CATALYTIC SYSTEM FOR PREPARATION OF HIGH BRANCHED ALKANE FROM OLEFINS

Abstract

The present invention discloses a catalytic system for preparing highly branched alkane from olefin, which contains novel nickel or palladium complexes. In the presence of the catalytic system, highly branched oily alkane mixture can be efficiently obtained from olefins (such as ethylene) under mild conditions. The alkane mixture has a low bromine number, and can be used as a processing aid(s) and lubricant base oil with high-performance. Provides also was a method for preparing the catalyst and a method for preparing an oily olefin polymer.

Claims

1-25. (canceled)

26. A process for preparing oily polyolefin, wherein comprising the following steps: (a) In the presence of a complex(es) as a catalyst for olefin polymerizatrion, catalyzing olefin polymerization, thereby forming an oily polyolefin; said complex(es) is formed by the following compound and a salt(s) of divalent metal selected from the following group: nickel, palladium or the combination thereof: ##STR00059## wherein, Z is hydrogen, C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 haloalkyl, unsubstituted or substituted phenyl; Y is unsubstituted or substituted phenyl; or Z and Y together with the adjacent carbon atom form an unsubstituted or substituted group selected from the following group: acenaphthyl, phenanthryl, and C.sub.5-C.sub.8 cycloalkyl, wherein the substituted phenyl, acenaphthyl, phenanthryl or cycloalkyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.1 and R.sup.2 are independently H, halogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.5 haloalkyl, unsubstituted or substituted phenyl, OR.sub.a, CH.sub.2OR.sub.a, SR.sub.b or CH.sub.2SR.sub.b, wherein R.sub.a and R.sub.b are independently C.sub.1-C.sub.8 alkyl, unsubstituted or substituted phenyl; R.sup.3 and R.sup.4 are independently H, halogen, C.sub.1-C.sub.8 haloalkyl, OR.sub.a, CH.sub.2OR.sub.a, SR.sub.b or CH.sub.2SR.sub.b, wherein R.sub.a and R.sub.b are independently C.sub.1-C.sub.8 alkyl, unsubstituted or substituted phenyl; and provided that of R.sup.1, R.sup.2, R.sup.3 and R.sup.4, R.sup.1(R.sup.3 and R.sup.4) and/or R.sup.2(R.sup.3 and R.sup.4); the substituted phenyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.5, R.sup.6 and R.sup.7 are independently halogen, nitro, hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 haloalkyl, OR.sub.a, or CH.sub.2OR.sub.a, wherein R.sub.a is C.sub.1-C.sub.8 alkyl, unsubstituted or substituted phenyl, and Rc is C.sub.1-C.sub.4 alkyl or haloalkyl; the substituted phenyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl.

27. The process in claim 26, wherein, the olefin is unsubstituted C1-C10 alkene, substituted C2-C10 alkene or the combination thereof.

28. The process in claim 26, wherein, the olefin is ethylene, propylene, butylene or the combination thereof.

29. The process in claim 26, wherein, the olefin is ethylene.

30. The process in claim 26, wherein, the oily polyethylene is highly branched; preferably, there is 100-500 methyl per 1000 methylene (CH2) in the highly branched polyethylene.

31. The process in claim 26, wherein, of the oily polyolefin, there is about 100-300 alkyl chains per 1000 methylene, and per each 100 methyl branched chain there is 50-100 ethyl branched chains, 5-20 propyl branched chains, 30-80 butyl branched chains, 5-pentyl branched chains and 50-100 hexyl or longer branched chains.

32. The process of claim 26, wherein, there is also a cocatalyst in step (a), the cocatalyst is selected from alkyl aluminum reagents; in a preferred embodiment, the alkyl aluminum reagents is selected from alkyl alunimoxanes, diethylalumiunm chloride, ethyl aluminum dichloride or their combination.

33. The process in claim 26, wherein, the reaction temperature of step (a) is 0-100 C.; the pressure is 0.1-3 MPa.

34. The process of claim 32, wherein, the molar ratio of aluminum in cocatalyst and catalyst is 10-5000.

35. The process of claim 26, wherein, in another preferred embodiment, step (a) is conducted in toluene, n-hexene, dichloromethane, 1,2-dichloroethane, chlorobenzene, tetrahydrofuran or the combination thereof.

36. The process in claim 26, wherein, further comprising a step of: (b) a hydrogenation process of the oily polyolefin thereby obtaining the oily alkane mixture.

37. The process in claim 36, wherein, there is also a reduction catalyst in step (b); the reduction catalyst is a catalyst for promoting the hydrogenation process.

38. The process in claim 37, wherein, reduction catalyst in step (b) is selected from Pd/C, Pd(OH).sub.2, PtO.sub.2, rhodium, nickel or ruthenium.

39. The process in claim 29, wherein, the oily highly branched polyethylene is hydrogenated and thereby obtaining the oily alkane mixture.

40. An oily alkane mixture, wherein prepared by the following steps: (a) In the presence of the complex(es) as a catalyst and alkyl aluminum reagents as cocatalyst, catalyzing ethylene polymerization, thereby forming an oily highly branched polyethylene; (b) a hydrogenation process of the oily polyethylene in the presence of a reduction catalyst; said complex(es) is formed by the following compound and a salt(s) of divalent metal selected from the following group: nickel, palladium or the combination thereof: ##STR00060## wherein, Z is hydrogen, C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 haloalkyl, unsubstituted or substituted phenyl; Y is unsubstituted or substituted phenyl; or Z and Y together with the adjacent carbon atom form an unsubstituted or substituted group selected from the following group: acenaphthyl, phenanthryl, and C.sub.5-C.sub.8 cycloalkyl, wherein the substituted phenyl, acenaphthyl, phenanthryl or cycloalkyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.1 and R.sup.2 are independently H, halogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 haloalkyl, unsubstituted or substituted phenyl, OR.sub.a, CH.sub.2OR.sub.a, SR.sub.b or CH.sub.2SR.sub.b, wherein R.sub.a and R.sub.b are independently C.sub.1-C.sub.5 alkyl, unsubstituted or substituted phenyl; R.sup.3 and R.sup.4 are independently H, halogen, C.sub.1-C.sub.8 haloalkyl, OR.sub.a, CH.sub.2OR.sub.a, SR.sub.b or CH.sub.2SR.sub.b, wherein R.sub.a and R.sub.b are independently C.sub.1-C.sub.8 alkyl, unsubstituted or substituted phenyl; and provided that of R.sup.1, R.sup.2, R.sup.3 and R.sup.4, R.sup.1(R.sup.3 and R.sup.4) and/or R.sup.2(R.sup.3 and R.sup.4); the substituted phenyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.5, R.sup.6 and R.sup.7 are independently halogen, nitro, hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.8 haloalkyl, OR.sub.a, or CH.sub.2OR.sub.a, wherein R.sub.a is C.sub.1-C.sub.5 alkyl, unsubstituted or substituted phenyl, and Rc is C.sub.1-C.sub.4 alkyl or haloalkyl; the substituted phenyl has 1 to 5 substituents selected from the following group: halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl.

41. An oily alkane mixture, wherein the oily alkane has a structure of R.sub.8R.sub.9CH(CH.sub.2).sub.n, CHR.sub.10R.sub.11 or R.sub.8R.sub.9R.sub.10C(CH.sub.2).sub.nCR.sub.10R.sub.11R.sub.12, wherein R.sub.8-R.sub.12 has a structure of R.sub.13R.sub.14CH(CH.sub.2).sub.mCHR.sub.15R.sub.16 or R.sub.13R.sub.14R.sub.15C(CH.sub.2).sub.nCR.sub.15R.sub.16R.sub.17; R.sub.13-R.sub.17 has a structure of R.sub.18R.sub.19CH(CH.sub.2).sub.xCHR.sub.20R.sub.21 or R.sub.18R.sub.19R.sub.20C(CH.sub.2).sub.xCR.sub.20R.sub.21R.sub.22, R.sub.18, R.sub.19, R.sub.20, R.sub.21, R.sub.22 is hydrogen, straight-chain or branched-chain alkanes; n, m and x is independently a integer of 1-100.

42. The oily alkane mixture in claim 40, wherein possessing the following characters: (a) the viscosity index is 100 to 300; (b) the pour point is 50 to 10 C.; (c) the bromine number <0.5 g/100 g.

43. A lubricant comprising 0.1-100 wt % base oil and an additive(s); wherein, the base oil is the oily alkane mixture of claim 40.

44. The oily alkane mixture of claim 40, wherein the co-catalyst is diethylalumiunm chloride, ethyl aluminum dichloride, or the combination thereof; step (a) is carried out at 0-100 C. under the pressure of 0.1-3 MPa; and the molar ratio of aluminum in cocatalyst and catalyst is 10-5000.

45. The process of claim 26, wherein the olefin polymerization is carried out under homogeneous condition; preferably, the catalyst is loaded on an inorganic carrier or an organic carrier.

Description

DESCRIPTION OF FIGURES OF THE INVENTION

[0113] FIG. 1 shows the .sup.13CNMR of the polymer prepared in one example of the present invention.

[0114] FIG. 2 shows the structure of the complex prepared in one example in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0115] After extensive and deeply studies, the present inventors have prepared a novel ligand compound, a complex and a catalytic system by changing the structure of the catalyst, thus highly branched oily polymer is firstly obtained by polymerizing ethylene directly with high catalytic activity. Through the adjustment of the catalyst structure, the catalytic system could polymerize propylene or butylene directly with high catalytic activity to obtain highly branched oily polymer. The oily polymer of the present invention could be used to prepare high branched alkanes with excellent performance, thus significantly reducing the cost of promising lubricant. On this basis, the present invention is completed.

[0116] Term

[0117] As used herein, group I base oil refers to the base oil of which the process is basically dominated by the physical process without changing the structure of the hydrocarbon. The quality of group I base oil is greatly effected by the raw material, and thus the performance is limited.

[0118] As used herein, group II base oil refers to the base oil obtained by a combined process (a combination of a solvent process and a hydrogenation process). Although their performance such as thermal stability improves, the viscosity index and the pour point and other properties are not yet satisfactory.

[0119] As used herein, group III base oil means the base oil obtained by hydrogenation process. Although the Group III base oil has advantages such as a low volatility, etc., some properties like the viscosity index and the pour point, etc. could not satisfy some specific application.

[0120] As used herein, olefin means polymerizable compounds containing CC bond. Representative olefin includes substituted or unsubstituted C.sub.2-C.sub.10 olefin, preferably C.sub.2-C.sub.6 olefin, such as ethylene, propylene, butene and so on. The substituent(s) is not particularly limited in species and number. Usually a monomer may contain 1-5 substituent(s). Representative substituents include (but are not limited to) hydroxyl, ester group, silylane group, amino (substituted amino), cyano, halogen, carbonyl of ketone, heterocyclic group, carboxyl, trifluoromethyl. Representative substituted olefin is a polar monomer containing various functional groups that still could be polymerized.

[0121] Ligand

[0122] The present invention provides a ligand compound of formula I.

##STR00005##

[0123] wherein, each group is defined as above.

[0124] The functional substituents of hydrocarbyl groups may be present in the Z, Y, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 include: hydroxyl, ether group, ester group, dialkylamino, carboxyl, oxo (aldehyde and ketone), nitro group, amide, thioether, preferably, hydroxyl, ether group, dialkyl amine.

[0125] Preferably, Z and Y are independently methyl, phenyl, or phenyl substituted by alkyl, halogen, alkoxyl; the halogen include: fluorine, chlorine, bromine or iodine; the alkoxyl is preferably methoxyl, ethoxyl, isopropoxyl; the alkyl-substituted phenyl is preferably C.sub.1-C.sub.6 alkyl-substituted phenyl, more preferably C.sub.1-C.sub.4 alkyl-substituted phenyl, most preferably methyl, ethyl, isopropyl or butyl-substituted phenyl. The substituents could be in any position of the phenyl ring.

[0126] Preferably, Z and Y together with the adjacent carbon atom form acenaphthenyl

##STR00006##

[0127] Preferably, Z and Y together with the adjacent carbon atom form cyclohexyl.

[0128] Preferably, R.sup.1, R.sup.2 is C.sub.1-C.sub.8 alkyl or substituted C.sub.1-C.sub.8 alkyl, and R.sup.3, R.sup.4 is hydrogen, halogen or CF3; provided that R.sup.1, R.sup.2 and R.sup.3, R.sup.4 are not identical;

[0129] Preferably, R.sup.1, R.sup.2 is C.sub.1-C.sub.8 alkyl or substituted C.sub.1-C.sub.5 alkyl, and R.sup.3 is hydrogen, halogen or CF3, and R.sup.4 is substituted C.sub.1-C.sub.8 alkyl.

[0130] Preferably, R.sup.1, R.sup.2 is C.sub.1-C.sub.4 alkyl or substituted C.sub.1-C.sub.4 alkyl, and R.sup.3 is halogen or CF3, and R.sup.4 is halogen.

[0131] In another preferred embodiment, R.sup.1 and R.sup.2 are H, methyl, halogen, CH.sub.2OR.sub.a or OR.sub.a.

[0132] In another preferred embodiment, R.sup.1 and R.sup.2 are phenyl, benzyl, halogen, CH.sub.2OR.sub.a or OR.sub.a.

[0133] In another preferred embodiment, R.sup.1 and R.sup.2 are selected from the group: SR.sub.b or CH.sub.2SR.sub.b.

[0134] Preferably, R.sup.5, R.sup.6, R.sup.7 is hydrogen, C.sub.1-C.sub.8 alkyl, substituted C.sub.1-C.sub.8 alkyl, halogen, nitro, methoxyl, dimethylamino, trifluoromethyl;

[0135] The substituted alkyl is preferably alkyl substituted by halogen, alkoxy, phenoxy; wherein halogen includes fluorine, chlorine, bromine or iodine; the alkoxyl is preferably methoxyl, ethoxyl, isopropoxyl, more preferably methoxyl.

[0136] The structure of the preferred ligand includes:

##STR00007##

[0137] wherein, each group is defined as above.

[0138] Complex

[0139] In the present invention, compounds of formula I could react with divalent nickel or palladium salts to form the corresponding nickel or palladium complex.

[0140] In the present invention, the complex of formula II is preferred:

##STR00008##

[0141] wherein, each group is defined as above.

[0142] X may be halogen, C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.6 alkenyl, allyl, benzyl; wherein the C.sub.1-C.sub.4 alkyl is preferably methyl; the halogen is preferably bromine, chlorine or iodine.

[0143] In another preferred embodiment, X is chlorine, bromine, iodine, methyl, allyl or benzyl.

[0144] In another preferred embodiment, X is chlorine, bromine or iodine.

[0145] In the present invention, the ligand compound of the present invention could react with a divalent metal precursor, thereby forming the corresponding complex.

[0146] In the present invention, the divalent metal precursor include: NiCl.sub.2, NiBr.sub.2, NiI.sub.2, (DME)NiBr.sub.2, (DME)NiCl.sub.2, (DME)NiI.sub.2, PdCl.sub.2, PdBr.sub.2, Pd(OTf).sub.2 and Pd(OAc).sub.2.

[0147] The metal complex of the present invention could catalyze ethylene polymerization to produce oily polymer in the presence of a cocatalyst(s).

[0148] Preparation of Ligand Compounds and Complexes

[0149] The present invention also provides the synthesis of the ligand compounds of formula I, comprising the steps of:

[0150] (a) reacting diketone A with amine compound B to obtain compound C.

[0151] (b) reacting compound C with amine compound D to obtain ligand I.

[0152] The compound A, B, C, or D is shown as below:

##STR00009##

[0153] 0.001 to 100% of a corresponding catalyst is needed to promote the condensation reaction, such as acetic acid, p-toluenesulfonic acid, TiCl4, orthosilicate ester. Particularly, dikeone A was mixed with amine B in inert solvent to form single imine C under the activation of a catalyst(s) such as 0.001-100% of acetic acid. Compound C reacts with amine D to form product of formula (I). The inert solvent used in the condensation reaction includes alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogentated hydrocarbons, ethers, and esters; preferably the alcohols, such as methanol, ethanol; the aromatic hydrocarbon can also show excellent results, such as toluene, xylene, mesitylene and so on. To obtain good results, different substituents should be selected on amine B and D, particularly, on R.sup.1, R.sup.2 and R.sup.3, R.sup.4, but the substituents at 2-position and 6-position of the same amine may be identical or different.

[0154] Preferably, step (a) or step (b) is respectively heated for 1-96 hours in inert solvent.

[0155] Preferably, in step (a) or step (b), 0.001-100% of a catalyst(s) to promote the condensation reaction is added, preferably, acetic acid, p-toluenesulfonic acid, TiCl4, orthosilicate.

[0156] Preferably, in step (a), the ratio of compound A and B is (0.7-1.2):1.

[0157] Preferably, in step (b), the ratio of compound C and D is (0.7-1.2):1.

[0158] Preferably, the inert solvent of step (a) or step (b) is alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters.

[0159] Preferably, the inert solvent of step (a) or step (b) is methanol, ethanol, toluene, xylene or mesitylene.

[0160] Compound C obtained in step (a) is used in step (b) with or without separation and purification.

[0161] The invention also provides a method for preparing complexes. For example, nickel complexes could be synthesized by compound I and metal precursors (including NiCl.sub.2, NiBr.sub.2, NiI.sub.2 or (DME)NiBr.sub.2, (DME)NiCl.sub.2, (DME)NiI.sub.2) under an anhydrous and anaerobic condition and in inert solvent. The inert solvent used may be any conventional solvent which does not affect the reaction, including alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters, and nitriles, preferably halogenated hydrocarbons. Better results could be obtained in solvent of halogenated hydrocarbon and esters, preferred examples are methylene chloride, 1,2-dichloroethane, ethyl acetate, tetrahydrofuran.

[0162] R.sup.1-R.sup.7, X is defined as above. DME refers to ethylene glycol dimethyl ether; complex II (when X is a hydrocarbon group, for example methyl or benzyl) usually could be prepared from the corresponding chloride or bromide II with methyl Grignard reagent or benzyl Grignard reagent under the conventional conditions of the similar reaction. No matter what is X (X is halogen, hydrocarbon group or any other group that can coordination with nickel, such as nitrogen-containing compound, oxygen-containing compound), as long as NiC bond or NiH bond could be formed in the presence of alkyl aluminum, the catalysis is realized. These compounds have the same active site in catalyzing ethylene polymerization, and thus exhibit the same or similar properties.

[0163] Catalytic Systems and the Applications

[0164] The present invention provides a catalytic system for olefin (such as ethylene) polymerization to obtain highly branched alkane mixture, the catalytic system comprises 1) the complexes formed by nickel or palladium metal precursor with ligand of formula I; 2) hydrogenation system.

##STR00010##

[0165] wherein, each group is defined as above.

[0166] Highly branched alkanes could be prepared directly from low-cost olefins (such as ethylene, propylene, butane) in the presense of a catalytic system constituted of the above catalytic system and hydrogenation catalyst. The highly branched alkanes mean aliphatic hydrocarbons having the following characteristic: there is 100-500 methyl per 1000 methylene in the polymer chain, and the bromine number is less than 0.5 g/100 g. Typically, the method includes the following two steps:

[0167] 1) under the co-action of the above-mentioned metal complexes and cocatalyst, preparing highly branched oily polyolefin (such as polyethylene) directly from olefin (such as ethylene).

[0168] 2) Hydrogenating the oily polyolefin (such as polyethylene) obtained in step (1) to obtain the hydrogenated oily alkane mixture.

[0169] The metal complex is that coordinated by compounds of formula I and divalent nickel or palladium, preferably, is nickel complexes of formula II.

[0170] The co-catalyst is reagents that can promote the catalytic reaction, and may be alkyl aluminum compounds or organic boron reagents.

[0171] The alkyl aluminum compound comprises any carbon-aluminum bond-containing compounds, including methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum, triisobutylaluminum, diethyl aluminum chloride, ethyl aluminum dichloride and so on. Wherein the ratio of aluminum in co-catalyst and nickel or palladium in catalyst is 10 to 5000; methyl aluminoxane or alkyl aluminum reagents herein may be implemented as co-catalyst to help nickel or palladium complex in catalyzing olefin polymerization to obtain oily polyolefin, and the structure of methyl aluminoxane or alkyl aluminum reagents would not affect the co-catalysis effect, except that the branching degree and the molecular weight of the obtained polymer would be different, due to the structure of co-catalyst, wherein methyaluminoxane, diethyl aluminum chloride, and ethyl aluminum dichloride could obtain the best results.

[0172] In another case, desired results could be obtained with the co-catalysis by AlCl3 alone or together with alkyl aluminum compounds.

[0173] The highly branched polyolefin (such as polyethylene) of the present invention can be hydrogenated to form highly branched alkanes.

[0174] The structure of the highly branched polyolefin (such as polyethylene) is determined by .sup.13CNMR and comparison of molecular weight measured by HT-GPC and the actual molecular weight measured by laser light scattering. For example, the molecular weight of polymer obtained in example 41 is 4,570 g/mol measured by GPC, and the molecular weight measured by laser light scattering is 46,400 g/mol, which proved the spherical structure of the highly branched polyethylene.

[0175] The highly branched alkane is clear and transparent oil with molecular weight of 500-500,000 g/mol. The highly branched alkane means that the alkane has a spherical or dendritic structure, i.e. has a structure of R.sup.8R.sup.9CH(CH.sub.2).sub.nCHR.sup.10R.sup.11 or R.sup.8R.sup.9R.sup.10C(CH.sub.2).sub.nCR.sup.11R.sup.12, wherein R.sup.8-R.sup.12 has a structure of R.sup.13R.sup.14CH(CH.sub.2).sub.mCHR.sup.15R.sup.16 or R.sup.13R.sup.14R.sup.15C(CH.sub.2).sub.nCR.sup.15R.sup.16R.sup.17; R.sup.13-R.sup.17 has a structure of R.sup.18R.sup.19CH(CH.sub.2).sub.xCHR.sup.20R.sup.21 or R.sup.18R.sup.19R.sup.20C(CH.sub.2).sub.xCR.sup.20R.sup.21R.sup.22; R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 is hydrogen, straight-chain or branched-chain alkanes; n, m and x is independently a integer of 1 to 500, preferably, a integer of 1 to 300, more preferably, a integer of 1 to 100.

[0176] Take ethylene for example, depending on the specific requirements, in step (1), the contacting time of ethylene and nickel or palladium complexes and alkyl aluminum compounds in inert solvent can be 0.5 to 72 hours, the reacting temperature range is 0-100 degrees, the pressure (means gauge pressure) range is 0.1-3 MPa (1-30 atm).

[0177] In step (2), the highly branched oily polyethylene obtained in step (1) was reacted with reduction agents, or in the presence of one or more reduction catalyst, contact the oily polyolefin with hydrogen to obtain highly branched oily alkane mixture with the bromine number less than 0.5 g/100 g. The reduction catalyst can be any catalyst for promoting the hydrogenation process, preferably, hydrogenation catalysts selected from Pd/C, Pd(OH)2, PtO2, rhodium, nickel, ruthenium and so on. The reduction reagents can be any agent that can reduce a double bond, mainly are borane compound, triethyl silane and so on.

[0178] In another preferred embodiment, between step (1) and step (2) further comprised is a step of separating oily polyethylene.

[0179] In another preferred embodiment, in step (1), hydrogenation reaction is simultaneously conducted.

[0180] In another preferred embodiment, the step (2) may be carried out in inert solvent or directly be carried out in the oily polyethylene as solvent; the step (1) may be carried out in inert solvent or be carried out in oily polyethylene as solvent.

[0181] Particularly, the step (2) can also complete by the following ways of: a) in step (1), highly branched oily alkane is directly obtained by purging hydrogen simultaneously; b) after step (1), the polymerizing system, without processing, is purged with hydrogen, thereby obtaining highly branched oily alkane; c) after step (1), the polymerizing system, without processing, is added with one or more reducing catalyst for hydrogenation, thereby giving highly branched oily alkane; d) after step (1), separating the oily polyethylene and conducting the hydrogenation reaction.

[0182] The above reaction can be conducted in inert solvent, preferably alcohols, alkanes, aromatic hydrocarbons and halogenated hydrocarbons. In step (1), saturated C.sub.5-C.sub.12 hydrocarbon is preferred, such as hexane, heptane; halogenated hydrocarbons (such as dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane), aromatic hydrocarbons (such as toluene, xylene). In step (2), saturated C.sub.5-C.sub.12 hydrocarbons are preferred, such as hexane, heptane, halogenated hydrocarbons (such as dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane), aromatic hydrocarbons (such as toluene, xylene).

[0183] In addition to ethylene, by adjusting the structure of catalysts' substituents, the catalytic system can efficiently catalyze propylene or butylene polymerization to form oily polymer, or contact with any combination of ethylene, propylene or butylenes to achieve the catalytic reaction and to obtain oily polymer. When the ethylene, propylene or butene system contains some other C.sub.5-C.sub.12 olefins (such as hexane, octene), it would not affect the catalytic polymerization, and the resulting polymer remains oily, which is highly branched, and is a dendritic or spherical polymer. The polymer can also be hydrogenated in step (2) to obtain highly branched alkane. In another preferred embodiment, between the step (1) and step (2) further comprised is a step of separating the oily polyethylene. The above-mentioned operation of directly obtaining highly branched alkane from ethylene can also be used for these olefins, i.e. in another preferred embodiment, in step (1), hydrogenation reaction is simultaneously conducted; in another preferred embodiment, step (2) can be carried out in inert solvent or can be carried out in oily polyolefin as solvent; step (1) may be carried out in inert solvent or in oily polyolefin as solvent.

[0184] In addition to ethylene, the other olefin used in the present invention may be with a double bond at the end or internal olefins, which would not affect the catalytic effect. The internal olefins mean the double bond is at any position other than the end. In the application, the internal olefin can be a mixture of various isomers or a single internal olefin. For example, as for butene, it can be 1-C4, 2-C4, and 2-C4 have cis-isomer and trans-isomer. As being used, it is not limited to 1-C4 or cis-2-C4 or trans-2-C4, and it also can be a mixture of one or more isomer(s), which would not affect the polymerization.

[0185] Oily Polyolefin and Oily Alkane Mixture

[0186] Catalysts disclosed in the present invention can be applied to the industrially current-used process equipment, for polymerizing all kind of ethylene, propylene and butane, and common reduction process equipment. Both of homogeneous conditions and non-homogeneous conditions with catalyst loaded on organic or inorganic carriers can be used.

[0187] The present invention also provides an oily ethylene polymer and the preparation thereof. The oily polyethylene of the invention is highly branched; which means in polyethylene there is 100-500 methyl per 1000 methylene (CH.sub.2).

[0188] In the present invention, a representative preparation method comprises steps of:

[0189] (a) at 0-100 C., under a pressure (gauge pressure) of 0.1-3 MPa (1-30 atm), catalyzing ethylene polymerization with complexes of the present invention as olefin polymerization catalyst, to form oily polyethylene.

[0190] Preferably, this step further comprises a co-catalyst; preferably, the co-catalyst is selected from the group: alkyl aluminums (such as alkyl aluminoxane, diethyl aluminum chloride and ethyl aluminum dichloride); wherein the molar ratio of aluminum in co-catalyst and nickel in catalyst is 10 to 5000.

[0191] In another preferred embodiment, step (a) is conducted in the solvent selected from: toluene, n-hexane, dichloromethane, 1,2-dichloroethane, cholorobenzene, tetrahydrofuran or the combination thereof.

[0192] In a preferred embodiment, the co-catalyst may be alkyl aluminoxane MAO (or modified alkyl aluminoxane MMAO), alkyl aluminum or organic boron reagents, wherein the molar ratio of cocatalyst and nickel or palladium in catalyst is 1-5000.

[0193] Since such nickel or palladium complexes have the following characteristic in the reaction process: 1) quick -H elimination occurs to generate the double bond-containing polyolefin and Ni(Pd)H bond-containing active species; 2) Ni(Pd)H bond-containing active species coordinate with -olefin and insert to obtain the Ni(Pd)C bond; 3) the obtained Ni(Pd)C bonds react with ethylene in the system to restart the polymerization; 4) finally terminate the catalytic cycle reaction via -H elimination. Therefore, the resulting polymer contains a lot of branched-chains, and the number of branched-chains is determined by the signal (integral area) of CH.sub.2 and CH.sub.3 in .sup.13CNMR quantitatively. As the catalytic cycle is terminated by metal's -H elimination, double bonds are inevitably contained in the polymer chain, and the resulting oily polyolefin is highly unsaturated. For example, in one preferred embodiment, the bromine number of the resulting oily polymer obtained by nickel catalyst-catalyzed ethylene polymerization is 38 g/100 g.

[0194] In a typical method of the present invention, in step (a), at 0-100 C., under the pressure (gauge pressure) of 0.1-3 MPa (1-30 atm), catalyzing the polymerization of propylene, butylene or any combination of ethylene, propylene, butylene and other C.sub.5-C.sub.12 olefin in the presence of complexes of the present invention as olefin polymerization catalyst, therefore forming oily polyolefin.

[0195] The present invention also provides a highly branched oily alkane mixture. The mixture is the hydrogenated product of the oily polyolefin, wherein the oily polyolefin comprises oily polyethylene, oily polypropylene, oily polybutene or oily polymer obtained from a mixture of the above-mentioned gases with a catalyst. The molecular weight of the oily alkane mixture of the present invention is 500-500,000 g/mol, and there is 100-500 methyl per 1000 methylene. The highly branched alkane has a spherical or dendritic structure, i.e. has a structure of R.sup.8R.sup.9CH(CH.sub.2).sub.nCHR.sup.10R.sup.11 or R.sup.8R.sup.9R.sub.10C(CH.sub.2).sub.nCR.sup.10R.sup.11R.sup.12, wherein R.sup.8-R.sup.12 has a structure of R.sup.13R.sup.14CH(CH.sub.2).sub.mCHR.sup.15R.sup.16 or R.sup.13R.sup.14R.sup.15C(CH.sub.2).sub.nCR.sup.15R.sup.16R.sup.17, R.sup.13-R.sup.17 has a structure of R.sup.18R.sup.19CH(CH.sub.2).sub.xCHR.sup.20R.sup.21 or R.sup.18R.sup.19R.sup.20C(CH.sub.2).sub.xCR.sup.20R.sup.21R.sup.22, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 is hydrogen, straight-chain or branched-chain alkanes, n, m and x is integer of 1 to 500, preferably integer of 1 to 300, more preferably integer of 1 to 100.

[0196] The highly branched alkane mixture of the present invention has high viscosity index of about 100-300 (preferably about 150-300), pour point of about 50 C. to about 10 C., and the kinematic viscosity at 100 C. of about 5 to 100 cSt. This kind of alkane mixture is oily polymer, of which the molecular weight is about 500 to 500,000 g/mol and the branching degree (BI) is at least 0.20.

[0197] A significant characteristic of the alkane mixture of the present invention is there is about 100 to 500 methyl per 1000 methylene, preferably 200-400, which makes the alkane mixture of the present invention microscopically different from normal linear polymer, show a spherical or dendritic structure, and therefore more suitable for a use as lubricant base oil.

[0198] Furthermore, there is about 20-100 ethyl branched-chains, about 2-50 propyl branched-chains, about 20-100 butyl branched-chains, about 2-50 pentyl branched-chains and about 20-200 hexyl or longer branched-chains per 100 methyl branched-chains in the alkane mixture of the present invention.

[0199] The bromine number of the alkane mixture of the present invention is low, which meets the requirement of base oil. For example, in one case, the bromine number of an oily polymer polymerized from ethylene catalyzed by a nickel catalyst is 38 g/100 g, and after hydrogenation, the bromine number is reduced to 0.38 g/100 g. In the use of lubricant base oil, the property of such highly-branched oily alkane is superial to current commercial PAO base oil, such as the viscosity index of commercial PAO is about 139, while the viscosity index of highly branched oily alkane obtained in one example of the present invention can reach 261.

[0200] In order to improve the physical properties accordingly, various additives or enhancers can be added while this kind of highly-branched saturated alkane is being used, such as antifreeze. In addition, such highly branched saturated hydrocarbon can also be used as an additive to improve resin's processing properties, such as being used as a plasticizer in polymer processing.

[0201] The main advantages of the present invention include:

[0202] (a) By using a novel catalytic system, firstly high-efficiently realize the preparation of the highly branched oily alkane directly from ethylene, which makes the preparation of base oil no longer dependent on expensive advanced -olefin and significantly reduce the cost.

[0203] (b) Either -olefin or internal olefin can be directly applied for such purpose and the internal olefin can be better utilized.

[0204] (c) Avoiding producing advanced -olefin as well as PAO from -olefin.

[0205] (d) The highly branched alkanes have low bromine number, high viscosity index, and can be used as base oil for advanced lubricant or processing aids.

[0206] With reference to specific embodiment, we further illustrate the present invention. It should be understood that these embodiments are merely intended to illustrate the invention and are no intended to limit the scope of the invention. If we don't indicate specific conditions of experimental methods, follow conventional conditions or in accordance with the conditions recommended by the manufacturer. Unless otherwise indicated, percentage and parts are by weight and percentages by weight.

Example 1

Synthesis of Ligand L1a

[0207] ##STR00011##

[0208] In 100 mL egg-shaped flask, acenaphthoquinone (3.644 g, 20 mmol), methanol (40 ml), 2,6-diisopropyl aniline (4.0 mL, 20 mmol), two drops of acetic acid were added and the mixture was stirred at room temperature. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE from 1:20 to 1:10 to give the single imine as orange yellow product (yield 60%). .sup.1H NMR (300 MHz, CDCl.sub.3): =8.21 (2H, m), 8.01 (1H, d), 7.82 (1H, t), 7.41 (1H, t), 7.27 (3H, s), 6.64 (1H, d), 2.84 (2H, m), 1.18 (6H, d), 0.90 (6H, d).

[0209] In 100 mL egg-shaped flask, the single imine (1.708 g, 5.0 mmol), methanol (40 ml), aniline (7.5 mmol) and two drops of anhydrous acetic acid were added. The reaction mixture was stirred at room temperature. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE=1:15 to give the orange yellow product L1a. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.88-6.62 (14H, m), 3.06 (2H, m), 1.25-0.93 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.4, 151.6, 147.0, 141.1, 135.4, 130.9, 129.1, 128.7, 128.5, 127.6, 127.4, 124.2, 124.1, 123.6, 123.3, 118.1, 77.0, 28.1, 23.4, 23.3.

Example 2

Synthesis of Ligand L1b

[0210] ##STR00012##

[0211] Following the synthesis of ligand L1a of example 1, an orange solid was obtained under the identical operating conditions except that aniline was replaced by 2,6-dichloro aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.32 (1H, d), 8.10 (1H, d), 7.96 (1.5H, m), 7.53 (2H, d), 7.41 (3H, m), 7.38 (2H, m), 6.91 (0.5H, m), 6.58 (1H, t), 2.77 (2H, m), 1.29 (2H, d), 0.97 (10H, d), .sup.13C NMR (75 MHz, CDCl3): =162.2, 157.8, 146.1, 133.1, 130.7, 127.5, 124.8, 124.4, 124.3, 123.39, 123.1, 122.7, 120.7, 77.4, 77.6, 28.5, 27.9, 23.5, 22.8. IR(KBr): (cm.sup.1)=3052, 2960, 2923, 2865, 1674, 1640, 1602, 1463, 1433, 1242, 1077, 1033, 831, 779, 760, 730; C.sub.30H.sub.26Cl.sub.2N.sub.2 (484.45): Anal. Calc. C, 74.22; H, 5.40; N, 5.77. Found C, 73.99; H, 5.39; N, 5.65.

Example 3

Synthesis of Ligand L1c

[0212] ##STR00013##

[0213] Following the synthesis of ligand L1a in example 1, an orange red solid was obtained under the identical operating conditions except that aniline was replaced by 2,6-dibromoaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.33 (1H, d), 8.05 (1H, d), 7.91 (2H, m), 7.69 (1.5H, d), 7.49 (2H, d), 7.28 (1H, m), 7.15 (2H, s), 6.71 (1H, m), 6.69 (1H, t), 6.51 (0.5H, d), 1.23 (2H, d), 0.97 (10H, d); .sup.13C NMR (75 MHz, CDCl3): =162.2, 157.5, 149.1, 146.2, 141.2, 135.3, 134.7, 131.3, 128.9, 124.4, 120.8, 112.1, 77.0, 58.4, 28.0, 23.8, 23.1, 23.0, 18.4. IR(KBr): (cm.sup.1)=3058, 2960, 2922, 2865, 1677, 1640, 1594, 1547, 1462, 1425, 1282, 1241, 1080, 1032, 925, 831, 792, 778, 759, 725; C.sub.30H.sub.26Br.sub.2N.sub.2 (574.35): Anal. Calc. C, 62.74; H, 4.56; N, 4.88. Found C, 62.69; H, 4.60; N, 4.73.

Example 4

Synthesis of Ligand L1d

[0214] ##STR00014##

[0215] In 100 mL egg-shaped flask, acenaphthoquinone (1.822 g, 10 mmol), 2,6-dichloroaniline (1.620 g, 10 mmol), TsOH (190 mg, 1 mmol) and toluene (50 mL) were added. The reaction mixture was stirred at reflux with water separating for 3 h. The reaction was monitored by TLC until ended. The reaction mixture was cooled, then concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE=1:20 to give the single imine as an orange product. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.28-6.92 (9H, m); IR(KBr): (cm.sup.1)=3059, 1734, 1651, 1600, 1590, 1558, 1279, 1233, 1151, 1072, 1028, 910, 832, 791, 778, 768, 745, 687.

[0216] In 100 mL egg-shaped flask, the single imine (1.631 g, 5.0 mmol), methanol (30 ml), two drops of anhydrous acetic acid and 2,6-dimethylanile (0.93 mL, 7.5 mmol) were added. The reaction mixture was stirred at room temperature. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and was purified by column chromatography on alumina N-neutral using EA:PE=1:15 to give the orange yellow product. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.30-6.57 (12H, m), 2.15-1.90 (6H, s); .sup.13C NMR (75 MHz, CDCl3): =162.7, 157.4, 148.8, 141.5, 131.0, 130.7, 129.3, 128.9, 128.5, 128.3, 128.1, 127.6, 124.9, 124.7, 124.5, 123.9, 123.0, 122.7, 122.3, 120.7, 77.0, 17.8, 17.6; IR(KBr): (cm.sup.1)=3059, 2918, 1681, 1640, 1592, 1557, 1469, 1431, 1282, 1243, 1199, 1075, 1031, 924, 828, 774, 764, 729; Anal. Calcd. C, 72.73; H, 4.23; N, 6.52. Found C, 73.01; H, 4.21; N, 6.46.

Example 5

Synthesis of Ligand L1e

[0217] ##STR00015##

[0218] Following the synthesis of ligand L1a in example 1, an orange red solid was obtained with the identical operating conditions except that aniline was replaced by p-methoxyaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.94-6.61 (13H, m), 3.00-2.52 (2H, m), 1.26-0.91 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.3, 154.7, 146.9, 141.4, 135.5, 131.2, 129.4, 129.1, 129.0, 128.3, 128.0, 127.6, 126.7, 124.5, 123.8, 123.7, 123.6, 123.2, 118.5, 117.7, 77.0, 28.3, 23.5, 23.4, 23.1, 22.3; Anal. Calcd. C, 76.84; H, 5.62; N, 5.78. Found C, 76.63; H, 5.62; N, 5.73.

Example 6

Synthesis of Ligand L1f

[0219] ##STR00016##

[0220] Following the synthesis of ligand L1a in example 1, an orange red solid was obtained with the identical operating conditions except that aniline was replaced by N,N-dimethyl aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.18-6.58 (13H, m), 3.04 (8H, m), 1.22-0.91 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.8, 159.2, 148.3, 147.4, 141.0, 135.6, 129.5, 129.2, 128.7, 128.3, 127.5, 124.1, 123.4, 123.3, 123.0, 120.7, 112.9, 77.0, 40.8, 28.3, 28.2, 23.7, 23.4, 23.3.

Example 7

Synthesis of Ligand L1g

[0221] ##STR00017##

[0222] Following the synthesis of ligand L1a in example 1, an orange red solid was obtained with the identical operating conditions except that aniline was replaced by p-chloroaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.17-6.60 (13H, m), 3.01-2.97 (2H, m), 1.23-0.93 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.4, 160.9, 150.1, 147.0, 131.1, 141.2, 129.5, 129.4, 129.1, 128.9, 128.4, 128.2, 127.8, 127.5, 124.4, 124.1, 123.7, 123.5, 123.1, 119.8, 119.2, 77.4, 77.0, 28.2, 23.5, 23.4, 23.3, 23.1; Anal. Calcd. C, 79.89; H, 6.03; N, 6.21. Found C, 79.82; H, 6.13; N, 6.07.

Example 8

Synthesis of Ligand L1h

[0223] ##STR00018##

[0224] In 100 mL egg-shaped flask, acenaphthoquinone (1.093 g, 6.0 mmol), methanol (40 ml), 4,6-dibromo-2-(trifluoromethyl)aniline (2.105 g, 6.6 mmol) and two drops of anhydrous acetic acid were added. The reaction mixture was stirred at reflux. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and methanol (20 mL) was added to the crude product, which was filtered after frozen in the freezer, to obtain the single imine as a red product. .sup.1H NMR (300 MHz, CDCl.sub.3): =6.846-8.245 (8H, m). .sup.13C NMR (75 MHz, CDCl.sub.3): =187.9, 184.5, 162.8, 161.0, 147.3, 144.4, 139.0, 138.2, 132.3, 130.6, 130.2, 129.5, 129.1, 128.9, 128.6, 128.4, 128.3, 123.1, 122.6, 122.4, 121.3, 117.2, 115.5, 113.3, 77.0; Anal. Calc. C, 47.24; H, 1.67; N, 2.90. Found C, 47.04; H, 1.90; N, 2.88. MS(ESI)(m/z): 483.7 (M+1).

[0225] In 100 mL egg-shaped flask, the single imine (1.449 g, 3 mmol), methanol (40 ml), 2-isopropylaniline (0.39 mL, 3.15 mmol) and two drops of anhydrous acetic acid were added. The reaction mixture was stirred at reflux. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using CH.sub.2Cl.sub.2:PE=1:2 to give the orange yellow product, which was then crystallized from methanol to give the diimine. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.27-6.70 (12H, m), 3.16-2.64 (1H, m), 1.25-0.96 (6H, m); .sup.13C NMR (75 MHz, CDCl.sub.3): =163.0, 147.7, 137.8, 132.7, 130.8, 128.9, 128.6, 128.4, 127.8, 126.3, 125.9, 125.4, 123.6, 121.0, 116.6, 114.1, 113.9, 77.0, 28.4, 23.0, 22.7; Anal. Calc. C, 56.02; H, 3.19; N, 4.67. Found C, 56.05; H, 3.20; N, 4.52.

Example 9

Synthesis of Ligand L1i

[0226] ##STR00019##

[0227] In 250 mL egg-shaped flask, phenanthrene-9,10-dione (2.0 g, 9.6 mmol), 2,6-diisopropylaniline (3.2 mL, 16.9 mmol), ten drops of anhydrous formic acid and 120 ml methanol were added. The reaction mixture was heated at reflux for 24 h. The reaction was monitored by TLC until ended. The reaction mixture was cooled in the freezer at 20 C. overnight, and was filtered to give the single imine as a green product. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.38 (1H, d), 8.06-7.98 (3H, d), 7.70-7.63 (2H, m), 7.50 (1H, t), 7.38 (1H, t), 7.18 (2H, d), 7.10 (1H, m), 2.66 (2H, m), 1.28-1.04 (12H, d).

[0228] In 50 mL egg-shaped flask, the single imine (311.4 mg, 1 mmol), methanol (25 ml), 2,6-dichloroaniline (199.4 mg, 1.2 mmol) were added. The reaction mixture was stirred at reflux. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE=1:50 to give the scarlet product, which was crystallized from methanol to give the L1i. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.46 (1H, d), 8.46-6.83 (14H, m), 2.77-1.96 (2H, m), 0.82-0.67 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): =162.2, 158.3, 146.4, 145.3, 135.0, 134.6, 134.4, 132.7, 132.3, 129.1, 129.0, 128.0, 127.8, 127.6, 127.1, 124.4, 124.2, 124.0, 123.5, 123.4, 123.2, 77.0, 27.6, 23.8, 22.7; Anal. Calcd. C, 75.14; H, 5.52; N, 5.48. Found C, 74.94; H, 5.49; N, 5.32.

Example 10

Synthesis of Ligand L1j

[0229] ##STR00020##

[0230] Following the procedure in example 9, the ligand L1j was obtained except that 2,6-dichloroaniline was replaced by 2,6-dibromoaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.48-6.77 (14H, m), 2.79-1.97 (2H, m), 1.13-0.69 (12H, m); .sup.13C NMR (75 MHz, CDCl.sub.3): =161.4, 158.0, 149.0, 145.3, 135.0, 134.6, 134.4, 132.7, 132.2, 131.3, 131.2, 129.2, 129.0, 128.0, 127.8, 127.1, 124.4, 124.2, 124.1, 123.5, 123.4, 113.3, 77.0, 27.6, 23.9, 22.9.

Example 11

Synthesis of Ligand L1k

[0231] ##STR00021##

[0232] In 50 mL egg-shaped flask, 1-phenylpropane-1,2-dione (1.4 mL, 10.5 mmol), 2,6-diisopropylaniline (2.2 mL, 10.5 mmol), six drops of formic acid and methanol (3 ml) were added. The reaction mixture was stirred at room temperature for 12 h. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE=1:50 to give the product, which was crystallized from methanol, and then filtered to give the single imine as a yellow solid. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.22 (2H, d), 7.60 (1H, t), 7.52 (2H, t), 7.19 (3H, m), 2.79 (2H, m), 2.04 (3H, s), 1.22 (2H, d), 1.17 (2H, d).

[0233] In 50 mL egg-shaped flask, the single imine (307.4 mg, 1 mmol), methanol (25 ml), 2,6-dichloroaniline (178.2 mg, 1.1 mmol) and two drops of acetic acid were added. The reaction mixture was stirred at reflux. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure, and purified by column chromatography on alumina N-neutral using EA:PE=1:50 to give the yellow product, which was crystallized from methanol to give the L1k. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.10-6.74 (11H, m), 2.68-2.33 (2H, m), 2.24-1.83 (3H, s), 1.21-1.05 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): =171.5, 168.1, 146.1, 145.4, 135.2, 134.6, 135.2, 134.6, 128.9, 128.7, 128.5, 127.8, 127.3, 127.2, 124.3, 123.9, 123.7, 123.2, 122.8, 77.0, 28.4, 27.6, 23.9, 23.7, 22.9, 22.6, 17.6; Anal. Calc. C, 71.84; H, 6.25; N, 6.21. Found C, 72.10; H, 6.52; N, 5.92.

Example 12

Synthesis of Ligand L1l

[0234] ##STR00022##

[0235] Following the synthesis of ligand L1k in example 11, an orange red solid was obtained with the identical operating conditions except that 2,6-dichloroaniline was replaced by 2,6-dibromoaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.01-6.67 (11H, m), 2.71-2.30 (2H, m), 2.26-1.86 (3H, s), 1.22-1.07 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): =170.7, 168.4, 147.8, 146.2, 134.7, 131.7, 131.6, 129.1, 128.7, 127.7, 127.2, 125.2, 123.8, 122.8, 119.3, 113.1, 77.0, 28.4, 23.0, 22.7, 27.7, 17.8; MS(ESI)(m/z): 541 (M+1).

Example 13

Synthesis of Ligand L1m

[0236] ##STR00023##

[0237] Following the procedure in example 8, the ligand L1m was obtained except that o-isopropylaniline was replaced by o-trifluoromethylaniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.27-6.62 (12H, m).

Example 14

Synthesis of Ligand L1n

[0238] ##STR00024##

[0239] Following the procedure in example 8, the ligand L1n was obtained except that o-isopropylaniline was replaced by o-tert-butyl-aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.26-6.50 (12H, m), 1.33-1.02 (9H, m); Anal. Calc. C, 56.70; H, 3.45; N, 4.56. Found C, 56.56; H, 3.33; N, 4.32.

Example 15

Synthesis of Ligand L1o

[0240] ##STR00025##

[0241] Following the procedure in example 1, the ligand L1o was obtained except that aniline was replaced by p-trifluoromethyl aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.94-6.61 (13H, m), 3.00-2.52 (2H, m), 1.26-0.91 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.3, 154.7, 146.9, 141.4, 135.5, 131.2, 129.4, 129.1, 129.0, 128.3, 128.0, 127.6, 126.7, 124.5, 123.8, 123.7, 123.6, 123.2, 118.5, 117.7, 77.0, 28.3, 23.5, 23.4, 23.1, 22.3; Anal. Calcd. C, 76.84; H, 5.62; N, 5.78. Found C, 76.63; H, 5.62; N, 5.73.

Example 16

Synthesis of Ligand L1p

[0242] ##STR00026##

[0243] Following the procedure in example 1, the ligand L1p was obtained except that aniline was replaced by 3,5-bis(trifluoromethyl) aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.08-6.47 (12H, m), 2.98-2.48 (2H, m), 1.24-0.88 (12H, m); .sup.13C NMR (75 MHz, CDCl.sub.3): 162.3, 161.1, 153.2, 152.8, 146.7, 146.3, 141.5, 140.8, 135.4, 134.3, 133.4, 133.0, 132.7, 131.9, 131.6, 130.8, 130.0, 129.5, 129.1, 128.9, 128.5, 128.1, 128.0, 127.7, 124.7, 124.6, 124.5, 123.9, 123.6, 123.5, 123.3, 123.2, 120.4, 119.2, 117.8, 116.3, 77.0, 28.4, 23.6, 23.5, 22.8, 22.6.

Example 17

Synthesis of Ligand L1q

[0244] ##STR00027##

[0245] Following the procedure in example 1, the ligand L1q was obtained except that aniline was replaced by o-phenoxymethylene aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.93-6.44 (18H, m), 5.03 (2H, s), 2.82 (2H, m), 1.14-0.84 (12H, d); .sup.13C NMR (75 MHz, CDCl.sub.3): 161.5, 161.2, 158.3, 150.5, 146.9, 141.1, 135.4, 130.9, 129.5, 129.1, 128.9, 127.7, 125.2, 124.3, 124.0, 123.4, 123.3, 120.4, 117.6, 113.9, 77.0, 66.6, 50.7, 28.3, 23.2, 23.1.

Example 18

Synthesis of Complex 1a

[0246] ##STR00028##

[0247] In a glovebox, to a 50 ml Schlenk tube was add NiBr.sub.2(DME) (1 mmol), and then L1a (1.05 mmol). After being purged with nitrogen for three times, dichloromethane (20 mL) was added. The reaction was stirred overnight. The reaction mixture was transferred into another 50 ml Schlenk tube by a double-ended needle and concentrated. Then the residue was washed by a mixture of dichloromethane (2 mL) and n-hexane (20 mL) for 2-3 times and filtered. The solid was dried in vacuo. Wash the Schlenk tube in the glovebox with hexane and then filtered, and the solid was collected as a red product Anal. Calcd. For C.sub.30H.sub.28Br.sub.2N.sub.2Ni: C, 56.74; H, 4.44; N, 4.41. Found: C, 56.14; H, 4.65; N, 4.25.

Example 19

Synthesis of Complex 1b

[0248] ##STR00029##

[0249] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1b, yield 85%. Anal. Calcd. For C.sub.30H.sub.26Br.sub.2Cl.sub.2N.sub.2Ni: C, 51.19; H, 3.72; N, 3.98. Found: C, 51.25; H, 3.64; N, 3.64.

Example 20

Synthesis of Complex 1c

[0250] ##STR00030##

[0251] A reddish brown complex was obtained by the same procedure as example 18 except that ligand La was replaced by ligand L1c, yield 90%. Anal. Calcd. For C.sub.30H.sub.26Br.sub.4N.sub.2Ni: C, 45.45; H, 3.31; N, 3.53. Found: C, 45.82; H, 3.30; N, 3.30.

Example 21

Synthesis of Complex 1d

[0252] ##STR00031##

[0253] A reddish brown complex was obtained by the same procedure as example 18 except that ligand La was replaced by ligand L1d, yield 72%. Anal. Calcd. For C.sub.26H.sub.18Br.sub.2Cl.sub.2N.sub.2Ni: C, 48.20; H, 2.80; N, 4.32. Found: C, 47.58; H, 2.99; N, 4.02.

Example 22

Synthesis of Complex 1e

[0254] ##STR00032##

[0255] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1e, yield 30%. Anal. Calcd. C, 55.98; H, 4.55; N, 4.21. Found: C, 56.24; H, 4.71; N, 3.94.

Example 23

Synthesis of Complex 1f

[0256] ##STR00033##

[0257] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1f, yield 60%. Anal. Calcd. C, 56.68; H, 4.90; N, 6.20. Found: C, 56.93; H, 5.13; N, 5.91.

Example 24

Synthesis of Complex 1g

[0258] ##STR00034##

[0259] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1g, yield 31%. Anal. Calcd. C, 53.82; H, 4.06; N, 4.18. Found: C, 54.41; H, 4.07; N, 3.92.

Example 25

Synthesis of Complex 1h

[0260] ##STR00035##

[0261] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1h, yield 75%. Anal. Calcd. C, 41.07; H, 2.34; N, 3.42. Found: C, 41.34; H, 2.54; N, 3.92.

Example 26

Synthesis of Complex 1i

[0262] ##STR00036##

[0263] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1i, yield 20%. Anal. Calcd. C, 52.65; H, 3.87; N, 3.84. Found: C, 52.90; H, 3.98; N, 3.92.

Example 27

Synthesis of Complex 1j

[0264] ##STR00037##

[0265] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1j, yield 30%. Anal. Calcd. C, 46.93; H, 3.45; N, 3.42. Found: C, 46.50; H, 3.23; N, 3.32.

Example 28

Synthesis of Complex 1k

[0266] ##STR00038##

[0267] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1k, yield 15%. Anal. Calcd. C, 48.41; H, 4.21; N, 4.18. Found: C, 48.20; H, 4.00; N, 4.02.

Example 29

Synthesis of Complex 1l

[0268] ##STR00039##

[0269] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1l, yield 10%. Anal. Calcd. C, 42.74; H, 3.72; N, 3.69. Found: C, 42.50; H, 3.56; N, 3.52.

Example 30

Synthesis of complex 1m

[0270] ##STR00040##

[0271] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1m, yield 60%. Anal. Calcd. C, 36.97; H, 1.43; N, 3.32. Found: C, 36.87; H, 1.32; N, 3.22.

Example 31

Synthesis of Complex 1n

[0272] ##STR00041##

[0273] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1n, yield 50%. Anal. Calcd. C, 41.82; H, 2.54; N, 3.36. Found: C, 41.90; H, 2.40; N, 3.42.

Example 32

Synthesis of Complex 1o

[0274] ##STR00042##

[0275] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1o, yield 35%. Anal. Calcd: C, 52.96; H, 3.87; N, 3.98. Found: C, 53.15; H, 3.93; N, 4.12.

Example 33

Synthesis of Complex 1p

[0276] ##STR00043##

[0277] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1p, yield 70%. Anal. Calcd: C, 49.85; H, 3.40; N, 3.63. Found: C, 49.80; H, 3.38; N, 3.57.

Example 34

Synthesis of Complex 1q

[0278] ##STR00044##

[0279] A reddish brown complex was obtained by the same procedure as example 18 except that ligand L1a was replaced by ligand L1q, yield 70%. Anal. Calcd: C, 59.96; H, 4.62; N, 3.78. Found: C, 60.80; H, 4.96; N, 3.62.

Example 35

Synthesis of Complex 1r

[0280] ##STR00045##

[0281] React complex 1q with methylmagnesium bromide, to obtain complex 1r. Anal. Calcd: C, 76.61; H, 6.59; N, 4.58. Found: C, 77.01; H, 6.89; N, 4.89.

Example 36

Synthesis of Complex 1t

[0282] ##STR00046##

[0283] Complex 1t was obtained by the same procedure as example 18 except that (DME)NiBr.sub.2 was replaced by (DME)NiCl.sub.2.

[0284] Anal. Calcd. C, 65.97; H, 5.17; N, 5.13. Found: C, 65.81; H, 5.00; N, 5.02.

Example 37

Synthesis of Complex 1u

[0285] ##STR00047##

[0286] Complex 1u was obtained by the same procedure as example 18 except that (DME)NiBr.sub.2 was replaced by (DME)NiI.sub.2.

[0287] Anal. Calcd. C, 49.42; H, 3.87; N, 3.84. Found: C, 49.85; H, 4.12; N, 4.00.

Example 38

Synthesis of Complex 1v

[0288] ##STR00048##

[0289] React complex 1a with benzylmagnesium bromide to obtain complex 1v. Anal. Calcd. C, 80.37; H, 6.44; N, 4.26. Found: C, 80.90; H, 6.85; N, 4.40.

Example 39

[0290] A Schlenk flask (200 mL) was purged firstly with nitrogen, then vacuumized and then purged with ethylene. Under the atmosphere of ethylene, 25 mL DCE and then AlEt.sub.2Cl (0.9M in toluene, 0.30 mL) were added. Then complex 1a (5 mol) was added at 60 C. and under 1 atm and the reaction mixture was stirred for 30 min. When the reaction completed, stop purging ethylene and concentrate the reaction mixture. The residue was purified by silica gel column with petroleum ether. The filtrate was concentrated to obtain oily polyethylene. Activity: 3.010.sup.6 g/mol.Math.h.Math.atm. .sup.1HNMR 250 Me/1000 CH.sub.2. Bromine number: 38 g/100 g. Molecular Weight (Mn): 2000 g/mol.

Example 40

[0291] Repeat the procedure of example 39, the difference is that using complex 1b (2 umol) instead of complex 1a, and co-catalyst AlEt.sub.2Cl (0.22 mL, 0.9M in toluene) was added.

[0292] Result: 7.0 g oily polyethylene was obtained. Activity: 7.010.sup.6 g/mol.Math.h.Math.atm. Bromine number: 33 g/100 g. Mn: 50,000 g/mol.

Example 41

[0293] Repeat the procedure of example 39, the difference is that using complex 1c (2 mol) instead of complex 1a.

[0294] Result: 9.0 g oily polyethylene. Activity: 9.010.sup.6 g/mol.Math.h.Math.atm, bromine number 35 g/100 g. M.sub.w, GPC 4,570 g/mol, M.sub.w, LLS 46,400 g/mol. It should be noted that the ratio of Mw, LLS and Mw, GPC reached 10:1, which indicated that the structure of the highly branched polyethylene is spherical.

Example 42

[0295] Repeat the procedure of example 39, the difference is that using complex 1d (5 mol) instead of complex 1a.

[0296] Result: 2.5 g oily polyethylene was obtained. Activity: 1.010.sup.6 g/mol.Math.h.Math.atm. .sup.1HNMR 260 Me/1000 CH.sub.2.

Example 43

[0297] Repeat the procedure of example 39, the difference is that using complex 1e (5 mol) instead of complex 1a.

[0298] Result: 5.0 g oily polyethylene was obtained. Activity: 2.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 280 Me/1000 CH.sub.2.

Example 44

[0299] Repeat the procedure of example 39, the difference is that using complex 1f (5 mol) instead of complex 1a.

[0300] Result: 5.0 g oily polyethylene was obtained. Activity: 2.010.sup.6 g/mol.Math.h.Math.atm. .sup.1HNMR 270 Me/1000 CH.sub.2. Bromine number 40 g/100 g.

Example 45

[0301] Repeat the procedure of example 39, the difference is that using complex 1g (5 mol) instead of complex 1a.

[0302] Result: 5.0 g oily polyethylene was obtained. Activity: 2.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 200 Me/1000 CH.sub.2.

Example 46

[0303] Repeat the procedure of example 39, the difference is that using complex 1h (5 mol) instead of complex 1a.

[0304] Result: 2.5 g oily polyethylene was obtained. Activity: 1.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 280 Me/1000 CH.sub.2. Bromine number: 60 g/100 g.

Example 47

[0305] Repeat the procedure of example 39, the difference is that using complex 1i (1 mol) instead of complex 1a and the time of polymerization is 5 min.

[0306] Result: 4.2 g oily polyethylene was obtained. Activity: 5.010.sup.7 g/mol.Math.h.Math.atm, .sup.1HNMR 200 Me/1000 CH.sub.2. Mn: 110,000 g/mol.

Example 48

[0307] Repeat the procedure of example 39, the difference is that using complex 1j (1 mol) instead of complex 1a.

[0308] Result: 10.0 g oily polyethylene was obtained. Activity: 4.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 200 Me/1000 CH.sub.2. Bromine number: 30 g/100 g. Mn: 120,000 g/mol.

Example 49

[0309] Repeat the procedure of example 39, the difference is that using complex 1k (1 mol) instead of complex 1a.

[0310] Result: oily polyethylene was obtained. Activity: 5.010.sup.6 g/mol.Math.h.Math.atm. .sup.1HNMR 110 Me/1000 CH.sub.2. Bromine number: 25 g/100 g.

Example 50

[0311] Repeat the procedure of example 39, the difference is that using complex 1l (5 mol) instead of complex 1a.

[0312] Result: oily polyethylene was obtained. Activity: 6.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 130 Me/1000 CH.sub.2.

Example 51

[0313] Repeat the procedure of example 39, the difference is that using complex 1m (5 mol) instead of complex 1a.

[0314] Result: oily polyethylene was obtained. Activity: 4.510.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 190 Me/1000 CH.sub.2. Bromine number 40 g/100 g.

Example 52

[0315] Repeat the procedure of example 39, the difference is that using complex 1n (1 mol) instead of complex 1a.

[0316] Result: oily polyethylene was obtained. Activity: 810.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 165 Me/1000 CH.sub.2.

Example 53

[0317] Repeat the procedure of example 39, using complex 1o (5 mol) instead of complex 1a.

[0318] Result: oily polyethylene was obtained. Activity: 2.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 280 Me/1000 CH.sub.2. Bromine number 55 g/100 g.

Example 54

[0319] Repeat the procedure of example 39, the difference is that using complex 1p (5 mol) instead of complex 1a.

[0320] Result: oily polyethylene was obtained. Activity: 2.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 320 Me/1000 CH.sub.2.

Example 55

[0321] Repeat the procedure of example 39, the difference is that using complex 1q (5 mol) instead of complex 1a.

[0322] Result: oily polyethylene was obtained. Activity: 1.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 300 Me/1000 CH.sub.2.

Example 56

Alkyl Nickel Catalyst

[0323] Repeat the procedure of example 39, the difference is that using complex 1r (5 mol) instead of complex 1a, and adding co-catalyst MMAO (0.30 mL, 1.9 M).

[0324] Result: oily polyethylene was obtained. Activity: 8.010.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 150 Me/1000 CH.sub.2.

Example 57

Solvent Toluene

[0325] Repeat the procedure of example 39, the difference is that using complex 1j (5 mol) instead of complex 1a and toluene as solvent.

[0326] Result: oily polyethylene was obtained. Activity: 5.010.sup.6 g/mol.Math.h.Math.atm. Bromine number 40 g/100 g. Mn: 200,000 g/mol.

Example 58

Solvent Hexane

[0327] Repeat the procedure of example 39, the difference is that using complex 1j (5 mol) instead of complex 1a and hexane as solvent.

[0328] Result: oily polyethylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm, Mn 125,000 g/mol.

Example 59

Solvent Chlorobenzene

[0329] Repeat the procedure of example 39, the difference is that using complex 1j (5 mol) instead of complex 1a and chlorobenzene as solvent.

[0330] Result: oily polyethylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm, bromine number 50 g/100 g.

Example 60

Solvent Dichloromethane

[0331] Repeat the procedure of example 39, the difference is that using complex 1j (5 mol) instead of complex 1a and DCM as solvent, the temperature is 20 C.

[0332] Result: oily polyethylene was obtained. Activity: 510.sup.6 g/mol.Math.h.Math.atm, bromine number 30 g/100 g.

Example 61

Co-Catalyst: MMAO

[0333] Repeat the procedure of example 39, the difference is that using complex 1j (5 mol) instead of complex 1a and add co-catalyst MMAO (0.30 mL, 1.9M).

[0334] Result: oily polyethylene was obtained. Activity: 610.sup.6 g/mol.Math.h.Math.atm, Bromine number: 35.6 g/100 g. .sup.1HNMR 200 Me/1000 CH.sub.2. Mn 350,000 g/mol

Example 62

Co-Catalyst: MAO

[0335] Repeat the procedure of example 39, the difference is that using complex 1j (5 umol) instead of complex 1a and add co-catalyst MAO (0.30 mL, 1.5M).

[0336] Result: oily polyethylene was obtained. Activity: 7.010.sup.6 g/mol.Math.h.Math.atm, Bromine number: 37 g/100 g. .sup.1HNMR 180 Me/1000 CH.sub.2. Mn 400,000 g/mol

Example 63

80 C.

[0337] Repeat the procedure of example 39, the difference is that the temperature is 80 C.

[0338] Result: oily polyethylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm, Bromine number 50 g/100 g. .sup.1HNMR 480 Me/1000 CH.sub.2. Mn: 1,000 g/mol.

Example 64

20 C.

[0339] Repeat the procedure of example, the difference is that the temperature is 20 C.

[0340] Result: oily polyethylene was obtained. Activity: 710.sup.6 g/mol.Math.h.Math.atm, Bromine number 30.8 g/100 g. .sup.1HNMR 120 Me/1000 CH.sub.2. Mn: 5,000 g/mol.

Example 65

Pressure 3 atm

[0341] A 300 mL Parr autoclave is dried in vacuo at 120 C. overnight. Then at 80 C., it was purged with nitrogen and added DCE (100 mL), and co-catalyst AlEt.sub.2Cl (1.0 mL, 0.9M). The reaction was stirred for 10 min, and then added complex 1a (5 mol). After that the autoclave is charged with ethylene (3 atm) immediately. After 30 min, ethylene was vented. The reaction mixture was concentrated and purified by silica gel column with petroleum ether. The filtrate was concentrated to obtain oily polyethylene. Activity: 610.sup.6 g/mol.Math.h.Math.atm, bromine number 39.8 g/100 g. Mn 10,000 g/mol.

Example 66

Pressure 5 atm

[0342] Repeat the procedure of example 65, the difference is that the pressure of ethylene is 5 atm, the solvent is toluene, and the polymerization temperature is 100 C.

[0343] Result: oily polyethylene was obtained. Activity: 310.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 100 Me/1000 CH.sub.2. Mn: 20,000 g/mol.

Example 67

Nickel Chloride

[0344] Repeat the procedure of example 39, the difference is that using complex 1t instead of complex 1a and add MMAO (0.30 mL, 1.9M) as cocatalyst.

[0345] Result: oily polyethylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm.

Example 68

Nickel Iodide

[0346] Repeat the procedure of example 39, the difference is that using complex 1u instead of complex 1a and add MAO (0.30 mL, 1.5M) as co-catalyst.

[0347] Result: oily polyethylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm.

Example 69

Benzyl Nickel

[0348] Repeat the procedure of example 39, the difference is that using complex 1v instead of complex 1a.

[0349] Result: oily polyethylene was obtained. Activity: 510.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 250 Me/1000 CH.sub.2.

Example 70

Nickel Perchlorate Hexahydrate

[0350] A Schlenk flask (200 mL) was purged first with nitrogen three times and then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 30 mL DCE, Ni(ClO.sub.4).sub.2 (5 mol) and L1a (5.0 mol) were added, and the reaction was stirred for 2 h. Then co-catalyst AlEt.sub.2Cl (0.9M, 1.0 mL) was added, and the reaction mixture was stirred under 1 atm at 60 C. for 30 min. When the reaction completed, the ethylene was vented. The reaction mixture was concentrated and purified by silica gel column with petroleum ether. The filtrate was concentrated to obtain oily polyethylene. Activity: 1.510.sup.6 g/mol.Math.h.Math.atm.

Example 71

Nickel Trifluoromethanesulfonate

[0351] Repeat the procedure of example 70, the difference is that using Ni(OTf).sub.2.

[0352] Result: oily polyethylene was obtained. Activity: 1.510.sup.6 g/mol.Math.h.Math.atm.

Example 72

(COD)N

[0353] Repeat the procedure of example 70, the difference is that using Ni(COD).

[0354] Result: oily polyethylene was obtained. Activity: 1.010.sup.6 g/mol.Math.h.Math.atm.

Example 73

Synthesis of Ligand L1w

[0355] ##STR00049##

[0356] Following the procedure of example 1, Ligand L1w was obtained except that using 2-(phenylthio)aniline instead of aniline in the second step. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.87-6.58 (18H, m), 3.00-2.66 (2H, m), 1.20-0.92 (12H, d); Anal. Calcd. C, 82.40; H, 6.15; N, 5.34. Found C, 82.41; H, 6.13; N, 5.16.

Example 74

Synthesis of Complex 1w

[0357] ##STR00050##

[0358] Following the procedure of example 18, complex was obtained except that using ligand L1w instead of L1a. The structure of the complex is as FIG. 2. Anal. Calcd. For C.sub.36H.sub.32Br.sub.2N.sub.2NiS: C, 58.18; H, 4.34; N, 3.77. Found: C, 58.05; H, 4.49; N, 3.71.

Example 75

[0359] Repeat the procedure of example 39, except that using complex 1w instead of complex 1a for ethylene polymerization to obtain 2.5 g oily polyethylene Activity: 1.010.sup.6 g/mol.Math.h.Math.atm.

[0360] Examples 78-82 is comparative examples using catalyst cited in the literature, only solid polyethylene was obtained using such catalyst under the same conditions as example 39, 63, 64, 57, 62.

Example 76

Synthesis of Ligand L1s

Comparative Ligand

[0361] ##STR00051##

[0362] In a 100 mL egg-shaped flask, acenaphthoquinone (1.822 g, 10 mmol), 2,6-diisopropylaniline (4.0 mL, 21 mmol) and two drops of anhydrous acetic acid were added. The reaction was heated at reflux and monitored by TLC until ended. After the reaction was completed, the orange red diimine product was obtained by crystallizing from anhydrous methanol. .sup.1H NMR (300 MHz, CDCl.sub.3): =7.89 (2H, d), 7.36 (2H, t), 7.26 (6H, s), 6.64 (2H, d), 3.03 (4H, m), 1.24 (12H, d), 0.98 (12H, d).

Example 77

Synthesis of Complex 1s

[0363] ##STR00052##

[0364] Following the procedure of example 18, a reddish brown complex was obtained except that using ligand L1s instead of L1a yield 80%. Anal. Calcd. For C.sub.36H.sub.40Br.sub.2N.sub.2Ni: C, 60.12; H, 5.61; N, 3.89. Found: C, 60.65; H, 5.87; N, 4.24.

Example 78

Comparative with Example 39

[0365] A Schlenk flask (200 mL) was purged first with nitrogen for 3 times, then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 25 mL DCE and then co-catalyst AlEt.sub.2Cl (0.9M, 0.3 mL) were added. Under 1 atm, at 60 C., complex 1s (5 mol) was added and the reaction mixture was stirred for 30 min. when the reaction completed, the ethylene was vented. The reaction mixture was poured into acidified ethanol. Then the solid polymer precipitated and was filtered. The solid was dried in vacuo to obtain 2.0 g solid polymer. Activity: 0.810.sup.6 g/mol.Math.h.Math.atm.

Example 79

Comparative with Example 63

[0366] A Schlenk flask (200 mL) was purged first with nitrogen for 3 times, then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 25 mL DCE and then co-catalyst AlEt.sub.2Cl (0.9M, 0.3 mL) were added. Under 1 atm, at 80 C., complex 1s (5 mol) was added and the reaction mixture was stirred for 30 min. when the reaction completed, the ethylene was vented. The reaction mixture was poured into acidified ethanol. Then the solid polymer precipitated and was filtered. The solid was dried in vacuo to obtain 1.5 g solid polymer. Activity: 0.610.sup.6 g/mol.Math.h.Math.atm.

Example 80

Comparative with Example 64

[0367] A Schlenk flask (200 mL) was purged first with nitrogen for 3 times, then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 25 mL toluene and then co-catalyst AlEt.sub.2Cl (0.9M, 0.3 mL) were added. Under 1 atm, at 20 C., complex 1s (5 mol) was added and the reaction mixture was stirred for 30 min. when the reaction completed, the ethylene was vented. The reaction mixture was poured into acidified ethanol. Then the solid polymer precipitated and filtered. The solid was dried in vacuo to obtain 7.5 g solid polymer. Activity: 3.010.sup.6 g/mol.Math.h.Math.atm.

Example 81

Comparative with Example 57

[0368] A Schlenk flask (200 mL) was purged first with nitrogen for 3 times, then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 25 mL toluene and then co-catalyst AlEt.sub.2Cl (0.9M, 0.3 mL) were added. Under 1 atm, at 60 C., complex 1s (5 mol) was added and the reaction mixture was stirred for 30 min. when the reaction completed, the ethylene was vented. The reaction mixture was poured into acidified ethanol. Then the solid polymer precipitated and filtered. The solid was dried in vacuo to obtain 1.0 g solid polymer. Activity: 0.410.sup.6 g/mol.Math.h.Math.atm.

Example 82

Comparative with Example 62

[0369] A Schlenk flask (200 mL) was purged first with nitrogen for 3 times, then vacuumized, and then purged with ethylene. Under the atmosphere of ethylene, 25 mL DCE and then co-catalyst MAO (1.5 M, 0.3 mL) were added. Under 1 atm, at 60 C., complex 1s (5 mol) was added and the reaction mixture was stirred for 30 min. when the reaction completed, the ethylene was vented. The reaction mixture was poured into acidified ethanol. Then the solid polymer precipitated and filtered. The solid was dried in vacuo to obtain 2.0 g solid polymer. Activity: 0.810.sup.6 g/mol.Math.h.Math.atm, there is no oily polyethylene in the filtrate.

Example 83

Synthesis of Ligand L1x

[0370] ##STR00053##

[0371] Following the procedure of example 1, except that using 2,6-diphenylaniline instead of 2,6-diisopropylaniline in the first step, ligand L1x was obtained. Anal. Calcd. C, 89.23; H, 4.99; N, 5.78. Found C, 82.50; H, 6.24; N, 5.30.

Example 84

Synthesis of Complex 1x

[0372] ##STR00054##

[0373] Following the procedure of example 18, except that using L1x instead of L1a, complex 1x was obtained. Anal. Calcd. C, 61.50; H, 3.44; N, 3.98. Found C, 61.75; H, 3.78; N, 4.20.

Example 85

[0374] Following the procedure of example 39, except that using complex 1x instead of 1a, 7.6 g oily polyethylene was obtained. Activity: 3.110.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 160 Me/1000 CH.sub.2.

Example 86

Synthesis of Ligand 1y

[0375] ##STR00055##

[0376] Following the procedure of example 1, except that using 4-nitroaniline instead of aniline, L1y was obtained. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.33-6.48 (13H, m), 2.91-2.43 (2H, m), 1.15-0.81 (12H, m); .sup.13C NMR (75 MHz, CDCl.sub.3): =161.0, 157.7, 146.9, 144.4, 141.4, 135.3, 134.0, 131.1, 129.9, 129.1, 128.8, 127.6, 125.5, 124.7, 124.5, 123.9, 123.8, 123.6, 123.4, 123.3, 123.2, 121.8, 120.6, 118.8, 117.8, 77.0, 28.3, 23.5, 23.4, 23.3, 22.4.

Example 87

Synthesis of Complex 1y

[0377] ##STR00056##

[0378] Following the procedure of example 18, except that using ligand L1y instead of L1a, and complex 1y was obtained. Anal. Calc. C, 52.98; H, 4.00; N, 6.18. Found C, 53.33; H, 4.34; N, 6.04.

Example 88

[0379] Following the procedure of example 39, except that using complex 1y instead of 1a, using propene instead of ethylene and 0.8 g oily polypropylene was obtained. Activity: 3.210.sup.6 g/mol.Math.h.Math.atm, .sup.1HNMR 260 Me/1000 CH.sub.2. Mn: 1500 g/mol.

Example 89

Synthesis of ligand 1z

[0380] ##STR00057##

[0381] Following the procedure of example 1, except that using 2-((methylthio)methyl)aniline instead of aniline, and L1z was obtained. .sup.1H NMR (300 MHz, CDCl.sub.3): =8.19-6.59 (13H, m), 3.75 (2H, s), 3.04 (2H, m), 1.89 (3H, s), 1.24-0.97 (12H, m); Anal. Calcd. C, 80.63; H, 6.77; N, 5.88. Found C, 80.55; H, 6.72; N, 5.75.

Example 90

Synthesis of Complex 1z

[0382] ##STR00058##

[0383] Following the procedure of example 18, except that using ligand L1z instead of L1a, and complex 1z was obtained. Anal. Calc. C, 55.29; H, 4.64; N, 4.03. Found C, 54.99; H, 4.55; N, 3.94.

Example 91

[0384] Following the procedure of example 39, except that using complex 1z instead of 1a and using but-2-ene instead of ethylene, and 2.5 g highly branched oily polybutylene was obtained. Activity: 110.sup.6 g/mol.Math.h.Math.atm.

[0385] The results are summarized in Table 1.

TABLE-US-00001 TABLE 1 Y and Z Activity together 10.sup.6 g/mol .Math. h .Math. atm Compound forming R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 Complex (product form) 1 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H H H 1a 3.0 (oil) 2 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 Cl Cl H H H 1b 7.0 (oil) 3 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 Br Br H H H 1c 9.0 (oil) 4 Naphthyl CH.sub.3 CH.sub.3 Cl Cl H H H 1d 1.0 (oil) 5 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H OCH.sub.3 H 1e 2.0 (oil) 6 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H N(CH.sub.3).sub.2 H 1f 2.0 (oil) 7 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H Cl H 1g 2.0 (oil) 8 Naphthyl CF.sub.3 Br CH(CH.sub.3).sub.2 H Br H H 1h 1.0 (oil) 9 phenanthryl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 Cl Cl H H H 1i 50 (oil) 10 phenanthryl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 Br Br H H H 1j 4.0 (oil) 11 Z: phenyl Cl Cl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H 1k 5.0 (oil) Y: CH.sub.3 12 Z: phenyl Br Br CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H 1l 6.0 (oil) Y: CH.sub.3 13 Naphthyl CF.sub.3 Br CF.sub.3 H Br H H 1m 4.5 (oil) 14 Naphthyl CF.sub.3 Br t-Bu H Br H H 1n 8.0 (oil) 15 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H CF.sub.3 H 1o 2.0 (oil) 16 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H H CF.sub.3 1p 2.0 (oil) 17 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 PhOCH.sub.2 H H H H 1q 1.0 (oil) 18 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 PhOCH.sub.2 H H H H 1r (X is CH.sub.3) 8.0 (oil) 19* Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H 1s 0.8 (solid) 20 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 PhS H H H H 1w 1.0 (oil) 21 Naphthyl phenyl phenyl H H H H H 1x 3.1 (oil) 22 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H H H NO.sub.2 H 1y 3.2 (oil) 23 Naphthyl CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 H CH.sub.3SCH.sub.2 H H H 1z 1.0 (oil) *Compound 19 as a comparative compound.

[0386] Preparing Highly Branched Oily Alkane by Hydrogenation (Oily Alkane Mixture)

Example 92

[0387] In a 50 mL egg-shaped flask, highly branched oily polyethylene (2.5 g) obtained in example 47, Pd/C (50 mg) and n-hexane (10 mL) were added. The flask was then purged with hydrogen for three times and at the atmospheric pressure, the reaction was stirred overnight at room temperature. Stop the hydrogenation until the raw material was hydrogenated completely determined by .sup.1HNMR. The reaction mixture was filtered through silica gel column. The filtrate was concentrated to obtain highly branched oily alkane. Bromine number: 0.31 g/100 g. .sup.1HNMR 230 Me/1000 CH.sub.2. VI 261. Kinetic viscosity (100 C.): 7.9 cSt. The .sup.13CNMR spectra is shown as FIG. 1. The molecular weight is about 110,000 g/mol. Pour point is 15 C., flash point is 194 C., Evaporation loss is 3.8% W/W.

Example 93

Neat

[0388] In a 50 mL egg-shaped flask, highly branched oily polyethylene (2.5 g) obtained in example 47, and Pd/C (50 mg) were added. The flask was then purged with hydrogen for three times and at the atmospheric pressure, the reaction was stirred overnight at room temperature. Stop the hydrogenation until the raw material was hydrogenated completely determined by .sup.1HNMR. The reaction mixture was filtered through silica gel column. The filtrate was concentrated to obtain highly branched oily alkane. Bromine number: 0.33 g/100 g. .sup.1HNMR 260 Me/1000 CH.sub.2.

Example 94

[0389] Repeat the procedure of example 92, except that using Pd(OH).sub.2 instead of Pd/C.

[0390] Result: oily polyethylene was obtained, bromine number: 0.39 g/100 g.

Example 95

[0391] Repeat the procedure of example 92, except that using oily polyethylene produced in example 48 as the substrate to be hydrogenated.

[0392] Result: highly branched oily alkane was obtained, bromine number: 0.38 g/100 g. .sup.1HNMR 240 Me/1000 CH.sub.2. VI: 300.

Example 96

[0393] Repeat the procedure of example 92, except that using oily polyethylene produced in example 41 instead.

[0394] Result: highly branched oily alkane was obtained, bromine number: 0.36 g/100 g.

Example 97

[0395] Repeat the procedure of example 39, except that using propylene instead of ethylene to obtain oily polypropylene. Then repeat the procedure of example 92, except that using the oily polypropylene instead.

[0396] Result: highly branched oily alkane was obtained, bromine number: 0.10 g/100 g. Pour point: 40 C. Flash point: 190 C.

Example 98

[0397] Repeat the procedure of example 39, except that using butene instead of ethylene to obtain oily polybutene. Then under the same condition as example 92, hydrogenate the oily polybutene to obtain highly branched oily alkane. Bromine number: 0.49 g/100 g.

Example 99

[0398] Repeat the procedure of example 39, except that using complex 1i to catalyze the polymerization of 1-butene instead of 1a, to obtain 3.2 g oily polybutylene. Then under the same condition as example 92, hydrogenate the oily polybutylene to obtain highly branched oily alkane.

[0399] Bromine number: 0.43 g/100 g. Pour point: 15 C. Flash point: 200 C. VI: 195.

Example 100

[0400] Repeat the procedure of example 39, except that using complex 1a to catalyze the copolymerization of ethylene and 1-butene to obtained 5.8 g oily polymer. Then under the same condition as example 92, hydrogenate the oily polymer to obtain highly branched oily alkane.

[0401] Bromine number: 0.31 g/100 g. Pour point: 17 C. Flash point: 193 C. VI: 186.

Example 101

[0402] Repeat the procedure of example 47, except that reacting ethylene with the catalyst for polymerization and purging hydrogen simultaneously. After the hydrogenation completed, filter the reaction mixture and concentrate the filtrate to obtain highly branched oily alkane.

[0403] Bromine number: 0.48 g/100 g. .sup.1HNMR 320 Me/1000 CH.sub.2. VI: 189. Pour point: 26 C. Flash point: 190 C.

Example 102

[0404] Repeat the procedure of example 47, except that after reacting ethylene with the catalyst for polymerization for 30 min, the reaction mixture was added Pd/C (50 mg) without processing and purged with hydrogen. After the hydrogenation completed, filter the reaction mixture and concentrate the filtrate to obtain highly branched oily alkane. .sup.1HNMR: 260 Me/1000 CH.sub.2.

Example 103

[0405] Repeat the procedure of example 47, except that after reacting ethylene with the catalyst for polymerization for 30 min, the reaction was directly purged with hydrogen without processing and reacted under the atmosphere of hydrogen until completed. The reaction mixture was filtered and the filtrate was concentrated to obtain highly branched oily alkane. Bromine number: 0.34 g/100 g.

Example 104

[0406] A 300 mL Parr autoclave is dried in vacuo in an oil bath at 120 C. overnight. It was purged with nitrogen for three times, and then in an oil bath at 60 C., DCE (50 mL) and MMAO (1.0 mL) were added. Then under the atmosphere of hydrogen (0.5 atm), catalyst 1b (5 mol) was added. Then ethylene was purged and the reaction was conducted for 30 min. After that, the reaction was cooled and the autoclave was opened. The reaction mixture was filtered and the filtrate was concentrated to obtain 3.0 g oily polyethylene. Bromine number 0.48 g/100 g. .sup.1HNMR: 230 Me/1000 CH.sub.2. Pour point: 23 C.

Example 105

[0407] A 300 mL Parr autoclave is dried in vacuo in an oil bath at 120 C. overnight. It was purged with nitrogen for three times, and then in an oil bath at 80 C., DCE (50 mL) and MMAO (1.0 mL) were added. Then under the atmosphere of hydrogen (0.5 atm), catalyst 1b (5 mol) was added. Then ethylene was purged and the reaction was conducted for 30 min. After that, the reaction was cooled and the autoclave was opened. The reaction mixture was filtered and the filtrate was concentrated to obtain 1.5 g oily polyethylene. Bromine number 0.28 g/100 g. .sup.1HNMR: 300 Me/1000 CH.sub.2.

Example 106

[0408] A 300 mL Parr autoclave is dried in vacuo in an oil bath at 120 C. overnight. It was purged with nitrogen for three times, and then in an oil bath at 80 C., DCE (50 mL) and AlEt.sub.2Cl (1.0 mL) were added. Then under the atmosphere of hydrogen (0.5 atm), catalyst 1b (5 umol) was added. Then ethylene was purged and the reaction was conducted for 30 min. After that, the reaction was cooled and the autoclave was opened. The reaction mixture was filtered and the filtrate was concentrated to obtain 1.3 g oily polyethylene. Bromine number 0.37 g/100 g. .sup.1HNMR: 450 Me/1000 CH.sub.2. Pour point: 32 C.

Example 107

[0409] A 300 mL Parr autoclave is dried in vacuo in an oil bath at 120 C. overnight. It was purged with nitrogen for three times, and then in an oil bath at 45 C., 50 mL of oily polyethylene (Mv: 1500 g/mL) and MMAO (1.0 mL) were added. Then under the atmosphere of hydrogen (0.5 atm), catalyst 1c (5 mol) was added. Then the reaction was purged with ethylene and conducted for 30 min. After that, the reaction was cooled and the autoclave was opened. The reaction mixture was filtered and the filtrate was concentrated to obtain 4.5 g oily polyethylene. Bromine number 0.39 g/100 g. .sup.1HNMR 320 Me/1000 CH.sub.2.

Example 108

[0410] Repeat the procedure of example 92, except that using oily polyethylene obtained in example 63 as the substrate for hydrogenation.

[0411] Result: highly branched oily alkane was obtained, bromine number: 0.25 g/100 g. .sup.1HNMR 490 Me/1000 CH.sub.2.

Example 109

[0412] Repeat the procedure of example 92, except that using oily polyethylene obtained in example 49 as the substrate for hydrogenation.

[0413] Result: highly branched oily alkane was obtained, bromine number: 0.14 g/100 g. .sup.1HNMR 110 Me/1000 CH.sub.2.

Example 110

[0414] Repeat the procedure of example 39, except that using complex 1a to catalyze the copolymerization of ethylene and hex-5-en-1-ol to produce oily copolymer 9.0 g.

[0415] Then under the same condition as example 92, hydrogenate the oily polymer to obtain highly branched oily alkane with alcoholic hydroxyl group. Bromine number: 0.30 g/100 g. Pour point: 30 C. Flash point: 193 C. VI: 180.

Example 111

[0416] Repeat the procedure of example 39, except that using complex 1a to catalyze the copolymerization of ethylene and dec-9-en-1-ol to produce oil copolymer 12.1 g.

[0417] Then under the same condition as example 92, hydrogenate the oily polymer to obtain highly branched oily alkane with alcoholic hydroxyl group. Pour point: 19 C.

Example 112

[0418] Repeat the procedure of example 39, except that using complex 1a to catalyze the copolymerization of ethylene and methyl dec-9-enoate to obtain oily polymer 5.6 g.

[0419] Then under the same condition as example 92, hydrogenate the oily polymer to obtain highly branched oily alkane with ester group. Pour point: 29 C. VI: 190. Flash point: 198 C.

[0420] There is no specific number of methyl groups in the oily alkane polymer in example 92-112, it is determined that, the number of corresponding methyl groups per 1000 methylene is 160 to 350.

Example 113

[0421] Refer to ASTM D97 (petroleum-based oil's pour point standard) to measure the product pour point.

[0422] Refer to ASTM D1500 standard method to measure chroma.

[0423] Refer to ASTM D4052 standard method to measure density at 15.6 C.

[0424] Refer to ASTM D445 standard method to measure kinematic viscosity at 100 C. and 40 C.

[0425] Refer to ASTM D92 standard method to measure bromine number.

[0426] Refer to ASTM D1159 standard method to determine flash point.

[0427] Refer to ASTM D664 standard method to determine acidity.

[0428] Wherein, as testing pour point and flash point needs more samples, enlarge the scale of polymerization under the same conditions as in various examples to obtain the test sample.

[0429] The results are shown in Table 2. The results show that the pour point, flash point, chroma, evaporation loss of the highly branched oil alkane of the present invention is equivalent to the commercially available PAO or Group III base oil, but the viscosity index is higher than the existing products, and can remain the viscosity in a larger temperature range and is more suitable for lubricant base oil.

TABLE-US-00002 TABLE 2 test results of Performance Pour Flash Evaporation viscosity viscosity Viscosity point point loss example chroma (cSt 100 C.) (cSt 40 C.) index ( C.) C.) (% W/W) 92 <0.5 7.9 29.3 261 15 194 3.8 93 <0.5 7.9 29.3 261 15 194 94 <0.5 7.9 29.3 261 15 194 95 <0.5 8.5 30.2 300 17 200 97 <0.5 4.5 20.1 150 40 190 98 <0.5 7.4 35.7 180 99 <0.5 8.4 40.1 195 15 200 100 <0.5 7.0 32.4 186 17 193 101 <0.5 4.5 18.2 189 26 190 102 <0.5 7.9 29.3 261 15 194 103 <0.5 7.9 29.3 261 15 194 104 <0.5 4.4 17.5 190 23 105 <0.5 4.3 16.8 188 106 <0.5 4.1 16.3 180 32 3.9 107 <0.5 7.0 28.6 230 108 <0.5 4.6 19.1 179 110 <0.5 180 30 193 111 <0.5 19 112 <0.5 190 29 198 PAO(Controle) <0.5 8.0 48.0 139 48 4.1 Group III base <0.5 4.0 120-130 18~20 13-14 oil (Controle)

[0430] Preparation of Lubricant

Example 114

[0431] Following the procedure of example 92, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base oil, 0.2 wt %-0.5 wt % of methyl acrylate copolymer or a polyacrylate was mixed with base oil to produce the lubricant. The pour point of the lubricant is 32 C. to 40 C.

Example 115

[0432] Following the procedure of example 92, enlarge the polymerization to obtain oil products to be used as base oil. Copolymer of long chain alkyl acrylate and acrylonitrile (500 mg/L oil products) was mixed with base oil to produce the lubricant. The pour point of the lubricant decreased to 20 C.-30 C.

Example 116

[0433] Following the procedure of example 97, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base oil, 0.02 wt % 2,6-di-tert-butyl--dimethylamino-4-methylphenol as antioxidation, and 0.5 wt %-2 wt % the dodecencyl succinic salts of heptadecenyl imidazoline or 0.5 wt %-4 wt % barium dinonyl naphthalene sulfonate, and the condensate of amine and epoxide were mixed with base oil to produce the antirust and antioxidative lubricant.

Example 117

[0434] Following the procedure of example 97, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base oil, 1 wt %-5 wt % multialkenyl succimide or monoalkenyl succimide or dialkenyl succimide as a dispersant, 0.8 wt %-1.3 wt % synthetic calcium sulfonate with high base number or 2 wt %-3 wt % calcium alkylsalicylate as a detergent, 0.1 wt %-0.5 wt % silicone grease as a defoaming agent, 0.4 wt %-0.6 wt % the condensate of amine and epoxide as anticreaming agent were mixed with base oil to produce a lubricant.

Example 118

[0435] Following the procedure of example 90, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base, 0.1 wt %-1.0 wt % alkyl naphthalene was mixed with base oil to produce a lubricant.

Example 119

[0436] Following the procedure of example 97, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base, 0.3 wt % phosphate as a friction modifier was mixed with base oil to produce a lubricant.

Example 120

[0437] Following the procedure of example 97, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base, 0.2 wt %-0.5 wt % zinc salt of dialkyl phosphorodithioic acid as a antioxidant corrosion inhibitor was mixed with base oil to produce a lubricant.

Example 121

[0438] Following the procedure of example 97, enlarge the polymerization to obtain oil products to be used as base oil. Basing on the quality of the base, 2 wt %-10 wt % of ethylene glycol oleate as an oiliness agent was mixed with base oil to produce a lubricant.

[0439] All literatures mentioned in the present application are incorporated by reference herein, as though individually incorporated by reference. Additionally, it should be understood that after reading the above teaching, many variations and modifications may be made by the skilled in the art, and these equivalents also fall within the scope as defined by the appended claims.