CN111333761A - Catalyst for preparing rare earth butadiene rubber and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of catalysts for preparing cis-butadiene rubber, and discloses a catalyst for preparing rare-earth cis-butadiene rubber and a preparation method. The catalyst components for preparing rare-earth cis-butadiene rubber include: organic rare earth compounds, conjugated dienes, organic Boron salt, alkyl aluminum compound, molecular weight regulator; the molar ratio of the organic rare earth compound, conjugated diene, organic boron salt, alkyl aluminum compound, and molecular weight regulator is 5-20:10-50:1-5 : 10～30: 30～50. In the catalyst and preparation method for preparing rare earth butadiene rubber provided by the invention, a molecular weight regulator is added and aged before the alkyl aluminum compound is added to form a catalytic system with a homogeneous phase and good fluidity. The system has high activity, less dosage and mild reaction conditions, which can effectively improve the monomer conversion rate of rare earth butadiene rubber.

Description

A kind of catalyst for preparing rare earth butadiene rubber and preparation method

technical field

The invention belongs to the technical field of catalysts for preparing cis-butadiene rubber, in particular to a catalyst for preparing rare earth cis-butadiene rubber and a preparation method.

Background technique

At present, the closest existing technology: rare earth butadiene rubber is obviously superior to ordinary rare earth butadiene rubber in terms of strength, constant elongation stress, elongation and other physical and mechanical properties. Narrow molecular weight distribution (distribution 1.3-2.5) rare earth butadiene rubber not only has better resilience and compression heat generation in the process of making tires, but also has obvious advantages in cutting resistance and crack growth resistance; due to the low modulus of vulcanizate Mooney rare earth rubber has a high modulus, which is conducive to improving the high temperature handling of the tread rubber. In addition, in the combined system of solution-polymerized styrene-butadiene rubber/natural rubber/cis-butadiene rubber, the narrow molecular weight distribution (1.3-2.5) rare earth cis-butadiene rubber has good comprehensive properties, high dynamic mechanical properties, high thermal-oxidative aging properties, cutting resistance and resistance to cutting. The crack growth performance is outstanding, so the prospect of rare earth butadiene rubber with molecular weight distribution (1.3 to 2.5) is very broad.

The existing rare earth catalysts mainly include ziegler-Natta type rare earth catalysts, rare earth locene type catalysts and non-rare earth locene type catalysts. The Ziegler-Natta type catalyst system was the first to be discovered and used for olefin polymerization. At present, it is the most mature and has been widely used in industry. A class of catalysts that provide high selectivity for the polymerization of olefins to (have) yielded numerous important synthetic polymer materials. However, due to its own shortcomings such as multiple active centers, the synthesized polymer has a relatively wide molecular weight distribution, resulting in certain defects in the performance of polymer materials, and there are certain shortcomings in industrial applications; heterogeneous, that is, the catalyst's Low solubility leads to low catalyst usage rate, which in turn affects polymerization activity. Rare earth-based catalysts also show certain drawbacks in industrial application. The main ones are that the cost of synthesizing metallocene catalysts is relatively high, and the price of aluminum alkoxides as co-catalysts is also relatively expensive. The olefin polymer in good shape synthesized on the equipment must be loaded. The non-rare earth locene compound itself also has shortcomings and deficiencies. Due to its poor temperature resistance, its activity as a catalyst for olefin polymerization will decrease with the increase of polymerization temperature.

To sum up, the problems existing in the prior art are: the existing rare earth catalysts all have certain defects, and have large limitations in industrial application, poor temperature resistance, high preparation cost, low catalyst solubility, and low catalytic efficiency.

SUMMARY OF THE INVENTION

Aiming at the problems existing in the prior art, the present invention provides a catalyst for preparing rare earth butadiene rubber and a preparation method.

The present invention is achieved in this way, a catalyst for preparing rare earth cis-butadiene rubber and a preparation method, the catalyst components for preparing rare earth cis-butadiene rubber include: organic rare earth compounds, conjugated dienes, organic boron salts, and alkyl aluminum compounds , Molecular weight regulator;

The molar ratio of the organic rare earth compound, the conjugated diene, the organic boron salt, the alkyl aluminum compound, and the molecular weight regulator is 5-20:10-50:1-5:10-30:30-50.

Further, the organic rare earth compound is one of neodymium phosphate, neodymium carboxylate, praseodymium carboxylate or cerium carboxylate; the neodymium carboxylate is an organic acid neodymium compound containing a carboxyl group, and the praseodymium carboxylate is a carboxyl group-containing neodymium carboxylate compound. The organic acid praseodymium compound, the cerium carboxylate is an organic acid cerium compound containing a carboxyl group.

Further, the carboxyl-containing organic acid neodymium compound is at least one of neodymium neodecanoate, neodymium naphthenate, neodymium isooctanoate or neodymium hexanoate; the carboxyl-containing organic acid praseodymium compound is praseodymium neodecanoate, At least one of praseodymium naphthenate, praseodymium isooctanoate or praseodymium hexanoate; the organic acid cerium compound containing a carboxyl group is at least one of cerium neodecanoate, cerium naphthenate, cerium isooctanoate or cerium hexanoate .

Further, the conjugated diene is one or more of isoprene and butadiene.

Further, the organic boron salts are [B(C ₆ H ₅ ) ₃ ], [Ph ₃ C][B(C ₆ H ₅ ) ₄ ], [PhNMe ₂ ][B(C ₆ H ₅ ) ₄ ] and /or [Ph ₃ C][B(C ₆ F ₅ )] ₄ .

Further, the molecular weight regulator is one or more of trimethylaluminum, triethylaluminum or triisobutylaluminum.

Further, the alkylaluminum compound is at least one of methylaluminum, ethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, trihexylaluminum, and diethylaluminum monochloride.

Another object of the present invention is to provide a method for preparing the catalyst of the rare earth cis-butadiene rubber, and the method for preparing the catalyst of the rare earth cis-butadiene rubber comprises the following steps:

Step 1, under the protection of inert gas and in the presence of inert solvent, add organic rare earth compound, conjugated diene and organic boron salt to the dried catalyst aging bottle in turn, and age at 30°C. 10-40 minutes, get mixed solution A;

In step 2, a molecular weight regulator is added to the mixed solution A obtained in step 1, and the mixture is aged for 2-10 hours at a temperature of 30° C. to obtain a mixed solution B;

In step 3, after the mixed solution B in step 2 forms a homogeneous transparent solution, the alkyl aluminum compound is added, and the mixture is aged at 30° C. for 10-20 hours to obtain a catalyst for preparing rare earth cis-butadiene rubber.

Further, in step 1, the inert solvent includes one of n-hexane, n-heptane, n-octane, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene.

Further, in step 1, the inert gas includes one of nitrogen gas and argon gas.

To sum up, the advantages and positive effects of the present invention are as follows: the catalyst and preparation method for preparing rare earth butadiene rubber provided by the present invention can form a homogeneous phase and fluidity by adding a molecular weight regulator and aging before adding the alkyl aluminum compound. A good catalytic system, at the same time the catalyst structure is clear, easy to synthesize, high catalytic system activity, less dosage, mild reaction conditions, can effectively improve the monomer conversion rate of rare earth butadiene rubber.

Description of drawings

FIG. 1 is a catalyst and a preparation method for preparing rare earth butadiene rubber provided by an embodiment of the present invention.

FIG. 2 is a schematic diagram showing the influence of the catalyst reaction temperature on the catalyst activity provided by the embodiment of the present invention.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

In view of the problems existing in the prior art, the present invention provides a catalyst for preparing rare earth cis-butadiene rubber and a preparation method. The present invention is described in detail below with reference to the accompanying drawings.

The catalyst components for preparing rare earth butadiene rubber provided in the embodiment of the present invention include: organic rare earth compounds, conjugated dienes, organic boron salts, alkyl aluminum compounds, and molecular weight regulators.

The molar ratio of the organic rare earth compound, the conjugated diene, the organic boron salt, the alkyl aluminum compound, and the molecular weight regulator provided in the embodiment of the present invention is 5-20:10-50:1-5:10-30:30-50 .

The organic rare earth compound provided in the embodiment of the present invention is one of neodymium phosphate, neodymium carboxylate, praseodymium carboxylate or cerium carboxylate; the neodymium carboxylate is a neodymium organic acid compound containing a carboxyl group, and the praseodymium carboxylate is a neodymium carboxylate compound containing a carboxyl group. The organic acid praseodymium compound of a carboxyl group, and the cerium carboxylate is an organic acid cerium compound containing a carboxyl group.

The carboxyl-containing organic acid neodymium compound provided in the embodiment of the present invention is at least one of neodymium neodecanoate, neodymium naphthenate, neodymium isooctanoate or neodymium hexanoate; the carboxyl-containing organic acid praseodymium compound is neodecanoic acid At least one of praseodymium, praseodymium naphthenate, praseodymium isooctanoate or praseodymium hexanoate; the organic acid cerium compound containing a carboxyl group is at least one of cerium neodecanoate, cerium naphthenate, cerium isooctanoate or cerium hexanoate A sort of.

The conjugated diene provided in the embodiment of the present invention is one or more of isoprene and butadiene.

The organic boron salts provided in the embodiments of the present invention are [B(C ₆ H ₅ ) ₃ ], [Ph ₃ C][B(C ₆ H ₅ ) ₄ ], [PhNMe ₂ ][B(C ₆ H ₅ ) ₄ ] and/or [Ph ₃ C][B(C ₆ F ₅ )] ₄ .

The molecular weight regulator provided in the embodiment of the present invention is one or more of trimethylaluminum, triethylaluminum or triisobutylaluminum.

The alkylaluminum compound provided in the embodiment of the present invention is at least one of methylaluminum, ethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, trihexylaluminum, and diethylaluminum monochloride.

As shown in Figure 1, the catalyst and preparation method for preparing rare earth cis-butadiene rubber provided by the embodiment of the present invention include the following steps:

S101, under the protection of an inert gas and in the presence of an inert solvent, add organic rare earth compounds, conjugated dienes, and organic boron salts to the dried catalyst aging bottle in sequence, and age at 30°C for 10 -40 minutes to get mixed solution A.

S102, adding a molecular weight regulator to the mixed solution A obtained in step S101, and aging for 2-10 hours in an environment of 30° C. to obtain a mixed solution B.

S103 , after the mixed solution B in step S102 forms a homogeneous transparent solution, the alkyl aluminum compound is added, and the mixture is aged at 30° C. for 10-20 hours to obtain a catalyst for preparing rare earth butadiene rubber.

In step S101, the inert solvent provided in the embodiment of the present invention includes: one of n-hexane, n-heptane, n-octane, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene. kind.

In step S101, the inert gas provided in the embodiment of the present invention includes one of nitrogen gas and argon gas.

The technical effects of the present invention will be further described below in conjunction with experiments.

(1) Under the protection of inert gas, in the presence of inert solvent, add organic rare earth compound, conjugated diene, and organic boron salt to the dried catalyst aging bottle in turn, at 10, 20, 30, Aged for 10-40 minutes at 40°C to obtain mixed solution A;

(2) adding a molecular weight regulator to the mixed solution A obtained in step 1, and ageing for 2-10 hours in an environment of 30° C. to obtain a mixed solution B;

(3) After the mixed solution B in step 2 forms a homogeneous transparent solution, the alkyl aluminum compound is added, and the mixture is aged at 30° C. for 10-20 hours to obtain a catalyst for preparing rare earth cis-butadiene rubber.

Proof part (specific examples/experiments/simulation/pharmacological analysis/positive experimental data, evidence materials, appraisal reports, business data, research and development evidence, business cooperation evidence, etc. that can prove the inventiveness of the present invention)

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (10)

1. a catalyst for preparing rare earth cis-butadiene rubber is characterized in that, the catalyst component for preparing rare earth cis-butadiene rubber comprises: organic rare earth compound, conjugated diene, organic boron salt, alkyl aluminum compound, molecular weight regulator ; The molar ratio of the organic rare earth compound, the conjugated diene, the organic boron salt, the alkyl aluminum compound, and the molecular weight regulator is 5-20:10-50:1-5:10-30:30-50. 2. The catalyst for preparing rare earth butadiene rubber according to claim 1, wherein the organic rare earth compound is one of neodymium phosphate, neodymium carboxylate, praseodymium carboxylate or cerium carboxylate; the neodymium carboxylate It is an organic acid neodymium compound containing a carboxyl group, the praseodymium carboxylate is a carboxyl group-containing organic acid praseodymium compound, and the cerium carboxylate is a carboxyl group-containing organic acid cerium compound. 3. The catalyst for preparing rare earth butadiene rubber according to claim 1, wherein the organic acid neodymium compound containing carboxyl group is at least one of neodymium neodecanoate, neodymium naphthenate, neodymium isooctanoate or neodymium hexanoate One; the organic acid praseodymium compound containing a carboxyl group is at least one of praseodymium neodecanoate, praseodymium naphthenate, praseodymium isooctanoate or praseodymium hexanoate; the organic acid cerium compound containing a carboxyl group is cerium neodecanoate , at least one of cerium naphthenate, cerium isooctanoate or cerium hexanoate. 4 . The catalyst for preparing rare earth butadiene rubber according to claim 1 , wherein the conjugated diene is one or more of isoprene and butadiene. 5 . 5. The catalyst for preparing rare earth butadiene rubber according to claim 1, wherein the organic boron salt is [B(C ₆ H ₅ ) ₃ ], [Ph ₃ C][B(C ₆ H ₅ ) ₄ ], [PhNMe ₂ ][B(C ₆ H ₅ ) ₄ ] and or [Ph ₃ C][B(C ₆ F ₅ )] ₄ . 6 . The catalyst for preparing rare earth cis-butadiene rubber according to claim 1 , wherein the molecular weight regulator is one or more of trimethylaluminum, triethylaluminum or triisobutylaluminum. 7 . 7. The catalyst for preparing rare earth butadiene rubber according to claim 1, wherein the alkyl aluminum compound is methyl aluminum, ethyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride, trihexyl aluminum At least one of aluminum and diethyl aluminum monochloride. 8. A preparation method for preparing a catalyst for the rare earth cis-butadiene rubber according to claim 1-7, wherein the catalyst preparation method for the rare earth cis-butadiene rubber comprises the following steps: Step 1, under the protection of inert gas and in the presence of inert solvent, add organic rare earth compound, conjugated diene and organic boron salt to the dried catalyst aging bottle in turn, and age at 30°C. 10-40 minutes, get mixed solution A; In step 2, a molecular weight regulator is added to the mixed solution A obtained in step 1, and the mixture is aged for 2-10 hours at a temperature of 30° C. to obtain a mixed solution B; In step 3, after the mixed solution B in step 2 forms a homogeneous transparent solution, the alkyl aluminum compound is added, and the mixture is aged at 30° C. for 10-20 hours to obtain a catalyst for preparing rare earth cis-butadiene rubber. 9 . The method for preparing a catalyst for rare earth butadiene rubber according to claim 8 , wherein, in step 1, the inert gas comprises one of nitrogen gas and argon gas. 10 . 10. The catalyst preparation method for rare earth butadiene rubber according to claim 8, wherein in step 1, the inert solvent comprises: n-hexane, n-heptane, n-octane, toluene, xylene, ethylbenzene, One of chlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene.

Images