight (Mw), mean root square radius of gyration (Rg), and viscosity correlations are oil additives that improve oil performance as a lubricant while maintaining the ability to handle and pump the oil . The preferred correlation of bimodal M w, R g, and viscosity values for one embodiment of the copolymers disclosed herein is represented by the 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)

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 from 500 to 900, more preferably from 550 to 800, most preferably 600 and 750 represent copolymers having properties particularly suitable for improving the performance of oils as lubricants.

Justice

, Lauryl methacrylate, as used herein, dodecyl methacrylate; is a mixture of C _14-16 alkyl methacrylates containing (C ₁₂ CAS 142-90-5) or dodecyl methacrylate. That is, lauryl methacrylate may include a mixture of dodecyl methacrylate, but it may be a mixture of tetradecyl methacrylate (C ₁₄ ; CAS 2549-53-3) and hexadecyl methacrylate (C ₁₆ ; CAS mixture comprising at least one other C _14-16 alkyl methacrylates, such as 2495-27-4) may also be included. For example, lauryl methacrylate can be prepared from about 40-70 wt.% Of dodecyl methacrylate, such as commercially available methacrylic ester 13.0 (Evonik® VISIOMER® Terra C13,0-MA), 15- 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.

The term "C ₈ alkyl" as used herein refers to a group of eight saturated carbon atoms connected in a linear or branched configuration. An example of a linear C ₈ alkyl group includes n-octyl. Examples of branched C ₈ alkyl groups include, but are not limited to, 2-ethylhexyl.

The term "alkyl methacrylate" as used herein means a compound of a methacryloyl radical bonded to a linear or branched, saturated or unsaturated alkyl group.

The term "substantially monomer-free" as used herein means that no more than 3.0 wt%, preferably no more than 1.0 wt%, more preferably no more than 0.5 wt% of monomers are present in the copolymer.

The term "substantially free of crosslinking agent" as used herein means that the monomer units connecting the backbone chains of two or more polymers are present in an amount of up to 1.0% by weight, preferably up to 0.5% by weight of the copolymer.

Any embodiment disclosed herein may be combined with any other embodiment, the result of which is claimed in accordance with the present invention.

Unless otherwise indicated, "%" means weight percent.

Example

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

Example  One

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 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 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 240.0 g of lauryl methacrylate, 60.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were then added to the reaction vessel. The reaction was heated to 43 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 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 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 180.0 g of lauryl methacrylate, 120.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were then added to the reaction vessel. The reaction was heated to 43 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 120.0 g of lauryl methacrylate, 180.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were then added to the reaction vessel. The reaction was heated to 43 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. Then, 60.0 g of lauryl methacrylate, 240.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. Then, 30.0 g of lauryl methacrylate, 270.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone were added to the reaction vessel. The reaction was heated to 43 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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

645.5 grams of water and 8.7 grams of Aerosol OT were added to a 4-neck 2000 mL flask equipped with overhead stirrer, condenser, thermocouple and nitrogen purging beneath the surface. Stirring was run at 200 rpm and nitrogen purge beneath the surface was initiated. 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 [deg.] C using a temperature control batch set at 45 [deg.] C. When the reaction reached 43 캜, 0.04 g of t-butyl hydroperoxide in 7.5 g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of 0.25% iron sulfate hexahydrate solution were 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.

In oil Copolymer 5%  Solid solution preparation

A 4-neck 1000 mL flask equipped with a Barrett distillation trap equipped with an overhead stirrer, condenser and thermocouple was charged with one of the emulsions of Examples 1-8 to obtain 20.0 g of a polymer. Respectively. A neutral solvent 600 was then added to bring the total to 400.0 g, followed by the addition of 150.0 g toluene. Stirring was run at 200 rpm and the mixture was refluxed. The water condenses out of the barrette trap. When the water did not overflow, the contents of the reactor were heated to 130 ° C to distill most of the toluene. The remaining material was transferred to a 1000 mL 1-neck round bottom flask and concentrated in vacuo with a 60 ° C bath until the material reached a constant weight.

How to Determine Molecular Weight and Rotation Radius

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

Eluent: HPLC grade stabilized with 0.01% butylated hydroxytoluene. Tetrahydrofuran

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

Flow rate: 0.50 ml / min.

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

Pump / Autosampler: Agilent 1100 Isocratic HPLC pump and autosampler

Column compartment: 40 캜.

Standard: There was no standard directly related to the analysis, but the Heleos-II MALS calibration constant was set to toluene and the Optilab T-rEX calibration constant was set to NaCl in water. In Heleos-II, 17 angles were normalized to a narrow range polystyrene standard of 28,500 molecular weight, and the detector delay volume was adjusted to the same standard.

SAMPLE PREPARATION: A sample was prepared by diluting about 8.0 mg of the sample with about 5.0 g of tetrahydrofuran by gravimetry. The actual concentration of 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% by weight).

Injection: 50 μl.

Running time: 20 minutes.

Software: Wyatt Astra version 6.1.4.25.

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

How to Determine Viscosity

The shear viscosity of a polymer sample fed in 5% solids in base oil was determined by a stress-controlled rheometer MCR 302 manufactured by Anton Paar GmbH, Graz, Austria, Anton Paar Strasse 20, 8054. The Double Gap System of Measurement has been 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 at 22 ° C with an accuracy of 0.1 ° C. The shear rate was gradually increased from 1 / sec to 100 / sec with a viscosity reading of 10 points per decade. At each of these points, a 10 second equilibration time was given before reading and lasted for 3 seconds. Table 2 shows the viscosity at a shear rate of 10 / sec. The equipment control and data acquisition software is RheoCompassTM, version 1.13.445.

[Table 1]

¹ is the mass percent of the total amount of monomers,

² Based on the total amount of monomers, weight percent

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

[Table 2] - Hydraulics (Hydrodynamic) chromatography / MALS

¹ is the mass percent of the total amount of monomers,

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

² vs = very short, s = short, m = moderate, l = steaming, vl = very steaming

³ Using the manufacturing method described in Example 7, two duplicate samples for Example 7 were prepared

Claims (13)

As non-crosslinked copolymers of alkyl methacrylate monomers,
The alkyl methacrylate monomer
a. A monomer (A) selected from C6-C10 alkyl methacrylate monomers, and
b. A monomer (B) selected from C10-C18 alkylmethacrylate monomers,
Lt; / RTI >
The weight ratio of monomer (B): monomer (A) in the copolymer is from 99: 1 to 60:40 by weight,
The monomer (A) and the monomer (B) are different from each other,
The copolymer is substantially free of methyl methacrylate, the non-crosslinked copolymer. As non-crosslinked copolymers,
The non-
At least a. A monomer (A) selected from C6-C10 alkylmethacrylate monomers, and b. Combining a monomer (B) selected from C10-C18 alkylmethacrylate monomers in a mixture, and
Step of copolymerizing the monomers
Lt; / RTI >
The monomer (A) and the monomer (B) are different from each other,
The copolymer is substantially free of methyl methacrylate, the non-crosslinked copolymer. 3. The method according to claim 1 or 2,
Monomer (B): monomer (A), wherein the weight ratio of monomers is about 80:20. 3. The method according to claim 1 or 2,
Monomer (B): monomers (A) in a weight ratio of about 90:10. 5. The method according to any one of claims 1 to 4,
And the monomer (B) is lauryl methacrylate. 6. The method according to any one of claims 1 to 5,
Wherein the monomer (A) is a C8 alkyl methacrylate. The method according to claim 6,
Wherein the C8 alkyl methacrylate is 2-ethylhexyl methacrylate. 8. The method according to any one of claims 1 to 7,
Wherein the copolymer is a substantially random copolymer. 9. The method according to any one of claims 1 to 8,
The copolymer is a partially random copolymer and is a partially block copolymer, a non-crosslinked copolymer. 10. The method according to any one of claims 1 to 9,
The monomer (A) and the monomer (B) may be present in an amount of at least 75% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, By weight, preferably 99% by weight. 11. The method according to any one of claims 1 to 10,
The copolymer is a mixture of C12 alkyl methacrylate, C14 alkyl methacrylate, C16 alkyl methacrylate, and C18 alkyl methacrylate, and C8 alkyl methacrylate. 12. The method according to any one of claims 1 to 11,
The copolymer is substantially free of cross-linking agent, the non-cross-linked copolymer. As non-crosslinked copolymers of C8 alkyl methacrylate and lauryl methacrylate,
Wherein the weight ratio of lauryl methacrylate monomer to C8 alkyl methacrylate monomer in the copolymer is from 99: 1 to 60:40 by weight.