JPH11279233A - Viscosity modifier for lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a viscosity modifier resisting to shear without unsuitably increasing low temperature viscosity of a lubricant composition, and suppressing the degree of viscosity loss at high temperatures. SOLUTION: This modifier is a copolymer including units obtained from following (a) and (b) and, if necessary from (c). (a); a methacrylate including about 9 to 25C atoms in the ester group, (b); a methacrylate including 7 to 12C atoms in the ester group and the ester group has 2-(a 1 to 4C alkyl) substituents and, if necessary, (c); at least one monomer selected from a methacrylate including 2 to 8C atoms in the ester group, different from (a) and (b), and a vinyl aromatic compound and a vinyl monomer including N atom, with the proviso that not exceeding 60% of the monomer includes carbon atoms not exceeding 11C atoms in the ester group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a viscosity improver for lubricating oils (including dispersants-viscosity improvers), lubricating oils containing such viscosity improvers, lubricating oil compositions and concentrates,
And a method for preparing this viscosity improver.

[0002]

BACKGROUND OF THE INVENTION When a fluid is subjected to external forces, it resists flow due to internal friction. Viscosity is a measure of this internal friction.

[0003] Generally, the viscosity of oil having lubricating viscosity is
Depends on temperature. As the temperature of the lubricating oil increases, its viscosity usually decreases, and as this temperature decreases, its viscosity usually increases.

The function of a viscosity improver is to narrow the range of viscosity decrease as its temperature increases, or to narrow the range of viscosity increase as its temperature decreases,
Or both. Thus, the viscosity improver improves the viscosity change of the oil containing the viscosity improver with changes in temperature. Thereby, the fluidity of the oil is improved.

[0005] Viscosity improvers are usually polymeric substances,
Often called viscosity index improvers.

[0006] Ester group containing polymers are well known additives that improve the flow properties of lubricating oils. Polyacrylate polymer (especially polymethacrylate polymer)
Are well known and widely used for this purpose.

[0007] Dispersants are also well known in the lubricant art. Dispersants are used in lubricants to retain impurities, particularly those formed in suspensions, during operation of machinery, rather than settling on the surface of the part to be lubricated. .

[0008] Multifunctional additives that provide both viscosity improving and dispersant properties are likewise well known in the art. Such products are available from Dieter Klaman
n, "Lubricants and Related
Products ", Verlag Chemie
Gmbh (1984), pp. 185-193;
V. Smallheer and R.S. K. Smit
h "Lubricant Additives", Le
zius-Hiles Co. (1967);
W. Ranney, "Lubricant Addi
ties, "Noyes Data Corp.
(1973), pp. 92-145; W. Ran
new, "Lubricant Additives,
Recent Developments ", Noy
es Data Corp. (1978), 139-
164 pages; W. Ranney, "Synth
etic Oils and Additives f
or Lubricants ", Noyes Data
Corp .. (1980), and numerous publications, including pages 96-166. The contents of each of these publications are incorporated herein by reference.

Derivatives of polyacrylates are well known as additives for lubricants, which not only provide improved viscosity properties, but can also enhance the dispersant properties of the lubricant.

The viscosity improver or dispersant-viscosity improver desirably does not adversely affect the low temperature viscosity of the lubricant containing it. Often, viscosity improvers or dispersants-
Viscosity improvers enhance the high temperature viscosity properties of lubricating oils, i.e., reduce viscosity loss with increasing temperature, but result in poorer low temperature properties of the treated lubricant. It is also desirable that viscosity improvers provide relatively constant flow properties over extended periods of use. Such materials typically include polymers that are resistant to shear.

Although the use of viscosity improvers may be beneficial in many lubricating oil compositions, gear lubricants and automatic transmission oils are particularly sensitive to viscosity.

Gear lubricants are subject to high levels of shear during use. Many of the conventional viscosity improvers, when first prepared, provide a representative viscosity characteristic lubricant and, after a short period of use, lubricate a gear set (eg, one found in an automobile axle or transmission). The viscosity modifier is subjected to shear, resulting in reduced viscosity improving properties. Gear lubricants also preferably have good low temperature viscosity properties.

One of the key requirements for automatic transmission fluids is improved low temperature performance. This is at -40 ° C,
Demonstrated by the requirement of a maximum Brookfield viscosity of 50,000, 20,000, 10,000 centipoise or less. This viscosity modifier can make up almost 50% by weight, and sometimes even more, of the total additive system used in automatic transmission oils, but can have a significant effect on its low temperature performance. If the viscosity modifier also accounts for a significant amount of the total additive system, the low temperature properties also
Other applications (gear lubricants and manual transmission fluids) are also desirable.

The copolymers of the present invention can also be used in many other lubricating oil compositions, including engine oils, hydraulic fluids, manual transmission oils, continuously variable transmissions (CVTs) such as Van
The well-known belt-driven lubricants invented by Doorne include industrial oils, but are not limited thereto.

Accordingly, it is desirable to provide a composition that reduces the degree of viscosity loss at high temperatures without inappropriately increasing the low temperature viscosity of the lubricating oil composition.

It would also be desirable to provide a viscosity improver that resists shear under use conditions.

There is a particular need for viscosity improvers that resist shearing and unduly increase the low temperature viscosity of lubricating oil compositions and reduce the degree of viscosity loss at elevated temperatures.

Another object of the present invention is to provide a novel multi-purpose lubricant additive.

A more specific object is to provide a multi-purpose additive that improves the viscosity and dispersant properties of lubricating compositions.

Yet another object is to provide a method for preparing a copolymer that improves the viscosity characteristics of a lubricant over a wide range of temperature conditions.

Yet another object is to provide an additive concentrate containing the novel copolymer of the present invention.

Still another object is to provide a lubricant having improved dispersant properties and viscosity properties.

Other objects will be apparent, in part, in view of the present disclosure, and in part, will be set forth hereinafter.

[0024]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a viscosity improver which does not inappropriately increase the low temperature viscosity of a lubricating oil composition, resists shearing, and reduces the degree of viscosity loss at high temperatures.

[0025]

The present invention provides the following (a):
And (b), and optionally a copolymer containing units derived from (c): (a) a methacrylate ester containing from about 9 to about 25 carbon atoms in its ester group And (b) a methacrylate ester containing from 7 to about 12 carbon atoms in the ester group, wherein the ester group is 2- (C
_1-4 alkyl) substituents, and optionally
(C) a methacrylic ester containing from 2 to about 8 carbon atoms in the ester group atom and different from methacrylic esters (a) and (b), a vinyl aromatic compound, and a nitrogen-containing vinyl monomer At least one monomer selected from the group, but not more than 60% by weight, contains not more than 11 carbon atoms in the ester group.

In a preferred embodiment, in the copolymer, the ester (a) has about 1
The ester (b) contains from 3 to about 16 carbon atoms and the ester (b) contains from about 9 to about 12 carbon atoms in the ester group, and the ester group in (b) is , A 2-ethyl substituent and the molar ratio of the ester (a) to the ester (b) ranges from about 90:10 to about 60:40.

In a preferred embodiment, the copolymer comprises from about 0.2 mol% to about 6 mol% of units derived from monomer (c).
It is contained at 0 mol%.

In one embodiment, the copolymer is substantially free of groups derived from methacrylic esters containing less than 7 carbon atoms in the ester group.

In one embodiment, the copolymer contains from about 0.2 mole% to about 20 mole% of a nitrogen-containing vinyl monomer.

In one embodiment, in the above copolymer, the ester (b) is 2-ethylhexyl methacrylate, and the nitrogen-containing vinyl monomer is
It is selected from the group consisting of dimethylaminopropyl methacrylamide and dimethylaminoethyl methacrylate.

In one embodiment, in the copolymer, the ester (b) contains 2-ethylhexyl methacrylate and (c) contains a lower alkyl methacrylate.

The present invention also relates to the following (a) and (b), and optionally (c) in the presence of a free radical initiator and, if necessary, in the presence of a chain transfer agent. A) a methacrylate containing from about 9 to about 25 carbon atoms in the ester group, and (b) 7 to about 12 methacrylates in the ester group. A methacrylate ester containing 2 carbon atoms, wherein the ester group is 2- (C
_1-4 alkyl) substituents, and optionally
(C) the group consisting of methacrylic esters, vinyl aromatic compounds, and nitrogen-containing vinyl monomers containing from 2 to about 8 carbon atoms in the ester group and different from methacrylic esters (a) and (b); At least one monomer selected from, but not exceeding 60% by weight, the ester group contains not more than 11 carbon atoms in its ester groups.

In a preferred embodiment, in the above method,
The monomers (a) and (b), the free radical initiator, and the chain transfer agent, if used, are compounded to form a mixture and from about 10% to about 8% by weight of the mixture.
0% by weight is heated until an exotherm is observed, then
While maintaining the reaction temperature, the remaining mixture is added over a period of about 0.25 hours to about 5 hours, and additional initiator is added as needed, so that the reaction continues to completion.

In one embodiment, in the above method,
About 0.2 mol% to about 60 mol% of the monomer is the monomer (c).

In one embodiment, in the above method,
The monomer (b) contains 2-ethylhexyl methacrylate, and the monomer (c) contains methyl methacrylate.

In one embodiment, in the above method,
The monomer (b) contains 2-ethylhexyl methacrylate, and the monomer (c) contains a nitrogen-containing vinyl monomer.

In one embodiment, in the above method,
The monomer (c) contains a nitrogen-containing vinyl monomer selected from the group consisting of dimethylaminopropyl methacrylamide and dimethylaminoethyl methacrylate.

In one embodiment, in the above method,
The monomers are reacted simultaneously.

In one embodiment, in the above method,
The monomer (c) is grafted onto a preformed polymethacrylate prepared by reacting the monomers (a) and (b).

[0040] In one embodiment, in the above method,
The monomers, the free radical initiator, and the chain transfer agent, if used, are combined to form a mixture, and about 10% to about 80% by weight of the mixture is heated until an exotherm is noted. Then, while maintaining the reaction temperature, the remaining mixture is added over about 0.25 hours to about 5 hours, and if necessary, additional initiator is added so that the reaction can continue. Complete.

In one embodiment, in the above method,
The monomers (a) and (b), the free radical initiator, and, if used, the chain transfer agent are compounded to prepare a first mixture, and the first mixture of the monomers (a) and (b) is prepared. About 10% to about 80% by weight of the mixture comprises
Blend with monomer (c) to form a second mixture, wherein about 20% to about 100% of the second mixture is heated until an exotherm is observed, and then while maintaining the reaction temperature, Over about 0.25 hours to about 5 hours, if present, the remainder of the second mixture is added, followed by
Over 0.25 hours to about 5 hours, the remaining first mixture is added, and if necessary, additional initiator is added;
Thereby, the reaction is continuously completed.

In one embodiment, in the above method,
Any of the lower alkyl methacrylate or nitrogen containing vinyl monomers from the monomers (a), (b), (c), the free radical initiator, and when used,
The chain transfer agent is compounded to prepare a first mixture, wherein about 10% to about 80% by weight of the first mixture is compounded with the remaining monomer (c) to form a second mixture; About 20% to about 100% of the second mixture is heated until an exotherm is observed, and then while maintaining the reaction temperature,
When present for about 0.25 hours to about 5 hours,
The remainder of the second mixture is added, followed by the remaining first mixture over a period of 0.25 hours to about 5 hours;
If necessary, an additional initiator is added, whereby
The reaction continues to completion.

In one embodiment, in the above method,
The monomers (a), (b), about 10% to about 90% of the monomers (c), the free radical initiator, and, if used, the chain transfer agent are blended to form a first mixture. About 10% to about 80% by weight of the first mixture is blended with the remaining monomer (c) to form a second mixture, wherein about 20% to about 100% of the second mixture comprises Heat until an exotherm is observed, then, while maintaining the reaction temperature, first for about 0.25 hours to about 5 hours
If present, the remainder of the second mixture is added, followed by the remaining first mixture over a period of 0.25 hours to about 5 hours, and if necessary, additional initiator. By this, the reaction is completed continuously.

In a preferred embodiment, in the above method,
The monomer (b) contains 2-ethylhexyl methacrylate, and the monomer (c) contains lower alkyl methacrylate.

In a preferred embodiment, in any one of the above methods, the monomer (b) is selected from the group consisting of methacrylic acid 2-
Containing ethylhexyl and the monomer (c)
Contain a lower alkyl methacrylate and a nitrogen-containing vinyl monomer.

The present invention also relates to the products prepared by any of the methods described above.

The present invention also relates to an additive concentrate containing a normally liquid organic diluent and from about 20% to about 95% by weight of any of the above copolymers or the above products.

The present invention also relates to a lubricating oil composition containing a major amount of an oil of lubricating viscosity and a minor amount of any of the above copolymers or products.

The present invention also relates to a gear lubricant composition comprising an oil of lubricating viscosity and from about 5% to about 40% by weight of any of the above copolymers or products.

The present invention also relates to an oil of lubricating viscosity and an automatic transmission oil containing from about 4% to about 20% by weight of any of the above copolymers or products.

[0051] In one embodiment, the lubricating oil composition is a manual transmission oil.

[0052] In one embodiment, the lubricating oil composition is a hydraulic working fluid.

In one embodiment, there is provided a copolymer containing units derived from (a) and (b), and optionally (c): (a) in its ester group A methacrylate containing from about 9 to about 25 carbon atoms, and (b) a methacrylate containing from 7 to about 12 carbon atoms in the ester group, wherein the ester is 2- (C
_1-4 alkyl) substituents, and optionally
(C) the group consisting of methacrylic esters, vinyl aromatic compounds, and nitrogen-containing vinyl monomers containing from 2 to about 8 carbon atoms in the ester group and different from methacrylic esters (a) and (b); At least one monomer selected from, but not exceeding 60% by weight, the ester group contains not more than 11 carbon atoms in its ester groups.

The present invention also relates to additive concentrates and lubricating oil compositions containing these copolymers, and methods for preparing these copolymers.

[0055]

DETAILED DESCRIPTION OF THE INVENTION As used herein, "hydrocarbon",
The term “hydrocarbyl” or “hydrocarbon-based” means that the groups described have, within the context of the present invention, predominantly hydrocarbon character. These include
Include groups that are essentially pure hydrocarbons (ie, they contain only carbon and hydrogen). They may also include groups containing substituents or atoms that do not primarily alter the hydrocarbon nature of the group. These substituents can include halo, alkoxy, nitro, and the like. These groups may also contain heteroatoms. Suitable heteroatoms will be apparent to those of skill in the art and include, for example, sulfur, nitrogen and oxygen. Thus, these groups, while retaining predominantly hydrocarbon character in the context of the present invention, may contain non-carbon atoms present in the chain or ring, while others are carbon atoms. Constituted, provided that they do not adversely affect the reactivity or use of the process or product of the present invention.

Generally, in the hydrocarbon or hydrocarbon-based group, no more than about 3 non-hydrocarbon substituents or heteroatoms, preferably no more than 1 non-hydrocarbon substituent, for each 10 carbon atoms. There are hydrocarbon substituents or heteroatoms. Most preferably, these groups are substantially
It is a pure hydrocarbon, that is, it contains essentially no atoms other than carbon and hydrogen.

Throughout the specification and claims,
The expression "oil-soluble" or "oil-dispersible" is used. "Oil-soluble" or "oil-dispersible" refers to the dispersing, dispersing, or suspending of, in an oil of lubricating viscosity, the amount necessary to provide the desired level of activity or performance. It means you can do it. Normal,
This means that the lubricating oil contains at least about 0.001% by weight.
Can be mixed. See US Pat. No. 4,320,019 for a more detailed discussion of the terms "oil-soluble" or "oil-dispersible", and in particular, the term "stablely dispersible". The contents of this patent are hereby incorporated by reference for the teachings in this regard.

Throughout the specification and claims,
The expression "lower" is used. The expression "lower" as used herein to describe the various groups refers to no more than 7 carbon atoms, often no more than 4 carbon atoms, often 1 or 2 It is intended to mean a group containing two carbon atoms.

It should be noted that, as used in the specification and the appended claims, the singular also includes the plural unless the context clearly indicates otherwise. Therefore, the singular forms "a", "an" and "t"
"he" includes a plurality. For example, "a monom
"er" includes mixtures of monomers of the same type. As another example, the singular "monomer" is intended to include both the singular and the plural unless the context clearly dictates otherwise.

In the context of the present invention, the term “copolymer” means a polymer derived from two or more different monomers. Thus, for example, a polymer derived from a mixture of two or more of methyl methacrylate, butyl methacrylate, heptyl methacrylate, nonyl methacrylate, decyl methacrylate, and the like, is a copolymer as defined herein. It is. Similarly, methacrylic acid C
_9-11 and the polymer derived from one methacrylic acid C _12-18, or two or polymer having a more distinct blocks, is a copolymer as defined herein.
The copolymer of the present invention may also contain units derived from a nitrogen-containing monomer.

Regarding the size of the ester group, the ester group is represented by the following formula, and the number of carbon atoms in the ester group is determined by the sum of the carbon atom of the carbonyl group and the carbon atom of the (OR) group. -C (O) (OR) Therefore, methyl methacrylate contains two carbon atoms in its ester group. Butyl esters contain 5 carbon atoms in the ester group.

The expression “substantially inert” is used in connection with a diluent. As used in this context, "substantially inert" means that the diluent is substantially inert with respect to any reactant or composition of the invention, i.e., Under normal circumstances, it is meant not only to not undergo any significant reaction with any of the reactants or compositions, but also to interfere with any of the reactions or compositions of the present invention.

The expression viscosity index (often abbreviated VI) is often used herein. The viscosity index is an empirical numerical value indicating a degree of a viscosity change within a certain temperature range. High VI means an oil that shows a relatively small change in viscosity with temperature.

According to the present invention, compositions suitable for use as viscosity improvers (including dispersants-viscosity improvers) for lubricating oil compositions comprise (a) about 9 acrylates in their ester groups. ~ About 2
Alkyl methacrylate monomers containing 5 carbon atoms, preferably from about 13 to about 19 carbon atoms, often about 16 carbon atoms, and (b) 7 to about 12 carbon atoms, preferably from about 9 to about 12 carbon atoms, most preferably 9
Methacrylic acid alkyl ester monomers containing 2-carbon atoms and having a 2- (C _1-4 alkyl) substituent, and optionally methacrylic acid containing 2 to about 8 carbon atoms in the ester group. Acid esters (a) and (b)
And a copolymer containing units derived from a mixture of methacrylic acid alkyl ester monomers containing at least one monomer selected from the group consisting of methacrylic acid esters, vinyl aromatic compounds, and nitrogen-containing vinyl monomers. Contains, but not more than 60% by weight (often not more than 50% by weight, frequently not more than about 35% by weight) of no more than 11 carbon atoms in the ester group It contains.

Typically, the molar ratio of ester (a) to ester (b) in the copolymer ranges from about 95: 5 to about 35:65, often from about 90:10 to about 60. :
It is in the range of 40, frequently from about 80:20 to about 50:50.

These esters are usually aliphatic esters, preferably alkyl esters. Preferably, ester (a) is _C12-15 alkyl methacrylate and ester (b) is 2-ethylhexyl methacrylate.

In one embodiment, the ester group in ester (a) contains a branched alkyl group. often,
About 2% to about 65%, often about 5%, of the ester groups
~ 60% contain branched alkyl groups.

As mentioned herein, this ester (b)
_Has a 2- (C _1-4 alkyl) substituent. This C _1-4
The alkyl substituent can be methyl, ethyl, and any isomer of propyl and butyl. Preferably, the 2-alkyl substituent is ethyl.

The presence of the group derived from the monomer (c) is optional. In one embodiment, the polymer is
(C) Does not contain a group derived from a monomer. In other embodiments, the copolymer may contain (c) groups derived from one or more of the monomers. Within the second embodiment, there are many possibilities. For example, this (c)
The components can consist essentially of one of the listed types of monomers. Therefore, in one embodiment, this (c)
The monomer may be a methacrylate containing from 2 to about 8 carbon atoms in the ester group. In other embodiments, the (c) monomer can be a vinyl aromatic monomer, for example, a styrenic monomer (eg, styrene, α-methylstyrene, ring-substituted styrene, vinylnaphthalene, vinylanthracene, etc.). In yet another embodiment, the (c) monomer is a nitrogen-containing vinyl monomer. When the (c) monomer is a nitrogen-containing vinyl monomer, the copolymer generally imparts high dispersibility to the lubricating oil composition. Useful nitrogen-containing vinyl monomers are described below.

In one particular embodiment, the copolymer has a group derived from a methacrylic ester containing less than 7 carbon atoms in the ester group, frequently less than 5 carbon atoms. Substantially not included. In another embodiment, the (c) monomer comprises a methacrylate monomer containing about 2 carbon atoms in the ester group. In one preferred embodiment, the copolymer contains groups derived from both methacrylate esters and nitrogen-containing vinyl monomers containing two carbon atoms in the ester group.

The copolymers of the present invention have a weight average molecular weight (Mw) in the range from about 10,000 to about 350,000, and in one embodiment, up to about 200,000. In another embodiment, the Mw is between about 15,000 and
In the range of about 150,000, often about 20,000 to
It is in the range of about 120,000.

Polydispersity (polydispersity index is abbreviated as PDI) value (Mw / Mn) (where Mn / Mn)
Represents the number average molecular weight) is in the range from about 1.5 to about 5, often from about 2 to about 4.

The molecular weight of the polymer is measured using a well-known method described in the literature. Examples of methods for measuring molecular weight include gel permeation chromatography (also,
(Known as size exclusion chromatography) and vapor phase permeation. These and other methods are described in numerous publications, including:
P. J. Flory, "Principles o
f Polymer Chemistry "Cornel
l University Press (1953),
Chapter VII, pages 266-316; and "Macr
omolecules, an Introducti
on to Polymer Science ", F.C.
A. Bovey and F.S. H. Winslo
w, Editors, Academic Press
(1979) pp. 296-312;
W. Yau, J .; J. Kirkland and
D. D. Bly, "Modern Size Ex
clusion Liquid Chromatogr
aphy ", John Wiley and Son
s, New York, 1979.

Various standards can be used in determining the molecular weight of the polymer. The standard is preferably chemically and physically similar to the polymer being measured. If a standard is used that is significantly separated from the polymer to be measured, the values obtained will often be significantly different from the actual values for this polymer. However, it is possible to indicate the relative molecular weights of several polymers.

A value complementary to the molecular weight of the polymer is the melt index (ASTMD-1238). Polymers with a high melt index generally have a low molecular weight, and vice versa. Mooney viscosity (A
STM Procedure D-1646-87)
Indirectly, it relates to the molecular weight of the polymer. When all other factors are the same, as the molecular weight of this polymer increases,
Thus, the Mooney viscosity also increases.

These esters can be obtained, for example, by esterification of methacrylic acid or anhydrides thereof or acyl halides, or methacrylic esters (usually
Lower alkyl esters, most often methyl esters). The acetone cyanohydrin method involves reacting acetone with HCN to form acetone cyanohydrin, which is then reacted with the desired alcohol to form the ester. Propylene carbonylation and many other methods are also used.

As mentioned above, the ester alkyl group is generally derived from an alcohol.

Alkali useful for preparing ester (a)
Cole has from about 8 to about 24 carbon atoms, preferably
Contains from about 12 to about 15 carbon atoms. alcohol
Are commercially available and are often preferred. S
The alcohol used to prepare the ter (a) is linear
Or it can be either branched or branched. In one embodiment
Is about 2% to about 65% of these alcohols, often
From about 5% to about 60% are branched. ester
Examples of alcohols useful for preparing (a) include n-
Octanol, n-decanol, n- and branched
C₁₂, C_Fifteen, C₁₆And C _{twenty two}Alcohol, alcohol blend
Compounds (eg, Dobanol 25, Neodol
25, Lial 125 and Alchem 125
(These differ in the degree of branching, for example, from about 5% to about 50%.
And Alfol 1214 (which has
Is substantially linear) C available under the trade name
_12-15Alcohol).

Alcohols useful for preparing ester (b) include from 6 to about 11 carbon atoms, preferably 8
It contains from about 11 to about 11 carbon atoms, most preferably 8 carbon atoms. These alcohols are 2- (C _1-4)
Alkyl) substituents, ie, methyl, ethyl, or any isomer of propyl and butyl. Examples of alcohols useful for preparing the ester (b) include 2-methylheptanol, 2-methyldecanol,
2-ethylpentanol, 2-ethylhexanol, 2
-Ethylnonanol, 2-propylheptanol, 2-
Butylheptanol and the like. 2-Ethylhexanol is particularly preferred.

Various methods for preparing methacrylate monomers are described in The Encyclopedia, Inc.
f Polymer Science and Eng
inering (Vol. 1, pp. 247-2)
51, Wiley-Interscience, New
York (1985)), "Acrylica
nd Metically Ester Poly
The section entitled "mers" is described in considerable detail.

Esterification reactions are well known and involve the reaction of an acid, anhydride or acyl halide with a suitable alcohol, depending on the methacrylic acid reactant, where the by-product water or hydrogen halide is Removed.

The transesterification generally involves the substitution of a lower alkyl ester group with a higher alcohol, and the substituted lower alkyl group is removed as the alcohol. A preferred method for transesterifying methyl methacrylate is described in U.S. Pat. No. 4,791,221, the contents of which are incorporated herein by reference.

In addition, a number of methacrylates are commercially available. For example, RohMax; Lu
brizol, San Esters Corp. (N
(with offices in New York, New York); Mitsubishi Rayon Co. Lt
d. Polysciences, Inc .; (War
rington, Pennsylvania); Sar
Tomer Co. (Exton, Pennsylva
nia) and the like.

In an optional embodiment, the copolymer is
(C) the group consisting of methacrylic esters, vinyl aromatic compounds, and nitrogen-containing vinyl monomers containing from 2 to about 8 carbon atoms in the ester group and different from methacrylic esters (a) and (b); Containing groups derived from at least one monomer selected from: When groups derived from monomer (c) are present, they represent from about 0.2 mol% to about 60 mol%, often from about 1 mol% to about 25 mol%, of the units present in the polymer. Occupy.

Esters containing from 2 to about 8 carbon atoms in the ester group are esters (a) and (b)
Are not encompassed by those described above, ie, they are different from these esters.

When the monomers (c) contain methacrylic esters containing 2 to about 8 carbon atoms, they preferably contain lower alkyl esters. Methyl methacrylate is particularly preferred.

Useful vinyl aromatic monomers include styrene and substituted styrene, but other vinyl aromatic monomers can also be used. The substituted styrene includes a halo substituent, an amino substituent, an alkoxy substituent, a carboxy substituent, a hydroxy substituent, a sulfonyl substituent, a hydrocarbyl substituent, wherein the hydrocarbyl group has 1 to about 12 carbon atoms. Atom) and styrene with other substituents. Representative examples of the hydrocarbyl-substituted styrene include α-methylstyrene, p-tert-butylstyrene, α-ethylstyrene, and p-lower alkoxystyrene.
Mixtures of two or more vinyl aromatic monomers can be used. Styrene is preferred.

Useful nitrogen-containing monomers include vinyl-substituted nitrogen heterocycle monomers such as vinylpyridine monomers and N-vinyl-substituted nitrogen heterocycle monomers (eg, N
-Vinylimidazoles, N-vinylpyrrolidinones and N-vinylcaprolactams), dialkylaminoalkyl monomers of acrylic acid and methacrylate, for example N, N-dialkylaminoalkyl acrylates (e.g.
Dimethylaminoethyl methacrylate), dialkylaminoalkylacrylamide and methacrylamide monomers such as di-lower alkylaminoalkylacrylamide (especially where each alkyl or aminoalkyl group is from 1 to about 8 carbon atoms, In particular, one to three
, Such as N, N-di-lower alkyl (especially dimethylaminopropyl acrylamide, N-tertiary alkyl acrylamide and the corresponding methacrylamide (e.g., tertiary butyl acrylamide), and Vinyl-substituted amines.

In one preferred embodiment, monomer (c) contains a nitrogen-containing vinyl monomer. When monomer (c) is or contains a nitrogen-containing vinyl monomer, the copolymer will generally have from about 0.2 mole%, often from about 1 mole% to about 20 mole%. %, Often up to about 8 mol%, of groups derived from monomer (c).

The copolymers of the present invention may be prepared by (a) in the presence of a free radical initiator, from about 9 to about 2
A methacrylic acid ester containing 5 carbon atoms, and (b) a methacrylic acid ester containing 7 to about 12 carbon atoms in the ester group, wherein the ester group is 2- (C ₁ Methacrylic acid having a ( _-4 alkyl) substituent and, optionally, (c) a methacrylic acid ester containing from 2 to about 8 carbon atoms in the ester group and different from (a) and (b) At least one monomer selected from the group consisting of an ester, a vinyl aromatic compound, and a nitrogen-containing vinyl monomer, if necessary,
It can be prepared by a method including reacting in the presence of a chain transfer agent.

These monomers can react simultaneously.

In one embodiment, the process often involves first reacting a portion (often from about 20% to about 60%) of a mixture of these monomers, usually by exothermic evidence. Until the desired copolymer is obtained.
This involves reacting the mixture by adding and reacting little by little, all at once or continuously over a period of time.

In certain embodiments, the monomers (a) and (b), the free radical initiator, and the chain transfer agent, if used, are formulated to form a mixture. About 10% to about 80% by weight of the mixture is heated until an exotherm is observed, then the remaining mixture is added over about 0.25 hours to about 5 hours while maintaining the reaction temperature, Depending on the additional initiator is added, so that the reaction continues to completion.

As mentioned above, these monomers can contain (c) a third monomer. In certain embodiments, monomer (c) contains a nitrogen-containing vinyl monomer. In another embodiment, monomer (c) contains an alkyl methacrylate monomer as defined above, especially a lower alkyl methacrylate, and more particularly methyl methacrylate. In a particularly preferred embodiment, monomer (c) contains both a nitrogen-containing monomer and an alkyl methacrylate monomer, the preferred embodiments of which are the same as defined above.

In one embodiment, monomer (c) is
Grafted on the preformed methacrylate copolymer. Methods for grafting (particularly grafting nitrogen-containing monomers) are known and are described in numerous publications (eg, US Pat. Nos. 3,067,163; 4,281,081).
No. 4,338,414).

When monomers (c) are present, in one embodiment these monomers, a free radical initiator,
And, if used, a chain transfer agent is compounded to prepare a mixture. About 10% to about 80% (often about 25% to about 50%) by weight of the mixture is heated until an exotherm is observed, and then usually after the exotherm has subsided, While maintaining the temperature, about 0.2
Over a period of 5 hours to about 5 hours, the remaining mixture is added and, if necessary, additional initiator is added, so that the reaction continues to completion.

When monomer (c) is a nitrogen-containing vinyl monomer, the preferred method is to use monomers (a) and (b), a free radical initiator and, if used,
Incorporating a chain transfer agent to prepare a first mixture. About 10% of the mixture of monomers (a) and (b)
% To about 80% by weight is blended with the monomer (c) to form a second mixture. About 20 of this second mixture
% To about 100% by weight is heated until an exotherm is observed. Next, while maintaining the reaction temperature, first, about 0.
Over 25 hours to about 5 hours, the remainder of this second mixture, if present, is added, followed by the remaining first mixture over 0.25 to about 5 hours, optionally with additional An initiator is added, so that the reaction continues to completion.

When monomer (c) contains both a nitrogen-containing vinyl monomer and a methacrylic ester monomer, especially a lower alkyl methacrylate monomer, the process comprises the steps of: , And, if used, by preparing a first mixture containing a chain transfer agent.
Then from about 10% to about 80% by weight of the first mixture
Is blended with the remaining monomer (c) to prepare a second mixture. About 20% to about 100% by weight of this second mixture
The weight percent is heated until an exotherm is observed. Then
While maintaining the reaction temperature, first add the remainder of the second mixture, if present, for about 0.25 hours to about 5 hours, followed by the remaining first mixture for about 0.25 to about 5 hours. The mixture is added and, if necessary, additional initiator is added so that the reaction continues to completion.

In another embodiment, the monomers (a),
(B), and about 10% to about 90% of monomer (c);
The free radical initiator, and the chain transfer agent, if used, are compounded to prepare a first mixture. Then
About 10% to about 80% by weight of the first mixture is blended with the remaining monomer (c) to form a second mixture. About 20% to about 100% by weight of the second mixture
Is heated until an exotherm is observed. Then, while maintaining the reaction temperature, first add the remainder of the second mixture, if any, over a period of about 0.25 hours to about 5 hours, followed by the remaining 0.25 hours to about 5 hours. The first mixture is added, and if necessary, additional initiator is added, so that the reaction continues to completion.

Although the process of the present invention is carried out essentially solvent-free, it is common to use one or more diluents to facilitate processing. (Diluent) As described above, the copolymer of the present invention can be prepared in the presence of a diluent. The diluent can also be added to the substantially diluent-free copolymer, usually by dissolving or dispersing the substantially diluent-free copolymer in a suitable diluent. In other embodiments, an additional diluent, often a high boiling diluent (eg, oil), can be added to the prepared copolymer, which further comprises:
It contains a low boiling diluent, which is then removed by common methods (eg, distillation). Preferably, when the polymer is prepared in the presence of a diluent, the diluent is an oil.

[0101] In one embodiment, the diluent is a mineral oil. In certain embodiments, the mineral oil consists essentially of hydrotreated naphthenic oil. Hydrodewaxed mineral oils are also contemplated.

The diluent can also be a synthetic oil. Common synthetic oils include ester type oils, polyolefin oligomers or alkylated benzenes. (Chain transfer agent) This method comprises the steps of:
It can be carried out. It is known to use chain transfer agents to control and limit molecular weight in polymer reactions.
For example, "Concise Encyclopedia
of Polymer Science and E
ngineering "(JI Kroschwi)
tz, Ed. , Wiley-Interscience
e (New York, 1990), page 13
See 9). An extensive discussion of chain transfer, its effects and chain transfer agents, along with an extensive bibliography, can be found in "Encyc
loopedia of Polymer Science
e and Technology "(HF Ma
rk, N.M. G. FIG. Gaylord, and N.W. M. B
ikales, Ed. , Interscience,
(New York, 1965); 575-6
See 10). The contents of both of these are incorporated herein by reference.

In the present application, sulfur compounds, especially mercaptans, especially dodecyl mercaptans, for example,
N- and tertiary dodecyl mercaptans are preferred.

Polymers can occur under a variety of conditions, including bulk, solution, emulsion, suspension and non-aqueous dispersion methods.

The method of the present invention utilizes a usual radical polymerization method.

Such a method is described in “Encyclope
dia of Polymer Science an
d Engineering "(HF Mark,
N. M. Bikales, C.I. G. FIG. Overber
ger and G.G. Menges), 2nd edition (198
8), published by Wiley Interscience).

These methods include free radical initiated polymerization using azo compounds or peroxides. This document also describes photochemical and radical initiation methods. Initiators Useful initiators include organic peroxides, hydroperoxides and azo compounds. Redox initiators are also useful.

Free radical generating reagents useful as polymerization initiators are well known to those skilled in the art. Numerous examples of free radical initiators are described by Flory and Bovey and W.
This is described in the related textbook listed above by inslow. An extensive list of free radical initiators can be found in Brandup and E.L. H. Imme
"Polymer Handbook" edited by rgut
2nd Edition, John Wiley and Sons, Ne
w York (1975), pages II-1 to II-40. Numerous free radical initiators are available, many of which are commercially available in large quantities. Free radical initiators include t-butyl peroxide, t-butyl hydroperoxide, t-amyl peroxide, cumyl peroxide, dibenzoyl peroxide (Aldrich), t-butyl m-chloroperbenzoate, azobisvaleronitrile T-butyl peroctonate and tertiary butyl perbenzoate (Trigonox obtained from AKZO, respectively)
21 and Trigonox C), and 2,2'-azobis (isobutyronitrile) (VAZO-64) and 2,2'-azobis (methylbutyronitrile) (VA
ZO-67) (both DuPont).

The free radical initiator is usually present in an amount from about 0.01% to about 10% by weight, based on the total weight of the reaction mixture.
It is used in an amount of% by weight. Generally, the initiator will comprise from about 0.05% to about 3% by weight, often from about 0.1% to about 2%, often from about 0.5% to about 1.5%. Used up to or about 1% by weight.

The choice of free radical initiator can be an important requirement. Requirements include the half-life of the initiator at a given temperature, the nature of these reactants, the reaction temperature, solvent or diluent, and the like.

The molecular weight of these polymers can be controlled using a number of techniques, including the choice of initiator, reaction temperature, monomer concentration and solvent type. As mentioned above, chain transfer agents can be used.

The products of the present invention generally have a reaction temperature in the range of from about 40 ° C to about 200 ° C, frequently from about 60 ° C to about 1 ° C.
It is prepared at a reaction temperature in the range of 60 ° C. The half-life of the initiator at a given temperature is an important requirement.

Since acrylic polymerization can usually involve a significant release of heat, care must be taken to avoid uncontrolled reactions. The temperature can be controlled by using a reactor with a cooling jacket, controlling the rate of addition, and using a reaction solvent.

Although the process of the present invention is often carried out in conventional reactors using stirring means including mechanical stirrers and / or circulating pumps, other useful processes for preparing the copolymers of the present invention. The measure is to use a high energy mechanical mixing device. These include roll mills, ball mills or extruders. Of these, extruders are preferred. This is because these comonomers can be fed to the feed hopper in any desired manner. Methods of using such devices (especially extruders) have been described in many patents, including Hay
No. 4,670,173 to Ashi et al.
No. 5,039,433 to opko et al., both contents of which are incorporated herein by reference.

[0115]

The following examples are intended to illustrate some compositions of the present invention, as well as methods of preparing them. Unless otherwise indicated, all parts are parts by weight. It is to be understood that these examples are intended to illustrate some compositions and methods of the present invention and are not intended to limit the scope of the present invention. Molecular weights were well characterized (well
Gel Permeation Chromatography (GP) Using a Characterized Polymethacrylate (PMA) Calibration Standard
Measured using C). PDI is the polydispersity index, Mw / Mn. The filtration is performed using a diatomaceous earth filter aid. (Example 1) container, C _12-15 methacrylate (C ₁₂ and C ₁₅ each about 20 wt%, C of each 30 wt%
₁₃ and C ₁₄ , and less than about 5% by weight of C ₁₁ or less and C ₁₆ or more) 320 parts (1.
18 equivalents), 80 parts of 2-ethylhexyl methacrylate (0.40 mol), 100 mineral oils (Total 85N)
And 8.24 parts each of Trigonox-21
(0.039 mol) and t-dodecanethiol (0.
04 mol). The materials were mixed for 0.25 hours, then 1/3 of the mixture was charged to a reactor equipped with a stirrer, N ₂ inlet with addition funnel, thermocouple and condenser, and the remaining 2 / 3 into this addition funnel.
The contents of these reactors were adjusted to 8.5 l / hr at approximately 0,1 l / hr.
Heating to 105 ° C. under N ₂ for 2 hours,
Thereby, an exotherm up to 137 ° C. is observed and the heating is stopped. After about 1 minute, the addition of the monomers from the addition funnel is started at 4.4 ml / min. After about 0.3 hours, the temperature has reached 90 ° C and the heating is started and maintained at 89-90 ° C. After 1.5 hours, the addition is complete, then heating is continued for 3.2 hours. At this point, the infrared spectrum reveals that the polymerization is complete. The batch is placed at 150 ° C. and 28 m
Strip to m Hg, filter through a filter aid through a Buchner funnel with a cloth pad, and then refilter with the same filter. The filtrate has Mw = 60,53
1, with Mn = 18,650 and PDI = 3.24. (Example 2) 280 parts (1.03 equivalent) of C _12-15 methacrylate, 2-ethylhexyl methacrylate 1
20 parts (0.605 mol), Total 85N (10
0) and 8.24 parts each of Trigonox-21.
(0.039 mol) and t-dodecanethiol (0.
04 mol) according to the method of Example 1. The peak temperature after exotherm is 141 ° C. The infrared spectrum reveals that the polymerization is complete after 2.8 hours following the completion of the addition. This batch is
Strip to 150 ° C. with Hg. This filtrate is
Mw = 56,399, Mn = 19,495 and PDI
= 2.89. (Example 3) C _12-15 340 parts of methacrylic acid ester (1.25 eq), 2-ethylhexyl methacrylate 6
0 parts (0.302 mol), Total 85N (100
Parts) and 8.24 parts of each Trigonox-21
(0.039 mol) and t-dodecanethiol (0.
04 mol) according to the method of Example 1. The peak temperature after exotherm is 135 ° C. The infrared spectrum reveals that the polymerization is complete after 3.2 hours following the completion of the addition. The reaction temperature is 89-92 ° C. The batch is stripped to 150 ° C. at 16 mm Hg. The filtrate has Mw = 57,87
2, with Mn = 19,585 and PDI = 2.95. (Example 4) _C12-15 methacrylate 2 was _{placed in a} container.
80 parts (1.03 equivalent), 80 parts (0.40 mol) of 2-ethylhexyl methacrylate, 40 methyl methacrylate
Parts (0.4 mol), Total 85N (100 parts),
And 8.24 parts of Trigonox-21 (0.0
39 mol) and t-dodecanethiol (0.04 mol). Mix these materials for 0.25 hours,
Then, 1/3 of this mixture, stirrer, addition funnel with N ₂ inlet, was charged into a reactor equipped with a thermocouple and condenser, the remaining 2/3 is charged to the addition funnel. The reactor contents were heated at 8.5 l / hr to 105 ° C. under N ₂ for about 0.2 hours, whereby an exotherm to 147 ° C. was observed and the heating was stopped. Abort. After about 1 minute, the addition of the monomers from the addition funnel is started at 4.4 ml / min. About 0.3
After an hour, the temperature reaches 90 ° C.
Maintain at 9-92 ° C. After 1.5 hours, the addition was complete,
The heating is then continued for 1.6 hours. At this point, the infrared spectrum reveals that the polymerization is complete. The batch was heated at 150 ° C. and 16 mm Hg
Strip and filter through a filter aid, then re-filter through a Buchner funnel with a cloth pad. This filtrate has Mw = 58,897, Mn = 19,403 and PDI = 3.03. Example 5 300 parts (1.11 equivalents) of C _12-15 methacrylate, 2-ethylhexyl methacrylate 1
00 parts (0.504 mol), Total 85N (10
0) and 8.24 parts each of Trigonox-21.
(0.039 mol) and t-dodecanethiol (0.
04 mol) according to the method of Example 1. The peak temperature after exotherm is 136 ° C. The infrared spectrum reveals that the polymerization is complete after 2 hours following the completion of the addition. The reaction temperature is 89-91 ° C. The batch is stripped to 150 ° C. at 14 mm Hg. The filtrate has Mw = 61,510,
It has Mn = 20,622 and PDI = 2.98. (Example 6) _C12-15 methacrylate 280 parts (1.03 equivalent), 2-ethylhexyl methacrylate 1
20 parts (0.605 mol), Total 85N (10
0 parts) and 7.6 parts of Trigonox-21
(0.035 mol) and t-dodecanethiol (0.
038 mol) according to the method of Example 1. The peak temperature after exotherm is 145 ° C. The infrared spectrum reveals that the polymerization is complete after 2 hours following the completion of the addition. The reaction temperature is 109-110 ° C
It is. The batch is stripped to 150 ° C. at 11 mm Hg. The filtrate has Mw = 52,26
3, with Mn = 17,254 and PDI = 3.03. (Example 7) _C12-15 methacrylate 3 was _{placed in a} container.
696 parts (13.64 equivalents), 1584 parts (7.99 mol) of 2-ethylhexyl methacrylate, mineral oil (Tota)
185N) 1320 parts and 100.3 parts of Tri each
gonox-21 (0.47 mol) and t-dodecanethiol (0.50 mol) are charged. The materials are mixed for 0.25 hours, then 1/3 of the mixture is
Stirrer, addition funnel with N ₂ inlet, was charged into a reactor equipped with a thermocouple and condenser, the remaining 2/3 is charged to the addition funnel. The reactor contents were reduced to 9.9 l /
hr under N ₂ for about 0.4 hours
Heat to 150 ° C., whereby an exotherm to 152 ° C. is observed and stop heating. After about 1 minute, the temperature is 15
Once at 1 ° C., the addition of these monomers from the addition funnel is started at 60 ml / min. After about 0.5 hours, the temperature reached 110 ° C. and heating was started to
Maintain at 13 ° C. After 1.6 hours, the addition was complete, then heating was continued for 2 hours, and the infrared spectrum reveals that the polymerization was not complete. Add additional Trigonox-21 (2 parts)
Heating was continued for 2 hours, then the infrared spectrum showed that the polymerization was complete. The batch is stripped to 150 ° C. and 12 mm Hg and filtered through a Buchner funnel with a cloth pad through a filter aid. The filtrate had Mw = 47,997, Mn
= 16,728 and PDI = 2.87. Example 8 90 parts of Trigonox-21 (0.
The procedure of Example 7 is followed except that 43 mol) and t-dodecanethiol (0.44 mol) were used. The exotherm is up to 150 ° C. and the reaction temperature is
9-116 [deg.] C and is complete after 3 hours of monomer addition, additional Trigonox-21 (3 parts) is added,
Then, after 0.5 hour, the mixture was further heated, and the infrared spectrum revealed that the polymerization was completed.
The filtrate had Mw = 51,200, Mn = 17,295.
And PDI = 2.96. Example 9 79.2 parts of Trigonox-21
(0.367 mol) and t-dodecanethiol (0.
392 mol) was used. The exotherm is up to 151 ° C., the reaction temperature is 108-113 ° C. and is complete 3.5 hours after the addition of the monomers, and the infrared spectrum reveals that the polymerization is complete. The filtrate has Mw = 56,0.
44, Mn = 19,157 and PDI = 2.92. Example 10 2.6 hours after completion of addition, additional Tri
After heating for another 2 hours according to the method of Example 9 except that gonox-21 (2 parts) was added, the infrared spectrum reveals that the polymerization was completed. The filtrate had Mw = 55,987, Mn = 18,6
35 and PDI = 3.00. (Example 11) In a container, 272.8 parts of C _12-15 methacrylate and 2-ethylhexyl methacrylate 120 were added.
Parts, 100 parts mineral oil (Total 85N), and 7.6 parts each of Trigonox-21 and t-dodecyl mercaptan. The materials are mixed for 0.25 hours, then about 1/3 of this mixture and 7.2 parts of dimethylaminopropyl methacrylamide are added to a stirrer,
Thermocouple, it is charged to a reactor equipped with an addition funnel with N ₂ inlet and condenser. The remaining 2/3 of the mixture is placed in the addition funnel. The mixture in the flask is heated to 110 ° C. under N ₂ for 0.2 hours, thereby confirming an exotherm with a temperature increase to 144 ° C. After about 0.1 hour, the temperature had reached 140 ° C. and the addition of the mixture from the addition funnel was continued at 4.4 ml / ml.
Start in minutes. Within 0.2 hours, this temperature is 110 ° C
become. The addition is continued for 1.5 hours and the temperature is
Maintain at 114 ° C. Heating was continued at about 110 ° C. for 3 hours, additional Trigonox-21 (0.4 parts) was added, and after an additional 2.5 hours at about 110 ° C., the reaction was complete by infrared spectroscopy. Becomes clear. The batch is stripped to 150 ° C. and 12 mm Hg, cooled to 85 ° C., and filtered twice through a Buchner funnel with filter aid. This filtrate has the Mw
= 50,018, Mn = 14,618 and PDI =
3.42. (Example 12) 272.8 parts of C _12-15 methacrylate and 2-ethylhexyl methacrylate 120 were placed in a container.
Parts, 100 parts of mineral oil (Total 85N), and 5 parts each
Charge Trigonox-21 and t-dodecyl mercaptan. The materials are mixed for 0.25 hour, then with about 1/3 and 7.2 parts of dimethylaminopropyl methacrylamide in the mixture, stirrer, thermocouple, addition funnel with N ₂ inlet and condenser Into the reactor. The remaining 2/3 of the mixture is placed in the addition funnel. The mixture in the flask was heated to 110 ° C. under N ₂ for 0.2 hours, thereby confirming an exotherm with a temperature increase to 141 ° C. After the fever subsides (1 minute),
At 40 ° C., start adding the remaining monomer and continue for 1.5 hours, the temperature range is from 108 to 1
12 ° C. After heating at 108-110 ° C. for 3 hours,
Add additional Trigonox-21 (0.5 parts),
Heating at 110 ° C. was continued for 2 hours, then the material was
Strip to 135 ° C. at 0 mm Hg. This residue is mixed with an additional 37.6 parts of oil. This product has Mw = 59,201, Mn = 24,232 and PDI = 2.44. (Example 13) The method of Example 7 is followed. The reaction after addition of all the monomers is 2.5 hours, at which point the infrared spectrum reveals that the reaction is not completely complete. Additional Trigonox-21
(2.5 parts) and after 2 hours at 110 ° C., the infrared spectrum reveals that the reaction is complete. This filtrate has Mw = 46,271, Mn = 14,689 and PDI = 3.15. Example 14 1320 parts of Total 85N oil was mixed with a mixture of Total 85N and 150N mineral oil 1
The method of Example 13 is repeated except that the replacement is made in 219.7 parts. Mw = 41,490, Mn = 18,77
0 and PDI = 2.21 (Example 15) In a container, 3601 parts of a C _12-15 methacrylate ester and 1584 of 2-ethylhexyl methacrylate were added.
Parts, Total 85N (1280 parts), and 40 parts each
Parts of 150N mineral oil, Trigonox 21 and t-
Fill with dodecyl mercaptan. These substances are
Was stirred for 25 h, then about 1/3 and 95 parts of dimethylaminopropyl methacrylamide in the mixture, stirrer, thermocouple, it is charged to a reactor equipped with an addition funnel with N ₂ inlet and condenser. The remaining 2/3 of this mixture
Into the addition funnel. The mixture in the flask was heated to 110 ° C. under N ₂ for 0.4 hours, thereby confirming an exotherm with a temperature increase to 149 ° C. After the fever subsides (3 minutes)
The temperature reaches 148 ° C., the addition of the remaining monomer begins, and lasts for 1.6 hours, the temperature being 1
10 ° C. 0.6 hours after the exothermic peak, the remaining additions are made at 108-113 ° C. 1. at 108-110 ° C.
After heating for 5 hours, the infrared spectrum reveals that the addition is not completely completed. Additional Tri
gonox-21 (2.5 parts) was added, heating at 110 ° C. was continued for 2 hours, and the infrared spectrum revealed that the reaction was complete. Material is stripped to 120 ° C. at 50 mmHg. This residue is mixed with additional Total 85N (503 parts). This product has Mw = 61,074, Mn = 27,521 and PDI = 2.22. (Example 16) containers, C _12-15 3696 parts of methacrylic acid ester (13.64 eq), 2-ethylhexyl 1584 parts of methacrylic acid (7.99 mol), Total
85N (1281.5 parts) and 15 of 38.5 parts each
Fill with 0N mineral oil, Trigonox-21 and t-dodecanethiol. The materials are mixed for 0.25 hour, then 1/3 of the mixture, stirrer, addition funnel with N ₂ inlet, is charged to a reactor equipped with a thermocouple and a condenser. The remaining 2/3 of the mixture is charged to the addition funnel. The reactor contents are heated to 110 ° C. under N ₂ for about 0.4 hours, whereby an exotherm to 150 ° C. is observed and heating is discontinued.
After about 2 minutes, the temperature is 149 ° C. and the addition of the monomers from the addition funnel is started at 60 ml / min. After about 0.5 hours, the temperature has reached 110 ° C. and the heating is started and maintained at 108-113 ° C. After 1.6 hours, the addition is complete, then heating is continued for 2.5 hours,
The infrared spectrum then reveals that the polymerization has not been completed. Additional Trigonox-21
(2.5 parts) was added and heating was continued for 2 hours, whereupon the infrared spectrum revealed that the polymerization was complete. This batch was transferred to Total 85 (351.
5) and then filtered through a Buchner funnel with a cloth pad. The filtrate has Mw = 86,29
9, with Mn = 36,473 and PDI = 2.37. (Example 17) C _12-15 (Lial 125) was added to a container.
7. 280 parts (1.02 equivalents) of methacrylic acid ester, 120 parts (0.605 mol) of 2-ethylhexyl methacrylate, Total 85N (100 parts), and 8.
Charge 0 parts Trigonox-21 (0.039 mol) and t-dodecanethiol (0.04 mol).
The materials are stirred for 0.25 hour, then filled with 1/3 of the mixture, stirrer, addition funnel with N ₂ inlet, a reactor equipped with a thermocouple and condenser, the remaining mixture Of the addition funnel is charged to the addition funnel. The reactor contents were cooled under N ₂ for about 0.2 hours.
Heat to 110 ° C., whereby an exotherm to 147 ° C. is observed and heating is stopped. After about 4 minutes, the addition of the monomers from the addition funnel is started at 4.4 ml / min. After about 0.3 hours, the temperature has reached 110 ° C and heating is started and maintained at 106-111 ° C.
After 1.5 hours, the addition is complete, then heating is continued for 1.6 hours. Additional Trigonox-21 (0.8
Part) and heating is continued for 3 hours. At this point, the infrared spectrum reveals that the polymerization is complete. The batch is stripped to 150 ° C. and 24 mm Hg. The residue is filtered over a filter aid. The filtrate had Mw = 49,245, Mn = 15,
903 and PDI = 3.10. Example 18 The method of Example 17 is repeated, substituting the methacrylate from Lial 125 with that derived from Alchem 125 alcohol. The maximum temperature after the exotherm is 140 ° C., and instead of 0.8 parts, additional Trigonox 21 (0.6 parts) is added,
Strip to 0 ° C. and 24 mm Hg. The filtrate contained Mn = 53,931, Mw = 17,3.
35 and PDI = 3.11. Oils of Lubricating Viscosity The lubricating compositions and methods of the present invention use oils of lubricating viscosity, including natural or synthetic lubricating oils and mixtures thereof.

Natural oils include animal and vegetable oils (eg, castor oil, lard oil) as well as mineral lubricating oils (eg, liquid petroleum oils and paraffin, naphthene or mixed paraffin-naphthene types). And solvent-treated mineral lubricating oils or acid-treated mineral lubricating oils). Oils of lubricating viscosity derived from coal or shale are also
Useful. Synthetic lubricating oils include the following hydrocarbon oils and halo-substituted hydrocarbon oils. The hydrocarbon oils and halo-substituted hydrocarbon oils include, for example, polymerized olefins and interpolymerized olefins, and mixtures thereof, alkylbenzenes, polyphenyls (eg, biphenyls, terphenyls, alkylated polyolefins). Phenyl and the like); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologs thereof.

Alkylene oxide polymers and interpolymers and their derivatives, whose terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another useful class of known synthetic lubricating oils.

Other suitable classes of synthetic lubricating oils which can be used include esters of di- and polycarboxylic acids, and C
₅ -C ₂₀ those made from monocarboxylic acids and polyols and polyol ethers are included.

Other synthetic lubricating oils include silicone-based oils such as liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, etc. (eg, polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils). Is mentioned.

Unrefined, refined and rerefined oils, which include not only natural or synthetic oils of the type disclosed above, but also mixtures of two or more of any of these It can be used in the composition of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. Refined oil is
Similar to unrefined oils except it has been further processed in one or more purification stages to improve one or more properties. Refined oils include solvent refined oils, hydrorefined oils, hydrofinished oils, hydrotreated oils, and oils obtained by hydrocracking and hydroisomerization.

Rerefined oils include the refined oils already used,
Obtained by applying steps similar to those used to obtain the refined oil. Such rerefined oils are often further processed by indicated methods to remove spent additives and oil breakdown products.

Specific examples of oils of the above lubricating viscosity are described in Chamberlin, III, US Pat.
26,972, European Patent Publication No. 107,282.
No., and A. Sequeria, Jr. , Lubr
icant Base Oil Wax Pro
cessing, Chapter 6, MarcelD
ecker, Inc. , New York (199
4), and the contents of each document are hereby incorporated by reference for the relevant disclosures contained herein.

A basic and concise description of lubricant base oils can be found in D.C.
V. Brook's reference, "Lubrication.
Engineering, Vol. 43, pp. 184-185 (March 1987), the contents of which are hereby incorporated by reference for the relevant disclosures contained herein. (Other additives) As described herein, the lubricating oil composition of the present invention may contain other components. The use of such additives is optional and their presence in the compositions of the invention depends on the particular application and the level of performance required.
Therefore, other additives may be included or excluded. The composition may contain a zinc salt of dithiophosphoric acid. The zinc salt of dithiophosphoric acid is often referred to by zinc dithiophosphate, O, O-dihydrocarbyl zinc dithiophosphate, and other commonly used names. These are sometimes referred to by the ZDP abbreviation. One or more zinc salts of dithiophosphoric acid may be present in small amounts to further provide extreme pressure, antiwear and antioxidant performance.

In addition to the above-mentioned zinc salts of dithiophosphoric acid, other additives which can be used as required in the lubricating oil of the present invention include, for example, detergents, dispersants, viscosity improvers , Antioxidants, pour point depressants, extreme pressure agents, antiwear agents, color stabilizers and defoamers. The dispersant and the viscosity improver can be used in combination with the additive of the present invention.

Auxiliary extreme pressure agents and corrosion and antioxidants which may be included in the compositions of the present invention include chlorinated aliphatic hydrocarbons, organic and polysulfides, phosphite dihydrocarbons and trihydrocarbons. Examples thereof include phosphorus-containing esters, phosphoric acid and salts thereof, and molybdenum compounds.

Auxiliary viscosity improvers (which are also sometimes
Viscosity index improvers or viscosity modifiers) can be included in the compositions of the present invention. Viscosity improvers are usually polymers, these include polyisobutene, polymethacrylate, diene polymer, polyalkylstyrene,
It includes esterified styrene-maleic anhydride copolymers, alkenyl arene-conjugated diene copolymers, and polyolefins. Multifunctional viscosity improvers other than the viscosity improvers of the present invention, which also have dispersant and / or antioxidant properties, are known and, optionally, in conjunction with the products of the present invention. Can be used. Such products are described in numerous documents, including those mentioned in the Background of the Invention. The contents of each of these references are specifically incorporated herein by reference.

Pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein. For example, C.I. V. Smallheer and R.A.
Kennedy Smith 「Lubricant
Additives "(Lezius-Hiles
Company Publisher, Clevela
nd, Ohio, 1967).
Pour point depressants useful for the purposes of the present invention, their method of preparation and their use are described in US Pat. No. 2,387,50.
No. 1, No. 2,015,748; No. 2,655,479
No. 1,815,022; No. 2,191,498
No. 2,666,748; No. 2,721,877
No. 2,721,878; and 3,250,7
No. 15, the contents of which are specifically incorporated herein by reference for their relevant disclosure.

Antifoams used to reduce or prevent the formation of stable foam include silicones or organic polymers. Examples of these and additional antifoam compositions are described in "Foam Control Agent".
s "(Henry T. Kerner, Noyes
Data Corporation, 1976)
It is described on pages 25-162.

The detergents and dispersants can be of the ash-forming or ashless type. Ash-forming detergents are oil-soluble with alkali or alkaline earth metals and sulfonic, carboxylic, phenolic or organic phosphorus-containing acids, which are characterized by at least one direct carbon-phosphorus bond. Are exemplified by neutral and basic salts of

The term "basic salt" is used to indicate a metal salt in which the metal is present in a stoichiometrically greater amount than the organic acid groups. Basic salts and methods for their preparation and use are well known to those skilled in the art and need not be described in detail here.

The fact that ashless detergents and dispersants, depending on their composition, can result in non-volatile residues (eg, boron oxide or phosphorus pentoxide) upon combustion of the detergent or dispersant. Nevertheless, it is so called; however, it usually does not contain metals and, therefore, does not produce ash containing metals when combusted. Many types of materials are known in the art, some of which are suitable for use in the lubricants of the present invention. Illustrated below are: (1) carboxylic acids (or derivatives thereof) containing at least about 34 carbon atoms (preferably at least about 54 carbon atoms) and nitrogen-containing compounds (eg, amines, phenols and Reaction products with organic hydroxy compounds such as alcohols and / or basic inorganic substances). Examples of these "carboxylic dispersants" are described in British Patent 1,306,
529, and a number of U.S. Patents, including: 3,163,603 3,381,022 3,542,680 3,184,474 3,399,141 3,567,637 3,215 , 707 3,415,750 3,574,101 3,219,666 3,433,744 3,576,743 3,217,310 3,444,170 3,630,904 3,272,746 3,448 , 048 3,632,510 3,281,357 3,448,049 3,632,511 3,306,908 3,451,933 3,697,428 3,311,558 3,454,607 3,725 , 441 3,316,177 3,467,668 4,194,886 3,340,281 3,501,405 4,234 435 3,341,542 3,522,179 4,491,527 3,346,493 3,541,012 5,696,067 3,351,552 3,541,678 5,696,068 RE 26,433 (2) a relatively high molecular weight aliphatic or alicyclic halide and an amine (preferably a polyalkylene polyamine)
Reaction product with These may be characterized as "amine dispersants", examples of which are described, for example, in the following U.S. Patents: 3,275,554 3,454,555 3,438,757 3,565 804 (3) The reaction product of an alkylphenol (where the alkyl group has at least about 30 carbon atoms) with an aldehyde (especially formaldehyde) and an amine (especially a polyalkylenepolyamine). This can be characterized as a "Mannich dispersant". The materials described in the following U.S. patents are illustrative: 3,413,347 3,725,480 3,697,574 3,726,882 3,725,277 (4) An amine carboxylate or Mannich dispersant , Urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron-containing compound, phosphorus Include compounds. Representative materials of this type are described in the following US patents:

[0132]

[Table 1]

(5) An oil-soluble monomer (for example, decyl methacrylate, vinyl decyl ether and a high molecular weight olefin) and a monomer having a polar substituent (for example,
Aminoalkyl acrylate or aminoalkyl methacrylate, acrylamide and poly (oxyethylene)
And substituted acrylates).
These may be characterized as "polymer dispersants", examples of which are disclosed in the following U.S. Patents: 3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The contents of the patents noted above disclose the disclosure of ashless dispersants.
It is incorporated herein by reference.

The “other” additives exemplified above are each
In the lubricating composition, at a small concentration of about 0.001% by weight, usually in the range of about 0.01% to about 20% by weight,
Can exist. In most cases, they are
From about 0.1% to about 10%, often up to about 5% by weight.

The lubricating oil composition contains a major amount of oil of lubricating viscosity and a minor amount of the composition of the present invention. By major amount is meant more than 50% by weight. When more than one component is present, the major amount usually constitutes more than 50% by weight, but always accounts for the largest part of the composition. In particular, the lubricating oil composition has an amount as small as about 1% by weight,
Often, from about 3 or 4% to about 40% by weight,
Often up to about 35% by weight, frequently about 25% by weight
Up to the products of the present invention. Gear lubricant compositions are often from about 5% to about 40% by weight, often
It contains up to about 35% by weight, often up to about 30% by weight, of the product of the present invention. Automatic transmission oils are typically
It contains from about 4% to about 20% by weight of the product of the present invention. In some embodiments, the lubricating oil composition can contain as little as 1% by weight to about 15% by weight, often from about 2% to about 9% by weight of the product of the present invention.

The various additives described herein can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent (eg, mineral oil, naphtha, benzene, toluene or xylene) to form an additive concentrate. Preferred additive concentrates contain the diluents mentioned above.

The additive concentrate is usually used in an amount of about 0.1% by weight to about 0.1% by weight.
It contains about 90% by weight, often more, of the composition of the present invention, and may additionally contain one or more other additives known in the art or described above. Fifteen
%, 20%, 30% or 50% or more concentrations can be used. When these additive concentrates contain other additives, frequently the amount of the composition of the present invention ranges from about 10% to about 90% by weight, often 15 to 5% by weight.
It is in the range of 0% by weight, often about 50% by weight.

The lubricating compositions of the present invention are illustrated by examples in the following table. These lubricating compositions are prepared by combining an amount of the specified components, individually or from a concentrate, with an oil of lubricating viscosity to make a total of 100 parts by weight. The amounts given here are parts by weight and, unless otherwise indicated, the amount of chemical substance present on an oil-free basis. Thus, for example, using 10% by weight of an additive containing 50% by weight of an oil in a formulation would give 5% by weight of the chemical. When using the products of the above examples, their amounts are the same as those prepared without adjustment for diluents, unless otherwise indicated. These examples are provided for illustrative purposes only and are not intended to limit the scope of the invention. (Examples AK) Mineral oil base stock (Exxon, 9
0 Neutral), 0.8 parts of a styrene-maleic acid ester-methyl methacrylate copolymer, and an additive concentrate (this is dithiophosphoric acid) di - product 20.3 which was obtained by the hydroxypropyl ester of (methylamyl) neutralized with P ₂ O ₅ are reacted and branched primary amine
2 parts, oleylamine 5.38 parts, oleylamide
54 parts, mineral oil 1.28 parts, carboxylic acid polymer defoamer 0.
92 parts, 68.19 parts of sulfurized isobutylene and 8 of the reaction product of heptylphenol, formaldehyde and 2,5-dimercapto-1,3,4-thiadiazole
(Contains 2.37 parts of 0% mineral spirits solution)
A gear lubricant composition is prepared by mixing with 6.5 parts to provide 100 parts of a lubricating oil composition.

[0139]

[Table 2]

The viscosity measurements of the lubricating oil compositions A to K are shown in the following table. The kinematic viscosity at 100 ° C. is determined by the ASTM proc
edure D-445, which generally involves measuring the kinematic viscosity of a liquid petroleum product by measuring the time under gravity that a fixed volume of liquid flows through a calibrated glass capillary viscometer. Measure using Brookfield viscosity is determined by ASTM procedure D
-2983 (Standard Test Method for Low Temperature Viscosity of Automotive Liquid Lubricants Measured with Brookfield Viscometer), both of which are Annual Book of AST.
M Standards, Section 5, AST
M, found in Philadelphia, PA, USA.

[0141]

[Table 3]

Synthetic oil basestock, which is 84 parts polyalphaolefin oil (4 centistokes at 100 ° C.) (Emery 3004) and 16 parts diester oil (3 centistokes) (Emery
2958)), the indicated amount (parts by weight)
'S product for a specified embodiment, the additive concentrate (which, dithiophosphate di - (obtained by the hydroxypropyl ester of methylamyl) neutralized with P ₂ O ₅ are reacted and branched primary amine 15.53 parts of mineral oil, 0.5 mineral oil
7 parts, magnesium over base (MR 14.
7) 8.4 parts of alkylbenzenesulfonic acid, 7.1 parts of succinic anhydride / ethylenepolyamine reaction product substituted with polyisobutene (Mn = about 1000), 2.9 parts of glycerol monooleate, 3.2 parts of triphenyl phosphite 0.96 parts of a carboxylic acid polymer defoamer, sulfurized isobutylene 4
1.19 parts, and polyisobutene (Mn = about 100
0) A reaction product of a substituted succinic anhydride / pentaerythritol polyester, which is further reacted with ethylene polyamine, and then reacted with 2,5-dimercapto-1,2
A gear lubricant composition is prepared by mixing with 10 parts (containing 5.2 parts reacted with 3,4-thiadiazole) to provide 100 parts of a lubricating oil composition.

[0143]

[Table 4]

The measurements of the viscosities of the lubricating oil compositions L to V are shown in the following table. The method is the same as in Examples AK.

[0145]

[Table 5]

Lubricating compositions are often subjected to conditions which can cause shearing of the polymer, resulting in reduced viscosity improving properties. Thus, the shear stability of a polymer-containing blend is often important. Several tests are available to determine the resistance of a composition to shear under high shear stress conditions.

One useful test includes KRL Tape
There is a red Bearing Shear Test. This is the “Visibility Shear St”
availability of Transmission L
ubricants ", a C
EC (61 New Cavendish Street
t, London WIM 8AR, England)
As described in CECL-45-T93, available from the company. The same test is also based on DIN 51 350, part
6 and Deutsches In
Situtfr Normung (Burgerfe
nshase 6, 1000 Berlin 30, G
ermany). The contents of both of these references are incorporated herein by reference.
Using this method for 20 hours, the shear loss of some of the above examples is measured:

[0148]

[Table 6]

Example W To a mineral oil base stock, 1.5 parts of a polyisobutene (Mn = about 1000) -substituted succinic anhydride-polyethylene polyamine reaction product, 0.15 part of dibutyl hydrogen phosphite, boronate (boronat)
ed) 0.25 polyisobutene (Mn = about 1000) substituted succinic anhydride-polyethylene polyamine reaction product
Part, boronated C ₁₆ epoxide 0.2 part, di- (nonylphenyl) amine 0.63 part, propylene oxide /
0.5 parts of t-dodecyl mercaptan reaction product, 0.05 parts of ethoxylated N-fatty propanediamine, 0.05 parts of ethoxylated oleyl imidazoline.
1 part, sulfolene-decyl alcohol reaction product 0.6
Parts, 0.03 part of tolyltriazole, 0.2 part of calcium overbased (MR = about 1.2) alkylbenzene sulfonate, 0.025 part of red dye, and 0.04 part of silicone defoamer An automatic transmission fluid composition is prepared by preparing 100 parts of a lubricant.
11.8 parts of the product of Example 1 were added to improve lubricant 1
Prepare 00 parts. The resulting composition has a viscosity at 40 ° C. =
34.47 centistokes, viscosity at 100 ° C. = 7.2
Has 5 centistokes, VI = 182, and Brookfield viscosity (−40 ° C.) = 12,200 centipoise. (Examples X to Z) Calcium overbased (MR)
1.1) 15.16 parts of sulfurized alkylphenol, 11.5 parts of calcium overbased (MR 16) petroleum sulfonate, 6.05 parts of barium overbased (MR 5) fatty acid / heptylphenol, sulfolene-decyl alcohol reaction An additive concentrate is prepared by compounding 3.7 parts product, 0.5 part silicone antifoam, 24.69 parts hydrocarbon diluent, and 100 parts mineral oil. Example X A lubricating oil composition is prepared by mixing together 8.97 parts of this additive concentrate and 91.03 parts of a mineral oil lubricating oil. 89.1 parts of this lubricating oil and Example 1
A final lubricating oil composition is prepared by mixing 10.9 parts of the product of Step 2. The resulting composition has a viscosity of 40 ° C. =
39.03 centistokes, 100 ° C. viscosity = 7.85
It has a centistokes, VI = 177, and a Brookfield viscosity (−40 ° C.) = 19,400 centipoise. Example Y 9.0 parts of this additive concentrate, red dye 28
A lubricating oil composition is prepared by mixing together 0 ppm and 91.0 parts mineral oil lubricating oil. This lubricating oil 90
A final lubricating oil composition is prepared by mixing parts and 10 parts of the product of Example 12. The resulting composition is
It has a 40 ° C. viscosity = 36.29 centistokes, a 100 ° C. viscosity = 7.51 centistokes, VI = 181, and a Brookfield viscosity (−40 ° C.) = 13,400 centipoise. Example Z 7.2 parts of this additive concentrate, red dye 22
A lubricating oil composition is prepared by mixing together 0 ppm and 92.8 parts mineral oil lubricating oil. This lubricating oil 9
A final lubricating oil composition is prepared by mixing 0.15 parts and 9.85 parts of the product of Example 12. The resulting composition had a viscosity at 40 ° C. = 36.97 centistokes, a viscosity at 100 ° C. = 7.65 centistokes, VI =
182, and Brookfield viscosity (−40 ° C.) =
It has 12,400 centipoise. Example AA Polyisobutene (Mn = about 1000) Substituted Succinic Anhydride-Polyethylene Polyamine Reaction Product 1
5.7 parts, CS ₂ post-treated polyisobutene (Mn = about 10
00) Substituted succinic anhydride-polyethylene polyamine reaction product 2.24 parts, dibutyl hydrogen phosphite 2.7 parts, 8
0.5% 5% phosphoric acid, boronated polyisobutene (M
n = about 1000) 4.5 parts of substituted succinic anhydride-polyethylene polyamine reaction product, 2.7 parts of boronated C ₁₆ epoxide, 5.9 parts of di- (nonylphenyl) amine,
5. 1.2 parts of N-phenyl-α-naphthylamine, propylene oxide / t-dodecyl mercaptan reaction product
7 parts, ethoxylated N-fatty propanediamine 0.27
Parts, dialkyl phosphite 1.1 parts and ethoxylated oleyl imidazoline 0.53 parts, and concentrate 100
An additive concentrate is prepared by mixing sufficient mineral oil diluent to make up parts by weight. 8.5 parts of this additive concentrate, 250 ppm of red dye and 91.
An automatic transmission lubricating oil composition is prepared by mixing 5 parts together. A final lubricating oil composition is prepared by mixing 11.7 parts of the product of Example 12, 0.8 parts of a styrene-maleic ester pour point depressant and 87.3 parts of the lubricating oil composition. The resulting composition had a 40 ° C. viscosity = 35.76 centistokes, a 100 ° C. viscosity = 7.
Has 72 centistokes, VI = 194, and Brookfield viscosity (−40 ° C.) = 8,520 centipoise. (Examples AB to AE) Mg overbased (MR 1
4.7) 7.28 parts of alkylbenzenesulfonic acid, 7.06 parts of polyisobutene (Mn = about 1000) -substituted succinic anhydride-polyethylene polyamine reaction product, 41.9 parts of sulfurized isobutylene, polyethylenepolyamine post-treated polyisobutene (Mn = about 1000) 1000) Substituted succinic anhydride-
4.60 parts of pentaerythritol reaction product, 1.77 parts of S-alkylated 2,5-dimercapto-1,3,4-thiadiazole, 2.94 of glycerol monooleate
Parts, 3.29 parts of triphenyl phosphite, a mixture of a silicone-containing defoamer and a carboxylic acid polymer defoamer 0.96
Parts, dithiophosphate di - product 15.53 parts obtained by neutralizing the hydroxypropyl ester P ₂ O ₅ and then reacted branched primary amine (methylamyl), and produce a concentrate 100 parts An additive concentrate is prepared by mixing sufficient mineral oil diluent to perform 1 part by weight (pbw) of an 80% oil solution of styrene-maleic acid ester-methyl methacrylate copolymer, indicated amount (pb
A manual transmission lubricant is prepared by mixing this additive concentrate of w), the product of Example 6 and the base stock shown in the table below:

[0150]

[Table 7]

The viscosity measurements of the gear oil compositions AB to AE are shown in the following table. The method is the same as in Examples AK.

[0152]

[Table 8]

It is known that some of the above substances may interact in the final formulation, so that the components of the final formulation may be different from those initially added.
For example, metal ions (eg, from detergents) can migrate to other acidic sites in other molecules. The products formed thereby, including those formed using the compositions of the present invention in its intended use, may not be easily described. Nevertheless, all such modifications and reaction products are included within the scope of the present invention. The present invention includes a composition prepared by mixing the above components.

While the invention has been described in connection with preferred embodiments thereof, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the present specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover those modifications that fall within the scope of the appended claims.

[0155]

According to the present invention, there is provided a viscosity improver which does not inappropriately increase the low-temperature viscosity of a lubricating oil composition, resists shearing, and reduces the degree of viscosity loss at high temperatures. You.

────────────────────────────────────────────────── ⁶ Continuation of the front page (51) Int.Cl. ⁶ Identification code FI // C10N 30:02 40:08 (71) Applicant 591131338 29400 Lakeland Boulevard, Wicklife, Ohio 44092, United States of America (United States) 72) Inventor Charles P. Bryant United States Ohio 44123, Uuklid, East 240 T.H. Street 675

Claims (28)

[Claims] 1. A copolymer containing the following (a) and (b) and, if necessary, units derived from (c): (a) from about 9 to about 25 in its ester group And (b) a methacrylate containing from 7 to about 12 carbon atoms in the ester group, wherein the ester group is 2- (C _1-4) (C) methacrylic esters different from (a) and (b), which optionally have (c) 2 to about 8 carbon atoms in the ester group atoms thereof At least one monomer selected from the group consisting of: a vinyl aromatic compound, and a nitrogen-containing vinyl monomer, provided that not more than 60% by weight of the ester contains not more than 11 carbon atoms in its ester group. That. 2. The ester (a) contains from about 13 to about 16 carbon atoms in the ester group, and the ester (b) contains from about 9 to about 9 carbon atoms in the ester group.
Containing about 12 carbon atoms, the ester group in (b) has a 2-ethyl substituent and the molar ratio of ester (a) to ester (b) is from about 90:10 to about 10:10. 2. The copolymer of claim 1, wherein the range is 60:40. 3. The copolymer of claim 1 which contains from about 0.2 mol% to about 60 mol% of units derived from monomer (c). 4. The copolymer of claim 3, wherein the ester group is substantially free of groups derived from methacrylic esters containing less than 7 carbon atoms. 5. The copolymer of claim 3 containing from about 0.2 mole percent to about 20 mole percent of the nitrogen-containing vinyl monomer. 6. The method according to claim 1, wherein the ester (b) is methacrylic acid 2
The copolymer of claim 5, which is -ethylhexyl, and wherein the nitrogen-containing vinyl monomer is selected from the group consisting of dimethylaminopropyl methacrylamide and dimethylaminoethyl methacrylate. 7. The method according to claim 1, wherein the ester (b) is methacrylic acid 2
The copolymer of claim 5, comprising -ethylhexyl, and (c) containing lower alkyl methacrylate. 8. The following (a) and (b), and optionally (c), are reacted in the presence of a free radical initiator, if necessary, and in the presence of a chain transfer agent. A) a methacrylate containing from about 9 to about 25 carbon atoms in the ester group; and (b) a 7 to about 12 carbon atoms in the ester group. Wherein the ester group has a 2- (C _1-4 alkyl) substituent, and optionally, (c) from 2 to about 8 in the ester group. At least one monomer selected from the group consisting of a methacrylate ester containing a carbon atom and different from methacrylate esters (a) and (b), a vinyl aromatic compound, and a nitrogen-containing vinyl monomer; Not exceeding Ester in the ester group containing carbon atoms not exceeding 11 a. 9. The monomer (a) and (b), the free radical initiator, and the chain transfer agent, if used, are blended to form a mixture, wherein about 1 part of the mixture is prepared.
0% to about 80% by weight is heated until an exotherm is observed, then the remaining mixture is added over about 0.25 hours to about 5 hours while maintaining the reaction temperature, optionally adding 9. The method of claim 8, wherein additional initiator is added, whereby the reaction continues to completion. 10. The composition according to claim 10, wherein said monomer comprises from about 0.2 mol% to about 6
9. The method according to claim 8, wherein 0 mol% is said monomer (c). 11. The monomer (b) contains 2-ethylhexyl methacrylate and the monomer (c) contains methyl methacrylate.
The method described in. 12. The method of claim 10, wherein said monomer (b) contains 2-ethylhexyl methacrylate and said monomer (c) contains a nitrogen-containing vinyl monomer. 13. The method according to claim 12, wherein said monomer (c) contains a nitrogen-containing vinyl monomer selected from the group consisting of dimethylaminopropyl methacrylamide and dimethylaminoethyl methacrylate. 14. The monomers are reacted simultaneously.
The method according to claim 10. 15. The monomer (c) is grafted to a preformed polymethacrylate prepared by reacting the monomers (a) and (b).
The method according to claim 10. 16. The mixture, wherein the monomer, the free radical initiator, and the chain transfer agent, if used, are formulated to form a mixture, from about 10% to about 80% by weight of the mixture.
Wt% is heated until an exotherm is observed, then the remaining mixture is added over about 0.25 hours to about 5 hours while maintaining the reaction temperature, and additional initiator is added as needed 15. The method of claim 14, wherein the reaction is continued to completion. 17. The monomers (a) and (b), the free radical initiator, and, if used, the chain transfer agent are blended to prepare a first mixture and the monomers (a) and (b) from about 10% to about 80% by weight of the first mixture of b) is blended with said monomer (c) to form a second mixture, from about 20% to about 100% of said second mixture.
Is heated until an exotherm is observed, and then, while maintaining the reaction temperature, first for about 0.25 hours to about 5 hours, the remainder of the second mixture is added,
Subsequently, over 0.25 hours to about 5 hours, the remaining first mixture is added, and if necessary, additional initiator is added, thereby continuing the reaction to completion. The method described in. 18. The monomers (a), (b) and (c)
From either lower alkyl methacrylate or a nitrogen-containing vinyl monomer, the free radical initiator, and the chain transfer agent, if used, is formulated to form a first mixture and about 10% of the first mixture. From about 20% to about 80% by weight is blended with the remaining monomer (c) to form a second mixture, wherein about 20% to about 100% of the second mixture comprises
Heat until an exotherm is observed, then add the remainder of the second mixture, if any, for about 0.25 hours to about 5 hours while maintaining the reaction temperature, followed by 0.25 hours 11. The method of claim 10, wherein over a period of time to about 5 hours, the remaining first mixture is added, and if necessary, additional initiator is added, thereby continuing the reaction to completion. 19. The monomer (a), (b), from about 10% to about 90% of the monomer (c), the free radical initiator, and if used, the chain transfer agent is compounded, A first mixture is prepared and about 10% to about 80% by weight of the first mixture is blended with the remaining monomer (c) to form a second mixture, wherein about 20% to about 20% of the second mixture is prepared.
About 100% is heated until an exotherm is observed, then, while maintaining the reaction temperature, first add the remainder of the second mixture, if present, for about 0.25 hours to about 5 hours, followed by 11. The method of claim 10, wherein the remaining first mixture is added over a period of from about 0.25 hours to about 5 hours, and additional initiator is added as needed, thereby continuing the reaction to completion. The described method. 20. The method according to claim 10, wherein the monomer (b) contains 2-ethylhexyl methacrylate and the monomer (c) contains a lower alkyl methacrylate. Method. 21. The method according to claim 10, wherein the monomer (b) contains 2-ethylhexyl methacrylate and the monomer (c) contains a lower alkyl methacrylate and a nitrogen-containing vinyl monomer. Item 2. The method according to item 1. 22. A product prepared by the method according to any one of claims 8 to 21. 23. A normally liquid organic diluent, and about 20
23. An additive concentrate comprising from about 25% to about 95% by weight of a copolymer of any one of claims 1 to 7 or a product of claim 22. 24. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor amount of a copolymer according to any one of claims 1 to 7 or a product according to claim 22. 25. An oil of lubricating viscosity, and from about 5% to about 40% by weight of a copolymer according to any one of claims 1 to 7 or a product according to claim 22. Gear lubricant composition. 26. An oil of lubricating viscosity and about 4% to about 20% by weight of a copolymer according to any one of claims 1 to 7 or a product according to claim 22. Automatic transmission oil. 27. The composition of claim 24, wherein said lubricating oil composition is a manual transmission oil. 28. The composition according to claim 24, wherein said lubricating oil composition is a hydraulic fluid.