CN107602734A

CN107602734A - A kind of palladium-containing catalyst, its preparation method, by its obtained composition and application

Info

Publication number: CN107602734A
Application number: CN201710930529.7A
Authority: CN
Inventors: 蔡正国; 丁琳; 伏夏; 张凌隽
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2017-10-09
Filing date: 2017-10-09
Publication date: 2018-01-19
Anticipated expiration: 2037-10-09
Also published as: CN107602734B

Abstract

The present invention relates to a kind of palladium-containing catalyst, its preparation method, as follows by its obtained composition and application, the structural formula of palladium-containing catalyst：

Description

A kind of palladium-containing catalyst, its preparation method, by its obtained composition and application

Technical field

The invention belongs to olefin catalytic field, is related to a kind of palladium-containing catalyst, its preparation method, by its obtained composition And application, and in particular to a kind of palladium-containing catalyst for being catalyzed ethene or ethene and polarity/function monomer, its preparation method, by it Obtained composition and application.

Background technology

As what coordination polymerization catalysts were studied gos deep into, successively there are a few major class olefin polymerization catalysis： Ziegler-Natta catalyst, metallocene catalyst, non-luxuriant Former transition metal catalyst and late transition metal catalyst, this The development of a little catalyst has greatly promoted industrialized progress.In recent years, late transition metal catalyst for olefin polymerization obtained Tremendous development, late transition metal catalyst for olefin polymerization refer to a kind of alkene that catalytic active center is VIII B races metallic element Polymerization catalyst.The late transition metal catalyst for olefin polymerization that early stage obtains is mostly olefin oligomerization catalyst, is because rear transition β-H easily occur in polyolefin and eliminates and generates oligomer for metallic catalyst, although also there is a small number of catalyst system and catalyzings to generate High polymer, but catalytic activity is general very low, so not attracting people's attention.

Late transition metal catalyst is α-two disclosed in nineteen ninety-five Brookhart et al. for the high poly- breakthrough first of alkene Imido grpup nickel, palladium catalyst (Brookhart.M., J.Am.Chem.Soc., 1995,117,6414.), this catalyst can be with The alpha-olefin homopolymerizations such as the catalysis ethene and 1- hexenes and propylene of high activity, and obtain the polymer of HMW.This series is urged The exploitation of agent has greatly promoted the development of late transition metal catalyst for olefin polymerization.2000, Grubbs et al. was by SHOP [P, O] part of catalyst system and catalyzing change into can bigger [N, the O] part of Coordination Space, synthesized in a kind of aqueous positive aldehyde part Property alkene catalyst (Grubbs.R.H., Science, 2000,287,460.), this kind of catalyst can obtain higher molecular weight Polyethylene, it is often more important that ethene and polar monomer copolymerization can be catalyzed.This series of discovery is in late transition metal alkene Polymerization catalyst field obtains very big concern, has started the research boom to this kind of neutral catalyst.

At present, there is series of advantages using late transition metal catalyst catalysis in olefine polymerization：To alkene and cyclic olefin polymerization Active very high, the narrow molecular weight distribution of gained polyolefin, synthesis is relatively easy, and yield is higher, relatively stable in atmosphere, can The copolymerization of catalyzed alkene and polar monomer, new varieties polyolefin can be produced and the new polymers with functional group can be synthesized. But appoint the needs further research that so comes with some shortcomings, mainly have：(1) Copolymerization activity of ethene and polar monomer, copolymerization are inserted Enter rate to have much room for improvement；(2) can be catalyzed less with the polar monomer species of ethylene copolymer；(3) molecular weight of copolymer is smaller, point Son amount wider distribution, can not realize the structure regulating to copolymer molecule chain；(4) each side such as yield, polymer performance, cost Industrial requirement can not be met.

Therefore, exploitation one kind has high catalytic activity, even without the new of co-catalyst can catalysis in olefine polymerization Late transition metal catalyst be extremely important.

The content of the invention

The purpose of the present invention is to overcome prior art late transition metal catalyst catalyzed alkene to be copolymerized with polarity/function monomer Activity is not high, and comonomer insertion rate is small, it is necessary to which the defects of adding a large amount of co-catalysts to improve catalytic activity or insertion rate, carries For the olefin polymerization catalyst that a kind of catalytic activity is high, comonomer insertion rate is high.A kind of aniline naphthalene has been made in the present invention Quinone late transition metal catalyst, carry out ethene or ethene using the catalyst and polymer be made with polymerizeing for polarity/function monomer, The catalyst activity is higher, has very strong copolymerized ability to polarity/function monomer, the catalyst can also coordinate co-catalysis Agent is used for polymerizeing for ethene or ethene and polarity/function monomer, stronger to the copolymerized ability of polarity/function monomer, and product polarity/ The insertion rate of function monomer is higher.

To achieve the above object, the present invention is solved by the following technical programs：

Palladium-containing catalyst, structural formula are as follows：

In formula, R₁~R₅Be each independently selected from hydrogen, alkyl, the substituent of alkyl, alkoxy, alkylthio group, halogen, nitro, Aryl or aryl substituent, work as R₁~R₅During middle adjacent group cyclization, the quantity of the ring structure of formation is less than 4, R₆For alkyl or virtue Base, L are pyridine.

As preferable technical scheme：

Palladium-containing catalyst as described above, for R₁~R₅The alkyl of selection is methyl, ethyl, isopropyl or the tert-butyl group, alkyl Substituent be chloromethyl, dichloromethyl, trichloromethyl or diphenyl methyl, alkoxy is methoxy or ethoxy, alkane sulphur Base is methyl mercapto or ethylmercapto group, and halogen is fluorine, chlorine, bromine or iodine, and aryl is phenyl or benzyl, and aryl substituent is chlorine substituted benzene Base or fluorine substituted-phenyl；

For R₆The alkyl of selection is methyl, and aryl is phenyl.

The invention provides a kind of method for preparing palladium-containing catalyst as described above, step are as follows：

(1) HNQ and substituted aniline are dissolved in organic solvent, adds catalyst A and react To aniline naphthoquinones class part；The structural formula of the substituted aniline is as follows：

(2) by the dissolving of aniline naphthoquinones class part in organic solvent, addition pulls out hydrogen reagent and is reacted to obtain part salinization Compound；

(3) add palladium forerunner's precursor reactant and obtain the metal complex of intermediate state；

(4) pyridine reagent is added to react to obtain catalyst.

As preferable technical scheme：

Method as described above, in step (1), when reaction starts, the HNQ and substituted aniline rub You are than being 1:1~1.2, the mol ratio of the catalyst A and HNQ are 0.32~0.35:1, the 2- hydroxyls- The concentration of 1,4- naphthoquinones in organic solvent is 0.1~0.15mol/L；

The organic solvent is normal heptane, toluene, chlorobenzene, 1,4- dioxane, octane, 4-methyl-2 pentanone, ethylenediamine Or metacresol, the catalyst A are trifluoroacetic acid；

The temperature of the reaction is 90~130 DEG C, and the time is 6~24h；

In step (2), when reaction starts, the hydrogen reagent and the mol ratio of aniline naphthoquinones class part of pulling out is 1~1.2:1, The concentration of the aniline naphthoquinones class part in organic solvent is 0.01~0.02mol/L；

The organic solvent is toluene, tetrahydrofuran, dichloromethane, ether, n-hexane, chlorobenzene or Isosorbide-5-Nitrae-dioxane, The hydrogen reagent that pulls out is sodium hydride, hydrofining, n-BuLi, potassium tert-butoxide or two (trimethyl silicon substrate) Sodamides；

The temperature of the reaction is 0~40 DEG C, and the time is 1~10h；

In step (3), the addition of the palladium presoma is rubbed with aniline naphthoquinones class part addition described in step (2) You are than being 1.1:1；

The palladium presoma is (1,5- cyclo-octadiene) methyl chloride palladium；

The temperature of the reaction is 0~40 DEG C, and the time is 3~5h；

In step (4), the mol ratio of the addition and palladium presoma addition described in step (3) of the pyridine reagent is 3:1；

The temperature of the reaction is 0~40 DEG C, and the time is 10~12h.

Method as described above, in step (1), the aniline naphthoquinones class part for reacting to obtain is recrystallized or extracted through organic solvent Carry out purification processes are taken, the organic solvent of purification processes is toluene, dichloromethane, tetrahydrofuran, ether, n-hexane, positive heptan Alkane, chlorobenzene, methanol or ethanol.

Present invention also offers a kind of application of palladium-containing catalyst as described above, catalyst is applied to catalyzed alkene list The homopolymerization or copolymerization of body.

As preferable technical scheme：

Application as described above, application process are：Under inert gas shielding, by catalyst dissolution in a solvent, add Polymerisation 10min~60min obtains olefin polymer at 20~60 DEG C after olefinic monomer；

The inert gas is high pure nitrogen, high-purity argon gas or high-purity helium, and the solvent is toluene, chlorobenzene, n-hexane Or normal heptane, the olefinic monomer are ethene, or it is ethene and polarity/function monomer；

When olefinic monomer is ethene, ethene is passed through in reaction system in gaseous form, the pressure of ethene for 10~ 30atm, the concentration of catalyst in a solvent are 1.67 × 10^-4Mol/L, the volume of solvent is 30mL；

When olefinic monomer is ethene and polarity/function monomer, ethene is passed through in reaction system in gaseous form, ethene Pressure be 1~30atm, the mol ratio of polarity/function monomer and catalyst is 2000~12000:1, polarity/function monomer exists Concentration in solvent is 0.33~2mol/L, and the volume of solvent is 30mL；

Polarity/the function monomer is acetic acid 5- hexenes base ester, vinyl acetate, allyl acetate, methyl acrylate, drop Bornylene, 5- ENB -2- yl acetates, 5- ENB -2- methanol or styrene；

The olefin polymer is ethylene low polymer or ethylene polymer, the molecular weight of ethylene low polymer for 550~ 4200g·mol^-1, molecular weight distributing index is 2.9~6.7, and glass transition temperature or fusing point are 83~100 DEG C, and ethene is high poly- The molecular weight of thing is 9900~21500gmol^-1, molecular weight distributing index is 2.5~4.6, glass transition temperature or fusing point For 83~113 DEG C；

When olefin polymer is copolymer, the insertion rate of polarity/function monomer is 0.149~56mol%.

Present invention also offers one kind using composition made from palladium-containing catalyst as described above, composition is by catalyst Formed with co-catalyst；

The co-catalyst is aluminum contained compound, and the mol ratio of catalyst and aluminium in aluminum contained compound is 1:20~500；

The aluminum contained compound is aikyiaiurnirsoxan beta, alkyl aluminum compound, alkyl aluminum chloride compound or alchlor；

The aikyiaiurnirsoxan beta is that the tert-butyl group aluminium of MAO, the MAO that tert-butyl group aluminium is modified or drying is modified MAO, the alkyl aluminum compound are that trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or three are just pungent Base aluminium, the alkyl aluminum chloride compound are diethylaluminum chloride or ethylaluminium dichloride.

The invention provides a kind of application of composition as described above, composition is applied to the equal of catalyzed alkene monomer Poly- or copolymerization.

As preferable technical scheme：

Application as described above, application process are：Under inert gas shielding, by composition dissolving in a solvent, add Polymerisation 5min~60min obtains olefin polymer under the conditions of 0~60 DEG C after olefinic monomer；

The olefin polymer is ethylene low polymer or ethylene polymer, and the molecular weight of ethylene low polymer is 5200g mol^-1, molecular weight distributing index 4.6, glass transition temperature is 93 DEG C, the molecular weight of ethylene polymer for 10120~ 36100g·mol^-1, molecular weight distributing index is 2.1~5.9, and glass transition temperature or fusing point are 93~133 DEG C；

When olefin polymer is copolymer, the insertion rate of polarity/function monomer is 0.38~60mol%.

Invention mechanism：

The catalyst of the present invention can be with synthesizing ethylene oligomer under the conditions of non-promoted dose, can also be in co-catalyst bar Synthesize ethylene polymer under part, the polyethylene of HMW can be obtained, the catalyst system also can be used for ethene and polarity/ The copolymerization of function monomer, and with higher molecular weight, higher active and higher insertion rate.The catalyst of the present invention can be single The polymerization of only catalyzed alkene, when substituent is larger on aniline, axial steric hindrance is larger, and the substituent centering ligand L there is Stronger repulsive interaction so that L is easy to leave away, and the activity of catalyst olefinic polymerization is higher；When substituent is smaller on aniline When, axial steric hindrance is smaller, and the neutral ligand L in Metal Palladium is difficult to remove, the active very little of catalyst olefinic polymerization, it is necessary to Co-catalyst is added to activate it.And under larger axial steric hindrance shielding action, in polar monomer and polymerization system Various hetero atoms and central metal palladium touch opportunity it is smaller, catalyst " poisoning " can be avoided to inactivate, it is single to improve copolymerization The insertion rate of body.Larger axial steric hindrance can also suppress β-H elimination, so as to obtain the polymer of HMW, narrow ditribution.

There is isolated oxygen atom in the catalyst structure of the present invention, when co-catalyst and oxygen atom effect, be initially formed A kind of amphion complex, the lewis acidity of effective control centre's metal, so as to effectively to Olefins Product Streams Molecular weight and chain structure regulated and controled.When carrying out polymerisation, catalyst can interact to be formed with co-catalyst and contain first Have the activated centre of unoccupied orbital, then olefinic monomer is coordinated on unoccupied orbital and forms growing chain, finally by chain termination reaction or Chain transfer reaction forms polymer.

For example, when making co-catalyst using MMAO, Lewis acid are complexed to the single anion of neutral palladium system complex On part, a kind of zwitterionic compound is formed, is departed from the neutral ligand pyridine ring of central metal palladium coordination from complex, Thus central metal forms unoccupied orbital, is converted, makes to neutral ligand by the property of the Lewis acid single anion ligands being complexed The increase of metal catalytic activity center electropositivity, the electronic property of catalytic activity kind is from neutrality to cationic transition, this activity Center has very strong electrophilicity so that alkene and the complexing speed at metal catalytic center are very fast, therefore catalytic activity is high, tool Vivo reaction type is as follows：

Beneficial effect：

(1) a kind of palladium-containing catalyst of the invention, there is isolated oxygen atom in catalyst, when different co-catalysts and oxygen are former During son effect, the amphion complex of different structure, the lewis acidity of effective control centre's metal, so as to have are formed Effect ground regulates and controls to the molecular weight and chain structure of Olefins Product Streams；

(2) a kind of palladium-containing catalyst of the invention, can be with synthesizing ethylene oligomer, to alkene under the conditions of non-promoted dose Monomer homopolymerization and copolymerization effect are good, and wherein molecular weight of product is higher and narrow molecular weight distribution made from alkene homopolymerization or copolymerization, right In the copolymerization of alkene and polarity/function monomer, also with polarity/function monomer insertion rate it is high the characteristics of, saved cost, had Good economy；

(3) a kind of palladium-containing catalyst of the invention, compared with the late transition metal catalyst of metal centered on nickel, to pole Property monomer has more preferable tolerance；

(4) composition as made from palladium-containing catalyst and co-catalyst of the invention, when co-catalyst dosage is seldom just Ethylene polymer can be synthesized, the polyethylene of HMW can be obtained, there is preferable catalytic activity, its molecular weight of product compared with High and narrow molecular weight distribution, the copolymerization for ethene and polarity/function monomer are also high with polarity/function monomer insertion rate Feature.

Embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.

Embodiment 1

A kind of preparation method of palladium-containing catalyst, step are as follows：

(1) HNQ and substituted aniline are dissolved in normal heptane, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 100 DEG C, time 15h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.15, the mol ratio of trifluoroacetic acid and HNQ is 0.33:1, HNQ Concentration in normal heptane is 0.125mol/L, and the structural formula of substituted aniline is as follows：

In formula, R₁For ethyl, R₂For ethyl, R₃For methyl, R₄For methyl, R₅For methyl, aniline naphthoquinones class is matched somebody with somebody after reaction Body carries out purification processes through re crystallization from toluene；

(2) aniline naphthoquinones class part is dissolved in toluene, adds sodium hydride and reacted to obtain part salt compound, instead The temperature answered is 20 DEG C, time 3h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.15:1, benzene Concentration of the amine naphthoquinones class part in toluene is 0.015mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 20 DEG C, time 3h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 20 DEG C, and time 10h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

The structural formula of final obtained catalyst is as follows：

In formula, R₆For phenyl, L is pyridine ring.

Embodiment 2

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 110 DEG C, time 6h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1, the mol ratio of trifluoroacetic acid and 2- hydroxyls -1,4-naphthoquinone is 0.32:1, HNQ is in first Concentration in benzene is 0.1mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For methyl, R₂For methyl, R₃ For ethyl, R₄For ethyl, R₅For ethyl, purification processes are carried out through n-hexane extraction to aniline naphthoquinones class part after reaction；

(2) aniline naphthoquinones class part is dissolved in tetrahydrofuran, adds sodium hydride and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 40 DEG C, time 1h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1:1, Concentration of the aniline naphthoquinones class part in tetrahydrofuran is 0.01mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 40 DEG C, time 3h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 40 DEG C, and time 10h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

The structural formula of final obtained catalyst as described in Example 1, in formula, R₆For phenyl, L is pyridine ring.

Embodiment 3

(1) HNQ and substituted aniline are dissolved in chlorobenzene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 130 DEG C, time 6h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.02, the mol ratio of trifluoroacetic acid and HNQ is 0.32:1, HNQ exists Concentration in chlorobenzene is 0.11mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For isopropyl, R₂For isopropyl Base, R₃For methyl, R₄For methyl, R₅For methyl, aniline naphthoquinones class part is carried out at purification through tetrahydrofuran recrystallization after reaction Reason；

(2) aniline naphthoquinones class part is dissolved in dichloromethane, adds hydrofining and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 0 DEG C, time 10h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.01:1, concentration of the aniline naphthoquinones class part in dichloromethane is 0.015mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 0 DEG C, time 4h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) pyridine reagent is added to be reacted to obtain catalyst, reaction temperature is 0 DEG C, time 12h, when reaction starts, The mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

The structural formula of final obtained catalyst as described in Example 1, in formula, R₆For methyl, L is pyridine ring.

Embodiment 4

(1) HNQ and substituted aniline are dissolved in Isosorbide-5-Nitrae-dioxane, add trifluoroacetic acid and carry out instead Should obtain aniline naphthoquinones class part, the temperature of reaction is 100 DEG C, time 18h, when reaction starts, HNQ with The mol ratio of substituted aniline is 1:1.04, the mol ratio of trifluoroacetic acid and HNQ is 0.35:1,2- hydroxyl -1, Concentration of the 4- naphthoquinones in Isosorbide-5-Nitrae-dioxane is 0.11mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁ For the tert-butyl group, R₂For the tert-butyl group, R₃For ethyl, R₄For ethyl, R₅For ethyl, to aniline naphthoquinones class part through ether weight after reaction Crystallization carries out purification processes；

(2) aniline naphthoquinones class part is dissolved in ether, adds n-BuLi and reacted to obtain part salt compound, The temperature of reaction is 10 DEG C, time 3h, and when reaction starts, the mol ratio of potassium tert-butoxide and aniline naphthoquinones class part is 1.02: 1, concentration of the aniline naphthoquinones class part in ether is 0.01mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 10 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 10 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 5

(1) HNQ and substituted aniline are dissolved in octane, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 125 DEG C, time 9h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.2, the mol ratio of trifluoroacetic acid and 2- hydroxyls -1,4-naphthoquinone is 0.34:1, HNQ exists Concentration in octane is 0.15mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For chloromethyl, R₂For one Chloromethyl, R₃For dichloromethyl, R₄For dichloromethyl, R₅For dichloromethyl, aniline naphthoquinones class part is extracted through n-hexane after reaction Take carry out purification processes；

(2) aniline naphthoquinones class part is dissolved in n-hexane, adds two (trimethyl silicon substrate) Sodamides and react To part salt compound, the temperature of reaction is 15 DEG C, time 4h, when reaction starts, two (trimethyl silicon substrate) Sodamides and benzene The mol ratio of amine naphthoquinones class part is 1.2:1, concentration of the aniline naphthoquinones class part in n-hexane is 0.02mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 15 DEG C, time 3.5h, when reaction starts, in the addition and step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of aniline naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 15 DEG C, and time 11h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 6

(1) HNQ and substituted aniline are dissolved in 4-methyl-2 pentanone, add trifluoroacetic acid and carry out Reaction obtains aniline naphthoquinones class part, and the temperature of reaction is 115 DEG C, time 9h, when reaction starts, HNQ Mol ratio with substituted aniline is 1:1, the mol ratio of trifluoroacetic acid and HNQ is 0.34:1,2- hydroxyl-Isosorbide-5-Nitrae- Concentration of the naphthoquinones in 4-methyl-2 pentanone is 0.12mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁ For dichloromethyl, R₂For dichloromethyl, R₃For chloromethyl, R₄For chloromethyl, R₅For chloromethyl, to aniline naphthalene after reaction Quinones part carries out purification processes through n-hexane extraction；

(2) aniline naphthoquinones class part is dissolved in chlorobenzene, adds sodium hydride and reacted to obtain part salt compound, instead The temperature answered is 20 DEG C, time 3h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.1:1, aniline Concentration of the naphthoquinones class part in chlorobenzene is 0.013mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 20 DEG C, time 4h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 20 DEG C, and time 10.5h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 7

(1) HNQ and substituted aniline are dissolved in ethylenediamine, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 115 DEG C, time 8h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1, the mol ratio of trifluoroacetic acid and HNQ is 0.34:1, HNQ exists Concentration in ethylenediamine is 0.12mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For trichloromethyl, R₂For Trichloromethyl, R₃For dichloromethyl, R₄For chloromethyl, R₅For dichloromethyl, aniline naphthoquinones class part is extracted through ethanol after reaction Take carry out purification processes；

(2) aniline naphthoquinones class part is dissolved in Isosorbide-5-Nitrae-dioxane, adds sodium hydride and reacted to obtain part salt Compound, the temperature of reaction is 20 DEG C, time 5h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.15:1, concentration of the aniline naphthoquinones class part in Isosorbide-5-Nitrae-dioxane is 0.01mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 20 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

Embodiment 8

(1) HNQ and substituted aniline are dissolved in metacresol, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 90 DEG C, time 24h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.35:1, HNQ Concentration in metacresol is 0.11mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For methoxyl group, R₂For Methoxyl group, R₃For ethyoxyl, R₄For ethyoxyl, R₅For ethyoxyl, aniline naphthoquinones class part is recrystallized through chlorobenzene after reaction and carried out Purification processes；

(2) aniline naphthoquinones class part is dissolved in toluene, adds sodium hydride and reacted to obtain part salt compound, instead The temperature answered is 20 DEG C, time 8h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.1:1, aniline Concentration of the naphthoquinones class part in toluene is 0.02mol/L；

Embodiment 9

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 105 DEG C, time 8h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.2, the mol ratio of trifluoroacetic acid and 2- hydroxyls -1,4-naphthoquinone is 0.34:1, HNQ exists Concentration in toluene is 0.13mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For ethyoxyl, R₂For ethoxy Base, R₃For methoxyl group, R₄For ethyoxyl, R₅For methoxyl group, aniline naphthoquinones class part is purified through n-hexane extraction after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in tetrahydrofuran, adds sodium hydride and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 25 DEG C, time 6h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.1: 1, concentration of the aniline naphthoquinones class part in tetrahydrofuran is 0.01mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 25 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 25 DEG C, and time 10.5h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 10

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 106 DEG C, time 9h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.1, the mol ratio of trifluoroacetic acid and 2- hydroxyls -1,4-naphthoquinone is 0.32:1, HNQ exists Concentration in toluene is 0.15mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For methyl mercapto, R₂For first sulphur Base, R₃For ethylmercapto group, R₄For methyl mercapto, R₅For ethylmercapto group, aniline naphthoquinones class part is purified through n-hexane extraction after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in dichloromethane, adds hydrofining and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 23 DEG C, time 6h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.15:1, concentration of the aniline naphthoquinones class part in dichloromethane is 0.02mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 23 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 23 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 11

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 107 DEG C, time 10h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:15, the mol ratio of trifluoroacetic acid and HNQ is 0.35:1, HNQ is in first Concentration in benzene is 0.13mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For ethylmercapto group, R₂For second sulphur Base, R₃For methyl mercapto, R₄For ethylmercapto group, R₅For methyl mercapto, aniline naphthoquinones class part is purified through n-hexane extraction after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in ether, adds hydrofining and reacted to obtain part salt compound, instead The temperature answered is 25 DEG C, time 6h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.15:1, benzene Concentration of the amine naphthoquinones class part in ether is 0.01mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 25 DEG C, time 4.5h, when reaction starts, in the addition and step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of aniline naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 25 DEG C, and time 11h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 12

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 108 DEG C, time 11h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.35:1, HNQ is in first Concentration in benzene is 0.14mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For fluorine, R₂For fluorine, R₃For benzene Base, R₄For fluorine, R₅For phenyl, purification processes are carried out through n-hexane extraction to aniline naphthoquinones class part after reaction；

(2) aniline naphthoquinones class part is dissolved in n-hexane, adds hydrofining and reacted to obtain part salt compound, The temperature of reaction is 28 DEG C, time 10h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.2:1, Concentration of the aniline naphthoquinones class part in n-hexane is 0.016mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 28 DEG C, time 4h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 28 DEG C, and time 10.5h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 13

(1) HNQ and substituted aniline are dissolved in normal heptane, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 109 DEG C, time 12h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.32:1, HNQ exists Concentration in normal heptane is 0.015mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For chlorine, R₂For chlorine, R₃ For benzyl, R₄For chlorine, R₅For phenyl, purification processes are carried out through n-hexane extraction to aniline naphthoquinones class part after reaction；

(2) aniline naphthoquinones class part is dissolved in chlorobenzene, adds hydrofining and reacted to obtain part salt compound, instead The temperature answered is 30 DEG C, time 5h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.1:1, aniline Concentration of the naphthoquinones class part in chlorobenzene is 0.012mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 30 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 30 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 14

(1) HNQ and substituted aniline are dissolved in normal heptane, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 110 DEG C, time 13h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.32:1, HNQ exists Concentration in normal heptane is 0.14mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For bromine, R₂For bromine, R₃ For fluorine substituted-phenyl, R₄For iodine, R₅For fluorine substituted-phenyl, aniline naphthoquinones class part is purified through re crystallization from toluene after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in chlorobenzene, adds n-BuLi and reacted to obtain part salt compound, The temperature of reaction is 32 DEG C, time 6h, and when reaction starts, the mol ratio of n-BuLi and aniline naphthoquinones class part is 1.2:1, Concentration of the aniline naphthoquinones class part in chlorobenzene is 0.013mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 32 DEG C, time 3h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 32 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 15

(1) HNQ and substituted aniline are dissolved in normal heptane, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 112 DEG C, time 14h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.34:1, HNQ exists Concentration in normal heptane is 0.135mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For iodine, R₂For iodine, R₃ For chlorine substituted-phenyl, R₄For bromine, R₅For fluorine substituted-phenyl, aniline naphthoquinones class part is carried out through recrystallize with dichloromethane after reaction Purification processes；

(2) aniline naphthoquinones class part is dissolved in chlorobenzene, adds n-BuLi and reacted to obtain part salt compound, The temperature of reaction is 34 DEG C, time 7h, and when reaction starts, the mol ratio of n-BuLi and aniline naphthoquinones class part is 1.2:1, Concentration of the aniline naphthoquinones class part in chlorobenzene is 0.017mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 34 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 34 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 16

(1) HNQ and substituted aniline are dissolved in chlorobenzene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 114 DEG C, time 15h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.1, the mol ratio of trifluoroacetic acid and HNQ is 0.33:1, HNQ exists Concentration in chlorobenzene is 0.1mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For phenyl, R₂For phenyl, R₃ For iodine, R₄For phenyl, R₅For iodine, purification processes are carried out through methanol extraction to aniline naphthoquinones class part after reaction；

(2) aniline naphthoquinones class part is dissolved in Isosorbide-5-Nitrae-dioxane, adds potassium tert-butoxide and reacted to obtain part Salt compound, the temperature of reaction is 35 DEG C, time 8h, when reaction starts, mole of potassium tert-butoxide and aniline naphthoquinones class part Than for 1.1:1, concentration of the aniline naphthoquinones class part in Isosorbide-5-Nitrae-dioxane is 0.02mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 35 DEG C, time 4.5h, when reaction starts, in the addition and step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of aniline naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 35 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 17

(1) HNQ and substituted aniline are dissolved in Isosorbide-5-Nitrae-dioxane, add trifluoroacetic acid and carry out instead Should obtain aniline naphthoquinones class part, the temperature of reaction is 130 DEG C, time 24h, when reaction starts, HNQ with The mol ratio of substituted aniline is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.35:1,2- hydroxyl-Isosorbide-5-Nitrae- Concentration of the naphthoquinones in Isosorbide-5-Nitrae-dioxane is 0.15mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For Fluorine substituted-phenyl, R₂For fluorine substituted-phenyl, R₃For iodine, R₄For chlorine substituted-phenyl, R₅For iodine, to aniline naphthoquinones class part after reaction Extracted through ethanol and carry out purification processes；

(2) aniline naphthoquinones class part is dissolved in Isosorbide-5-Nitrae-dioxane, adds potassium tert-butoxide and reacted to obtain part Salt compound, the temperature of reaction is 40 DEG C, time 10h, when reaction starts, mole of potassium tert-butoxide and aniline naphthoquinones class part Than for 1.2:1, concentration of the aniline naphthoquinones class part in Isosorbide-5-Nitrae-dioxane is 0.02mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 40 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 40 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 18

(1) HNQ and substituted aniline are dissolved in octane, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 125 DEG C, time 17h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1, the mol ratio of trifluoroacetic acid and 2- hydroxyls -1,4-naphthoquinone is 0.34:1, HNQ is pungent Concentration in alkane is 0.14mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For benzyl, R₂Substitute for fluorine Phenyl, R₃For chlorine, R₄For chlorine, R₅For chlorine substituted-phenyl, aniline naphthoquinones class part is carried out at purification through n-hexane extraction after reaction Reason；

(2) aniline naphthoquinones class part is dissolved in Isosorbide-5-Nitrae-dioxane, adds two (trimethyl silicon substrate) Sodamides and carry out Reaction obtains part salt compound, and the temperature of reaction is 36 DEG C, time 9h, when reaction starts, two (trimethyl silicon substrate) amino The mol ratio of sodium and aniline naphthoquinones class part is 1.2:1, concentration of the aniline naphthoquinones class part in Isosorbide-5-Nitrae-dioxane is 0.015mol/L；

Embodiment 19

(1) HNQ and substituted aniline are dissolved in ethylenediamine, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 128 DEG C, time 20h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.18, the mol ratio of trifluoroacetic acid and HNQ is 0.345:1, HNQ Concentration in ethylenediamine is 0.145mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For fluorine substituted benzene Base, R₂For benzyl, R₃For bromine, R₄For bromine, R₅For bromine, aniline naphthoquinones class part is purified through n-hexane extraction after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in Isosorbide-5-Nitrae-dioxane, adds two (trimethyl silicon substrate) Sodamides and carry out Reaction obtains part salt compound, and the temperature of reaction is 38 DEG C, time 9h, when reaction starts, two (trimethyl silicon substrate) amino The mol ratio of sodium and aniline naphthoquinones class part is 1.17:1, concentration of the aniline naphthoquinones class part in Isosorbide-5-Nitrae-dioxane is 0.02mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 38 DEG C, time 5h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 38 DEG C, and time 12h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 20

(1) HNQ and substituted aniline are dissolved in toluene, add trifluoroacetic acid and reacted to obtain benzene Amine naphthoquinones class part, the temperature of reaction is 110 DEG C, time 14h, when reaction starts, HNQ and substituted aniline Mol ratio be 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.34:1, HNQ exists Concentration in toluene is 0.135mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For diphenyl methyl, R₂ For diphenyl methyl, R₃For hydrogen, R₄For methyl, R₅For hydrogen, aniline naphthoquinones class part is purified through Diethyl ether recrystallization after reaction Processing；

(2) aniline naphthoquinones class part is dissolved in tetrahydrofuran, adds hydrofining and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 34 DEG C, time 6h, and when reaction starts, the mol ratio of hydrofining and aniline naphthoquinones class part is 1.2: 1, concentration of the aniline naphthoquinones class part in tetrahydrofuran is 0.017mol/L；

Embodiment 21

(1) HNQ and substituted aniline are dissolved in metacresol, add trifluoroacetic acid and reacted to obtain Aniline naphthoquinones class part, the temperature of reaction is 112 DEG C, time 14h, when reaction starts, HNQ and substituted benzene The mol ratio of amine is 1:1.2, the mol ratio of trifluoroacetic acid and HNQ is 0.34:1, HNQ exists Concentration in metacresol is 0.135mol/L, the structural formula of substituted aniline as described in Example 1, in formula, R₁For methoxyl group, R₂For Methoxyl group, R₃For hydrogen, R₄For hydrogen, R₅For hydrogen, purification processes are carried out through Diethyl ether recrystallization to aniline naphthoquinones class part after reaction；

(2) aniline naphthoquinones class part is dissolved in dichloromethane, adds sodium hydride and reacted to obtain part salt chemical combination Thing, the temperature of reaction is 34 DEG C, time 3h, and when reaction starts, the mol ratio of sodium hydride and aniline naphthoquinones class part is 1.2: 1, concentration of the aniline naphthoquinones class part in dichloromethane is 0.017mol/L；

(3) (1,5- cyclo-octadiene) methyl chloride palladium is added to be reacted to obtain intermediate state metal complex, the temperature of reaction Spend for 34 DEG C, time 3h, when reaction starts, the addition and the benzene in step (2) of (1,5- cyclo-octadiene) methyl chloride palladium The mol ratio of amine naphthoquinones class part addition is 1.1:1；

(4) add pyridine reagent to be reacted to obtain catalyst, reaction temperature is 34 DEG C, and time 10h, reaction starts When, the mol ratio of the addition of pyridine reagent and (1,5- cyclo-octadiene) methyl chloride palladium addition is 3:1.

Embodiment 22

The application of palladium-containing catalyst prepared by a kind of embodiment 1, under high pure nitrogen protection, first by catalyst dissolution in first In benzene, then ethene is passed through to after reaction system polymerisation 10min obtains ethylene low polymer at 40 DEG C in gaseous form, Wherein the pressure of ethene is 30atm, and concentration of the catalyst in toluene is 1.67 × 10^-4Mol/L, the volume of toluene is 30mL.

Catalytic reaction activity is up to 257kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of oligomer is 3000gmol^-1, molecular weight distributing index 4.4, fusing point is 88 DEG C.

Comparative example 1

A kind of application of catalyst, specific steps are with embodiment 22, and difference is, the species of the catalyst of addition is not Together, the structural formula of catalyst is shown below：

In formula, diis is diisopropyl phenyl

Catalytic reaction activity is up to 180kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of oligomer is 1000gmol^-1, molecular weight distributing index 5.7, fusing point is 70 DEG C.By comparative example 1 and embodiment 22 compare as can be seen that the catalyst activity of the present invention is high, and the ethylene low polymer fusing point for being catalyzed to obtain is high, molecular weight Height, and narrow molecular weight distribution excellent performance, catalyst of the invention achieve significant progress compared to prior art.

Comparative example 2

Catalytic reaction activity is up to 212kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of oligomer is 2300gmol^-1, molecular weight distributing index 5.2, fusing point is 82 DEG C.By comparative example 2 and embodiment 22 compare as can be seen that the catalyst activity of the present invention is high, and the ethylene low polymer fusing point for being catalyzed to obtain is high, molecular weight Height, and narrow molecular weight distribution excellent performance, catalyst of the invention achieve significant progress compared to prior art.

Embodiment 23~30

A kind of application of palladium-containing catalyst, for basic step with embodiment 22, difference is the kind for the catalyst chosen Class, catalyst-solvent solvent species, the species of inert gas, the pressure of ethene, the time of polymerisation and temperature, specifically It is as follows：

Catalyst

Solvent

Inert gas

Ethylene pressure

Polymerization time

Polymerization temperature

Embodiment 23

Embodiment 2

Toluene

High-purity helium

10atm

60min

40℃

Embodiment 24

Embodiment 3

Chlorobenzene

High-purity argon gas

20atm

60min

30℃

Embodiment 25

Embodiment 4

N-hexane

High pure nitrogen

25atm

40min

20℃

Embodiment 26

Embodiment 5

Normal heptane

High pure nitrogen

25atm

40min

40℃

Embodiment 27

Embodiment 6

Toluene

High pure nitrogen

28atm

30min

60℃

Embodiment 28

Embodiment 7

Chlorobenzene

High pure nitrogen

28atm

40min

40℃

Embodiment 29

Embodiment 8

N-hexane

High pure nitrogen

30atm

20min

20℃

Embodiment 30

Embodiment 9

Normal heptane

High pure nitrogen

30atm

10min

30℃

Molecular weight (the gmol of final obtained product and product^-1), molecular weight distributing index, fusing point (DEG C) and reaction During catalytic reaction activity peak (kg polymer/ (mol Pdh)) it is as shown in the table：

Embodiment 31

A kind of application of palladium-containing catalyst prepared by embodiment 10, under high pure nitrogen protection, first catalyst dissolution is existed In toluene, adding after ethene and polarity/function monomer ENB the polymerisation 10min at 40 DEG C, to obtain ethene high poly- Thing, wherein ethene are passed through in reaction system in gaseous form, and the pressure of ethene is 1atm, ENB and catalyst mole Than for 2000:1, concentration of the ENB in toluene is 0.2mol/L, and the volume of toluene is 30mL.

Catalytic reaction activity is up to 220kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 10800gmol^-1, molecular weight distributing index 2.8, glass transition temperature is 126 DEG C, wherein The insertion rate of ENB is 42mol%.

Comparative example 3

A kind of application of catalyst, specific steps are with embodiment 31, and difference is, the species of the catalyst of addition is not Together, the structural formula of catalyst is shown below：

In formula, diis is diisopropyl phenyl.

Catalytic reaction activity is up to 112kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 9600gmol^-1, molecular weight distributing index 4.7, glass transition temperature is 105 DEG C, wherein dropping The insertion rate of bornylene is 32mol%.Comparative example 3 and embodiment 31 are compared as can be seen that the catalyst of the present invention Active high, the ethylene polymer glass transition temperature for being catalyzed to obtain is high, and molecular weight is high, narrow molecular weight distribution excellent performance, and The insertion rate of polarity/function monomer is high, and catalyst of the invention achieves significant progress compared to prior art.

Comparative example 4

Catalytic reaction activity is up to 160kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 8800gmol^-1, molecular weight distributing index 4.3, glass transition temperature is 96 DEG C, wherein dropping Bornylene insertion rate is 28mol%.Comparative example 4 and embodiment 31 are compared as can be seen that the catalyst of the present invention is lived Property it is high, the ethylene polymer glass transition temperature for being catalyzed to obtain is high, and molecular weight is high, narrow molecular weight distribution excellent performance, and pole Property/function monomer insertion rate it is high, catalyst of the invention achieves significant progress compared to prior art.

Comparative example 5

In formula, R₁~R₆Same as in Example 10, L is triphenylphosphine.

Catalytic reaction activity is up to 157kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 9681gmol^-1, molecular weight distributing index 3.1, glass transition temperature is 120 DEG C, wherein dropping The insertion rate of bornylene is 35%.Comparative example 5 and embodiment 31 are compared as can be seen that being the catalysis of nickel with central metal Agent is compared, and catalyst of the invention can significantly improve the insertion rate of polarity/function monomer, the catalyst phase of the invention containing palladium Significant progress is achieved for nickeliferous catalyst.

Comparative example 6

In formula, R₁~R₅Same as in Example 10, L is trimethyl-phosphine.

Catalytic reaction activity is up to 143kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 10100gmol^-1, molecular weight distributing index 3.6, glass transition temperature is 118 DEG C, wherein The insertion rate of ENB is 33%.Comparative example 6 and embodiment 31 are compared as can be seen that being the catalysis of nickel with central metal Agent is compared, and catalyst of the invention can significantly improve the insertion rate of polarity/function monomer, the catalyst phase of the invention containing palladium Significant progress is achieved for nickeliferous catalyst.

Embodiment 32

A kind of application of palladium-containing catalyst prepared by embodiment 11, under high pure nitrogen protection, first catalyst dissolution is existed In n-hexane, the polymerisation at 40 DEG C is added after ethene and polarity/function monomer 5- ENB -2- yl acetates 30min obtains ethylene polymer, and wherein ethene is passed through in reaction system in gaseous form, and the pressure of ethene is 10atm, and 5- drops The mol ratio of bornylene -2- yl acetates and catalyst is 2000:1,5- ENB -2- yl acetates are in n-hexane Concentration is 0.67mol/L, and the volume of n-hexane is 30mL.

Catalytic reaction activity is up to 300kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 21500gmol^-1, molecular weight distributing index 2.5, glass transition temperature is 90 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 56mol%.

Comparative example 7

A kind of application of catalyst, specific steps are with embodiment 32, and difference is, the species of the catalyst of addition is not Together, the structural formula of catalyst is shown below：

In formula, R₁~R₆Identical with embodiment 11, L is triphenylphosphine.

Catalytic reaction activity is up to 256kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 19200gmol^-1, molecular weight distributing index 2.8, glass transition temperature is 80 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 43%.Comparative example 7 and embodiment 32 are compared as can be seen that golden with center Belong to and being compared for the catalyst of nickel, catalyst of the invention can significantly improve the insertion rate of polarity/function monomer, and of the invention contains The catalyst of palladium achieves significant progress relative to nickeliferous catalyst.

Comparative example 8

In formula, R₁~R₅Identical with embodiment 11, L is trimethyl-phosphine.

Catalytic reaction activity is up to 215kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 20200gmol^-1, molecular weight distributing index 3.3, glass transition temperature is 85 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 48%.Comparative example 8 and embodiment 32 are compared as can be seen that golden with center Belong to and being compared for the catalyst of nickel, catalyst of the invention can significantly improve the insertion rate of polarity/function monomer, and of the invention contains The catalyst of palladium achieves significant progress relative to nickeliferous catalyst.

Embodiment 33~40

A kind of application of palladium-containing catalyst, for basic step with embodiment 32, difference is the kind for the catalyst chosen Class, the pressure of ethene (atm), the species of polarity/function monomer, polarity/function monomer are dense in the solvent of catalyst-solvent The mol ratio of (mol/L), polar functionalities monomer and catalyst is spent, its is specific as follows：

	Catalyst	Pressure	Polarity/function monomer	Concentration	Mol ratio
						Embodiment 33	Embodiment 12	1	ENB	0.33	2000:1
Embodiment 34	Embodiment 13	10	5- ENB -2- yl acetates	2	12000:1
						Embodiment 35	Embodiment 14	20	5- ENB -2- methanol	0.34	3000:1
Embodiment 36	Embodiment 15	10	Acetic acid 5- hexene base esters	0.45	4000:1
						Embodiment 37	Embodiment 16	20	Allyl acetate	0.65	5000:1
Embodiment 38	Embodiment 17	20	Vinyl acetate	0.9	6000:1
						Embodiment 39	Embodiment 18	30	Methyl acrylate	1.2	8000:1
Embodiment 40	Embodiment 19	10	Styrene	1.5	10000:1

Molecular weight (the gmol of final obtained product and product^-1), molecular weight distributing index, fusing point or glass transition Catalytic reaction activity peak (kg in temperature (DEG C), the insertion rate (mol%) of polarity/function monomer and course of reaction Polymer/ (mol Pdh)) it is as shown in the table：

Embodiment 41

The composition that a kind of palladium-containing catalyst prepared by embodiment 1 and co-catalyst MAO form, wherein urging Agent and the mol ratio of aluminium in MAO are 1:20.

Embodiment 42~51

A kind of composition being made up of palladium-containing catalyst and co-catalyst, wherein catalyst, co-catalyst and catalyst with (when co-catalyst is aluminum contained compound, the mol ratio of catalyst and co-catalyst refers specifically to be catalyzed the mol ratio of co-catalyst Agent and the mol ratio of aluminium in aluminum contained compound) it is as shown in the table：

	From catalyst	Co-catalyst	Mol ratio
				Embodiment 42	Embodiment 2	MAO	1:20
Embodiment 43	Embodiment 3	The MAO that tert-butyl group aluminium is modified	1:500
				Embodiment 44	Embodiment 4	The MAO that dry tert-butyl group aluminium is modified	1:50
Embodiment 45	Embodiment 5	Trimethyl aluminium	1:500
				Embodiment 46	Embodiment 6	Triethyl aluminum	1:500
Embodiment 47	Embodiment 7	Triisobutyl aluminium	1:200
				Embodiment 48	Embodiment 8	Tri-n-hexyl aluminum	1:250
Embodiment 49	Embodiment 9	Tri-n-octylaluminium	1:300
				Embodiment 50	Embodiment 10	Diethylaluminum chloride	1:400
Embodiment 51	Embodiment 11	Ethylaluminium dichloride	1:450

Embodiment 52

A kind of application of the composition prepared by embodiment 41, under high pure nitrogen protection, composition is dissolved in toluene In, then ethene is passed through to after reaction system the polymerisation 10min under the conditions of 40 DEG C in gaseous form to obtain ethene high poly- The pressure of thing, wherein ethene is 10atm, and concentration of the catalyst in toluene is 1.67 × 10^-4Mol/L, the volume of toluene are 30mL。

Catalytic reaction activity is up to 457kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 20500gmol^-1, molecular weight distributing index 2.4, fusing point is 121 DEG C.

Comparative example 9

A kind of application of composition, specific steps are with embodiment 52, and difference is, palladium-containing catalyst in composition Species is different, and the structural formula of palladium-containing catalyst is shown below：

In formula, diis is diisopropyl phenyl.

Catalytic reaction activity is up to 252kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 10100gmol^-1, molecular weight distributing index 3.8, fusing point is 107 DEG C.By comparative example 9 with implementing Example 52 compares as can be seen that the catalytic activity of the composition as made from the catalyst of the present invention is high, and the ethene for being catalyzed to obtain is high Polymers fusing point is high, and molecular weight is high, and narrow molecular weight distribution excellent performance, combination catalyst of the invention take compared to prior art Obtained significant progress.

Comparative example 10

A kind of application of catalyst, specific steps are with embodiment 52, and difference is, palladium-containing catalyst in composition Species is different, and the structural formula of catalyst is shown below：

Catalytic reaction activity is up to 269kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 19100gmol^-1, molecular weight distributing index 3.9, fusing point is 98 DEG C.By comparative example 10 with implementing Example 52 compares as can be seen that composition catalytic activity is high as made from the catalyst of the present invention, and the ethene for being catalyzed to obtain is high poly- Thing fusing point is high, and molecular weight is high, and narrow molecular weight distribution excellent performance, and combination catalyst of the invention obtains compared to prior art Significant progress.

Embodiment 53~60

A kind of application of composition, for basic step with embodiment 52, difference is the species, molten for the composition chosen Species, the species of inert gas, reaction pressure, the time of polymerisation and the temperature of the solvent of composition are solved, it is specific as follows：

Embodiment 61

A kind of application of the composition prepared by embodiment 42, under high pure nitrogen protection, first composition is dissolved in just In heptane, adding after ethene and polarity/function monomer ENB the polymerisation 10min at 40 DEG C, to obtain ethene high poly- Thing, wherein ethene are passed through in reaction system in gaseous form, and the pressure of ethene is 1atm, ENB and catalyst mole Than for 2000:1, concentration of the ENB in normal heptane is 0.2mol/L, and the volume of normal heptane is 30mL.

Catalytic reaction activity is up to 390kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 22560gmol^-1, molecular weight distributing index 1.9, glass transition temperature is 133 DEG C, wherein The insertion rate of ENB is 58mol%.

Comparative example 11

A kind of application of catalyst, specific steps are with embodiment 61, and difference is, palladium-containing catalyst in composition Species is different, and the structural formula of palladium-containing catalyst is shown below：

In formula, diis is diisopropyl phenyl.

Catalytic reaction activity is up to 234kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 10900gmol^-1, molecular weight distributing index 3.7, glass transition temperature is 121 DEG C, drops ice Piece alkene insertion rate is 42mol%.Comparative example 11 and embodiment 61 are compared as can be seen that by palladium-containing catalyst of the invention The catalytic activity of obtained composition is high, and the ethylene polymer molecular weight for being catalyzed to obtain is high, narrow molecular weight distribution, glass transition Temperature is high, and the insertion rate of polarity/function monomer is high, and combination catalyst of the invention achieves significantly compared to prior art It is progressive.

Comparative example 12

Catalytic reaction activity is up to 268kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 12700gmol^-1, molecular weight distributing index 2.9, glass transition temperature is 118 DEG C, drops ice Piece alkene insertion rate is 34mol%.Comparative example 12 and embodiment 61 are compared as can be seen that by palladium-containing catalyst of the invention The catalytic activity of obtained composition is high, and the ethylene polymer molecular weight for being catalyzed to obtain is high, narrow molecular weight distribution, glass transition Temperature is high, and the insertion rate of polarity/function monomer is high, and combination catalyst of the invention achieves significantly compared to prior art It is progressive.

Comparative example 13

A kind of application of catalyst, specific steps are with embodiment 61, and difference is, the species of catalyst in composition Difference, the structural formula of catalyst are shown below：

In formula, R₁~R₆Same as Example 2, L is triphenylphosphine.

Catalytic reaction activity is up to 220kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 12560gmol^-1, molecular weight distributing index 2.6, glass transition temperature is 124 DEG C, wherein The insertion rate of ENB is 50mol%.Comparative example 13 and embodiment 61 are compared as can be seen that being nickel with central metal Catalyst is compared, and the composition as made from the catalyst of the present invention can significantly improve the insertion rate of polarity/function monomer, this hair The bright catalyst containing palladium can obtain superior technique effect relative to nickeliferous catalyst.

Comparative example 14

In formula, R₁~R₅Same as Example 2, L is trimethyl-phosphine.

Catalytic reaction activity is up to 200kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 11560gmol^-1, molecular weight distributing index 2.4, glass transition temperature is 126 DEG C, wherein The insertion rate of ENB is 52mol%.Comparative example 14 and embodiment 61 are compared as can be seen that being nickel with central metal Catalyst is compared, and the composition as made from the catalyst of the present invention can significantly improve the insertion rate of polarity/function monomer, this hair The bright catalyst containing palladium can obtain superior technique effect relative to nickeliferous catalyst.

Embodiment 62

A kind of application of the composition prepared by embodiment 43, under high pure nitrogen protection, composition is first dissolved in first In benzene, add after ethene and polarity/function monomer 5- ENB -2- yl acetates that polymerisation 30min is obtained at 40 DEG C To ethylene polymer, wherein ethene is passed through in reaction system in gaseous form, and the pressure of ethene is 10atm, and 5- ENBs- The mol ratio of 2- yl acetates and catalyst is 2000:Concentration of 1, the 5- ENB -2- yl acetates in toluene is 0.67mol/L, the volume of toluene is 30mL.

Catalytic reaction activity is up to 366kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 29100gmol^-1, molecular weight distributing index 2.1, glass transition temperature is 97 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 60mol%.

Comparative example 15

A kind of application of catalyst, specific steps are with embodiment 62, and difference is, the species of catalyst in composition Difference, the structural formula of catalyst are shown below：

In formula, R₁~R₆Same as Example 3, L is triphenylphosphine.

Catalytic reaction activity is up to 288kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 20100gmol^-1, molecular weight distributing index 2.6, glass transition temperature is 90 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 52mol%.Comparative example 15 and embodiment 62 are compared as can be seen that with Heart metal is compared for the catalyst of nickel, and the composition as made from the catalyst of the present invention can significantly improve polarity/function monomer Insertion rate, the catalyst of the invention containing palladium can obtain superior technique effect relative to nickeliferous catalyst.

Comparative example 16

In formula, R₁~R₅Same as Example 3, L is trimethyl-phosphine.

Catalytic reaction activity is up to 312kg polymer/ (mol Pdh) in course of reaction, final obtained ethene The molecular weight of high polymer is 22300gmol^-1, molecular weight distributing index 2.2, glass transition temperature is 92 DEG C, wherein 5- The insertion rate of ENB -2- yl acetates is 55mol%.Comparative example 16 and embodiment 62 are compared as can be seen that with Heart metal is compared for the catalyst of nickel, and the composition as made from the catalyst of the present invention can significantly improve polarity/function monomer Insertion rate, the catalyst of the invention containing palladium can obtain superior technique effect relative to nickeliferous catalyst.

Embodiment 63~70

A kind of application of composition, for basic step with embodiment 61, difference is species, the second for the composition chosen Concentration of the pressure (atm), the species, polarity/function monomer of polarity/function monomer of alkene in the solvent of dissolved composition (mol/L), the mol ratio of polar functionalities monomer and catalyst, its is specific as follows：

	Catalyst	Pressure	Polarity/function monomer	Concentration	Mol ratio
						Embodiment 63	Embodiment 52	1	ENB	0.33	2000:1
Embodiment 64	Embodiment 53	10	5- ENB -2- yl acetates	2	12000:1
						Embodiment 65	Embodiment 54	20	5- ENB -2- methanol	0.34	3000:1
Embodiment 66	Embodiment 55	10	Acetic acid 5- hexene base esters	0.45	4000:1
						Embodiment 67	Embodiment 56	20	Allyl acetate	0.65	5000:1
Embodiment 68	Embodiment 57	20	Vinyl acetate	0.9	6000:1
						Embodiment 69	Embodiment 58	30	Methyl acrylate	1.2	8000:1
Embodiment 70	Embodiment 59	10	Styrene	1.5	10000:1

Claims

1. palladium-containing catalyst, it is characterized in that, structural formula is as follows：

In formula, R₁~R₅It is each independently selected from hydrogen, alkyl, the substituent of alkyl, alkoxy, alkylthio group, halogen, nitro, aryl Or aryl substituent, work as R₁~R₅During middle adjacent group cyclization, the quantity of the ring structure of formation is less than 4, R₆For alkyl or aryl, L For pyridine.

2. palladium-containing catalyst according to claim 1, it is characterised in that for R₁~R₅The alkyl of selection is methyl, ethyl, Isopropyl or the tert-butyl group, the substituent of alkyl is chloromethyl, dichloromethyl, trichloromethyl or diphenyl methyl, and alkoxy is Methoxy or ethoxy, alkylthio group are methyl mercapto or ethylmercapto group, and halogen is fluorine, chlorine, bromine or iodine, and aryl is phenyl or benzyl, Aryl substituent is chlorine substituted-phenyl or fluorine substituted-phenyl；

For R₆The alkyl of selection is methyl, and aryl is phenyl.

3. the method for palladium-containing catalyst as claimed in claim 1 or 2 is prepared, it is characterized in that, step is as follows：

(1) HNQ and substituted aniline are dissolved in organic solvent, adds catalyst A and reacted to obtain benzene Amine naphthoquinones class part；The structural formula of the substituted aniline is as follows：

(2) by the dissolving of aniline naphthoquinones class part in organic solvent, addition pulls out hydrogen reagent and is reacted to obtain part salt compound；

(4) pyridine reagent is added to react to obtain catalyst.

4. according to the method for claim 3, it is characterised in that in step (1), when reaction starts, the 2- hydroxyls-Isosorbide-5-Nitrae- The mol ratio of naphthoquinones and substituted aniline is 1:1~1.2, the mol ratio of the catalyst A and HNQ for 0.32~ 0.35:1, the concentration of the HNQ in organic solvent is 0.1~0.15mol/L；

The organic solvent be normal heptane, toluene, chlorobenzene, 1,4- dioxane, octane, 4-methyl-2 pentanone, ethylenediamine or Cresols, the catalyst A are trifluoroacetic acid；

The temperature of the reaction is 90~130 DEG C, and the time is 6~24h；

In step (2), when reaction starts, the hydrogen reagent and the mol ratio of aniline naphthoquinones class part of pulling out is 1~1.2:1, it is described The concentration of aniline naphthoquinones class part in organic solvent is 0.01~0.02mol/L；

The organic solvent is toluene, tetrahydrofuran, dichloromethane, ether, n-hexane, chlorobenzene or Isosorbide-5-Nitrae-dioxane, described It is sodium hydride, hydrofining, n-BuLi, potassium tert-butoxide or two (trimethyl silicon substrate) Sodamides to pull out hydrogen reagent；

The temperature of the reaction is 0~40 DEG C, and the time is 1~10h；

In step (3), the mol ratio of the addition and aniline naphthoquinones class part addition described in step (2) of the palladium presoma For 1.1:1；

The palladium presoma is (1,5- cyclo-octadiene) methyl chloride palladium；

The temperature of the reaction is 0~40 DEG C, and the time is 3~5h；

In step (4), the addition of the pyridine reagent is 3 with the mol ratio of palladium presoma addition described in step (3):1；

The temperature of the reaction is 0~40 DEG C, and the time is 10~12h.

5. according to the method for claim 4, it is characterised in that in step (1), react obtained aniline naphthoquinones class part warp Organic solvent recrystallizes or extraction carries out purification processes, and the organic solvent of purification processes is toluene, dichloromethane, tetrahydrochysene furan Mutter, ether, n-hexane, normal heptane, chlorobenzene, methanol or ethanol.

6. the application of palladium-containing catalyst as claimed in claim 1 or 2, it is characterized in that：Catalyst is applied to catalyzed alkene list The homopolymerization or copolymerization of body.

7. application according to claim 6, it is characterised in that application process is：Under inert gas shielding, by catalyst In a solvent, polymerisation 10min~60min obtains olefin polymer at 20~60 DEG C after addition olefinic monomer for dissolving；

The inert gas is high pure nitrogen, high-purity argon gas or high-purity helium, and the solvent is toluene, chlorobenzene, n-hexane or just Heptane, the olefinic monomer are ethene, or are ethene and polarity/function monomer；

When olefinic monomer is ethene, ethene is passed through in reaction system in gaseous form, and the pressure of ethene is 10~30atm, The concentration of catalyst in a solvent is 1.67 × 10^-4Mol/L, the volume of solvent is 30mL；

When olefinic monomer is ethene and polarity/function monomer, ethene is passed through in reaction system in gaseous form, the pressure of ethene Power is 1~30atm, and the mol ratio of polarity/function monomer and catalyst is 2000~12000:1, polarity/function monomer is in solvent In concentration be 0.33~2mol/L, the volume of solvent is 30mL；

Polarity/the function monomer is acetic acid 5- hexenes base ester, vinyl acetate, allyl acetate, methyl acrylate, norborneol Alkene, 5- ENB -2- yl acetates, 5- ENB -2- methanol or styrene；

The olefin polymer is ethylene low polymer or ethylene polymer, and the molecular weight of ethylene low polymer is 550~4200g mol^-1, molecular weight distributing index is 2.9~6.7, and glass transition temperature or fusing point are 83~100 DEG C, point of ethylene polymer Son amount is 9900~21500gmol^-1, molecular weight distributing index is 2.5~4.6, glass transition temperature or fusing point be 83~ 113℃；

8. using composition made from palladium-containing catalyst as claimed in claim 1 or 2, it is characterized in that：Composition is by catalyst Formed with co-catalyst；

The aikyiaiurnirsoxan beta is the methyl that the tert-butyl group aluminium of MAO, the MAO that tert-butyl group aluminium is modified or drying is modified Aikyiaiurnirsoxan beta, the alkyl aluminum compound are trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium, The alkyl aluminum chloride compound is diethylaluminum chloride or ethylaluminium dichloride.

9. the application of composition as claimed in claim 8, it is characterized in that：Composition is applied to the homopolymerization of catalyzed alkene monomer Or copolymerization.

10. application according to claim 9, it is characterised in that application process is：Under inert gas shielding, it will combine Thing dissolves in a solvent, and polymerisation 5min~60min obtains olefinic polymerization under the conditions of 0~60 DEG C after addition olefinic monomer Thing；

The olefin polymer is ethylene low polymer or ethylene polymer, and the molecular weight of ethylene low polymer is 5200gmol^-1, point Son amount profile exponent is 4.6, and glass transition temperature is 93 DEG C, and the molecular weight of ethylene polymer is 10120~36100g mol^-1, molecular weight distributing index is 2.1~5.9, and glass transition temperature or fusing point are 93~133 DEG C；