CN113754805A

CN113754805A - Rare earth catalyst and preparation and application thereof

Info

Publication number: CN113754805A
Application number: CN202010500440.9A
Authority: CN
Inventors: 周光远; 胡雁鸣; 于琦周
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2020-06-04
Filing date: 2020-06-04
Publication date: 2021-12-07

Abstract

The invention provides a rare earth catalyst and a preparation method and application thereof. The rare earth catalyst comprises the following components: rare earth compounds, aluminum compounds, conjugated dienes and halogen-containing compounds. The rare earth compound is selected from rare earth carboxylate, rare earth phosphate, alkoxy rare earth compound or chlorinated rare earth electron donor complex. The aluminum compound is one shown in formula (1) or the aluminum compound is mixed with AlR in the general formula₃Or AlHR₂Or mixtures of alkylaluminums or alkylaluminum hydrides. The molar ratio of the aluminum compound to the rare earth compound is (10-200): 1, and the molar ratio of the halogen compound to the rare earth compound is (0-5): 1. The invention provides a preparation method for preparing conjugated diene polymers and copolymers. Hair brushThe rare earth catalyst has high catalytic activity and cis-orientation when used for polymerization and copolymerization of conjugated diene, and the polymer obtained by direct polymerization has good ageing resistance, and an anti-aging agent is not required to be added after the polymerization is finished.

Description

Rare earth catalyst and preparation and application thereof

Technical Field

The invention belongs to the technical field of catalysts, and relates to a rare earth catalyst, a preparation method and application thereof, in particular to application of the rare earth catalyst in preparation of polybutadiene, polyisoprene and a butadiene-isoprene copolymer.

Background

The rare earth catalyst has the characteristics of high activity and high cis-1, 4 selectivity when used for catalyzing the polymerization of conjugated diene. When the butadiene rubber prepared by the rare earth catalyst is used for preparing tires, the wear resistance and fatigue resistance can be obviously improved, the heat generation is reduced, the service life of the tires is prolonged, and the effect of saving oil can be achieved to a certain extent. The rare earth isoprene rubber has the structure and performance closest to those of natural rubber, is called as synthetic natural rubber, and is widely applied to tires, adhesive tapes and other rubber products. The monomer units in the copolymer obtained by the copolymerization of butadiene and isoprene catalyzed by the rare earth catalyst are mainly cis-1, 4-structure, which cannot be realized by other Ziegler-Natta catalysts such as Ti, Ni and the like. The high cis-butadiene-isoprene copolymer has good physical and mechanical properties and processing behaviors, more excellent low-temperature performance than butadiene rubber, high wet skid resistance and low rolling resistance, and is a synthetic rubber variety with both general and special purposes. These unique properties of rare earth catalysts have made them a focus of research in the synthesis of rubber in recent years.

Rubber inevitably ages during storage and use, so that the rubber loses elasticity, the mechanical property is reduced, and the service life is shortened. An anti-aging agent is added in the production process of the synthetic rubber so as to improve the anti-aging performance and the stability of the product. Commonly used antioxidants are hindered phenols such as 2, 6-di-tert-butyl-p-cresol and 2,2' -methylenebis- (4-methyl-6-tert-butylphenol). At present, the anti-aging agent is industrially added at the later stage of polymerization, but because the compatibility of the phenol anti-aging agent and the synthetic rubber is poor, the added anti-aging agent is difficult to be uniformly distributed in a rubber matrix, and the loss of the anti-aging agent can be caused.

Barron and Ittel et al reported on the basis of 2, 6-di-tert-butyl-p-cresol (BHT) and AlR, respectively₃Preparation of aryloxy substituted aluminum compound AlR by (R-Me, Et and i-Bu) reaction₂BHT, AlRBHT and AlBHT₃(Organometallics1998, 7, 409; Angew Chem Int Ed, 1992, 31, 921). Lin et al reported the preparation of aryloxy substituted aluminum compounds by reacting 2,2' -methylenebis- (4-methyl-6-tert-butylphenol) with aluminum alkyls (Inorg Chem, 2000, 39, 1463). However, the above-mentioned aluminum compounds are not catalyzed as catalyst componentsAnd (3) carrying out chemical polymerization reaction.

Collins et al report metallocene catalyst systems [ Cp ] for ethylene polymerization₂ZrMe][MeB(C₆F₅)₃]/AlMe₃/MeAl(BHT)₂(Organometallics, 2006, 25, 5083), but MeAl (BHT) in the system₂Acting as an impurity remover.

U.S. Pat. No. 4,34313 discloses a zirconium tetrachloride/diethyl 2, 4-di-tert-butyl-4-methoxyaluminium catalyst for the oligomerization of ethylene, but this catalyst is only capable of catalyzing the polymerization of ethylene to give an oil having a number average molecular weight of 285.

The hindered phenol substituted aluminum compound is simple and convenient to synthesize, is developed as a rare earth catalyst serving as one of catalyst components, can be used for preparing a high cis-1, 4 conjugated diene polymer, and can be used for improving the anti-aging performance of the polymer without adding an anti-aging agent after the hindered phenol compound generated after polymerization is in-situ dispersed in a polymer matrix.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a rare earth catalyst based on a hindered phenol-substituted aluminum compound, and a preparation method and application thereof. Through reasonable proportioning and preparation of catalyst components, the obtained rare earth catalyst is used for polymerizing conjugated diene with high activity and high cis-form directionality, and preparing conjugated diene polymer containing in-situ dispersed hindered phenol anti-aging agent and copolymer thereof.

The invention provides a rare earth catalyst, comprising:

a. a rare earth compound;

b. a conjugated diene;

c. an aluminum compound; is one or a mixture of aluminum compounds 1-7 of the following structural formula, or the aluminum compounds and AlR of the general formula₃Or AlHR₂Mixtures of alkylaluminum or alkylaluminum hydride of (a);

d. a halogen-containing compound;

wherein the molar ratio of each component is a: b: c: d is 1: (0-60): (10-200): (1-5).

The rare earth catalyst is prepared by the reasonable proportion of the simple components.

The rare earth elements in the rare earth compound are selected from lanthanide elements, selected from lanthanum, praseodymium and neodymium, wherein neodymium is preferred;

the rare earth compound is selected from rare earth carboxylate, rare earth phosphate and chlorinated rare earth electron donor complex (MtCl)₃·)；

The above conjugated diolefins refer to conjugated diolefins having conjugated double bonds in the molecular structure, including but not limited to C₄～C₆Conjugated diolefins, and also mixtures thereof. Typically selected from butadiene, isoprene, piperylene.

The halogen-containing compound is represented by the general formula AlR₂Alkylaluminum halide of X, formula Al₂R₃X₃Wherein R is ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc., and X is bromine or chlorine. Also possible are chloromethylsilanes: monochlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane or silicon tetrachloride.

In the specific implementation process of the invention, the molar ratio of the components is generally a: b: c: d is 1: (0-60): (10-200): (0-6), and the preferable molar ratio is a: b: c: d is 1: (0-15): (20-200): (1-3).

The invention also provides a preparation method of the rare earth catalyst, which comprises the following steps:

in an inert organic solvent, firstly, mixing the component a and the component b for 1-10 min; then adding the component c, and reacting for 20-120 min; and finally, adding the component d, and reacting for 20-120 min.

The temperature in the preparation process of the catalyst is 20-60 ℃.

The invention also provides application of the rare earth catalyst in preparation of polybutadiene, polyisoprene and butadiene-isoprene copolymer.

The present invention also provides a process for preparing a conjugated diene polymer using the above rare earth catalyst as a catalyst, which comprises:

under the protection of inert gas, mixing the rare earth catalyst with a conjugated diene monomer in an inert organic solvent, and carrying out catalytic polymerization reaction to obtain a conjugated diene polymer;

wherein the molar ratio of the rare earth element to the conjugated diene monomer in the rare earth catalyst is 1.0 multiplied by 10^-4～1.0×10^-6. The polymerization reaction temperature is 30-120 DEG C

Compared with the prior art, the rare earth catalyst provided by the invention has high catalytic activity, can be used for preparing high cis-polybutadiene, high cis-polyisoprene and high cis-butadiene-isoprene copolymer, and because the catalyst contains an aluminum compound modified by hindered phenol, the hindered phenol compound generated in situ after polymerization is dispersed in a polymer matrix, and an anti-aging agent is not required to be added in the later polymerization stage, so that the obtained polymer has good anti-aging performance. The rare earth catalyst has low cost and is suitable for industrial popularization.

Detailed Description

The technical solutions in the embodiments of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified. Wherein the aluminum compound is prepared according to a literature synthetic method. Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein the hindered phenol-modified aluminum compounds were prepared according to literature synthetic methods. Aluminum compounds 1-7 were synthesized according to Organometallics1998, 7, 409, Angew Chem Int Ed, 1992, 31, 921 and Inorg Chem, 2000, 39, 1463.

The analysis method in the examples of the present application is as follows:

the microstructure of the polymer was determined by means of a Vertex-70 FTIR type IR spectrometer from Bruker, Germany and a AVANCE400 type superconducting NMR spectrometer from Bruker, Germany. The number average molecular weight (Mw) and the molecular weight distribution index (Mw/Mn) were determined by means of Gel Permeation Chromatography (GPC) model TDA302 from Viscotek, USA, with tetrahydrofuran as the mobile phase, narrow-distribution polystyrene as the standard, a flow rate of 1.0ml/min and a test temperature of 30 ℃. The Mooney viscosity is measured by a Mooney viscometer and the test method is carried out according to GB/T1232.1-2000 standard. Mixing and vulcanizing rubber, and measuring aging performance: wherein the polybutadiene rubber is subjected to mixing, vulcanization molding and mechanical property measurement according to GB/T8660-2018 solution polymerization type Butadiene Rubber (BR) evaluation method; mixing, vulcanization molding and mechanical property measurement are carried out on the polyisoprene and the butadiene-isoprene copolymer according to T/CSTM 00024-; the aging properties were determined according to the GB/T3512-.

Example 1

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution and 15mmol of aluminum compound 1 are added into a catalyst preparation device, and then the mixture reacts for 120min at 30 ℃ to obtain the rare earth catalyst.

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 1.0X 10 was fed^-4The reaction was carried out at 60 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polybutadiene.

Example 2

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution and 30mmol of aluminum compound 1 are added into a catalyst preparation device, and the mixture reacts for 120min at 30 ℃ to obtain the rare earth catalyst.

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 1.0X 10 was fed^-4At 60 ℃ by reactionThe reaction was terminated after 4h by adding 100mL of ethanol to obtain polybutadiene.

Example 3

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution and 30mmol of aluminum compound 1 are added into a catalyst preparation device, reaction is carried out for 120min at 30 ℃, then 1.0mL of 1.0mol/L monochlorodiethyl aluminum is added, and reaction is carried out for 1h at 50 ℃, so as to obtain the rare earth catalyst.

Example 4

Under the protection of nitrogen, 1mmol of rare earth chloride tert-butyl triphosphate compound (NdCl) is added into a catalyst preparation device_3·3TBP), 2.7mL of 1.85mol/L butadiene hexane solution and 100mmol of aluminum compound 1, and reacting at 50 ℃ for 2h to obtain the rare earth catalyst.

Example 5

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L and 200mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the reaction is carried out for 1h at the temperature of 50 ℃ to obtain the catalyst. Al/Nd-200

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 1.0X 10 was fed^-4Reacting for 2h at 60 ℃, and then adding a small amount of ethanol to terminate the reaction to obtain the polybutadiene.

Example 6

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L and 200mmol of aluminum compound 1 are sequentially added into a catalyst preparation device to react for 1h at 50 ℃, and then 1.0mL of diethylaluminum monochloride with the concentration of 1.0mol/L is added to react for 1h at 50 ℃ to obtain the catalyst. Al/Nd-200, Cl/Nd-1

Example 7

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device to react for 1h at 50 ℃, and then 2mL of diethylaluminum monochloride with the concentration of 1.0mol/L are added to react for 30min at 50 ℃ to obtain the catalyst. Al/Nd-100 Cl/Nd-2

Example 8

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device to react for 1h at 50 ℃, and then 4mL of diethylaluminum monochloride with the concentration of 1.0mol/L are added to react for 30min at 50 ℃ to obtain the catalyst. Al/Nd-100 Cl/Nd-4

Example 9

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device to react for 1h at 50 ℃, and then 6mL of diethylaluminum monochloride with the concentration of 1.0mol/L is added to react for 30min at 50 ℃ to obtain the catalyst. Al/Nd 100 Cl/Nd 6

Example 10

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 2.7mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the mixture is reacted at 50 ℃ for 1h, then 2.5mL of 1.0mol/L diethylaluminum monochloride is added, and the reaction is carried out at 50 ℃ for 30min, so as to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

Example 11

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the mixture is reacted at 50 ℃ for 1h, then 2.5mL of 1.0mol/L diethylaluminum monochloride is added, and the reaction is carried out at 50 ℃ for 30min, so as to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

Example 12

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 8mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the mixture is reacted at 50 ℃ for 1h, then 2.5mL of 1.0mol/L diethylaluminum monochloride is added and the reaction is carried out at 50 ℃ for 30min, so as to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

Example 13

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 16.2mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the mixture is reacted at 50 ℃ for 1h, then 2.5mL of 1.0mol/L diethylaluminum monochloride is added, and the reaction is carried out at 50 ℃ for 30min, so as to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

Example 14

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 30mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 1 are sequentially added into a catalyst preparation device, and the mixture is reacted at 50 ℃ for 1h, then 2.5mL of 1.0mol/L diethylaluminum monochloride is added and the reaction is carried out at 50 ℃ for 30min, so as to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

Under the protection of nitrogen, drying2L of a butadiene hexane solution having a monomer concentration of 100g/L was charged into the dry polymerization reactor, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 1.0X 10 was added^-4Reacting for 2h at 60 ℃, and then adding a small amount of ethanol to terminate the reaction to obtain the polybutadiene.

Example 15

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 2 are sequentially added into a catalyst preparation device, and the mixture is reacted for 1h at 60 ℃, then 3mL of 1.0mol/L tert-butyl chloride is added, and the reaction is carried out for 120min at 50 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

2L of a hexane solution of butadiene having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 8.0X 10 was fed^-5The reaction was carried out at 60 ℃ for 2 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polybutadiene.

Example 16

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 100mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and react for 1h at 60 ℃, then 3mL of 1.0mol/L diisobutylaluminum chloride is added, and the reaction is carried out for 30min at 60 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

Example 17

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 50mmol of aluminum compound 4 are sequentially added into a catalyst preparation device, and react for 1h at 60 ℃, then 3mL of 1.0mol/L diisobutylaluminum chloride is added, and the reaction is carried out for 30min at 60 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

Example 18

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 50mmol of aluminum compound 5 are sequentially added into a catalyst preparation device, and the mixture is reacted for 1h at 60 ℃, then 3mL of 1.0mol/L diisobutylaluminum chloride is added, and the reaction is carried out for 30min at 60 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

Example 19

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 50mmol of aluminum compound 6 are sequentially added into a catalyst preparation device, and react for 1h at 60 ℃, then 3mL of 1.0mol/L diisobutylaluminum chloride is added, and the reaction is carried out for 30min at 60 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

Example 20

Under the protection of nitrogen, 6mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L and 50mmol of aluminum compound 7 are sequentially added into a catalyst preparation device, and the mixture is reacted for 1h at 60 ℃, then 3mL of 1.0mol/L diisobutylaluminum chloride is added, and the reaction is carried out for 60min at 60 ℃, so as to obtain the rare earth catalyst. Al/Nd 100 Cl/Nd 3.0

Example 21

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L diisobutylaluminum hydride and 15mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts for 20min at the temperature of 60 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 30, Cl/Nd 3.0 containing AlH

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst having a molar ratio of Nd element to butadiene monomer of 5.0X 10 was fed^-5The reaction was carried out at 60 ℃ for 2 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polybutadiene.

Example 22

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 5mL of 1.0mol/L diisobutylaluminum hydride and 10mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts for 60min at the temperature of 50 ℃; then 1.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 60min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 15, Cl/Nd 1.0 containing AlH

2L of a butadiene hexane solution having a monomer concentration of 100g/L were introduced into a dry polymerization reactor under nitrogen protection, and thenThe molar ratio of Nd element to butadiene monomer in the rare earth catalyst is 5.0X 10^-5The reaction was carried out at 60 ℃ for 6 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polybutadiene.

Example 23

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 16.2mL of butadiene hexane solution with the concentration of 1.85mol/L, 10mL of 1.0mol/L diisobutylaluminum hydride and 10mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts for 30min at the temperature of 50 ℃; then 1.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 20, Cl/Nd 1.0 AlH

Example 24

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 16.2mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L diisobutylaluminum hydride and 30mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts for 30min at the temperature of 50 ℃; then 1.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 40, Cl/Nd 1.0 containing AlH

Example 25

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L triisobutyl aluminum and 15mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts for 60min at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 60min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 30, Cl/Nd 3.0 containing AlH

Example 26

Under the protection of nitrogen, 1mmol of neodymium bis (2-ethylhexyl) phosphate, 5.4mL of 1.85mol/L butadiene hexane solution, 10mL of 1.0mol/L diisobutylaluminum hydride and 15mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and then the mixture reacts at 50 ℃ for 30 min; then 1.0mL of 1.0mol/L of ethyl aluminum sesquichloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 30, Cl/Nd 3.0 containing AlH

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 6.0X 10 was fed^-5The reaction was carried out at 60 ℃ for 2 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polybutadiene.

Comparative example 1

Under the protection of nitrogen, 1mmol of neodymium bis (2-ethylhexyl) phosphate, 5.4mL of 1.85mol/L butadiene hexane solution and 15mL of 1.0mol/L diisobutylaluminum hydride are sequentially added into a catalyst preparation device, and then the mixture is reacted for 30min at 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 15, Cl/Nd 3.0

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 6.0X 10 was fed^-5Reacting at 60 ℃ for 2h, then addingThe reaction was terminated by adding 100mL of ethanol to obtain polybutadiene.

Comparative example 2

2L of a butadiene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst in which the molar ratio of Nd element to butadiene monomer was 6.0X 10 was fed^-5The reaction was carried out at 60 ℃ for 2 hours, and then 100mL of ethanol containing 2g of 2, 6-di-t-butyl-p-cresol was added to terminate the reaction, thereby obtaining polybutadiene.

Comparative example 3

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 54mL of 1.85mol/L Methylaluminoxane (MAO) and 2.5mL of 1.0mol/L diethylaluminum monochloride are sequentially added into a catalyst preparation device and reacted for 1h at the temperature of 50 ℃ to obtain the catalyst. Al/Nd 100 Cl/Nd 2.5

TABLE 1 results of polymerization experiments in examples 1-26

The polymer yields, molecular weights and distribution indices and cis-1, 4 structure contents of the polybutadienes prepared in examples 1-18 and comparative example are listed in Table 1. When the catalyst consists of components a and d (examples 2 and 4) and a is a halogen-free rare earth compound, d is an aluminum compound of the formula 1, and the molar ratio of a: d is 30 and 200, polymers having a high molecular weight and a narrow molecular weight distribution index, but having a low cis-1, 4 content, can be obtained in a high polymer yield. The catalyst is further added with a component d (examples 3 and 5), and the obtained polymer not only has high yield, high molecular weight and narrow molecular weight distribution index, but also has high cis-1, 4 structure content. When the molar ratio of a to b to c to b in the rare earth catalyst is 1 (0-30) to (20-200) to (1-4), the obtained polymer has high molecular weight, narrow molecular weight distribution index and high cis-1, 4 structure content. When the amount of d component in the catalyst is too high (example 8) and the molar ratio of a: d exceeds 4, a polymer having a high molecular weight and a high cis-1, 4 structure content can be obtained, but the molecular weight distribution index is broad (4.80). It is to be noted that in example 13, the amount of the b component used during the aging of the catalyst is high, the molar ratio of a to b exceeding 30 does not adversely affect the polymerization obtained, but the viscosity of the catalyst prepared is too high to be practically used.

Example 27

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution and 30mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and the mixture reacts for 1h at 30 ℃ to obtain the rare earth catalyst. Al/Nd-30 Cl/Nd-0

1L of an isoprene hexane solution having a monomer concentration of 100g/L was fed into a dry polymerization reactor under nitrogen protection, and then the above-mentioned rare earth catalyst having a molar ratio of Nd element to butadiene monomer of 1.0X 10 was fed^-4The reaction was carried out at 60 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining polyisoprene.

Example 28

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution, 30mmol of aluminum compound 3 and 3.0mL of 1.0mol/L monochloro diethyl aluminum are sequentially added into a catalyst preparation device, and the mixture reacts for 4 hours at 30 ℃ to obtain the rare earth catalyst. Nd/Al-30 Cl/Nd-3.0

Example 29

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution, 30mmol of aluminum compound 3 and 3.0mL of 1.0mol/L tert-butyl chloride are sequentially added into a catalyst preparation device, and the mixture reacts for 2 hours at 50 ℃ to obtain the rare earth catalyst.

Example 30

Under the protection of nitrogen, 10mL of 0.10mol/L isopropoxy neodymium toluene solution, 10mL of 1.0mol/L diisobutylaluminum hydride and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device, and the mixture reacts for 4 hours at 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 30, Cl/Nd 3.0 containing AlH

Example 31

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 20mL of 1.0mol/L triisobutyl aluminum and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 40, Cl/Nd 3.0 AlH

TABLE 2 results of polymerization experiments for examples 27-31

Table 2 shows the results of isoprene polymerization catalyzed by the rare earth catalyst of the present invention. By adopting the optimized catalyst component ratio, the polymerized isoprene has high activity, the polymer yield is more than 85 percent, and the obtained polyisoprene has high molecular weight, narrow molecular weight distribution index and high cis-1, 4 structure content (> 97 percent). When the catalyst component had no d component (example 27), the cis-1, 4 structure content was lower than that of the former, at 91.1%, although the resulting polymer also had a high molecular weight and a narrow molecular weight distribution index.

Example 32

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L diisobutylaluminum hydride and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 35, Cl/Nd 3.0 AlH

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 80:20, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 1.0X 10^-4The reaction was carried out at 80 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

Example 33

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L triisobutyl aluminum and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst. Al/Nd 35, Cl/Nd 3.0 AlH

Example 34

Under the protection of nitrogen, 1.0mmol of neodymium bis (2-ethylhexyl) phosphate, 5.4mL of 1.85mol/L butadiene hexane solution, 10mL of 1.0mol/L diisobutylaluminum hydride and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 30min at 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst.

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 80:20, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5The reaction was carried out at 80 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

Example 35

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L triisobutyl aluminum and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 50 ℃ to obtain the rare earth catalyst.

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 50:50, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5Reacting at 80 ℃ for 2h, adding 100mL of ethanol to stop the reaction, and treating with hot water to obtain the butadiene-isoprene copolymer.

Example 36

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 20:80, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5The reaction was carried out at 80 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

Example 37

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L triisobutyl aluminum and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 20 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 30min at 20 ℃ to obtain the rare earth catalyst.

1L of butadiene-iso-butylene with a monomer concentration of 1g/10mL was fed to a dry polymerization reactor under nitrogen protectionA pentadiene hexane solution, wherein the molar ratio of butadiene to isoprene monomer is 20:80, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5The reaction was carried out at 80 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

Example 38

Under the protection of nitrogen, 5mL of neodymium neodecanoate with the concentration of 0.2mol/L, 5.4mL of butadiene hexane solution with the concentration of 1.85mol/L, 15mL of 1.0mol/L triisobutyl aluminum and 20mmol of aluminum compound 3 are sequentially added into a catalyst preparation device and reacted for 2 hours at the temperature of 50 ℃; then 3.0mL of 1.0mol/L diethyl aluminum chloride is added to react for 60min at 50 ℃ to obtain the rare earth catalyst.

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 20:80, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5The reaction was carried out at 30 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

Example 39

Under the protection of nitrogen, 1L of butadiene-isoprene hexane solution with the monomer concentration of 1g/10mL is added into a dry polymerization reactor, wherein the molar ratio of butadiene to isoprene monomer is 20:80, and then the rare earth catalyst is added; the molar ratio of Nd element to the added monomer in the catalyst is 5.0X 10^-5The reaction was carried out at 120 ℃ for 4 hours, and then 100mL of ethanol was added to terminate the reaction, thereby obtaining a copolymer of butadiene and isoprene.

TABLE 3 results of polymerization experiments for examples 32-36

Table 3 shows the results of the copolymerization of butadiene and isoprene using the rare earth catalyst of the present invention. By adopting the optimized catalyst component proportion, the obtained butadiene-isoprene copolymer not only has high molecular weight and narrow molecular weight distribution, but also has high cis-1, 4 structure of butadiene and isoprene chain links in the copolymer.

TABLE 4 aging Properties of the polybutadiene, polyisoprene and butadiene-isoprene copolymer prepared

Table 4 shows the tensile strength and elongation at break before and after aging of the polybutadiene, polyisoprene and butadiene-isoprene copolymers prepared. The ageing resistance of the polybutadiene prepared by the rare earth catalyst is obviously better than that of the polymer prepared in the comparative examples 1-3. The change rates of the tensile strength and the elongation at break of the polybutadiene prepared by the rare earth catalyst after hot air aging are respectively 10.2-13.0% and 13.5-16.8%, the change rates are obviously lower than those of the polymers in the comparative examples 1-3, and the change rates of the tensile strength and the elongation at break of the polybutadiene after hot air aging are respectively 18.0-21% and 25.2-28.2%.

The change rates of the tensile strength and the elongation at break of the polyisoprene obtained by the catalyst of the invention after hot air aging are respectively 14.0-14.8 percent and 24.2-25.0 percent, and the change rates of the tensile strength and the elongation at break of the prepared butadiene-isoprene copolymer after hot air aging are respectively 12.9-15.6 percent and 14.0-21.2 percent, which also shows that the polyisoprene and the butadiene-isoprene copolymer obtained by the catalyst of the invention have good aging resistant effect.

Polybutadiene, polyisoprene and butadiene-isoprene copolymer prepared by the rare earth catalyst of the invention all show good aging resistance effect, because the catalyst component c is obtained by the reaction of alkyl aluminum and antioxidant, 2, 6-di-tert-butyl-p-cresol and 2,2' -methylene bis- (4-methyl-6-tert-butylphenol). By adopting the optimized catalyst formula, the polymer with high molecular weight, narrow molecular weight distribution index and high cis-1, 4 structure content is obtained, and the antioxidant generated in situ is well dispersed in the polymer matrix after the polymerization is terminated, so that the obtained polymer has good aging resistance.

Claims

1. A rare earth catalyst is characterized by comprising a and c in the following components, wherein one or more than two of b and/or d in the following components can be added:

component a, rare earth compounds;

the component b, optional additive or optional additive component, is conjugated diene;

component c, an aluminum compound; is one or a mixture of more than two of compounds A and B with the structure shown in formula (I);

or one or more than two of the structural compounds A and/or B shown in the formula (I) and the general formula of AlR₃Wherein R is one or two or three of methyl, ethyl, isobutyl and octyl and/or the general formula is AlHR₂The alkyl aluminum hydride (wherein R is one or two of ethyl and isobutyl) of (1);

wherein R is₁And R₂Can be respectively and independently selectedFrom methyl, ethyl, isobutyl or 2, 6-di-tert-butyl-4-methylphenoxy; two R₃Each independently selected from methyl or hydrogen, two R₄Each independently selected from methyl, ethyl or isobutyl;

the component d can be optionally added or not, and the halogen-containing compound is one or more than two of the following compounds;

has the general formula AlR₂Alkylaluminum halide of X, formula Al₂R₃X₃Wherein R is one or more than two of ethyl, propyl, isopropyl, isobutyl, tert-butyl and the like, and X is one or two of bromine or chlorine; also possible are chloromethylsilanes: one or more of chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane and silicon tetrachloride;

wherein the molar ratio of each component is a: b: c: d is 1: (0-60): (10-200): (0-5).

2. The rare earth catalyst according to claim 1,

when the component C is only one or more than two of the aluminum compounds A and/or B shown in the formula I, the molar ratio of the components is a: b: c: d is 1: (0-60): (10-200): (0-5), and the molar ratio of each component is preferably a: b: c: d is 1: (0-30): (30-200): (1-4), and the preferable molar ratio is a: b: c: d is 1: (0-15): (30-200): (1-3), and the molar ratio of each component is more preferably a: b: c: d is 1: (0-10): (30-200): (1-3);

or when the component C selects one or more than two of the aluminum compounds A and/or B shown in the formula I and AlR₃And/or AlHR₂In the case of a mixture of one or more than two of A and/or B, one or more than two of A and/or B and AlR₃And/or AlHR₂One or more than two of the (B) is/are in a molar ratio of 2: 8-8: 2; the molar ratio of the components is generally a: b: c: d is 1: (0-60): (15-200): (0-6), and the molar ratio of each component is preferably a: b: c: d is 1: (0-30): (20-200): (1 to 4) are compared withPreferred molar ratios are a: b: c: d is 1: (0-10): (20-100): (1-3), and the molar ratio of each component is more preferably a: b: c: d is 1: (0-10): (20-50): (1-3).

3. The rare earth catalyst according to claim 1,

the conjugated diene is selected from one or more of butadiene, isoprene and piperylene;

the rare earth elements in the rare earth compound are selected from one or more of lanthanum, praseodymium and neodymium, wherein neodymium is preferred;

the rare earth compound is one or more than two of the following compounds:

selected from rare earth carboxylates, being M (RCOO)₃(ii) a M is one or more than two of the rare earth elements, and RCOO is selected from: one or more than two of naphthenate, decanoate, 2-ethylhexanoate, octanoate and neodecanoate;

one or more selected from rare earth phosphate compounds, such as neodymium (lanthanum or praseodymium) bis (2-ethylhexyl) phosphate, neodymium (lanthanum or praseodymium) mono 2-ethylhexyl phosphate, or neodymium (lanthanum or praseodymium) bis (2-ethylhexyl) phosphate;

selected from alkoxy rare earth compounds, being M (OR)₃M is one or more of the rare earth elements, R is one or more of C3-C9 straight-chain or branched-chain alkyl or phenyl containing substituent (the substituent is C1-C9 straight-chain or branched-chain alkyl), preferably one or more of ethyl, isopropyl, 2, 6-dimethylphenyl and 2,4, 6-trimethylphenyl;

selected from chlorinated rare earth complexes, MCl₃nL, n is 1 to 4, M is one or two or more of the above rare earth elements, L is an organic ligand selected from one or two or more of alcohols, ethers, or organic phosphates, wherein the alcohol is a C1 to C8 alcohol, preferably one or two or more selected from methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol; the ether is C1-C8 ether, preferably selected from one of diethyl ether, methyl ethyl ether, butyl ether, tetrahydrofuran and dioxaneOne or more than two; the organic phosphate is selected from one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, and diphenyl phosphate.

4. The rare earth catalyst according to claim 3, characterized in that:

the RCOO in the carboxylic acid rare earth compound is selected from: one or more than two of naphthenate, neodecanoate or 2-ethylhexanoate;

alkoxy rare earth compounds M (OR)₃Wherein R is selected from one or more than two of isopropyl, phenyl or 2, 6-dimethylphenyl;

chlorinated rare earth complex MCl₃The alcohol in L in nL is one or more than two selected from methanol, ethanol, isopropanol, butanol, pentanol or 2-ethylhexanol; the ether is selected from tetrahydrofuran; the organic phosphate is one or more of tripropyl phosphate, tributyl phosphate and triphenyl phosphate.

5. The rare earth catalyst according to claim 2, 3 or 4, characterized in that:

when the rare earth compound in the rare earth catalyst is an alkoxy rare earth compound and the component c is one or a mixture of two of an aluminum compound A or B in the formula I, the required aluminum compound is less in dosage, and [ Al ] and [ M ] are 30-50, but the alkoxy rare earth compound is high in cost; or, considering the cost of the catalyst in practical application, one or more of rare earth carboxylate compound, rare earth phosphate compound or rare earth chloride complex is selected, and although the aluminum compound is high in dosage when the component c is one or a mixture of two of the aluminum compounds A or B in the formula I, the cost is lower.

6. A method for preparing a rare earth catalyst according to any one of claims 1 to 5, comprising the steps of:

in an inert organic solvent, firstly, mixing the component a and the component b for 1-10 min; then adding the component c, and reacting for 30-120 min; finally, adding the component d, and reacting for 30-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;

or, in an inert organic solvent, firstly, reacting the component a with the component c for 30-120 min; finally, adding the component d, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;

or, in an inert organic solvent, firstly mixing the component a and the component b for 1-10 min; then adding the component c, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;

or, mixing the component a and the component b in an inert organic solvent, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃.

7. Use of a rare earth catalyst according to any one of claims 1 to 5 as a catalyst in the preparation of a conjugated diene polymer (preferably in the preparation of polybutadiene, polyisoprene or butadiene-isoprene copolymer).

8. Use according to claim 7, wherein the rare earth catalyst according to any one of claims 1 to 5 is used as a catalyst, and the method comprises:

mixing the rare earth catalyst with a conjugated diene monomer in an inert organic solvent, and carrying out catalytic polymerization reaction to obtain a conjugated diene polymer;

the conjugated diolefins include but are not limited to C₄～C₆One or more than two conjugated dienes (the conjugated diene is preferably selected from butadiene, isoprene or a mixture of the two).

9. Use according to claim 7 or 8, wherein the inert organic solvent is selected from C₅～C₈One or a mixture of more than two of alkane or cycloalkane.

10. Use according to claim 8, characterized in that said rare earthThe mole ratio of rare earth element to conjugated diene monomer in the catalyst is 1.0 x 10^-4～5.0×10^-5(ii) a The polymerization temperature is 30-120 ℃, and the polymerization time is 30 min-5 h.