CN107312115B

CN107312115B - Bis-indole rare earth metal catalyst, preparation method and application

Info

Publication number: CN107312115B
Application number: CN201710483240.5A
Authority: CN
Inventors: 李晓芳; 刘安; 王航航; 杨帆致
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2017-06-22
Filing date: 2017-06-22
Publication date: 2020-06-12
Anticipated expiration: 2037-06-22
Also published as: CN107312115A

Abstract

The invention discloses a bisindole rare earth metal catalyst, a preparation method and application thereof, belonging to the field of catalystsThe technical field is as follows. The novel bis-indole rare earth metal catalyst can catalyze olefin, alkyne and CO₂Polar monomer homopolymerization or copolymerization or ternary polymerization reaction. Wherein in the application of catalyzing polymerization of isoprene, the cis 1,4 content in the obtained polyisoprene can reach 100 percent at most. In addition, in the application of catalyzing polymerization of myrcene, the cis 1,4 content of the obtained polylaurene is up to 94%. In particular, in the polymerization of styrene, the first time a non-metallocene rare earth catalyst was used to obtain polystyrene with 100% syndiotactic rrrr. The catalyst has the advantages of novel structure, high synthesis yield and easy preparation; the method is simple, environment-friendly, low in cost and suitable for industrial production; the catalyst of the invention has high selectivity and high activity in polymerization.

Description

Bis-indole rare earth metal catalyst, preparation method and application

Technical Field

The invention relates to a bisindole rare earth metal catalyst, a preparation method and application, and belongs to the technical field of catalysts.

Background

Rubber is an important strategic material, and people's daily life, transportation, national defense construction and the like can not be separated from the rubber. Rubber usage by humans began with natural rubber, and in 1839, the american human has invented natural rubber vulcanization technology, making it increasingly widespread. With the development of society, natural rubber cannot meet the requirements of human beings on rubber materials, and people are successfully researched and begin to produce synthetic rubber in 30-40 years of the 20 th century. With the development of petrochemical technology, the technology of synthetic rubber is rapidly improved. Among them, high cis-1, 4-polyisoprene is one of synthetic rubber varieties with excellent comprehensive performance, and has wide application in civil use, automobile, airplane manufacturing, aerospace and other aspects. Particularly, when the cis 1, 4-content is more than 99%, the performance of the rubber can be compared with that of natural rubber, and even the rubber is better than the natural rubber in some aspects. Therefore, the industrial production of polymers with high molecular weight, high cis-1, 4 structure content and narrow molecular weight distribution is a development trend for synthesizing isoprene rubber in the future.

At present, natural rubber and petroleum are main sources for preparing polyolefin rubber materials, and the preparation of the polyolefin rubber materials is limited due to the shortage of natural rubber resources and the non-sustainable development of petroleum resources, so that the active development of biochemicals is the future of the sustainable development of the tire rubber industry in China. Direct polymerization of biomass monomers structurally resembling petroleum monomers (butadiene, isoprene, etc.) is the most efficient route to non-petroleum synthetic rubbers. The monoterpene compound not only has a structure similar to that of isoprene, but also is an unsaturated hydrocarbon widely existing in plants, and can be obtained from various plants, particularly conifers. Myrcene is a most studied straight-chain monoterpene compound, and the monoterpene content in phellodendron oil of Jilin in China is as high as 80%. Therefore, in the development of new green tire materials, the myrcene with rich resources is used as a polymerization monomer to synthesize the bio-based green rubber, and the bio-based green rubber has important application value.

Synthetic resins are the main component of plastics, one of the three major synthetic materials. With the development of society, synthetic resins are becoming an important class of materials. Polystyrene is one of five synthetic resins, the properties and application areas of which are determined by the stereoregularity and the molecular weight. Polystyrene is divided into three different spatial configurations according to the difference of the orientation of side chain benzene in molecules to the chain skeleton space: atactic, isotactic, syndiotactic. Low molecular weight atactic polystyrene, generally used as plasticizer; high molecular weight atactic polystyrene has the advantages of low price, easy processing, good transparency, hard quality, good dimensional stability and the like, can be applied to the fields of toys, daily necessities, packaging materials, household appliance parts, building materials and the like, but has great brittleness and poor heat resistance, so that the application of the atactic polystyrene in other fields is limited. As the molecular weight of polystyrene increases, the tensile strength, bending strength, impact strength and heat resistance of the polystyrene are all improved. Crystallizable stereoregular polystyrene products are prepared primarily by coordination polymerization processes. The Isotactic Polystyrene (iPS) has slow crystallization rate and melting point of about 240 ℃. The syndiotactic polystyrene (sPS) generally has a number average molecular weight of 5X 10⁴～ 1.5×10⁵g.mol < -1 >, the crystallization rate is relatively fast, and the melting point is about 273 ℃. sPS has the advantages of good heat resistance, good chemical resistance, low density, low dielectric constant and the like, and can be applied to the fields of electrical equipment, automobile parts and daily necessities. However, the existing sPS has low syndiotacticity and is difficult to adjust, resulting in high processing temperature, which affects its large-scale application. The traditional catalyst is used for styrene coordination polymerization, and can only prepare low molecular weight atactic polystyrene in most cases. By preparing the novel catalyst, stereoregularity can be improved or molecular weight can be increased.

Polyisoprene and polylaurene generally contain three microstructures: cis-1, 4, trans-1, 4, 3,4 or 1,2 (polylaurene). Which microstructure the polymer is present in depends on the catalyst used in the polymerization process. In the homopolymerization of conjugated diene and styrene, it is found that many polymers with high selectivity can be prepared by changing the molecular structure of the catalyst. For example, by modifying the structure of the ligand, changing the steric hindrance and electronic effect of the ligand, a suitable structure is found to control the coordination of the olefin to the metal center of the catalyst, thereby achieving the effect of controlling high stereoselectivity. In addition, in addition to the consideration of ligands, it is also possible to use the choice of different metals as a regulatory factor. Different metal centers have different electronic effects and radii, and these slight differences easily cause differences in stereoselectivity of the polymers. Polymers of different selectivities can also be obtained by using different anionic groups or aluminium compounds. Therefore, designing and synthesizing a catalyst with high selectivity and high activity is the core content of metal organic chemistry.

The valence electron shells of rare earth elements not only have s orbitals, p orbitals and d orbitals, but also have f orbitals, and the structural characteristics of the electron shells determine that the valence electron shells have unique chemical properties different from those of transition metal elements: if the rare earth elements are mainly ionic and the ionic radius is large, the higher coordination numbers (8-12) can be accommodated, and the coordination numbers are not easily met; in addition, the rare earth metal ions have strong Lewis acidity and strong oxophilicity, so that the rare earth metal organic complex is easily coordinated by weak Lewis base (such as tetrahydrofuran) or easily forms a dimer and undergoes disproportionation reaction, which is a challenge in synthesizing highly active and stable rare earth metal complexes.

In recent decades, rare earth metal organic complexes have received much attention due to their abundant and unique chemical reactivity (e.g., hydrogenation, amination, alkynylation, carbon dioxide fixation) and high catalytic activity (e.g., organic reactions such as catalytic α -olefin, conjugated olefin, polar monomer polymerization and hydrosilation, amine hydrogenation, phosphine hydrogenation, etc.) the reactivity of rare earth metal organic complexes is less affected by whether the bonding orbitals of the central metal are matched or not.

In recent years, transition metal complexes taking indole as ligand have attracted interest, because indole and derivatives thereof are important N-containing heterocyclic compounds, and the indole and derivatives thereof have the advantages of strong electron donating capability, easy functionalization and the like as ligands, and the research on the aspect is helpful for further modification of regioselectivity and stereoselectivity of the ligands. At present, the research on indole rare earth metal complexes is still few, the research on the performance of the indole rare earth metal complexes in catalyzing olefin polymerization is rare, and the research in the field is urgent to break through. The bis-indole rare earth metal catalyst, the preparation method and the application thereof in polymerization reaction have not been reported.

Disclosure of Invention

One of the purposes of the invention is to provide a bisindole rare earth metal catalyst; the second purpose of the invention is to provide a preparation method of the bis-indole rare earth metal catalyst; the invention also aims to provide application of the bisindole rare earth metal catalyst.

In order to achieve the purpose, the invention adopts the following technical scheme:

a bis-indole rare earth metal catalyst is characterized in that: the structural formula of the bis-indole rare earth metal catalyst is as follows I, II and III:

wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₁₆、R₁₇、R₁₈、R₁₉Is a substituent on a benzene ring; r₉、R₁₀、R₁₁、R₁₂Is a substituent on the pyrrole ring; r₁₃Is a substituent bridging two indole carbons; r₁₄，R₁₅Is an initiating group attached to a rare earth metal; ln is a rare earth metal.

Wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₁₆、R₁₇、R₁₈、R₁₉The groups are the same or different and are one of hydrogen atom, methyl, ethyl, isopropyl, tert-butyl, n-butyl, alkoxy, amino, chlorine atom, fluorine atom, iodine atom, bromine atom, nitro, phenyl, benzyl and naphthyl;

R₉、R₁₀、R₁₁、R₁₂is one of hydrogen atom, methyl group, ethyl group, isopropyl group, tert-butyl group, n-butyl group, alkoxy group, amino group, chlorine atom, fluorine atom, iodine atom, bromine atom, nitro group, phenyl group, benzyl group, anthracenyl group, naphthyl group, phenanthrenyl group, anilino group, phenolic group, phenylthio group and 3, 5-difluoromethylenephenylthio group;

R₁₃is one of hydrogen atom, methyl, ethyl, isopropyl, tert-butyl, n-butyl, alkoxy, chlorine atom, fluorine atom, iodine atom, bromine atom, nitro, phenyl, benzyl and naphthyl;

R₁₄，R₁₅are identical or different radicals and are each alkyl, alkynylTrimethylsilyl, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen (F, Cl, Br, I).

Wherein Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

A preparation method of a bis-indole rare earth metal catalyst comprises the following steps:

(1) preparation of bis-indole ligands

First, di-tert-butyl peroxide is added dropwise to a mixture of N-methylindole, tetrahydrofuran and ferrous chloride at room temperature under a nitrogen or argon atmosphere. Wherein the mol ratio of the N-methylindole to the tetrahydrofuran to the ferrous chloride to the di-tert-butyl peroxide is 1:12:0.1: 0.6; heating the reaction solution to 80 ℃, reacting for 1h, and cooling to room temperature; washing the obtained product with a large amount of petroleum ether, and drying to obtain the target product.

(2) Preparation of bis-indole rare earth metal catalysts

Firstly, placing a reactor in a glove box, adding the bis-indole ligand in the step (1) into the reactor, and using toluene as a solvent; secondly, dropwise adding the toluene solution into a toluene solution dissolved with a metal source, and stirring for 2 hours at the temperature of 20-25 ℃; wherein the molar ratio of the bisindole ligand to the metal source is 1: 1.1; and finally, pumping the reaction liquid to dry, extracting for 3-5 times by using normal hexane, filtering to obtain filter residues, dissolving the solid by using toluene, and then placing in a refrigerator for crystallization at the temperature of-20 to-35 ℃ to obtain the bis-indole rare earth metal catalyst.

The metal source in step (2) is preferably a compound of a bistetrahydrofuran-tris (trimethylsilylmethyl) rare earth metal (Ln (CH)₂SiMe₃)₃(thf)₂) (ii) a And the Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

An application of a bis-indole rare earth metal catalyst. The diindole rare earth metal catalyst, an alkyl aluminum reagent and an organic boron salt form a catalytic system for catalyzing homopolymerization of one of alkene, cycloolefin, alkyne and polar monomer or alkeneCopolymerization of any two of hydrocarbon, cycloolefine, alkyne and polar monomer, or copolymerization of olefin, cycloolefine, alkyne and polar monomer with CO respectively₂Copolymerization reaction of (a); wherein the molar ratio of the alkyl aluminum reagent to the organic boron salt to the bis-indole rare earth metal catalyst is 0-200: 0-4: 1; the alkyl aluminum reagent is of the formula AlX₃Alkyl aluminum of formula HAlX₂Of the formula AlX₂Cl, aluminum alkyl chloride or aluminoxane, and X is an alkyl group.

The steps of the catalytic homopolymerization reaction are as follows:

placing a reactor in a glove box, sequentially adding a bisindole rare earth metal catalyst, a good solvent, an alkyl aluminum reagent, a monomer and an organic boron salt into the reactor, reacting for 0.1-72 hours under stirring, taking out the reactor, and adding a chain terminator to stop the reaction; settling the reaction solution by using ethanol, separating out a solid matter, drying the solid matter at 40 ℃ in vacuum, and removing the solvent until the weight is constant to obtain a homopolymerization product;

wherein the molar ratio of the monomer, the alkyl aluminum reagent, the organic boron salt and the bisindole rare earth metal catalyst is 50-5000: 0-200: 0-4: 1; the reaction temperature is-60-120 ℃; the dosage of the good solvent is 5-50 mL; the monomer is one of alkene, cycloalkene, alkyne or polar monomer.

The steps of the catalytic copolymerization reaction are as follows:

placing a reactor in a glove box, sequentially adding a bisindole rare earth metal catalyst, a good solvent, an alkyl aluminum reagent, a monomer and an organic boron salt into the reactor, reacting for 0.1-72 hours under stirring, taking out the reactor, and adding a chain terminator to stop the reaction; settling the reaction solution by using ethanol, separating out a solid matter, drying the solid matter at 40 ℃ in vacuum, and removing the solvent to constant weight to obtain a copolymerization product;

wherein the molar ratio of the monomer, the alkyl aluminum reagent, the organic boron salt and the bisindole rare earth metal catalyst is 50-5000: 0-200: 0-4: 1; the reaction temperature is-60-120 ℃; the dosage of the good solvent is 5-50 mL; the monomer is alkene, cycloalkene, alkyne, polar monomer CO₂Two of (1)And (4) seed preparation.

The aluminum alkyl (or other aluminum reagent) is one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum, and diethylbenzylaluminum;

the aluminum hydride reagent is one of dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, ethylbenzylaluminum hydride and ethyl-p-tolylaluminum hydride;

the aluminum chloride reagent is one of dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, ethylbenzylaluminum chloride and ethyl-p-tolylaluminum chloride;

the aluminoxane is one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane.

The organic boron salt is triphenyl (methyl) -tetra (pentafluorobenzene) boron salt, N-dimethyl anilinium tetra (pentafluorophenyl) borate, tri (pentafluorobenzene) boron salt, tri-tert-butylphosphine tetrafluoroborate, triethylphosphine fluoborate, 1-heptyl-3-methylimidazole tetrafluoroborate, N-hexylpyridine tetrafluoroborate, tetramethylurea-O- (3,4-2H-4-O-1,2, 3-benzotriazole) tetrafluoroborate, N-heptylpyridine tetrafluoroborate, 1-octyl-3-methylimidazole tetrafluoroborate, N-pentylpyridine tetrafluoroborate, succinyltetramethylurea tetrafluoroborate, 1-N-butyl-3-methylimidazole tetrafluoroborate, tetramethylurea benzotriazolyl tetrafluoroborate, N-dimethylphenylammonium tetrafluoroborate, N-hexylpyridine tetrafluoroborate, N-hexylurea tetrafluoroborate, N-propylurea, p-Nitrobenzotetrafluoroborate, 1-methyl-3-butylimidazolium tetrafluoroborate, trimethoxy tetrafluoroborate, 1-nitrilopropyl-2, 3-methylimidazolium tetrafluoroborate, N-cetylpyridinium tetrafluoroborate, 1-vinyl-3-hexylimidazolium tetrafluoroborate, 1-vinyl-3-octylimidazolium tetrafluoroborate, dodecyltributylammonium tetrafluoroborate, trimethylhydroxyethylammonium tetrafluoroborate, 1-allyl-3-ethylimidazolium tetrafluoroborate, 1, 3-dimethylimidazolium tetrafluoroborate, 1-nitrilopropyl-3-methylimidazolium tetrafluoroborate, N-octylpyridinium tetrafluoroborate, 1-decylimidazole tetrafluoroborate, 1-octylimidazolium tetrafluoroborate, N-octylpyridinium tetrafluoroborate, N-propylphosphonium tetrafluoroborate, N-octylphosphonium tetrafluoroborate, One of 1-ethylimidazole tetrafluoroborate, 1-methylimidazole tetrafluoroborate, 1-hexylimidazole tetrafluoroborate, tributylhexylphosphine tetrafluoroborate, 1-butylimidazole tetrafluoroborate, tetramethylguanidine fluoroborate, triethylamine tetrafluoroborate, tributylethylphosphine tetrafluoroborate, 1-octadecyl-3-methylimidazole tetrafluoroborate, 1-pentyl-3-methylimidazole tetrafluoroborate, and 1-propyl-3-methylimidazole tetrafluoroborate;

the alkene is one of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, styrene, α -methylstyrene, p-methoxystyrene, 3-chloromethylstyrene, 1, 3-butadiene, isoprene, myrcene, E-1-phenyl-1, 3-butadiene, ocimene, 1, 5-pentadiene and derivatives thereof, 1, 6-hexadiene, 1, 7-octadiene and divinylbenzene;

the cycloolefin is one of norbornene, polar norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene cyclopentene, cyclohexene, dicyclopentadiene and 1, 3-cyclohexadiene;

the alkyne is one of acetylene, p-phenylenediacetylene, diacetylene arene or phenylacetylene (phenyl para-position contains hydrogen, methyl, ethyl, isopropyl or tert-butyl, amino, sulfonate group (methyl ester and ethyl ester), sulfydryl, methoxyl, ethoxyl and nitryl; meta-position contains hydrogen, methyl, ethyl, isopropyl or tert-butyl or phenylacetylene (phenyl para-position contains hydrogen, methyl, ethyl, isopropyl or tert-butyl, amino, sulfonate group (methyl ester and ethyl ester), sulfydryl, methoxyl, ethoxyl and nitryl; ortho-position contains hydrogen, methyl, ethyl, isopropyl or tert-butyl and trimethyl or triethyl or phenylacetylene (phenyl para-position contains hydrogen, methyl, ethyl, isopropyl or tert-butyl, amino, sulfonate group (methyl ester and ethyl ester), sulfydryl, methoxyl, ethoxyl and nitryl);

the polar monomer is epoxyalkane, lactone and 2-vinylpyridine, wherein the epoxyalkane is epoxyethane, epoxypropane, 1, 2-epoxybutane, 2, 3-epoxybutane, iso-epoxybutane, epichlorohydrin, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether and trifluoro epoxypropane, and the lactone is one of epsilon-caprolactone, β -butyrolactone, delta-valerolactone, lactide, glycolide and 3-methyl-glycolide.

The chain terminator is an ethanol solution of 5 percent of 2, 6-di-tert-butyl-p-cresol, 2,3, 4-trimethylphenol, m-diphenol, 2, 6-diethylphenol or p-tert-butylphenol;

the good solvent is one or more of n-hexane, n-heptane, benzene, toluene, cyclohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene or tetrahydrofuran.

Advantageous effects

(1) The bis-indole rare earth metal catalyst takes N-methylindole, tetrahydrofuran and the like as initial raw materials, and the raw materials are cheap and easy to obtain and easy to modify;

(2) the preparation method of the bis-indole rare earth metal catalyst is simple, high in economic efficiency and good in environmental protection property, and is suitable for industrial production;

(3) the catalyst system composed of the bisindole rare earth metal catalyst, the alkyl aluminum reagent and the organic boron salt can be used for homopolymerization and copolymerization of alkene, cycloolefin, alkyne and polar monomer or respectively react with CO₂To obtain a series of novel polymeric materials with specific structures;

(4) the bisindole rare earth metal catalyst, particularly the bisindole scandium catalyst, has high selectivity in the process of catalyzing the polymerization reaction of styrene, wherein the syndiotactic rrrr is 100 percent, which is the result that the syndiotactic selectivity of the polymerization of styrene reaches 100 percent when the first non-metallocene rare earth metal catalyst catalyzes the polymerization of styrene, and the catalyst has high selectivity in the polymerization reaction of conjugated diene, wherein the polymerization selectivity of polyisoprene cis-1, 4-is as high as 100 percent, and the polymerization selectivity of polylaurene cis-1, 4-is as high as 94 percent.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the following embodiments.

In the following examples, polymerization Activity is represented by the formula Activity ═ m · yed)/(n_catTime) is calculated. Wherein Activity is living polymerization, and the unit is kg & mol^-1·h^-1M is branched olefin, cycloolefin, alkyne, polar monomer or CO₂Quality of (2), yield, n_catTime is the time taken for the polymerization, as the amount of catalyst material.

a. The polyisoprene microstructure may be prepared from¹H-NMR and¹³the C-NMR spectrum shows that the selectivity is specifically calculated by the following formula:

(1) selectivity (ratio) of 1, 4-polyisoprene:

Mol 1,4-IP％＝{I_H1/(I_H1+0.5I_H2)}×100

(2) selectivity (ratio) of 3, 4-polyisoprene:

Mol 3,4-IP％＝{0.5I_H2/(I_H1+0.5I_H2)}×100

(3) selectivity (ratio) of cis 1, 4-polyisoprene:

Mol cis-1,4-IP％＝{I_C1/(I_C1+I_C2+I_C3)}×100

(4) selectivity (ratio) of trans-1, 4-polyisoprene:

Mol trans-1,4-IP％＝{I_C3/(I_C1+I_C2+I_C3)}×100

(5) selectivity (ratio) of 3, 4-polyisoprene:

Mol 3,4-IP％＝{I_C2/(I_C1+I_C2+I_C3)}×100

wherein IP is polyisoprene, I_H1Is composed of¹Integral at 5.13ppm in the H spectrum; i is_H2Is composed of¹Integral at 4.72ppm in the H spectrum; i is_C1Is composed of¹³Integral at 23.2ppm in the C spectrum; i is_C2Is composed of¹³Integral at 18.5ppm in C spectrum; i is_C3Is composed of¹³Integral at 15.9ppm in the C spectrum.

b. The polylaurene microstructure may be composed of¹H-NMR and¹³the C-NMR spectrum is given, and the specific calculation formula is as follows:

formula 1.1 Main Structure of Polymyrcene

In the structural unit of polylaurene, the content of each configuration in the polymer can be calculated by the formula (formula 1.2)¹An H-NMR spectrum showed that a nuclear magnetic peak at 5.30ppm showed hydrogen at the 3-position in 1, 2-polylaurene, and was represented by I_5.30Represents; nuclear magnetic peaks at 5.11ppm indicating the hydrogen in the 3-and 7-positions of 1, 4-and 1, 2-polylaurene, denoted by I_5.11Represents; nuclear magnetic peaks at 4.76ppm indicating the hydrogen content of 3,4- (1-position) and 1,2- (4-position) polylaurenes, denoted by I_4.76And (4) showing.

Mol1，2-My％＝{2 I_5.30/(I_5.11+I_4.76/2)}×100 (1)

Mol3，4-My％＝{(I_4.76-2 I_5.30)/(I_5.11+I_4.76/2)}×100 (2)

Mol1，4-My％＝{(I_5.11-I_4.76/2)/(I_5.11+I_4.76/2)}×100 (3)

Formula 1.2 calculating the content of polylaurene configuration according to nuclear magnetic hydrogen spectrum

By¹³C-NMR spectrum, wherein polylaurene with cis-1, 4-and trans-1, 4-configurations is determined by aliphatic carbon (1 site), and peaks are respectively 37.09ppm and 37.51 ppm;1, 2-polylaurene was determined from the aliphatic carbon (position 1) and peaked at 29.07 ppm; the 3, 4-polylaurene is determined by aliphatic carbon (3-position), and the peak condition is 42.18ppm, which is shown in formula 1.3.

Mol1，2-My％＝{I_29.07/(I_29.07+I_37.09+I_37.51+I_42.18)}×100 (1)

Mol3，4-My％＝{I_42.18/(I_29.07+I_37.09+I_37.51+I_42.18)}×100 (2)

Mol cis-1，4-My％＝{I_37.09/(I_29.07+I_37.09+I_37.51+I_42.18)}×100 (3)

Mol trans-1，4-My％＝{I_37.51/(I_29.07+I_37.09+I_37.51+I_42.18)}×100 (4)

Formula 1.3 calculating the content of the polylaurene configuration according to the nuclear magnetic carbon spectrum

c. The polystyrene microstructure may be composed of¹³The C-NMR spectrum is given as follows:

the polystyrene stereoregularity is determined mainly by C1, corresponding to a NMR spectrum of 140-150 ppm. Wherein, when deuterated chloroform is used as the deuterated reagent, 146.8ppm corresponds to isotactic (mmmm); 145.7ppm corresponds to syndiotactic (rrrr); when a broad peak centered at 146.4 occurs, it corresponds to atactic.

Example 1

(1) Preparing a bis-indole ligand;

first, 0.829mL (4.4mmol) of di-t-butyl peroxide was added dropwise to a mixture of 1g (7.3mmol) of N-methylindole, 7.3mL (87.6mmol) of tetrahydrofuran and 92mg (0.73mmol) of ferrous chloride at room temperature under a nitrogen or argon atmosphere. Heating Schlenk bottle containing the above mixture to 80 deg.C, reacting for 1 hr, cooling to room temperature, washing the obtained product with petroleum ether, and drying to obtain target product 2.35g with yield of 97.0%.

(2) Preparation of bis-indole rare earth metal scandium catalyst

Firstly, in a glove box, 433.2mg (1.3mmol) of the bis-indole ligand is added into a round-bottom flask, and 5mL of toluene is used as a solvent to be fully dissolved; then, Sc (CH)₂SiMe₃)₃thf₂587.5mg (1.3mmol) is dissolved in 3mL toluene, the toluene solution dissolved with the bis-indole ligand is dripped into the toluene solution dissolved with the metal source, and the mixture is stirred for 2h at the temperature of 20-25 ℃; and finally, after 3-5 times of extraction by using n-hexane, dissolving the residual solid by using toluene, filtering to obtain filtrate, standing in a refrigerator at the temperature of-20 to-35 ℃, and after 1-7 days, carrying out solid-liquid separation to drain the obtained crystal to obtain 512.4mg of the bis-indole scandium catalyst, wherein the yield is 63.1%.

Example 2

Preparation of bis-indole lutetium catalyst

Firstly, in a glove box, 135.6mg (0.71mmol) of the bis-indole ligand is added into a round-bottom flask, and 5mL of toluene is used as a solvent to be fully dissolved; secondly, mixing Lu (CH)₂SiMe₃)₃thf₂236.9mg (0.71mmol) of the double-indole ligand is dissolved in 3mL of toluene, the toluene solution dissolved with the double-indole ligand is dripped into the toluene solution dissolved with the metal source, and the mixture is stirred for 2 hours at the temperature of 20-25 ℃; and finally, after 3-5 times of extraction by using normal hexane, dissolving the residual solid by using toluene, filtering to obtain filtrate, placing the filtrate in a refrigerator at the temperature of-20 to-35 ℃, and after 1-7 days, carrying out solid-liquid separation to drain the obtained crystal to obtain 333mg of the bis-indole lutetium catalyst, wherein the yield is 62.3%.

Example 3

Preparation of bis-indolyl yttrium catalyst

First, a glove boxAdding 525mg (1.58mmol) of the bis-indole ligand into a round-bottom flask, and fully dissolving the bis-indole ligand by using 5mL of toluene as a solvent; secondly, mixing Y (CH)₂SiMe₃)₃thf₂786.1mg (1.58mmol) is dissolved in 3mL toluene, the toluene solution dissolved with the bis-indole ligand is dripped into the toluene solution dissolved with the metal source, and the mixture is stirred for 2h at the temperature of 20-25 ℃; and finally, after 3-5 times of extraction by using normal hexane, dissolving the residual solid by using toluene, filtering to obtain filtrate, placing the filtrate in a refrigerator at the temperature of-20 to-35 ℃, and after 1-7 days, carrying out solid-liquid separation to obtain crystals, and pumping the crystals to dryness to obtain the bis (indolyl) yttrium catalyst 628mg with the yield of 59.6%.

Example 4

The reactor was placed in a glove box, and 20. mu. mol bis (indolyl) scandium catalyst, 5mL toluene, 400. mu. mol Al were added to the eggplant flask in this orderⁱBu₃4mmol of isoprene and 20. mu. mol of [ Ph ]₃C][B(C₆F₅)₄]The reaction time is 1h, and the reaction temperature is 30 ℃. Adding 30mL of ethanol containing 5% of 2, 6-di-tert-butyl-4-methylphenol to stop the reaction; precipitating the reaction solution with ethanol to obtain white solid, vacuum drying the solid at 40 deg.C, removing solvent to constant weight to obtain polyisoprene with net weight of 0.272g, conversion rate of 100%, and polymerization activity of 13.6 kg. mol%^-1·h^-1. GPC analysis of the number average molecular weight M of polyisoprene_n＝6.45×10⁵Molecular weight distribution M_w/M_n1.91 cis-1, 4-polymerization selectivity 100%.

Example 5

The reactor was placed in a glove box, and 20. mu. mol bis (indolyl) scandium catalyst, 5mL toluene, 400. mu. mol Al were added to the eggplant flask in this orderⁱBu₃4mmol of isoprene and 20. mu. mol of [ PhMe ]₂NH][B(C₆F₅)₄]The reaction time is 1h, and the reaction temperature is 30 ℃. The same procedures as in example 5 were repeated to give polyisoprene having a dry weight of 0.272g, a conversion of 100% and a polymerization activity of 13.6 kg. mol^-1.h^-1. GPC analysis of the number average molecular weight M of polyisoprene_n＝6.73×10⁵Molecular weight distribution M_w/M_n1.99. Cis-1, 4-polymerization Selectivity 100％。

Example 6

The reactor was placed in a glove box and to an eggplant flask were added 20. mu. mol of bis-indole scandium catalyst, 5mL of chlorobenzene, 400. mu. mol of AlMe in that order₃4mmol of isoprene and 20. mu. mol of [ Ph ]₃C][B(C₆F₅)₄]The reaction time is 1h, and the reaction temperature is 30 ℃. The same procedure as in example 5 was repeated except that polyisoprene was obtained in an amount of 0.272g net weight, conversion of 100% and polymerization activity of 13.6 kg. mol^-1.h^-1. GPC analysis of the number average molecular weight M of polyisoprene_n＝1.39×10⁵The molecular weight distribution Mw/Mn was 1.97. Cis-1, 4-polymerization selectivity was 96%.

Example 7

The reactor was placed in a glove box and to an eggplant flask were added 20. mu. mol1, bis-indole scandium catalyst, 5mL tetrachloroethane, 400. mu. mol AlMe₃10mmol of myrcene, and 20. mu. mol of [ Ph3C ]][B(C6F5)4]The reaction time is 60 hours, the reaction temperature is-30 ℃, the other operations are the same as example 5, the polylaurene is obtained, the net weight is 88mg, and the conversion rate is 6.5%. The number average molecular weight Mn of the copolymer was 4.16X 10 by GPC analysis⁵The molecular weight distribution Mw/Mn was 1.99, and the cis-1, 4-polymerization selectivity was 94%.

Example 7

The reactor was placed in a glove box, and 20. mu. mol bis-indole scandium catalyst, 5mL o-dichlorobenzene, 200. mu. mol Al were added to the eggplant flask in this orderⁱBu₃10mmol of styrene and 20. mu. mol of [ PhMe ]₂NH][B(C₆F₅)₄]The reaction time is 24h, and the reaction temperature is 30 ℃. The same procedures as in example 5 were repeated to obtain polystyrene having a dry weight of 0.921g, a conversion of 88.1% and a polymerization activity of 9.3 kg. mol^-1·h^-1. GPC analysis number average molecular weight M of polystyrene_n＝10×10³Molecular weight distribution M_w/M_n3.52. Cis-1, 4-polymerization selectivity was 100%.

Example 7

In a glove box, 1.88g (20mmol) of norbornene was weighed out into a 100mL two-necked flask and dissolved in 25mL of toluene, and the resulting solution was added to the toluene solution containing norbornene by a micro syringeAdding 20. mu.L (20. mu. mol) of AlⁱBu₃Another 25ml Schlenk flask was charged with 5. mu. mol of bis-indole scandium catalyst and 0.0046g of [ Ph ]₃C][B(C₆F₅)₄](5. mu. mol) was dissolved in 15mL of toluene, and 30. mu.L (30. mu. mol) of Al was addedⁱBu₃Adding the mixture into a toluene solution by using a micro syringe for standby. Taking the two-mouth bottle out of the glove box, connecting the two-mouth bottle to the double-row pipe, and introducing ethylene gas for 5min under the anhydrous and oxygen-free conditions to uniformly mix ethylene and norbornene. Taking out Schlenk tube from glove box, injecting catalyst solution into mixed solution of ethylene and norbornene with injector under nitrogen protection, reacting for 6min, stopping reaction with ethanol, precipitating solid substance, filtering, vacuum drying the solid substance at 30 deg.C, removing solvent to constant weight to obtain copolymer of norbornene and ethylene with net weight of 0.135g and polymerization activity of 270 kg. mol^-1·h^-1. GPC analysis of number average molecular weight M of copolymer_n＝6×10³Molecular weight distribution M_w/M_n＝2.29。

Example 8

The reactor was placed in a glove box, 20. mu. mol bis-indole scandium catalyst was added to the eggplant flask, dissolved with 5mL tetrahydrofuran, and then 10mmol of ε -caprolactone was directly added for 1min at 30 ℃. Adding 10% HCl ethanol solution to stop reaction after the solution becomes viscous, adding into ethanol for settling, filtering, washing to obtain white polymer, vacuum drying the solid at 40 deg.C, removing solvent to constant weight to obtain polycaprolactone with net weight of 1.1414g and polymerization activity of 6840 kg. mol^-1·h^-1. GPC analysis of number average molecular weight M of copolymer_n＝9.38×10⁴Molecular weight distribution M_w/M_n＝1.35。

Example 9

The reactor was placed in a glove box, and 20. mu. mol of bis (indole-scandium) catalyst, 5mL of tetrahydrofuran, and 10mmol of L-lactide were sequentially added to an eggplant flask, and the reaction time was 3min, the reaction temperature was 30 ℃, and the rest of the operation was the same as in example 5, to obtain poly-L-lactide, the conversion rate was 100% at a dry weight of 1.4413 g. GPC analysisNumber average molecular weight M of the copolymer_n＝7.53×10⁴Molecular weight distribution M_w/M_n＝1.22。

Example 10

The reactor was placed in a glove box, and 20. mu. mol bis (indolyl) scandium catalyst, 5mL toluene, and 40. mu. mol Al were sequentially added to the eggplant flaskⁱBu₃5mmol of phenylacetylene and 20. mu. mol of [ PhMe₂NH][B(C₆F₅)₄]The reaction time was 30min, the reaction temperature was 50 ℃ and the other operations were the same as in example 5 to obtain polyphenylacetylene with a dry weight of 0.5g and a conversion of 97.67%. GPC analysis of number average molecular weight M of polyphenylacetylene_n＝7.5×10³Molecular weight distribution M_w/M_n＝2.54。

Example 11

Placing the reactor in a glove box, adding 40mmol of bis (indole) scandium catalyst, 1mL of toluene and 20mol of propylene oxide into an eggplant bottle in sequence, sealing the reactor, transferring out of the glove box, and introducing CO into the reactor₂Adjusting pressure to 6Mpa, heating to 70 deg.C, reacting for 10 hr, cooling to room temperature, dissolving with chloroform, adding methanol to obtain white solid, washing with methanol, and vacuum drying to obtain propylene oxide and CO₂The copolymer of (1). Yield 26%, molecular weight Mn 32X 10³Molecular weight distribution M_w/M_n＝2.1。

The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.

Claims

1. A bis-indole rare earth metal catalyst is characterized in that: the structural formula of the bis-indole rare earth metal catalyst is as follows I, II and III:

wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₁₆、R₁₇、R₁₈、R₁₉The substituent groups on the benzene ring are the same or different groups and are one of hydrogen atoms, methyl groups, ethyl groups, isopropyl groups, tert-butyl groups, n-butyl groups, alkoxy groups, amino groups, chlorine atoms, fluorine atoms, iodine atoms, bromine atoms, nitro groups, phenyl groups, benzyl groups and naphthyl groups; r₉、R₁₀、R₁₁、R₁₂The substituent group on the pyrrole ring is one of hydrogen atom, methyl, ethyl, isopropyl, tert-butyl, n-butyl, alkoxy, amino, chlorine atom, fluorine atom, iodine atom, bromine atom, nitro, phenyl, benzyl, anthryl, naphthyl, phenanthryl, anilino, phenol group, thiophenyl and 3, 5-difluoromethane thiophenyl; r₁₃Is a substituent bridging two indole carbons and is one of hydrogen atom, methyl, ethyl, isopropyl, tert-butyl, n-butyl, alkoxy, chlorine atom, fluorine atom, iodine atom, bromine atom, nitro, phenyl, benzyl and naphthyl; r₁₄，R₁₅The initiating group is the same or different and is one of alkyl, alkynyl, trimethylsilyl, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen; ln is a rare earth metal.

2. The bis-indole rare earth metal catalyst of claim 1, wherein: ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

3. A process for the preparation of a bis-indole rare earth metal catalyst according to claim 1 or 2, characterized in that: the method comprises the following steps:

(1) preparing a bis-indole ligand;

firstly, dropwise adding di-tert-butyl peroxide into a mixed solution of N-methylindole, tetrahydrofuran and ferrous chloride at room temperature under the atmosphere of nitrogen or argon, wherein the molar ratio of the N-methylindole to the tetrahydrofuran to the ferrous chloride to the di-tert-butyl peroxide is 1:12:0.1: 0.6; heating the mixed solution to 80 ℃, reacting for 1h, and cooling to room temperature; washing the obtained product with petroleum ether, drying to obtain the target product,

(2) preparation of bis-indole rare earth metal catalysts

4. The process for preparing a bis-indole rare earth metal catalyst according to claim 3, wherein: in the step (2), the metal source is a ditetrahydrofuran-tri (trimethylsilylmethyl) rare earth metal compound Ln (CH)₂SiMe₃)₃(thf)₂(ii) a And the Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

5. Use of a bis-indole rare earth metal catalyst according to claim 1 or 2, wherein: the diindole rare earth metal catalyst, an alkyl aluminum reagent and an organic boron salt form a catalytic system for catalyzing homopolymerization of one of alkene, cycloolefin and alkyne or copolymerization of any two of alkene, cycloolefin and alkyne or respectively reacting alkene, cycloolefin and alkyne with CO₂Copolymerization reaction of (a); wherein the molar ratio of the alkyl aluminum reagent to the organic boron salt to the bis-indole rare earth metal catalyst is 0-200: 0-4: 1; the alkyl aluminum reagent is of the formula AlX₃Alkyl aluminum of formula HAlX₂Of the formula AlX₂One of the alkylaluminum chlorides of Cl and X is an alkyl group.

6. The use of a bis-indole rare earth metal catalyst according to claim 5, wherein: the steps of the homopolymerization are as follows:

wherein the molar ratio of the monomer, the alkyl aluminum reagent, the organic boron salt and the bisindole rare earth metal catalyst is 50-5000: 0-200: 0-4: 1; the reaction temperature is-60-120 ℃; the dosage of the good solvent is 5-50 mL; the monomer is one of alkene, cycloolefine and alkyne.

7. The use of a bis-indole rare earth metal catalyst according to claim 5, wherein the copolymerization reaction comprises the steps of:

wherein the molar ratio of the monomer, the alkyl aluminum reagent, the organic boron salt and the bisindole rare earth metal catalyst is 50-5000: 0-200: 0-4: 1; the reaction temperature is-60-120 ℃; the dosage of the good solvent is 5-50 mL.

8. The use of a bis-indole rare earth metal catalyst according to claim 5, wherein:

the alkyl aluminum is one of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum and trioctyl aluminum;

the alkyl aluminum hydride reagent is one of dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride and dioctyl aluminum hydride;

the alkyl aluminum chloride reagent is one of dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride and dioctylaluminum chloride;

the organic boron salt is triphenyl (methyl) -tetra (pentafluorobenzene) boron salt, N-dimethyl anilinium tetra (pentafluorophenyl) borate, tri (pentafluorobenzene) boron salt, tri-tert-butylphosphine tetrafluoroborate, triethylphosphine fluoborate, 1-heptyl-3-methylimidazole tetrafluoroborate, N-hexylpyridine tetrafluoroborate, tetramethylurea-O- (3,4-2H-4-O-1,2, 3-benzotriazole) tetrafluoroborate, N-heptylpyridine tetrafluoroborate, 1-octyl-3-methylimidazole tetrafluoroborate, N-pentylpyridine tetrafluoroborate, succinyltetramethylurea tetrafluoroborate, 1-N-butyl-3-methylimidazole tetrafluoroborate, tetramethylurea benzotriazolyl tetrafluoroborate, N-dimethylphenylammonium tetrafluoroborate, N-hexylpyridine tetrafluoroborate, N-hexylurea tetrafluoroborate, N-propylurea, p-Nitrobenzenedifluoroborate, 1-methyl-3-butylimidazolium tetrafluoroborate, trimethoxy tetrafluoroborate, 1-nitrilopropyl-2, 3-methylimidazolium tetrafluoroborate, N-cetylpyridinium tetrafluoroborate, 1-vinyl-3-hexylimidazolium tetrafluoroborate, 1-vinyl-3-octylimidazolium tetrafluoroborate, dodecyltributylammonium tetrafluoroborate, trimethylhydroxyethylammonium tetrafluoroborate, 1-allyl-3-ethylimidazolium tetrafluoroborate, 1, 3-dimethylimidazolium tetrafluoroborate, 1-nitrilopropyl-3-methylimidazolium tetrafluoroborate, N-octylpyridinium tetrafluoroborate, 1-decylimidazole tetrafluoroborate, 1-octylimidazolium tetrafluoroborate, N-octylpyridinium tetrafluoroborate, N-decylimidazole tetrafluoroborate, one of 1-ethylimidazole tetrafluoroborate, 1-methylimidazole tetrafluoroborate, 1-hexylimidazole tetrafluoroborate, tributylhexylphosphine tetrafluoroborate, 1-butylimidazole tetrafluoroborate, tetramethylguanidine fluoroborate, triethylamine tetrafluoroborate, tributylethylphosphine tetrafluoroborate, 1-octadecyl-3-methylimidazole tetrafluoroborate, 1-pentyl-3-methylimidazole tetrafluoroborate, and 1-propyl-3-methylimidazole tetrafluoroborate;

the cycloolefin is one of norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene cyclopentene, cyclohexene, dicyclopentadiene and 1, 3-cyclohexadiene;

the alkyne is one of acetylene, p-phenylenedialkyne, diacetylene arene or phenyl acetylene.