CN103732636A

CN103732636A - Polymers prepared by ring opening/cross metathesis

Info

Publication number: CN103732636A
Application number: CN201280039353.1A
Authority: CN
Inventors: M·W·赫尔特卡普; J·R·哈格多恩; C·P·赫夫; M·S·贝多雅; C·A·费勒
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2011-08-12
Filing date: 2012-06-25
Publication date: 2014-04-16
Anticipated expiration: 2032-06-25
Also published as: EP2742074A1; EP2742074A4; CN103732636B; WO2013025284A1

Abstract

This invention relates to a process for producing a polymer of a cyclic olefin and a linear mono-olefin, the process comprising contacting at least one C5 based cyclic olefin with at least one linear mono-olefin having from two to twenty carbon atoms in the presence of an alkene metathesis catalyst, and the polymer so produced.

Description

Polymers prepared by ring opening/cross metathesis

The inventors Matthew.Holtcamp, John R.Hagadorn, Caol P.Huff, Matthew S.Bedoya, Catherine A.Faler

Priority requirement

This application claims the benefits and priority of USSN13/209,242 filed on 12/8/2011 and EP111822877.1 filed on 22/9/2011.

Technical Field

The present invention relates to the metathesis of cyclic monomers and linear mono-olefins to produce polymers.

Background

Metathesis is generally considered to be the interchange of groups between two compounds during a chemical reaction. There are many metathesis reactions, such as ring opening metathesis, acyclic diene metathesis, ring closing metathesis, and cross metathesis. However, these reactions have had limited success in the metathesis of functionalized olefins.

The process for producing polyolefins having terminal functionalized groups is typically a multi-step process that often produces undesirable by-products and wastes reactants and energy.

Examples of functionalizing polyolefins comprising vinyl side groups to form polar functionalized products having a graft-type structure using cross-metathesis are disclosed in r.t. mathers and g.w. coates, chem.commun.,2004, page 422-423.

Examples of the use of cross-metathesis to functionalize vinyl-containing non-polymeric molecules are disclosed in c.orn et al, j.am.chem.soc.2008,130, pages 1495-1506, and c.orn et al, angelw.chem.int.ed., 2005,44, pages 7399-7404.

For a review of the methods of forming terminally functionalized polyolefins, see (a) s.b.amin and t.j.marks, angelw.chem.int.ed., 2008,47, page 2006-.

USSN12/488,093, filed on 6/19/2009, discloses terminal-functionalized polyolefins prepared from vinyl-terminated polyolefins by cross-metathesis.

Additional references of interest include US4,988,764 and US6,225,432.

Today, the vast majority of lubricant base stocks are produced from crude oil distillate fractions by processes such as hydrocracking, catalytic dewaxing, and solvent dewaxing, which adjust the size and degree of branching of the distillate fractions. However, due to the high cost of crude oil and the unstable nature of global crude oil supplies, there is an increasing incentive to produce lubricant base stocks from alternative sources.

Important alternative sources of hydrocarbons available in large supply in most modern refineries include norbornene and norbornadiene, as they can be produced by the Diels-Alder reaction of cyclopentadiene with ethylene and acetylene, respectively. Cyclopentadiene itself is available in large quantities as a by-product of distillation for steam cracking naphtha and gas oils to produce ethylene and coal tar. Therefore, there is great interest in developing new uses for norbornene and norbornadiene.

For example, norbornene is converted to polynorbornene by Ring Opening Metathesis Polymerization (ROMP) using a complex ruthenium catalyst (e.g., Walker' catalyst):

the polynorbornenes obtained are used mainly in the rubber industry and generally have a high glass transition temperature and a high optical clarity.

Furthermore, Walker and his colleagues have produced block copolymers of norbornene and cyclooctene, see Macromolecules,2009,42, 599-. In addition, La and colleagues have shown that certain alkylidene molybdes catalyze the chain transfer of polynorbornenes with dienes and styrenes, see J.Am.chem.Soc.,1999,121, 11603-11604. However, olefins such as 1-pentene are reported to be non-reactive towards this chain termination.

A variant of ring-opening metathesis polymerisation which has been studied only to date is ring-opening cross metathesis (ROCM). ROCM involves a tandem sequence (tandem sequence) in which a cyclic olefin is opened and then a second acyclic olefin is crossed over the newly formed end.

For example, U.S. patent No.6,803,429 discloses that certain group 8 metal alkylidene complexes substituted with N-heterocyclic carbene ligands catalyze the ring-opening cross-metathesis of cyclic olefins with acyclic olefin reactants (particularly α, β -unsaturated carbonyl compounds). ROCM products are considered to be predominantly monomeric, dimeric or oligomeric species, rather than polymers.

Likewise, US2008/0064891 discloses ring opening cross metathesis of cyclic olefins with seed oils and the like, comprising: contacting (a) at least one olefinic substrate selected from the group consisting of (i) unsaturated fatty acids, (ii) unsaturated fatty alcohols, (iii) esterification products of unsaturated fatty acids and alcohols, and (iv) esterification products of saturated fatty acids and unsaturated alcohols, with (b) at least one cyclic olefin as a cross-metathesis partner, in the presence of (c) a ruthenium alkylidene olefin metathesis catalyst, under conditions (d) effective to allow cross-metathesis of ring insertions such that the cyclic olefins are simultaneously opened and inserted into the olefinic substrate.

Furthermore, WO98/40373 discloses ROCM on a solid support to separate olefins immobilized on a resin, preventing undesired polymerization of olefins.

EP 16993357 discloses the utilization of Re in a fixed bed system₂O₇-B₂O₃/Al₂O₃A process for producing 1, 9-decadiene by ring-opening cross-metathesis between a liquid cyclic olefin and a gaseous acyclic olefin.

In accordance with the present invention, it has now been found that novel polymers of cyclic monomers and linear mono-olefins which are particularly useful in the production of lubricant base stocks and the like can be made by reacting a cyclic monomer (e.g., a C5-based cyclic olefin) with a linear mono-olefin (e.g., C5) using an olefin metathesis catalyst (such as an asymmetric ruthenium alkylidene complex)₂-C₂₀Linear mono-olefins) by ring opening cross metathesis. In a preferred embodiment, the present invention provides for reacting in one reactionIn-situ with cyclic olefins (e.g. based on C)₅Cyclic olefins) and cross-metathesis reactions with linear monoolefin olefins.

Polymers prepared by metathesis herein are of interest for use in many applications, such as lubricants, compatibilizers, tie-layer modifiers (tie-layer modifiers), surfactants, and surface modifiers, among others. In addition, their hydrogenation results in unique polymers that can be used in applications such as lubricants, compatibilizers, tie layer modifiers, surfactants, and surface metathesis polymerization.

Disclosure of Invention

Summary of The Invention

The present invention relates to a polymer represented by formula (X):

wherein the dotted line represents an optional double bond; x is 0 or 1; r¹And R²May be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms; r³And R⁴May be identical or different and are each hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or R³And R⁴Can be represented by the above formula (X), provided that R³And R⁴May be joined to form a five or six membered ring; and n is an integer of 1 to 100.

The invention also relates to a process for producing the above polymers.

Brief Description of Drawings

FIG. 1 shows some possible products of ring-opening cross metathesis.

Detailed Description

The term "polyolefin" as used herein means an oligomer or polymer of two or more olefin monomer units, and specifically includes oligomers and polymers as defined below. An "olefinic hydrocarbon," alternatively referred to as an "olefin," is a compound of carbon and hydrogen having at least one double bond, which is straight-chain, branched-chain, or cyclic. "monoolefins" have one double bond and are alpha-olefins or internal olefins.

Propylene polymers or oligomers contain at least 50 mol% propylene, ethylene polymers or oligomers contain at least 50 mol% ethylene, and the like.

For purposes of this specification and the appended claims, when a polymer or copolymer is described as comprising olefins (including but not limited to ethylene, propylene, and butylene), the olefins present in such polymer or copolymer are polymerized forms of olefins. For example, when a copolymer is described as having an "ethylene" content of 35 wt% to 55 wt%, it is understood that the monomer units (merunit) in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that differ from each other. The term "different" as used to describe monomeric units means that the monomeric units differ from each other by at least one atom or are isomeric. Thus, the definition of copolymer as used herein includes terpolymers and the like. Oligomers are typically polymers having low molecular weight (e.g., less than 25,000g/mol Mn, preferably less than 2,500g/mol Mn) or low number of monomer units (e.g., 75 monomer units or less, typically 50 monomer units or less, even 20 monomer units or less, even 10 monomer units or less).

As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight. wt% is weight percent and mol% is mole percent. Molecular Weight Distribution (MWD) is defined as Mw divided by Mn. All molecular weights (e.g., Mw, Mn, Mz) are in units of g/mol, unless otherwise specified. Carbon number was determined by 1H NMR as described in the experimental section below.

As used herein, the new numbering scheme for the groups of the periodic Table as described by Chemical and Engineering News,63(5),27(1985) is used. The room temperature was 23 ℃ unless otherwise stated.

The term "substituted" means that the hydrogen radical has been replaced by a hydrocarbyl radical, a heteroatom or a heteroatom-containing radical. For example, methylcyclopentadiene is cyclopentadiene (Cp) substituted with methyl groups, and ethyl alcohol is ethyl substituted with — OH groups.

The terms "hydrocarbyl", and "hydrocarbyl group" are used interchangeably throughout this document. Likewise, the terms "group" and "substituent" are also used interchangeably herein. For the purposes of the present invention, "hydrocarbyl" is defined as C₁-C₂₀Which may be linear, branched or cyclic (aromatic or non-aromatic) and includes substituted hydrocarbon radicals as defined below.

Substituted hydrocarbon radicals are radicals in which at least one hydrogen atom has been replaced by a heteroatom or heteroatom-containing radical, preferably by at least one functional group such as halogen (Cl, Br, I, F), NR₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、SR*、BR*₂、SiR*₃、GeR*₃、SnR*₃、PbR*₃Etc., or at least one heteroatom (e.g., halogen (Cl, Br, I, F), O, S, Se, Te, NR, PR, AsR, SbR, BR, SiR) therein₂、GeR*₂、SnR*₂、PbR*₂Etc.) have been inserted into a hydrocarbyl group, wherein R is independently hydrogen or a hydrocarbyl group.

"substituted alkyl" or "substituted aryl" is an alkyl or aryl group formed from carbon and hydrogen wherein at least one hydrogen is replaced by a heteroatom, a heteroatom-containing group, or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having from 1 to 30 carbon atoms.

The present invention relates to a polymer represented by formula (X):

wherein the dotted line represents an optional double bond; x is 0 or 1; r¹And R²May be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, preferably 1 to 6, preferably 5 carbon atoms); r³And R⁴May be identical or different and are each hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms (preferably from 1 to 20, preferably from 1 to 12, preferably from 2 to 6 carbon atoms), or R³And R⁴Can be represented by the above formula (X), provided that R³And R⁴May be joined to form a five or six membered ring; and n is an integer of 1 to 100 (preferably 1 to 60, preferably 1 to 20, preferably 2 to 10, preferably 2 to 5).

In a preferred embodiment, C in formula (X)₅All or part of the ring(s) is saturated. In another embodiment, C in formula (X)₅All or part of the ring(s) is unsaturated. In another embodiment, the pentane ring(s) in formula (X) are saturated.

In another preferred embodiment, R¹Is C_5-9Hydrocarbyl and R²Is C_5-9A hydrocarbyl group.

In another preferred embodiment, R¹Is C_5-9Hydrocarbyl radical, R²Is C_5-9Hydrocarbyl radical, R³And R⁴Is H, and n is an integer from 1 to 100 (preferably from 1 to 50, preferably from 2 to 20, preferably from 4 to 10).

In another preferred embodiment, R¹Is C₅Or C₉Hydrocarbyl radical, R²Is C₅Or C₉Hydrocarbyl radical, R³And R⁴Is H, and n is an integer from 1 to 100 (preferably from 1 to 50, preferably from 2 to 20, preferably 4)-10)。

In another preferred embodiment, R¹Is C₉A hydrocarbon radical, and R²Is C₉A hydrocarbyl group.

In another preferred embodiment, R¹Is C₉Hydrocarbyl radical, R²Is C₉Hydrocarbyl radical, R³And R⁴Is H, n is an integer from 1 to 100 (preferably from 1 to 50, preferably from 2 to 20, preferably from 4 to 10).

In another embodiment, R³And R⁴Form C₅Unsaturated cyclic groups such as cyclopentene. In another embodiment, R³And R⁴Form C₅Saturated cyclic groups, such as cyclopentane. In another embodiment, R³And R⁴Forming cyclopentene and/or cyclopentane.

Ring opening Cross metathesis polymerization (ROCM)

In particular embodiments, the present invention relates to a process for conducting metathesis reactions with cyclic olefins and linear mono-olefins. In such embodiments, the metathesis product comprises a ROCM product of cyclic olefins and linear mono-olefins. The wide synthetic availability of cyclic olefins makes this route attractive, and cyclic compounds are of particular importance in synthesis. Most importantly, the ring system is critical for stereochemical control; the understanding of the ring configuration generally represents the fastest way to the construction of a stereocenter. The ability to convert these general carbocycles into highly functionalized linear molecules (which ideally would have differentially protected end groups) would be extremely valuable to the synthetic chemist.

ROCM involves a tandem sequence in which cyclic olefins are opened and linear mono-olefins are crossed over newly formed end groups. After the initial ring opening, there are two options for the metal-bonded intermediate: with another cyclic olefin or with other olefins. It is understood that the ROCM reaction between a cyclic olefin and a linear mono-olefin reactant can result in several different types of reaction products, depending largely on the ring-opening metathesis reaction between the mono-olefin reactant and the cyclic olefin andrelative rates of cross-metathesis reactions, as shown in figure 1; wherein n =1-100,000 and R is C formed from a mono-olefin₁-C₃₀Hydrocarbyl radical, preferably C₂-C₂₀A hydrocarbyl group; preferably C₂-C₁₂Hydrocarbyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl and substituted and cyclic analogues thereof.

Thus, the cyclic olefin will have a rate constant k in the presence of the catalyst_ROUndergoes a ring opening reaction and the second olefinic reactant will have a rate constant k_CMUndergoes a cross-metathesis reaction with the ring-opened cyclic olefin. When k is_CMGreater than or equal to k_ROWhen ROCM products are predominantly monomeric, dimeric and/or oligomeric. More specifically, when k is_CMIs approximately equal to k_ROWhen the ROCM product is predominantly dimer or oligomer, and when k is_ROGreater than k_CMWhen ROCM products are predominantly higher Mw. Dimers and oligomers are of particular interest because their internal olefin moieties can be further functionalized by metathesis or other transformations. It should be understood that k_ROWill be higher for moderately and highly strained (strained) cyclic olefins (e.g. norbornadiene) but will be lower for low strain olefins (e.g. cyclopentene and cyclohexene). For example, ROCM of norbornadiene and 1-decene in the presence of the catalysts described herein produces decene-capped oligomers of oligo (norbornadiene), as shown in the following scheme:

the present invention also relates to a method for preparing a polymer represented by formula (X):

wherein the dotted line represents an optional double bond; x is 0 or 1; r¹And R²May be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, preferably 1 to 6, preferably 5 carbon atoms); r³And R⁴May be identical or different and are each hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms (preferably from 1 to 20, preferably from 1 to 12, preferably from 2 to 6 carbon atoms), or R³And R⁴Can be represented by the above formula (X), provided that R³And R⁴May be joined to form a five or six membered ring; and n is an integer from 1 to 100 (preferably from 1 to 60, preferably from 1 to 20, preferably from 2 to 10, preferably from 2 to 5);

the process comprises contacting an olefin metathesis catalyst with a cyclic olefin (preferably a C5-based cyclic olefin) and a linear monoolefin.

The reactants, including linear mono-olefins and cyclic olefins, are typically combined in a reaction vessel at a temperature of from 20 ℃ to 200 ℃ (preferably from 50 ℃ to 160 ℃, preferably from 60 ℃ to 140 ℃) and at a pressure of from 0 to 1000MPa (preferably from 0.5 to 500MPa, preferably from 1 to 250MPa) for a residence time of from 0.5 seconds to 10 hours (preferably from 1 second to 5 hours, preferably from 1 minute to 1 hour). The molecular weight of the polymer product can be controlled by, inter alia, the choice of catalyst, the ratio of linear monoolefin to cyclic olefin, and/or possibly the temperature.

In certain embodiments, when the olefin is a gaseous olefin, the olefin pressure is generally greater than 5psig (34.5kPa), preferably greater than 10psig (68.9kPa), and more preferably greater than 45psig (310 kPa). When a diluent is used with the gaseous olefin, the above pressure ranges may also be suitable for use as the total pressure of the olefin and the diluent. Likewise, when a liquid olefin is used and the process is conducted under an inert gas atmosphere, then the above pressure ranges may be suitable for the inert gas pressure.

The amount of metathesis catalyst employed in the process of the invention is any amount that provides an operable metathesis reaction. Preferably, the molar ratio of monomer (e.g., cyclic olefins and linear mono-olefins) to metathesis catalyst is generally greater than 10:1, preferably greater than 100:1, preferably greater than 1,000:1, preferably greater than 10,000:1, preferably greater than 25,000:1, preferably greater than 50,000:1, preferably greater than 100,000: 1.

Generally, the reactor is charged with from 0.00001 to 1.0 moles, preferably from 0.0001 to 0.05 moles, preferably from 0.0005 to 0.01 moles, of catalyst per mole of linear mono-olefin.

Generally, the catalyst is charged into the reactor in an amount of 0.00001 to 1.0 mole, preferably 0.0001 to 0.05 mole, preferably 0.0005 to 0.01 mole per mole of the cyclic olefin.

The ratio of linear monoolefin monomer to cyclic olefin monomer is preferably from 0.01:1 to 1000:1, preferably from 1:1 to 100:1, depending on the requirements of the final polymer. It has been found that in the present invention, the ratio of linear monoolefin monomer to cyclic olefin monomer has an effect on the molecular weight.

The process is typically a solution process, although it may be a bulk process or a high pressure process. Homogeneous processes are preferred. (homogeneous processes are defined as processes in which at least 90 wt% of the product is soluble in the reaction medium). The bulk homogeneous method is particularly preferred. (A bulk process is defined as a process in which the concentration of reactants in the total feed to the reactor is 70 vol% or more). Alternatively, no solvent or diluent is present or added to the reaction medium, (except for small amounts of carrier used as catalyst or other additives, or except in amounts typically present in the reactants; e.g., propane in propylene).

Suitable diluents/solvents for the process include non-coordinating, inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g. cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, e.g. with (Isopar)^TM) Is obtained commercially; perhalogenated hydrocarbons such as perfluoro C4-10 alkanes, chlorobenzene and aromatic or alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene and xylene. In a preferred embodiment, aliphatic hydrocarbon solvents such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof are preferredCyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. In another embodiment, the solvent is non-aromatic. Preferably the aromatic compound is present in an amount of less than 1 wt%, preferably 0.5 wt%, preferably 0 wt%, based on the weight of the solvent. In another embodiment, suitable diluents/solvents also include aromatic hydrocarbons, such as toluene or xylene, and chlorinated solvents such as methylene chloride. In a preferred embodiment, the feed to the process comprises 60 vol% or less of solvent, preferably 40 vol% or less, preferably 20 vol% or less, based on the total volume of the feed.

In another embodiment, the process is a slurry process. The term "slurry process" or "slurry polymerization process" as used herein means the following polymerization process: wherein a supported catalyst is used and the monomers are polymerized on the supported catalyst particles. At least 95 wt% of the polymer product formed from the supported catalyst is in spherical form as solid particles (insoluble in the diluent).

The process may be batch, semi-batch or continuous. As used herein, the term "continuous" means a system that operates without interruption or suspension. For example, a continuous process for producing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruders, pipes or pumps).

In a preferred embodiment, the process has a yield of at least 200g of polymer (preferably a polymer represented by formula (X)), preferably at least 5000g/mmol/hr, preferably at least 10,000g/mmol/hr, preferably at least 300,000g/mmol/hr, per mmol of catalyst per hour.

The present invention also relates to a process, preferably an in-line process, preferably a continuous process, for producing a polymer represented by formula (X), which process comprises introducing a cyclic olefin, a linear monoolefin and an olefin metathesis catalyst into a reactor to obtain a reactor effluent containing polymer (optionally with removal (e.g. flashing) of solvent), unused monomer and/or other volatile species to obtain a polymer, and then hydrogenating or functionalizing the polymer.

A "reaction zone", also referred to as a "polymerization zone", is defined as the region in which the activated catalyst and monomer are brought into contact and polymerization occurs. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization reaction zone.

In a particularly preferred embodiment, an olefin metathesis catalyst (e.g. 1-cyclohexylmethyl-3- (2, 6-diisopropylphenyl) -4, 5-dihydro-1H-imidazole) ruthenium (II) dichloride and/or 2- (2, 6-diethylphenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methylene ruthenium dichloride) is used for the ring-opening/cross-metathesis of norbornene and trans-5-decene to produce a polymer described below (wherein cat. is the metathesis catalyst and N is 1 to 100, preferably 1 to 50, preferably 1 to 10):

olefin metathesis catalysts

An olefin metathesis catalyst is a compound that catalyzes the reaction between a cyclic olefin and a linear monoolefin to produce a polymer represented by formula (X).

In a preferred embodiment, the olefin metathesis catalyst is represented by formula (I):

wherein:

m is a group 8 metal, preferably Ru or Os, preferably Ru;

x and X¹Independently any anionic ligand, preferably halogen (preferably chlorine), alkoxy, or triflate, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l and L¹Independently a neutral two electron donor, preferably a phosphine or an N-heterocyclic carbene, L and L¹May be linked to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l and X may be linked to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

L¹and X¹May be linked to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

r and R¹Independently is hydrogen or C₁-C₃₀Substituted or unsubstituted hydrocarbyl (preferably C)₁-C₃₀Substituted or unsubstituted alkyl or substituted or unsubstituted C₄-C₃₀Aryl groups of (a);

R¹and L¹Or X¹May be linked to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; and

r and L or X may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

Preferred alkoxy groups include those wherein the alkyl group is phenol, substituted phenols (wherein the phenol may be substituted with up to 1, 2,3,4 or 5C₁-C₁₂Is substituted with a hydrocarbon group) or C₁-C₁₀Hydrocarbyl, preferably C₁-C₁₀Alkyl, preferably methyl, ethyl, propyl, butyl or phenyl.

Preferred phosphines are represented by the formula PR³'R⁴'R⁵', wherein R³' is secondary alkyl or cycloalkyl (preferably C)₃-C₁₂Secondary alkyl or cycloalkyl), and R⁴' and R⁵' is aryl, C₁-C₁₀Primary alkyl, secondary alkyl or cycloalkyl. R4 'and R5' may be the same or different. Preferred phosphines include P (cyclohexyl) 3, P (cyclopentyl) 3 and/or P (isopropyl) 3.

Preferred triflates are represented by formula (II):

wherein R is²Is hydrogen or C₁-C₃₀Hydrocarbyl, preferably C₁-C₁₂Alkyl, preferably methyl, ethyl, propyl, butyl or phenyl.

Preferred N-heterocyclic carbenes are represented by formula (III) or formula (IV):

wherein:

each R is⁴Independently a hydrocarbyl or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl,

alkyl, adamantyl, phenyl, benzyl, toluyl, chlorophenyl, phenol, substituted phenol or CH₂C(CH₃)₃And are

Each R is⁵Is a hydrogen atom, and is,halogen or C₁-C₁₂Hydrocarbyl, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl or phenyl.

In other useful embodiments, one of the N groups bound to the carbene in formula (III) or (IV) is replaced with S, O or a P atom, preferably a S atom.

Other useful N-heterocyclic carbenes include the compounds described in Hermann, W.A.Chem.Eur.J.,1996,2, pages 772 and 1627, Enders, D et al, Angew.Chem.Int.Ed.,1995,34, page 1021, Alder R.W., Angew.Chem.Int.Ed.,1996,35, page 1121, and Bertrand, G et al, chem.Rev.,2000,100, page 39.

In preferred embodiments, the olefin metathesis catalyst is one or more of the following: tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) imidazol-2-ylidene ] [ 3-phenyl-1H-inden-1-ylidene ] ruthenium (II) dichloride, tricyclohexylphosphine [ 3-phenyl-1H-inden-1-ylidene ] [1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydro-imidazol-2-ylidene ] ruthenium (II) dichloride, tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene ] [ (phenylthio) methylene ] ruthenium (II) dichloride, bis (tricyclohexylphosphine) -3-phenyl-1H-inden-1-ylideneruthenium (II) dichloride, 1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methyleneruthenium (II) dichloride and [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] - [2- [ [ (4-methylphenyl) imino ] methyl ] -4-nitrophenol (phenyl) ] - [ 3-phenyl-1H-inden-1-ylidene ] ruthenium (II) chloride. In a preferred embodiment, the catalyst is 1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methyleneruthenium (II) dichloride and/or tricyclohexylphosphine [ 3-phenyl-1H-inden-1-ylidene ] [1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene ] ruthenium (II) dichloride.

In another embodiment, the olefin metathesis catalyst is represented by the formula (I) above, where M is Os or Ru and R¹Is hydrogen, X and X¹May be different or identical and may be any anionic ligand, L and L¹May be different or the sameAnd is any neutral electron donor, and R may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R is preferably hydrogen, C₁-C₂₀Alkyl or aryl. C₁-C₂₀The alkyl group may optionally be substituted with one or more aryl, halogen, hydroxy, C₁-C₂₀Alkoxy or C₂-C₂₀Alkoxycarbonyl is substituted. The aryl group may optionally be substituted by one or more C₁-C₂₀Alkyl, aryl, hydroxy, C₁-C₅Alkoxy, amino, nitro or halogen substitution. L and L¹Preferably of the formula PR³'R⁴'R⁵' the phosphine of (A), wherein R³' is secondary alkyl or cycloalkyl, and R⁴' and R⁵' is aryl, C₁-C₁₀Primary alkyl, secondary alkyl or cycloalkyl. R⁴' and R⁵' may be the same or different. L and L¹Preferably identical and are-P (cyclohexyl) 3, -P (cyclopentyl) 3 or-P (isopropyl) 3. X and X¹Most preferably the same and chlorine.

In another embodiment of the present invention, the olefin metathesis catalyst is a compound of carbene ruthenium and/or carbene osmium represented by formula (V):

wherein M is Os or Ru, preferably Ru X, X¹L and L¹As described above, and R⁹And R¹⁰May be the same or different and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl. R⁹And R¹⁰The groups may optionally include one or more of the following functional groups: alcohols, thiols, ketones, aldehydes, esters, ethers, amines, imines, amides, nitro groups, carboxylic acids, disulfides, carbonates, isocyanates, carbodiimides, carboalkoxy groups, and halogens. Such compounds and their synthesis are described, inter alia, in U.S. patent No.6,111,121.

In another embodiment, the olefin metathesis catalyst that may be used herein may be any of the catalysts described in U.S. Pat. Nos.6,111,121, 5,312,940, 5,342,909, 7,329,758, 5,831,108, 5,969,170, 6,759,537, 6,921,735, and U.S. Pat. publication No.2005-0261451A1, including, but not limited to, benzylidene-bis (tricyclohexylphosphine) dichlororuthenium, benzylidene [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro (tricyclohexylphosphine) ruthenium, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium (II), (1, 3-bis- (2,4, 6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium, 1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] dichloro (2-isopropoxyphenylmethylene) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro [3- (2-pyridinyl) propylidene ] ruthenium (II), [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro (3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium (II), and [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro (benzylidene) bis (3-bromopyridine) ruthenium (II).

In another embodiment, the olefin metathesis catalyst is represented by the formula:

wherein:

m is a group 8 metal, preferably Ru or Os, preferably Ru;

x and X¹Independently any anionic ligand, preferably a halogen (preferably chlorine), alkoxy or alkyl sulfonate group, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l is N-R, O, P-R or S, preferably N-R or O (R is C)₁-C₃₀Hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethylPropyl or butyl);

r is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl, preferably methyl;

R¹*、R²*、R³*、R⁴*、R⁵*、R⁶*、R⁷a and R⁸Independently is hydrogen or C¹-C³⁰Hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R¹*、R²*、R³A and R⁴Is methyl;

each R is⁹A and R¹³Independently is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl, preferably C₂-C₆Preferably ethyl;

R¹⁰*、R¹¹*、R¹²independently is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl;

each G is independently hydrogen, halogen or C₁-C₃₀Substituted or unsubstituted hydrocarbyl (preferably C)₁-C₃₀Substituted or unsubstituted alkyl or substituted or unsubstituted C₄-C₃₀Aryl groups); and

wherein any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or up to₃₀A multinuclear ring system of non-hydrogen atoms.

Preferably, any two adjacent R groups may form a fused ring having 5 to 8 non-hydrogen atoms. Preferably, the non-hydrogen atoms are C and/or O. Preferably, adjacent R groups form a fused ring of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms. Adjacent means that any two R groups are next to each other, e.g. R³A and R⁴May form a ring and/or R¹¹A and R¹²May form a ring.

In a preferred embodiment, the olefin metathesis catalyst compound includes one or more of the following: 2- (2, 6-diethylphenyl) -3,5,5, 5-tetramethylpyrrolidine [ 2]- (Isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2-, (

3,3,5, 5-Tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2- (2-isopropyl) -3,3,5, 5-tetramethyl pyrrolidine [2- (isopropyl) -5- (N, N-dimethyl amino sulfonyl) phenyl]Methylene ruthenium dichloride, 2- (2, 6-diethyl-4-fluorophenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride or mixtures thereof.

For further information on such olefin metathesis catalysts, please see USSN12/939054 filed 11/3/2010, claiming priority and benefit of USSN61/259,514 filed 11/9/2009.

Many of the above named catalysts are commonly available from Sigma-Aldrich Corp. (st. louis, MO) or Strem Chemicals, Inc. (Newburyport, MA).

In a particularly preferred embodiment, ruthenium (II) chloride (1-cyclohexylmethyl-3- (2, 6-diisopropylphenyl) -4, 5-dihydro-1H-imidazole) and/or ruthenium (2- (2, 6-diethylphenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methylene dichloride are used as metathesis catalyst.

In another embodiment of the invention, the olefin metathesis catalyst is a group 8 carbene compound represented by formula (VIII):

wherein:

m is a group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);

each X is independently an anionic ligand (preferably selected from the group consisting of halogen, alkoxy, aryloxy and alkylsulfonate, preferably halogen, preferably chlorine);

R¹and R²Independently selected from hydrogen, C₁-C₃₀Hydrocarbyl and C₁-C₃₀Substituted hydrocarbyl (preferably R)¹And R²Independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl and substituted analogues and isomers thereof, preferably selected from the group consisting of t-butyl, sec-butyl, cyclohexyl and cyclooctyl);

R³and R⁴Independently selected from hydrogen, C₁-C₁₂Hydrocarbyl, substituted C₁-C₁₂Hydrocarbyl and halogen (preferably R)³And R⁴Independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of t-butyl, sec-butyl, cyclohexyl, and cyclooctyl), and

l is a neutral donor ligand, preferably L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, and,

Ethers, amines, imines, sulfoxides, carboxyls, nitrosyl, pyridines, thioesters, cyclic carbenes, and substituted analogs thereof; preferably a phosphine, a sulfonated phosphine, an N x-heterocyclic carbene, a cyclic alkylamino carbene and substituted analogues thereof (preferably L is selected from the group consisting of phosphine, N-heterocyclic carbene, cyclic alkylamino carbene and substituted analogues thereof). For more information on these catalysts, please see USSN13/149012 filed 5/31/2011.

For purposes of the present invention and the appended claims, a "cyclic carbene" may be defined as a cyclic compound having a neutral bidentate carbon center, characterized by a single pair of electrons. Such cyclic carbenes may be represented by the following formula (IX):

wherein:

n is a linking group comprising 1 to 4 ring vertices (ring vertices) selected from C, Si, N, P, O and S, and may be occupied by valences optionally occupied by H, oxo (oxo), hydrocarbyl or substituted hydrocarbyl; preferably, n comprises two ring vertices having carbons with available valences occupied by H, oxo, hydrocarbyl or substituted hydrocarbyl; preferably, n is C₂H₂、C₂H₄Or substituted variants thereof;

each E is independently selected from C, N, S, O and P, and available valency is optionally occupied by Lx, Ly, Lz and Lz'; preferably, at least one E is C; preferably, one E is C and the other E is N; preferably, both E are C; and

lx, Ly, Lz and Lz' are independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl; preferably, Lx, Ly, Lz and Lz' are independently selected from hydrocarbyl and substituted hydrocarbyl groups having 1 to 40 carbon atoms; preferably, Lx, Ly, Lz and Lz' are independently selected from C_1-10Alkyl, substituted C_1-10Alkyl radical, C_2-10Alkenyl, substituted C_2-10Alkenyl radical, C_2-10Alkynyl, substituted C_2-10Alkynyl, aryl and substituted aryl; preferably, Lx, Ly, Lz and Lz' are independently selected from the group consisting of: methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl,

Phenyl, benzyl, toluyl, chlorophenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3, 5-di-tert-butylphenyl, 2-tert-butylphenyl and 2,3,4,5, 6-pentamethylphenyl. Useful substituents include C_1-10Alkyl radical, C_2-10Alkenyl radical, C_2-10Alkynyl, aryl, heteroaryl,C_1-10Alkoxy radical, C_2-10Alkenyloxy radical, C_2-10Alkynyloxy, aryloxy, C_2-10Alkoxycarbonyl group, C_1-10Alkylthio radical, C_1-10Alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imino, azacyclo, hydroxy, thiol, thiocarbonyl, phosphorous (phosphorus) and carbene.

Examples of cyclic carbenes useful in embodiments of the invention include:

wherein Lx, Ly and Lz are as defined above.

In some embodiments, at least two of Lx, Ly, Lz and Lz' may be joined to form a 3-12 membered spiro cyclic ring, and may be occupied by valences optionally occupied by H, oxo, halogen, hydrocarbyl or substituted hydrocarbyl. Useful substituents include C_1-10Alkyl radical, C_2-10Alkenyl radical, C_2-10Alkynyl, aryl, C_1-10Alkoxy radical, C_2-10Alkenyloxy radical, C_2-10Alkynyloxy, aryloxy, C_2-10Alkoxycarbonyl group, C_1-10Alkylthio radical, C_1-10Alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imino, azacyclo, hydroxy, thiol, thiocarbonyl, phosphorous, and carbene.

Preferred cyclic carbenes include N-heterocyclic carbenes (N HC). For purposes of the present invention and appended claims, N HC is a cyclic carbene of the type described above by formula IX, wherein each E is N and the available valences on N are occupied by Lx and Ly. Preferred N + HC may be represented by the formula

Wherein:

n, Lx and Ly are as shown above in formula (IX).

Some particularly useful N + HCs include

Wherein Lx and Ly are as described above. Other useful N + HCs include the compounds described in Hermann, W.A.chem.Eur.J.1996,2,772 and 1627, Enders, D.et al, Angew.chem.int.Ed.1995,34,1021, Alder R.W., Angew.chem.int.Ed.1996,35,1121, USSN61/314,388, and Bertrand, G.et al, chem.Rev.2000,100, 39.

Particularly preferred cyclic carbenes include cyclic alkylamino carbenes (CAACs). In all embodiments herein, the CAAC is a cyclic carbene of the type described by formula (IX) above, wherein one E is N and the other E is C, and the available valencies on N and C are occupied by Lx, Ly and Lz. CAAC may be represented by the following formula:

wherein

n, Lx, Ly and Lz are as described above for formula (IX).

Some particularly useful CAACs include:

other useful CAACs include those described in U.S. Pat. No.7,312,331, USSN61/259,514, and Bertrand et al, Angew.chem.int.Ed.2005,44,7236-.

Cyclic olefins

The cyclic olefin can be a single cyclic olefin or a combination of cyclic olefins, which is a mixture of two or more cyclic olefins. The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. Suitable cyclic olefins include, but are not limited to, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, and substituted derivatives derived therefrom. Illustrative examples of suitable substituents include, but are not limited to, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, halogen. Preferred cyclic olefins include cyclooctene, 1, 5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, preferably norbornene, norbornadiene, and dicyclopentadiene.

In a preferred embodiment, the cyclic olefin is a strained olefin. Alternatively, the cyclic olefin is polycyclic. For the purposes of classification, dicyclopentadiene, norbornene, norbornadiene, ethylidene norbornene and vinyl norbornene are polycyclic.

In a preferred embodiment, the cyclic olefin is based on C₅The cyclic olefin of (1). Based on C₅The cyclic olefin of (A) is an olefin (preferably C)₅-C₂₀Olefins) derived from substituted or unsubstituted cyclopentadiene such as dicyclopentadiene, norbornene, norbornadiene, ethylidene norbornene, vinyl norbornene, and the like.

Linear mono-olefins

Any linear mono-olefin may be used in the metathesis reaction described herein. For example, alpha-olefins may be used. For the purposes of the present invention and the appended claims, the term "alpha-olefin" refers to an olefin in which a carbon-carbon double bond occurs between the alpha and beta carbons of the chain. The alpha-olefin may be represented by the formula H₂C = CH-R, wherein each R is independently hydrogen or C₁-C₃₀Hydrocarbyl radical, preferably C₂-C₂₀Hydrocarbyl radical, preferably C₃-C₁₂Preferably methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and substituted analogues thereof. For example, 1-pentene, 1-hexene, 1-heptene, and 1-decene are particularly useful alpha olefins in embodiments herein.

In other embodiments, internal olefins may be used. For the purposes of the present invention and appended claims, the term "internal olefin" means a double bond that is not vinyl, vinylidene (vinylidene), or vinylidene (vinylidene) unsaturation, preferably the term "internal olefin" means an olefin in which the double bond does not occur between the alpha and beta carbons of the chain. The internal olefin may be represented by the formula: r HC = CH-R, wherein each R is independently C₁-C₃₀Preferably C₂-C₂₀Hydrocarbyl radical, preferably C₂-C₁₂Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl and substituted analogues thereof. For example, hex-2-ene, hept-3-ene, dec-5-ene are particularly suitable for use in embodiments herein.

The linear monoolefin can also be substituted with one or more substituents at any position along the carbon chain. In some embodiments, the one or more substituents are substantially inert with respect to the metathesis process. Suitable substituents include, but are not limited to, alkyl, preferably C_1-6Alkyl, cycloalkyl, preferably C_3-6Cycloalkyl, and hydroxyl, ether, ketone, aldehyde, and halogen functional groups.

Preferred linear mono-olefins include ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and isomers thereof (particularly isomers wherein the double bond is in the alpha-position and isomers wherein the double bond is not in the alpha-position).

Particularly preferred linear mono-olefins include dec-5-ene, 1-pentene, 1-decene and 1-octene.

Any of the isomers of the linear mono-olefins are useful herein. In some embodiments, cis-isomers and/or trans-isomers may be used.

Polymer and method of making same

The polymers produced herein preferably have at least 30 wt% (preferably at least 40 wt%, preferably at least 50 wt%, preferably at least 60 wt%, preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt%, preferably at least 99 wt% of C20 and higher polymers (or C25-C2500, or C30-C2000, or C40-C1500, or C50-C1000, or C100-C900, or C200-C800) based on the weight of the product produced.

The polymers produced herein can be hydrogenated by contacting the polymer with hydrogen and a hydrogenation catalyst. This hydrogenation step is generally used to reduce the bromine number (to preferably below 2.0, preferably below 1.8). Bromine number is determined by ASTM D1159. In a preferred embodiment, the bromine number of the hydrogenated polymer is reduced by at least 50% (preferably at least 75%) compared to the starting polymer.

Preferably, the hydrogenation catalyst is selected from the group consisting of supported group 7, 8, 9 and 10 metals, preferably the hydrogenation catalyst is selected from one or more of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo and W supported on silica, alumina, clay, titania, zirconia or mixed metal oxide supports. Preferred hydrogenation catalysts are nickel supported on kieselguhr, or platinum or palladium supported on alumina, or cobalt-molybdenum supported on alumina. Typically, high nickel content catalysts are used, such as 60% Ni on Kieselguhr catalysts, or supported catalysts with substantial Co — Mo loading. Alternatively, the hydrogenation catalyst is nickel supported on Kieselguhr, silica, alumina, clay or silica-alumina.

In a preferred embodiment, the polymer is contacted with hydrogen, preferably at a hydrogen pressure of 25psi to 2500psi (0.17MPa to 17.24MPa), preferably 100-. The hydrogenation process may be accomplished in a slurry reactor operated in batch or in a Continuous Stirred Tank Reactor (CSTR) wherein the catalyst, hydrogen and polymer are continuously added to the reactor for a residence time, typically 5 minutes to 10 hours, to allow complete hydrogenation of the unsaturated olefins. The amount of catalyst added is generally very small, for example, from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight, of the polymer feed, merely to compensate for catalyst deactivation. The catalyst and the hydrogenated polymer are continuously withdrawn from the reactor. The product mixture may then be filtered, centrifuged or settled to remove the solid hydrogenation catalyst. The catalyst can be regenerated and reused.

The hydrogenation process can also be carried out by a fixed bed process, in which a solid catalyst is packed in a tubular reactor and heated to the reactor temperature.

In a preferred embodiment, hydrogenation of the polymers produced herein (e.g., pentene-terminated norbornene polymers) produces products that are useful as lubricants.

In another embodiment, the novel lubricant comprises the polymer produced in the present invention alone or together with one or more other base stocks, including group I to group V base stocks having a viscosity of 1.5 to 100cSt at 100 ℃ to formulate an appropriate viscosity grade. In addition, one or more of thickeners, viscosity index improvers, antioxidants, anti-wear additives, detergent/dispersant/inhibitor wraps, and/or anti-rust additives may be added. In a preferred embodiment, the polymers produced herein are combined with one or more of dispersants, detergents, friction modifiers, traction modifying additives, demulsifiers, defoamers, chromophores (dyes), and/or haze inhibitors. These well-formulated lubricants can be used in automotive crankcase oils (engine oils), industrial oils, greases, or gas turbine engine oils. There are examples of additives used to refine lubricant formulations. Further information on additives used for the preparation of products can be found in "Lubricants and Lubricants", ed.by t.mang and w.dresel, Wiley-VCH GmbH, Weinheim 2001.

The polymers prepared herein can be functionalized by reacting heteroatom-containing groups (preferably amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and/or maleic anhydride) with the polymer, with or without a catalyst. Examples include catalytic hydrosilation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination (hydroxylation), or maleation, with or without an activator such as a free radical initiator (generator) (e.g., peroxide). In some embodiments, the polymers produced herein are functionalized as described in U.S. patent No.6,022,929, a.toyota, t.tsutsutsuti, and n.kashiwa, Polymer Bulletin48, pp 213-219,2002, j.am.chem.soc.,1990,112, pp 7433-7434, and USSN12/487,739 (disclosed in WO 2009/155472) filed on 6/19 th 2009.

The functionalized polymers may be used in lubricants, oil additives, and many other applications.

The choice of cyclic olefin and linear mono-olefin for the ROCM reaction may allow for tailoring (tailoring) of the resulting polymer. The use of olefins having protected functional groups, such as TBS-protected 4-penten-1-ol, may allow the introduction of functional groups into the capped poly (cyclic olefin). Some examples of functionalized polymers include those functionalized with maleic acid or maleic anhydride groups. Functionalized polymers may also be derivatized with derivative compounds as described in U.S. Pat. Nos.6,022,929, A.Toyota, T.Tsutsui, and N.Kashiwa, Polymer bulletin48,213-219,2002, and J.Am.chem.Soc.,1990,112,7433-. The derivatizing compound may be reacted with the functional groups of the functionalized capped polymer in any manner known in the art, such as nucleophilic substitution, Mannich base condensation, and the like. The derivatizing compound may be polar and/or comprise reactive derivatizing groups. Preferred derivative compounds are selected from the group consisting of hydroxyl-containing compounds, amines, metal salts, anhydride-containing compounds and acetyl halide-containing compounds. The derivatizing compound may comprise at least one nucleophilic group and preferably at least two nucleophilic groups. Exemplary derivatized end-capped polymers can be prepared by contacting a functionalized end-capped polymer (e.g., a polymer substituted with a carboxylic acid/anhydride or ester) with an affinity reagent (e.g., an amine, an alcohol (including polyols), an amino alcohol, a reactive metal compound, etc.). (for more information see U.S. patent No.6,022,929, column 33, line 27 to column 74, line 63).

In another embodiment, the present invention relates to:

1. a polymer represented by formula (X):

2. The polymer of paragraph 1, wherein R¹And R²May be the same or different and are each a hydrocarbon group having 1 to 12 carbon atoms; r³And R⁴May be the same or different and are each hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, with the proviso that R³And R⁴May be joined to form a five or six membered ring; and n is an integer of 1 to 60.

3. The polymer of paragraph 1 or 2, wherein R³Is hydrogen and R⁴Is ethylidene, or wherein R³Is hydrogen and R⁴Is hydrogen.

4. The polymer of paragraph 1 or 2, wherein R³And R⁴Form C₅Or C₆Cyclic group, preferably C₅The cyclic groups, preferably pentane and/or pentene, preferably the pentane rings in formula (X) are fully or partially saturated, or fully unsaturated.

5. The polymer of paragraph 1, 2,3 or 4, wherein R¹Is C_5-9Hydrocarbyl and R²Is C_5-9Hydrocarbyl, preferably C₅Or C₉A hydrocarbyl group.

6. The polymer of paragraph 1, 2,3,4 or 5, wherein R¹Is C9 hydrocarbyl, R²Is C₉Hydrocarbyl radical, R³And R⁴Is H and n is an integer from 1 to 100 (preferably from 1 to 50, preferably from 2 to 20, preferably from 4 to 10).

7. The polymer of paragraph 1, 2,3,4 or 5, wherein R¹Is C₅Hydrocarbyl radical, R²Is C₅Hydrocarbyl radical, R³And R⁴Is H and n is an integer from 1 to 100 (preferably from 1 to 50, preferably from 2 to 20, preferably from 4 to 10).

8. The polymer of any one of the above paragraphs 1 to 7, wherein R³And R⁴Forming cyclopentene.

9. The polymer of any one of the above paragraphs 1 to 7, wherein R³And R⁴Forming cyclopentane.

10. The polymer of paragraph 8 or 9, wherein R¹And R²Are identical and are C_5-9A hydrocarbyl group.

11. A method of making the polymer of any of the above paragraphs 1-10, the method comprising:

an olefin metathesis catalyst is contacted with a cyclic olefin and a linear monoolefin.

12. The process of paragraph 11, wherein the olefin metathesis catalyst is represented by formula (I) and/or formula (V):

wherein,

m is a group 8 metal; preferably Ru or Os, preferably Ru;

x and X¹Independently any anionic ligand, preferably halogen (preferably Cl), alkoxy or triflate, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l1 and X1 may be linked to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

r and R¹Independently is hydrogen or C₁-C₃₀Substituted or unsubstituted hydrocarbyl (preferably substituted or unsubstituted C)₁-C₃₀Alkyl or substituted or unsubstituted C₄-C₃₀Aryl groups);

R⁹and R¹⁰May be different or the same, and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;

13. The method of paragraph 12, wherein:

m is Ru or Os;

x and X¹Independently halogen, alkoxy or triflate, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l and L¹Independently a phosphine or an N-heterocyclic carbene, L and L¹May be linked to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

r and R¹Independently is hydrogen or C₁-C₃₀Substituted or unsubstituted alkyl or substituted or unsubstituted C₄-C₃₀An aryl group;

14. The process of paragraph 11, wherein the olefin metathesis catalyst is one or more of: tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) imidazol-2-ylidene][ 3-phenyl-1H-inden-1-ylidene group]Ruthenium (II) dichloride, tricyclohexylphosphine [ 3-phenyl-1H-inden-1-ylidene][1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydro-imidazol-2-ylidene]Ruthenium (II) dichloride, tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene][ (Phenylthio) methylene group]Ruthenium (II) dichloride, bis (tricyclohexylphosphine) -3-phenyl-1H-inden-1-ylideneruthenium dichloride(II), 1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium (II) dichloride, [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]- [2- [ [ (4-methylphenyl) imino group]Methyl radical]-4-nitrophenol radical]- [ 3-phenyl-1H-inden-1-ylidene]Ruthenium (II) chloride, benzylidene-bis (tricyclohexylphosphine) dichlororuthenium, benzylidene [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (tricyclohexylphosphine) ruthenium, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium (II), (1, 3-bis- (2,4, 6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium, 1, 3-bis (2-methylphenyl) -2-imidazolidinylidene]Dichloro (2-isopropoxyphenylmethylene) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro [3- (2-pyridyl) propylidene group]Ruthenium (II), [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene group]Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (benzylidene) bis (3-bromopyridine) ruthenium (II), 2- (2, 6-diethylphenyl) -3,5,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2-, (

3,3,5, 5-Tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2- (2-isopropyl) -3,3,5, 5-tetramethyl pyrrolidine [2- (isopropyl) -5- (N, N-dimethyl amino sulfonyl) phenyl]Methylene ruthenium dichloride and 2- (2, 6-diethyl-4-fluorophenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, and (1-cyclohexylmethyl-3- (2, 6-diisopropylphenyl) -4, 5-dihydro-1H-imidazole) ruthenium (II) chloride and 2- (2, 6-diethylphenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride.

15. The process of paragraph 11, wherein the olefin metathesis catalyst is represented by the formula:

wherein: m is a group 8 metal;

each X is independently an anionic ligand;

R¹and R²Independently selected from hydrogen, C₁-C₃₀Hydrocarbyl and C₁-C₃₀A substituted hydrocarbyl group;

R³and R⁴Independently selected from hydrogen, C₁-C₁₂Hydrocarbyl radical, C₁-C₁₂Substituted hydrocarbyl and halogen; and

l is a neutral donor ligand.

16. The process of paragraph 11, wherein the olefin metathesis catalyst is represented by the formula:

wherein:

m is a group 8 metal;

x and X¹Independently any anionic ligand, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l is N-R, O, P-R or S, (R is C)₁-C₃₀Hydrocarbyl or substituted hydrocarbyl);

r is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

R¹*、R²*、R³*、R⁴*、R⁵*、R⁶*、R⁷and R8The place is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

each R is⁹A and R¹³Independently is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

R¹⁰*、R¹¹*、R¹²independently is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

each G is independently hydrogen, halogen or C₁-C₃₀A substituted or unsubstituted hydrocarbyl group; and

wherein any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

17. The process of paragraph 11, wherein the olefin metathesis catalyst is represented by the formula:

wherein:

n is a linking group comprising 1-4 ring vertices selected from C, Si, N, P, O and S, and may be occupied by valences optionally occupied by H, oxo, hydrocarbyl or substituted hydrocarbyl;

each E is independently selected from C, N, S, O and P, and available valencies are optionally occupied by Lx, Ly, Lz and Lz'; and

lx, Ly, Lz and Lz' are independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl.

18. The process of any of paragraphs 11 to 17, wherein the linear monoolefin has from 4 to 12 carbon atoms.

19. The method of any of paragraphs 11-18, wherein the linear mono-olefin is an alpha-olefin and/or has an internal olefin (wherein the internal olefin is a cis-isomer or a trans-isomer).

20. The process of any of paragraphs 11-19, wherein the linear monoolefin is selected from the group consisting of pentene, hexene, octene, and decene.

21. The process of any of paragraphs 11-20, wherein the cyclic olefin is a strained cyclic olefin, preferably based on C₅Preferably selected from the group consisting of norbornene, norbornadiene, ethylidene norbornene, dicyclopentadiene and vinyl norbornene.

22. The polymer of any one of paragraphs 1 to 10 or produced by the process of any one of paragraphs 1 to 21, wherein the polymer has been hydrogenated or functionalized.

23. A lubricant comprising the polymer of any of paragraphs 1-10 or a polymer produced by the process of any of paragraphs 1-21 or 22.

24. A lubricant base stock comprising the polymer of any of paragraphs 1-10 or produced by the process of any of paragraphs 1-21 or 22.

Experiment of

Testing and materials

The following abbreviations are used in the examples: h is hours and min is minutes.

Gas chromatography

Gas chromatography was performed on Agilent6890 with J & W scientific DB-1 column (l =60m, ID =0.25mm, film thickness =1 μm) using Chemstation software (rev.b.02.01-SR 1).

1H NMR

All NMR data were collected at room temperature (approximately 23 ℃ C.) on a Bruker Avance III400MHz spectrum running Topspin3.0 software. Tetrachloroethane (d)₄) Used as solvent for all materials (chemical shift of 5.98ppm was used as reference).

The degree of ROMP relative to CM was calculated using 1H NMR spectra. The ratio of the integral of the methyl region to the integral of the olefin region is defined by the following relationship

Solving n as a function of R yields the following equation

n = \frac{3 - R}{R}

This equation helps estimate the size of the polymer produced by the ROMP/CM reaction.

General purpose

All reactions were carried out under an inert nitrogen atmosphere. The solvent was an anhydrous grade purchased from Sigma Aldrich, which was bubbled with nitrogen and stored on alumina beads (activated at 300 ℃) prior to use.

Ring opening cross metathesis of norbornene and trans-5-decene

2- (2, 6-diethylphenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride (1.2mgs) was slurried with 2.0 grams of trans-5-decene. Norbornene (0.3mL, 86.5 wt% in toluene) was added via syringe. The resulting solution was heated at 40 ℃ for about 12 hours. The resulting solution was exposed to air for 1 hour and then filtered through an alumina plug. The excess trans-5-decene was removed under vacuum and the resulting polymer was obtained as a colorless rubbery solid. 1H NMR (CDCl)₃) δ 5.34(m,1.0H),5.24(m,0.12H),5.19(d,0.65H),2.78(m, 77H),2.42(m,1.01H),1.80(m,2.72H),1.30(m,2.40H),1.04(m,0.90H),0.87(m, 0.44H). The degree of polymerization was calculated as 11.3.

Ring opening cross metathesis of norbornene and trans-5-decene

Ruthenium (II) (1.2mgs) chloride (1-cyclohexylmethyl-3- (2, 6-diisopropylphenyl) -4, 5-dihydro-1H-imidazole) was slurried with 4.8 grams of trans-5-decene. Norbornene (0.5mL, 86.5 wt% in toluene) was added via syringe. The resulting solution was heated at 40 ℃ for about 2 hours. The resulting solution was exposed to air for 1 hour and then filtered through an alumina plug. The excess trans-5-decene was removed under vacuum and the resulting polymer was obtained as a colorless viscous mass. 1H NMR (CDCl3) < delta > 5.34(m,1.0H),5.24(m,0.14H),5.19(d,0.51H),2.78(m,.62H),2.42(m,0.92H),1.80(m,2.71H),1.30(m,2.45H),1.04(m,0.81H),0.87(m, 0.63H). The degree of polymerization was calculated to be 7.

ROCM of dicyclopentadiene and 1-pentene

The 3L reaction vessel was kept under vacuum at 70 ℃ overnight in a fume hood to dry the inside. Before use, all solvents and reagents were in N₂Degassed under flow and stored under alumina beads. An oven dried 1000mL round bottom flask was charged with 400mL 1-pentene and 331g dicyclopentadiene (DCPD). The reaction vessel was cooled to 0 ℃ with an ice bath and a mixture of pentene and DCPD was added via cannula. 450mL of CH was added via cannula₂Cl₂. In the drybox, the oven-dried addition funnel was charged with { [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene } (1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene) ruthenium dichloride (180mg) in 100mL CH₂Cl₂The solution of (1). The addition funnel was then connected to the reaction apparatus and placed under an atmosphere of N2. The catalyst solution was added to the reaction mixture which was stirred for more than 40 minutes. The slow addition allowed the temperature to remain at 25 ℃. The reaction was kept stirring at 0 ℃ for another 1 hour. The reaction was then heated to reflux for 4 hours. As the reaction proceeds, more heat is required to generate reflux. However, GC analysis at 1h, 2h and 4h showed no significant change in conversion. The reaction was then cooled to room temperature and stirred over the weekend.

The reaction mixture was filtered through a silica plug and the lightest component was removed with a rotary evaporator. The resulting oil was subjected to Kugelrohr distillation (170 ℃ C. at 60mTorr (8Pa)), and 251.6g remained in the still as a yellow oil. Collecting another 120g at room temperature while collecting at 0 deg.CThe material is discarded. Heavy residual oil: 1H NMR250MHz (CDCl)₃):δ5.9(m,1H),5.2-5.8(m,8.2H),4.9-5.0(m,1.9H),3.25(m,1.7H),2.8(m,3.3H),2.6(m,2.8H),1.75-2.4(m,7.8H),1.5-1.6(m,3.4H),1.0-1.4(m,4.9H),0.88(m,3.8H)。GCMS:C₁₅H₂₂(9％),C₁₈H₂₈(16%), unknown Components (17%), C₂₂H₂₈(11％),C₂₅H₃₄(39％),C₂₈H₄₀(2%) light oil: (60 mTorr at 145 ℃),1H NMR-250MHz (CDCl)₃):δ5.9(m,1H),5.2-5.8(m,4.1H),4.9-5.0(m,2.1H),3.25(m,0.99H),2.8(m,1.3H),2.6(m,1.8H),1.75-2.4(m,4.1H),1.5-1.6(m,1.6H),1.0-1.4(m,3.1H),0.88(m,2.9H)。GCMS:C₁₂H₁₆(24％),C₁₅H₂₂(42％),C₁₈H₂₈(21%), unknown Components (21%), C₂₂H₂₈(0.5％)。

Hydrogenation of ROCM DCPD/1-pentene oligomers

In the dry box, 84.52g of heavy material from the previous reaction was charged to a 400mL Parr high pressure cylinder. Then 60mL of hexane and 1.95g 10% Pd on carbon were added. Parr high pressure cylinders were charged with approximately 800psi (5.5MPa) H₂Heated to 55 ℃ and stirred for 4.5 hours. When the pressure drops, repeatedly pressurizing the Parr high-pressure steel cylinder until the pressure is H₂Is no longer consumed. At this point, the reaction is considered complete. The Parr bomb was then cooled to room temperature and approximately 30g of Celite was added to the reaction mixture. The resulting mixture was filtered over a Celite bed and combined with pentane and CH₂Cl₂Washing is carried out for several times. The resulting solution was concentrated under vacuum overnight at 35 ℃ to give 74g of a clear, colorless oil.¹H NMR-250MHz(C₆D₆):δ2.4(m,1.2H),1.0-2.2(m,9.75H),0.8-1.0(m,1.8H)。GCMS:C₁₈H₃₄(2％),C₂₂H₃₈(11％),C₂₅H₄₄(79％),C₂₈H₅₀(7％)。

ROCM of dicyclopentadiene and 1-decene

Approximately 42.4g of 1-decene was charged to a 500mL3 neck round bottom flask. 1mg/mL of { [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl group was obtained]Methylene } (1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene) ruthenium dichloride catalyst. The ruthenium catalyst was measured in a volume of 5mL and added to 25mL of dichloromethane. The catalyst in dichloromethane was added to the addition funnel. Approximately 20g of dicyclopentadiene (DCPD) was weighed and dissolved with methylene chloride and placed in a second addition funnel. The total volume of DCPD and dichloromethane was less than 50 mL. The addition funnel was labeled with approximately five equal volumes. The round bottom flask was placed in an oil bath at 50.5 deg.C (working temperature 50 deg.C-52 deg.C). At the beginning of the reaction, the catalyst in half of the dichloromethane was added to the 1-decene. Immediately after the catalyst addition, DCPD was added dropwise to 1-decene. The reaction was then placed in an oil bath at 50 ℃. An additional 5.0mL, 1-mg/mL of catalyst was added and the reaction was held at 50 ℃ for approximately 24 hours. 26.5 g of oil are obtained. GC analysis showed the product to contain 18 mol% C18 (9-octadecene), 30 mol% C20 and 50 mole%>C20。¹H NMR(CDCl3):δ5.9(m,0.31H),5.7(m,1.02H),5.2-5.6(m,3.78H),5.0(m,0.63H),3.22(m,1.0H),2.8(m,1.58H),2.6(m,1.47),2.25(m,2.09H),2.0(m,2.07H),1.6(m,1.06H),1.1-1.4(m,13.1H),0.88(t,3H)。

ROMP/CM of 5-vinyl-2-norbornene and 1-decene

An amount of 70.0 grams of 1-decene was weighed and placed in a 500mL, 3-necked round bottom flask and placed in an oil bath at 50 ℃. A20 gram amount of 5-vinyl-2-norbornene (VNB) was weighed and placed in the addition funnel. An amount of 5mg of { [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methylene } (1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene) ruthenium dichloride was dissolved in 1ml of dichloromethane and added to 1-decene. Immediately after the catalyst addition, Vinylnorbornene (VNB) was then slowly added dropwise to the 1-decene and catalyst solution. The reaction was stirred at 50 ℃ for 72 hours. Dichloromethane and silica were added to the product, allowed to stir at ambient temperature for 4 hours, and filtered through a frit to remove the catalyst. The solvent is removed by vacuum and/or evaporation by nitrogen purge. The final weight of the product was 33.74g (. about.38% yield). 1H NMR (CDCl3) < delta > 5.75(m,0.28H),5.2-5.6(m,2.69H),4.8-5.0(m,0.57H),2.9(m,0.32H),2.4-2.7(m,1.43H),1.9(m,3.10H),1.5-1.8(m,0.57H),1.29(m,13.15H),0.88(t, 3H).

Ring opening cross metathesis of ethylidene norbornene and 1-hexene

5mg of [ (HP (C4H9)2)2Ru (C5H8) Cl2] were dissolved in 1mL of anhydrous nitrogen purged toluene. About 11.7g 1-hexene were added to the Ru-catalyst in a 500mL 3-necked round bottom flask with a stir bar. Approximately 50g of Ethylidenenorbornene (ENB) was added to the addition funnel on the round bottom flask. 1-1.5mL of GC samples were taken from the 1-hexene and ENB solutions each time. The ENB solution was added to 1-hexene and Ru-catalyst in a dropwise manner. The addition funnel was labeled at approximately five equal volumes. After each labeling, 1-1.5mL of GC sample was removed from the reaction in the round bottom flask. The product was left to stand overnight. About 10mL of methylene chloride and less than 1g of silica were added to the product. The solution was stirred for about 4 hours. The solution was filtered using a glass frit using a weak vacuum. The resulting solution was then placed in an oil bath purged with nitrogen at 60 ℃. The percent conversion was 65% and included product loss during the transfer(s).

All documents described herein, including any priority documents, related applications and/or test procedures, are incorporated by reference herein to the extent they are not inconsistent herewith, provided however that any priority document not specified in the initially filed application or filing document is not incorporated by reference herein. While forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention, as will be apparent from the foregoing general description and the specific embodiments. Accordingly, it is not intended that the invention be limited thereto. Likewise, for purposes of australian law, the term "comprising" is considered synonymous with the term "including". Likewise, whether a composition, element, or group of elements is directed by the conjunction "comprising," it is understood that we also contemplate the recitations of the same composition or group of elements as the conjunction "consisting essentially of …," "consisting of …," "selected from" or "being," and vice versa.

Claims

1. A polymer represented by formula (X):

wherein the dotted line represents an optional double bond; x is 0 or 1; r¹And R²May be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms; r³And R⁴May be identical or different and are each hydrogen or have from 1 to 40 carbon atomsOr R is a hydrocarbon group³And R⁴Can be represented by the above formula (X), provided that R³And R⁴May be joined to form a five or six membered ring; and n is an integer of 1 to 100.

2. The polymer of claim 1, wherein R¹And R²Each being an alkyl group having 1 to 12 carbon atoms.

3. The polymer of claim 1, wherein R¹And R²Each being an alkyl group having 1 to 6 carbon atoms.

4. The polymer of claim 1, wherein R³And R⁴Each is hydrogen or a C1-C20 hydrocarbyl group.

5. The polymer of claim 1, wherein R³Is hydrogen and R⁴Is an ethylidene group.

6. The polymer of claim 1 wherein each pentane ring is saturated.

7. The polymer of claim 1, wherein R³And R⁴Forming a cyclic group.

8. The polymer of claim 1, wherein R¹And R²May be the same or different and are each a hydrocarbon group having 1 to 12 carbon atoms; r³And R⁴May be identical or different and are each hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms, with the proviso that R³And R⁴May be joined to form a five or six membered ring; and n is an integer of 1 to 60.

9. The polymer of claim 1, wherein R¹Is C_5-9Hydrocarbyl and R²Is C_5-9A hydrocarbyl group.

10. The polymer of claim 1, wherein R³And R⁴Forming cyclopentene and/or cyclopentane.

11. A process for preparing a polymer according to claim 1, which comprises reacting at least one C-base₅Is contacted with at least one linear mono-olefin having from 2 to 20 carbon atoms in the presence of an olefin metathesis catalyst.

12. The process of claim 11 wherein the linear monoolefin has from 4 to 12 carbon atoms.

13. The process of claim 11 wherein the linear monoolefin is an alpha-olefin.

14. The process of claim 11 wherein the linear monoolefin has an internal olefin.

15. The process of claim 14, wherein the internal olefin is a cis isomer.

16. The process of claim 11, wherein the olefin metathesis catalyst is selected from the group consisting of (1-cyclohexylmethyl-3- (2, 6-diisopropylphenyl) -4, 5-dihydro-1H-imidazole) ruthenium (II) chloride and 2- (2, 6-diethylphenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methylene ruthenium dichloride.

17. The method of claim 11, wherein the cyclic olefin is selected from the group consisting of norbornene, norbornadiene, ethylidene norbornene, dicyclopentadiene, and vinyl norbornene.

18. The process of claim 11 wherein the linear monoolefin is selected from the group consisting of pentene, hexene, octene and decene.

19. The method of claim 11, wherein the olefin metathesis catalyst is represented by formula (I):

wherein:

m is a group 8 metal;

l and L¹Being a neutral two electron donor, L and L¹May be linked to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

l and X may be linked to form a bidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

r and R¹Independently is hydrogen or C₁To C30 substituted or unsubstituted hydrocarbyl;

20. The method of claim 19, wherein:

m is Ru or Os;

x and X¹Independently halogen, alkoxy, triflate, or X and X¹May be linked to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

R¹and L¹Or X¹May be linked to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms, and

21. The method of claim 11, wherein the olefin metathesis catalyst is one or more of the following: tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) imidazol-2-ylidene][ 3-phenyl-1H-inden-1-ylidene group]Ruthenium (II) dichloride, tricyclohexylphosphine [ 3-phenyl-1H-inden-1-ylidene][1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydro-imidazol-2-ylidene]Ruthenium (II) dichloride, tricyclohexylphosphine [1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene][ (Phenylthio) methylene group]Ruthenium (II) dichloride, bis (tricyclohexylphosphine) -3-phenyl-1H-indene-1-ylideneruthenium (II) dichloride, 1, 3-bis (2,4, 6-trimethylphenyl) -4, 5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium (II) dichloride, [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]- [2- [ [ (4-methylphenyl) sulfineAmino group]Methyl radical]-4-nitrophenol radical]- [ 3-phenyl-1H-inden-1-ylidene]Ruthenium (II) chloride, benzylidene-bis (tricyclohexylphosphine) dichlororuthenium, benzylidene [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (tricyclohexylphosphine) ruthenium, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium (II), (1, 3-bis- (2,4, 6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium, 1, 3-bis (2-methylphenyl) -2-imidazolidinylidene]Dichloro (2-isopropoxyphenylmethylene) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro [3- (2-pyridyl) propylidene group]Ruthenium (II), [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene group]Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium (II), [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene]Dichloro (benzylidene) bis (3-bromopyridine) ruthenium (II), 2- (2, 6-diethylphenyl) -3,5,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2-, (

3,3,5, 5-Tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride, 2- (2-isopropyl) -3,3,5, 5-tetramethyl pyrrolidine [2- (isopropyl) -5- (N, N-dimethyl amino sulfonyl) phenyl]Methylene ruthenium dichloride and 2- (2, 6-diethyl-4-fluorophenyl) -3,3,5, 5-tetramethylpyrrolidine [2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]Methylene ruthenium dichloride.

22. The method of claim 1, wherein the olefin metathesis catalyst is represented by the formula

Wherein:

m is a group 8 metal;

each X is independently an anionic ligand;

l is a neutral donor ligand.

23. The method of claim 1, wherein the olefin metathesis catalyst is represented by the formula

Wherein:

m is a group 8 metal;

r is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

R¹*、R²*、R³*、R⁴*、R⁵*、R⁶*、R⁷a and R⁸Independently is hydrogen or C₁-C₃₀Hydrocarbyl or substituted hydrocarbyl;

24. The method of claim 1, wherein the olefin metathesis catalyst is represented by the formula

Wherein:

25. A lubricant or lubricant base stock comprising the polymer of claim 1.

26. The polymer of claim 1, wherein the polymer has been hydrogenated or functionalized.

27. A lubricant or lubricant base stock comprising the polymer of claim 26.