Narrow-distribution rare earth butadiene rubber catalyst capable of adjusting content of trans-1, 4 structure and preparation method of narrow-distribution rare earth butadiene rubber catalyst

Abstract

The invention relates to the technical field of rare earth catalyst preparation, in particular to a narrow-distribution rare earth butadiene rubber catalyst capable of adjusting the content of a trans-1, 4 structure and a preparation method of the narrow-distribution rare earth butadiene rubber catalyst. The catalyst comprises the following components: a mixed auxiliary agent, an organic chloride, dialkene, a phosphoric acid rare earth compound or a carboxylic acid rare earth compound, the mixed auxiliary agent is generated by mixing aluminum alkyl and a molecular structure regulator, and the molecular structure regulator accounts for 10-80% of the mass of the mixed auxiliary agent; the molar ratio of the mixed additive to the organic chloride to the dialkene to the phosphoric acid rare earth compound or the carboxylic acid rare earth compound is (5-25): (2-5): (2-20): 1. The catalyst is high in activity, homogeneous and stable in phase state and good in fluidity, the content of a polymerization product trans-1, 4 structure can be controlled to be 5%-50%, molecular weight distribution is narrow, the catalyst is used for activity evaluation of butadiene polymerization, and the monomer conversion rate is high.

Description

Technical field:

[0001] The invention relates to the technical field of rare earth catalyst preparation, and in particular to a narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure and a preparation method thereof. Background technology:

[0002] After the implementation of the EU tire labeling regulations, high-performance tires and green tires that are "high-speed, environmentally friendly, safe, and energy-saving" have attracted worldwide attention. At present, it is internationally recognized that rare earth cis-1,4-butadiene rubber is a key material for preparing double B-grade (rolling resistance and anti-slip) tires. In the process of making tires, narrow molecular weight distribution (distribution 1.3-2.5) rare earth cis-1,4-butadiene rubber not only has better resilience and compression heat generation, but also has obvious advantages in cut resistance and crack growth resistance, which is conducive to improving the high-temperature controllability of tread rubber.

[0003] The narrow distribution cis-1,4-butadiene rubber prepared by the existing rare earth catalytic system belongs to high cis-1,4-butadiene rubber, and the trans-1,4-content in its molecular structure is ≤4%. In the processing and application of rubber downstream products, the trans-1,4-content in the molecular structure of rare earth cis-1,4-butadiene rubber needs to be controlled between 5% and 10%, which can not only maintain the good properties of rare earth cis-1,4-butadiene rubber, such as low rolling resistance, high anti-slip performance, high wear resistance, high tensile strength, high hardness, excellent fatigue resistance, etc., but also improve the mixing effect with other rubbers such as natural rubber, and improve the extrusion performance of rubber.

[0004] So far, the report on rare earth cis-1,4 rubber is from the State Key Laboratory of Effective Utilization of Chemical Resources of Beijing University of Chemical Technology. The mass fraction of cis-1,4 structure of rare earth cis-1,4 rubber prepared can reach 98.5%. The preparation method of ultra-high cis-polybutadiene rubber of Shandong Yuhuang Chemical Co., Ltd. uses organic phosphate rare earth, intermittent vial polymerization, temperature -50℃-30℃, and the cis-1,4 structure exceeds 99%. The above two patented technologies cannot achieve the control of the content of anti-1,4 structure of the polymerization product ≥5%.

[0005] There are no similar literatures at home or abroad on the report of adjusting and controlling the content of trans-1,4 structure in narrow distribution rare earth butadiene rubber to 5%-50%. Summary of the invention:

[0006] The technical problem to be solved by the present invention is to provide a narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content and a preparation method thereof. The catalyst has high activity, homogeneous and stable phase state, good fluidity, and the trans-1,4 structure content of the polymerization product can be controlled at 5%-50%. The molecular weight distribution is narrow. The catalyst is used for activity evaluation of butadiene polymerization and has a high monomer conversion rate. The disadvantage that the existing rare earth catalytic system cannot control the trans-1,4 structure content of its polymerization product to be ≥5% is overcome.

[0007] The technical scheme adopted by the present invention is: a narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content, the catalyst comprising the following components: a mixing auxiliary agent, an organic chloride, a diene, a rare earth phosphate compound or a carboxylic acid rare earth compound, the mixing auxiliary agent is a mixture of an alkyl aluminum and a molecular structure regulator, the molecular structure regulator accounts for 10%-80% of the mixing auxiliary agent by mass; the molar ratio of the above components is: mixing auxiliary agent: organic chloride: diene: rare earth phosphate compound or carboxylic acid rare earth compound = (5-25): (2-5): (2-20): 1.

[0008] Furthermore, the molar ratio of the components is: mixing auxiliary agent: organic chloride: diene: rare earth phosphate compound or carboxylic acid rare earth compound = (7-15): (2-5): (3-20): 1, and the molecular structure regulator accounts for 25%-65% of the mass percentage of the mixing auxiliary agent.

[0009] Furthermore, the rare earth phosphate compound is neodymium phosphate.

[0010] Furthermore, the neodymium phosphate is a neodymium phosphate complex containing an acidic organic phosphate, wherein the organic phosphate is (RO)2POOH, R(RO)POOH or R2POOH, and R is an alkyl group with 2 to 13 carbon atoms or an isomer thereof.

[0011] Furthermore, the organic phosphate is one or more of di(2-ethylhexyl) phosphate, 2-ethylhexyl 2-ethylhexyl phosphate and dimethylheptyl methyl phosphate.

[0012] Furthermore, the carboxylic acid rare earth compound is a rare earth compound containing a carboxyl group, and the rare earth compound containing a carboxyl group is neodymium neodecanoate, neodymium cyclohexaneate, neodymium isooctanoate or neodymium hexanoate.

[0013] Furthermore, the alkylaluminum is dialkylaluminum hydride.

[0014] Furthermore, the organic chloride is alkylaluminum chloride.

[0015] Furthermore, the chloroalkylaluminum is ethylaluminum dichloride, isobutylaluminum dichloride or ethylaluminum monochloride / dichloride.

[0016] Furthermore, the molecular structure regulator is a mixture of triethylaluminum and N heteroatom heterocyclic compounds.

[0017] Furthermore, the molecular structure regulator is a mixture of triethylaluminum and pyridine or triethylaluminum and bipyridine, wherein the mass percentage of pyridine or bipyridine in the molecular structure regulator is 0.1-2%.

[0018] Furthermore, the diene is butadiene.

[0019] A preparation method of a narrow distribution rare earth cis-1,4-butadiene rubber catalyst with adjustable trans-1,4 structure content, the method comprising the following steps: under nitrogen protection, mixing alkyl aluminum with a molecular structure regulator to generate a mixed auxiliary agent and sealing and storing the mixed auxiliary agent for standby use; under nitrogen protection, sequentially adding a phosphate rare earth compound solution or a carboxylic acid rare earth compound solution, a diene, and a mixed auxiliary agent into a catalyst aging bottle that has been dried, aging the solution at -10 to 60°C for 10 to 30 minutes, then adding an organic chloride, aging the solution at -10 to 60°C for 5 to 20 minutes, generating a homogeneous transparent solution, and thus obtaining a narrow distribution rare earth cis-1,4-butadiene rubber catalyst with adjustable trans-1,4 structure content.

[0020] The beneficial effects of the present invention are as follows: the catalyst prepared by the present invention has high activity, is homogeneous and stable in phase, has good fluidity, the content of the reverse 1,4 structure of the polymerization product can be controlled within 5%-50%, has a narrow molecular weight distribution, and the catalyst is used for activity evaluation of butadiene polymerization, with a high monomer conversion rate. Specific implementation method:

[0021] Example 1

[0022] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium phosphate (wherein the organic phosphate is di(2-ethylhexyl) phosphate), the mixing aid being a mixture of alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and pyridine, and the mass percentage of pyridine in the molecular structure regulator is 0.1%), and the mass percentage of the molecular structure regulator in the mixing aid is 25%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium phosphate = 7:2:2:1.

[0023] The catalyst was prepared as follows: 1.70×10 -3 mol diisobutylaluminum hydride, 7.23×10 -4 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium phosphate was added to the dried catalyst aging bottle in sequence. -4 mol, butadiene 1.04×10 -3 mol, mixed additives 2.42×10 -3 mol was aged at -10°C for 30 minutes, followed by the addition of 6.92×10 -4 mol, aged at -10°C for 20 minutes to generate a homogeneous transparent solution, and a 0.5×10 -5mol / ml of narrow distribution rare earth butadiene rubber catalyst A with adjustable trans-1,4 structure content.

[0024] Example 2

[0025] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium neodecanoate; the mixing aid is prepared by mixing alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and pyridine, and the mass percentage of pyridine in the molecular structure regulator is 1%), and the mass percentage of the molecular structure regulator in the mixing aid is 25%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium neodecanoate = 5:2:2:1.

[0026] The catalyst was prepared as follows: 1.70×10 -3 mol diisobutylaluminum hydride, 7.23×10 -4 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium neodecanoate was added to the dried catalyst aging bottle in sequence. -4 mol, butadiene 1.04×10 -3 mol, mixed additives 2.42×10 -3 mol, aged at -10°C for 30 minutes, then added 6.92×10 -4 mol, aged at -10°C for 20 minutes to generate a homogeneous transparent solution, and a 0.5×10 -5 mol / ml of narrow distribution rare earth butadiene rubber catalyst B with adjustable trans-1,4 structure content.

[0027] Example 3

[0028] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium phosphate (wherein the organic phosphate is 2-ethylhexyl phosphate 2-ethylhexyl ester), the mixing aid being a mixture of alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and pyridine, and the mass percentage of pyridine in the molecular structure regulator is 2%), and the mass percentage of the molecular structure regulator in the mixing aid is 45%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium phosphate = 15:3.5:10:1.

[0029] The catalyst was prepared as follows: 2.595×10 -3mol diisobutylaluminum hydride, 2.595×10 -3 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium phosphate was added to the dried catalyst aging bottle in sequence. -4 mol, butadiene 3.46×10 -3 mol, mixed additives 5.19×10 -3 mol, aged at 30°C for 20 minutes, and then added 1.21×10 -3 mol, aged at 30°C for 10 minutes to generate a homogeneous transparent solution, and a 2.5×10 -5 mol / ml of narrow distribution rare earth butadiene rubber catalyst C with adjustable trans-1,4 structure content.

[0030] Example 4

[0031] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium neodecanoate, wherein the mixing aid is a mixture of alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and bipyridine, and the mass percentage of bipyridine in the molecular structure regulator is 0.1%), and the mass percentage of the molecular structure regulator in the mixing aid is 45%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium neodecanoate = 15:3.5:10:1.

[0032] The catalyst was prepared as follows: 2.595×10 -3 mol diisobutylaluminum hydride, 2.595×10 -3 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium neodecanoate was added to the dried catalyst aging bottle in sequence. -4 mol, butadiene 3.46×10 -3 mol, mixed additives 5.19×10 -3 mol, aged at 30°C for 20 minutes, and then added 1.21×10 -3 mol, aged at 30°C for 10 minutes to generate a homogeneous transparent solution, and a 2.5×10 -5 mol / ml of narrow distribution rare earth butadiene rubber catalyst D with adjustable trans-1,4 structure content.

[0033] Example 5

[0034] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium phosphate (wherein the organic phosphate is dimethylheptyl methyl phosphate), wherein the mixing aid is a mixture of alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and bipyridine, and the mass percentage of bipyridine in the molecular structure regulator is 1%), and the mass percentage of the molecular structure regulator in the mixing aid is 65%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium phosphate = 15:5:20:1.

[0035] The catalyst was prepared as follows: 1.557×10 -3 mol diisobutylaluminum hydride, 3.633×10 -3 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium phosphate was added to the dried catalyst aging bottle in sequence. -4 mol, butadiene 6.92×10 -3 mol, mixed additives 5.19×10 -3 mol, aged at 60°C for 10 minutes, and then added 1.73×10 -3 mol, aged at 60°C for 5 minutes to generate a homogeneous transparent solution, and a 5×10 -5 mol / ml of narrow distribution rare earth butadiene rubber catalyst E with adjustable trans-1,4 structure content.

[0036] Example 6

[0037] A narrow distribution rare earth butadiene rubber catalyst capable of adjusting the content of trans-1,4 structure, the catalyst comprises the following components: a mixing aid, ethylaluminum monochloride / dichloride, butadiene, and neodymium neodecanoate, wherein the mixing aid is a mixture of alkylaluminum and a molecular structure regulator (the molecular structure regulator is a mixture of triethylaluminum and bipyridine, and the mass percentage of bipyridine in the molecular structure regulator is 2%), and the mass percentage of the molecular structure regulator in the mixing aid is 65%; the molar ratio of the above components is: mixing aid: ethylaluminum monochloride / dichloride: butadiene: neodymium neodecanoate = 15:5:20:1.

[0038] The catalyst was prepared as follows: 1.557×10 -3 mol diisobutylaluminum hydride, 3.633×10 -3 mol molecular structure regulator was mixed to form a mixed auxiliary agent, which was sealed and stored for later use. Under nitrogen protection, 3.46×10 neodymium neodecanoate was added to the dried catalyst aging bottle in sequence. -4mol, butadiene 6.92×10 -3 mol, mixed additives 5.19×10 -3 mol, aged at 60°C for 10 minutes, and then added 1.73×10 -3 mol, aged at 60°C for 5 minutes to generate a homogeneous transparent solution, and a 5×10 -5 mol / ml of narrow distribution rare earth butadiene rubber catalyst F with adjustable trans-1,4 structure content.

[0039] Comparative Example 1

[0040] A narrow distribution rare earth butadiene rubber catalyst comprises the following components: alkyl aluminum, ethyl aluminum monochloride / dichloride, butadiene, and neodymium phosphate (wherein the organic phosphate is 2-ethylhexyl phosphate 2-ethylhexyl ester), wherein the molar ratio of the above components is: alkyl aluminum: ethyl aluminum monochloride / dichloride: butadiene: neodymium phosphate = 15:3.5:10:1.

[0041] The preparation method of the catalyst is as follows: under nitrogen protection, 3.46×10 neodymium phosphate and -4 mol, butadiene 3.46×10 -3 mol, diisobutylaluminum hydride 5.19×10 -3 mol, aged at 30°C for 20 minutes, and then added 1.21×10 -3 mol, aged at 30°C for 10 minutes to generate a homogeneous transparent solution, and a 2.5×10 -5 mol / ml narrow distribution rare earth butadiene rubber catalyst G.

[0042] The activity and product molecular structure of catalysts A, B, C, D, E, F prepared in Examples 1, 2, 3, 4, 5, 6 and catalyst G prepared in Comparative Example 1 were evaluated as follows:

[0043] Under nitrogen protection, 2833 ml of C6 oil and 500 ml of butadiene were added to a polymerization reactor without water or oxygen, so that the volume fraction of butadiene monomer in the solution generated by the two was 15%, and then the prepared catalyst was added, and the reaction was carried out at 70°C for 4 hours. After the reaction was completed, it was terminated with a mixed solution of ethanol and C6 oil containing 1% by mass of 2,6-di-tert-butyl-p-methylphenol, and then extruded, dried, dehydrated and devolatilized at 120°C to obtain a rare earth butadiene rubber product.

[0044] The evaluation results of catalyst activity and molecular structure of polymerization products are shown in Table 1.

[0045] Table 1 Catalyst evaluation data comparison table

[0046]

[0047] Evaluation conclusion: The prepared catalyst was used in a 5L polymerization kettle for solution polymerization to synthesize rare earth butadiene rubber. The results showed that the catalyst prepared by the present invention had good polymerization activity, the monomer conversion rate reached more than 90%, the sample molecular weight distribution was less than 2.5, and the trans-1,4 structure content could be controlled at 5%-50%, meeting the actual needs.

[0048] It can be understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content, characterized in that: The catalyst comprises the following components: a mixing auxiliary, an organic chloride, a diene, a rare earth phosphate compound or a rare earth carboxylate compound, wherein the mixing auxiliary is a mixture of an alkyl aluminum and a molecular structure regulator, and the molecular structure regulator accounts for 10%-80% of the mixing auxiliary by mass; the molar ratio of the above components is: mixing auxiliary: organic chloride: diene: rare earth phosphate compound or rare earth carboxylate compound = (5-25): (2-5): (2-20):

1.

2. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The molar ratio of the components is: mixing auxiliary agent: organic chloride: diene: rare earth phosphate compound or rare earth carboxylate compound = (7-15): (2-5): (3-20): 1, and the molecular structure regulator accounts for 25%-65% of the mass percentage of the mixing auxiliary agent.

3. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The rare earth phosphate compound is neodymium phosphate.

4. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 3, characterized in that: The neodymium phosphate is a neodymium phosphate complex containing an acidic organic phosphate, wherein the organic phosphate is (RO)2POOH, R(RO)POOH or R2POOH, and R is an alkyl group with 2 to 13 carbon atoms or an isomer thereof.

5. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 4, characterized in that: The organic phosphate is one or more of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester and dimethylheptyl methyl phosphate.

6. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The carboxylic acid rare earth compound is a rare earth compound containing a carboxyl group, and the rare earth compound containing a carboxyl group is neodymium neodecanoate, neodymium cyclohexaneate, neodymium isooctanoate or neodymium hexanoate.

7. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The alkylaluminum is dialkylaluminum hydride.

8. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The organic chloride is alkylaluminum chloride.

9. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 8, characterized in that: The chloroalkylaluminum is ethylaluminum dichloride, isobutylaluminum dichloride or ethylaluminum monochloride / dichloride.

10. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The molecular structure regulator is a mixture of triethylaluminum and N heteroatom heterocyclic compounds.

11. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 10, characterized in that: The molecular structure regulator is a mixture of triethylaluminum and pyridine or triethylaluminum and bipyridine, wherein the mass percentage of pyridine or bipyridine in the molecular structure regulator is 0.1-2%.

12. The narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The diene is butadiene.

13. A method for preparing a narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content according to claim 1, characterized in that: The method comprises the following steps: under nitrogen protection, mixing alkyl aluminum with a molecular structure regulator to generate a mixed auxiliary agent and sealing and storing the mixed auxiliary agent for later use; under nitrogen protection, sequentially adding a phosphate rare earth compound solution or a carboxylic acid rare earth compound solution, a diene, and a mixed auxiliary agent into a catalyst aging bottle that has been dried, aging the mixture at -10 to 60°C for 10 to 30 minutes, then adding an organic chloride, aging the mixture at -10 to 60°C for 5 to 20 minutes, generating a homogeneous transparent solution, and thus obtaining a narrow distribution rare earth butadiene rubber catalyst with adjustable trans-1,4 structure content.

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