阅读说明：本技术 镍系顺丁橡胶聚合用催化剂的制备及应用 (Preparation and application of nickel-based catalyst for butadiene rubber polymerization ) 是由 李伟 于希水 严忠庆 孙书义 唐金辉 牛玉龙 于 2021-01-11 设计创作，主要内容包括：本发明的目的在于提供一种镍系顺丁橡胶合成用催化剂及其制备和应用,具体为：采用异辛酸镍取代或部分取代环烷酸镍作为合成镍系顺丁橡胶的催化剂,该催化剂催化效果好于传统的环烷酸镍,且成本更低。同时,本发明采用异辛酸和碱式碳酸镍在反应釜中直接合成异辛酸镍,反应完成后,所用溶剂蒸出,可循环使用。该方法取代了传统采用液相皂化法工艺制备异辛酸镍,具有工艺简单、节能环保等特点。(The invention aims to provide a nickel-based catalyst for synthesizing butadiene rubber, and preparation and application thereof, and the catalyst comprises the following specific components: the catalyst for synthesizing nickel-based butadiene rubber adopts nickel isooctanoate to replace or partially replace nickel naphthenate, has better catalytic effect than the traditional nickel naphthenate, and has lower cost. Meanwhile, the nickel isooctanoate is directly synthesized by adopting isooctanoic acid and basic nickel carbonate in a reaction kettle, and the solvent is evaporated after the reaction is finished and can be recycled. The method replaces the traditional liquid phase saponification method for preparing nickel isooctanoate, and has the characteristics of simple process, energy conservation, environmental protection and the like.)

1. A catalyst for polymerizing nickel-based butadiene rubber, which is characterized in that: the catalyst is nickel isooctanoate, or the combination of nickel isooctanoate and one or more of nickel naphthenate and nickel neodecanoate.

2. The catalyst for polymerization of nickel-based butadiene rubber according to claim 1, wherein: when nickel isooctanoate is mixed with nickel naphthenate and/or nickel neodecanoate, the content of nickel isooctanoate is 50-95 percent and the content of nickel naphthenate and/or nickel neodecanoate is 5-50 percent in the catalyst by mass percentage.

3. The catalyst for polymerization of nickel-based butadiene rubber according to claim 1, wherein: in the catalyst, the nickel content is 8.0% +/-0.5%.

4. A method of preparing the catalyst of claim 1, wherein: the nickel isooctanoate is synthesized by adopting isooctanoic acid and basic nickel carbonate or nickel hydroxide in a reaction kettle by a direct synthesis method.

5. The preparation method according to claim 4, characterized in that the specific process flow is as follows:

1) adding isooctanoic acid and a solvent accounting for 100% +/-10% of the volume of the isooctanoic acid into a stainless steel reactor;

2) heating to 60-65 ℃ under the stirring condition, gradually adding calculated amount of basic nickel carbonate, and dispersing for 1 hour;

3) closing the reactor, slowly heating to 95-100 ℃ within 1.5-2 hours, distilling off the solvent and water by azeotropy, cooling, refluxing the solvent, and separating out reaction water until no reaction water is generated;

4) continuously heating to evaporate the solvent, wherein when the reaction end temperature is 170-175 ℃, the reaction is finished after no solvent is evaporated;

5) cooling the material to 55-60 ℃, adding calculated amount of normal hexane, fully and uniformly stirring, and obtaining a finished product when the nickel content is measured to be 8.0% +/-0.5%.

6. The method according to claim 5, wherein: in the step 1), the solvent is D30 environment-friendly solvent oil.

7. Use of the catalyst of claim 1 for the synthesis of nickel-based butadiene rubber.

Technical Field

The invention relates to the field of nickel-based butadiene rubber polymerization, and particularly provides a preparation method and application of a nickel-based butadiene rubber polymerization catalyst.

Background

At present, the main catalyst used in the nickel-based butadiene rubber polymerization reaction is nickel naphthenate, the nickel naphthenate adopts petroleum byproduct naphthenic acid as a raw material, the naphthenic acid is saponified by sodium hydroxide to form sodium naphthenate soap, and then the sodium naphthenate soap and nickel sulfate are subjected to double decomposition reaction in the presence of 120# solvent oil, the generated nickel naphthenate is extracted into the 120# solvent oil, the produced sodium sulfate is remained in a water phase, and meanwhile, a hydrolyzed and precipitated nickel hydroxide micelle wrapped by the naphthenic acid and the sodium naphthenate is also generated, so that a third phase suspended between the water phase and an oil phase is formed. After the organic phase is separated into a water phase and a third phase, the residual sodium sulfate in the organic phase is removed through multiple times of water washing, the mixture is kept stand to separate water, then the No. 120 solvent oil is distilled and separated, and after the mixture is cooled, the normal hexane is used for diluting the mixture to the specified nickel content, so that the nickel naphthenate product is obtained. However, the use of nickel naphthenate as a main catalyst for the polymerization of butadiene rubber has the following problems to be solved:

1. naphthenic acid is a byproduct of naphthenic petroleum, and although refined, the naphthenic acid still contains impurities such as light oil, butter, paraffin, asphalt and the like, the purity of the naphthenic acid is usually only about 80%, and domestic resources are in short supply and the price is high.

2. Naphthenic acid is a dark brown viscous oily liquid, has special pungent odor, and is harsh in production environment.

3. The liquid phase saponification method is adopted to prepare the nickel naphthenate, the method is complex to operate, generates a large amount of wastewater containing inorganic salts and organic matters, and is troublesome to treat.

Disclosure of Invention

Based on the problems in the prior art, the invention provides a preparation method and application of a catalyst for nickel-based butadiene rubber polymerization. The preparation method uses a direct synthesis process to replace the traditional liquid phase saponification process to prepare nickel isooctanoate, and has the characteristics of simple process, energy conservation, environmental protection and the like.

The technical scheme of the invention is as follows:

a catalyst for polymerizing nickel-based butadiene rubber, which is characterized in that: the catalyst is nickel isooctanoate, or the combination of nickel isooctanoate and one or more of nickel naphthenate and nickel neodecanoate.

The catalyst for nickel-based butadiene rubber polymerization is characterized in that: when nickel isooctanoate is mixed with nickel naphthenate and/or nickel neodecanoate, the content of nickel isooctanoate is 50-95 percent and the content of nickel naphthenate and/or nickel neodecanoate is 5-50 percent in the catalyst by mass percentage.

The catalyst for nickel-based butadiene rubber polymerization is characterized in that: in the catalyst, the nickel content is 8.0% +/-0.5%.

The invention also provides a preparation method of the catalyst, which is characterized by comprising the following steps: the nickel isooctanoate is synthesized by adopting isooctanoic acid and basic nickel carbonate or nickel hydroxide in a reaction kettle by a direct synthesis method. The specific process flow is as follows:

1) adding isooctanoic acid and a solvent (preferably D30 environment-friendly solvent oil) accounting for 100% +/-10% of the volume of the isooctanoic acid into a stainless steel reactor in calculated amount;

2) heating to 60-65 ℃ under the stirring condition, gradually adding calculated amount of basic nickel carbonate, and dispersing for 1 hour;

3) closing the reactor, slowly heating to 95-100 ℃ within 1.5-2 hours, distilling off the solvent and water by azeotropy, cooling, refluxing the solvent, and separating out reaction water until no reaction water is generated;

4) continuously heating to evaporate the solvent, wherein when the reaction end temperature is 170-175 ℃, the reaction is finished after no solvent is evaporated;

5) cooling the material to 55-60 ℃, adding calculated amount of normal hexane, fully and uniformly stirring, and obtaining a finished product when the nickel content is measured to be 8.0% +/-0.5%.

The process of the invention is characterized in that:

1) the process adopts a method of adding environment-friendly D30 solvent oil, and after the solvent is added, the viscosity of a reaction system is reduced, the migration of material ions is facilitated, meanwhile, the reaction temperature is increased, the rapid completion of the reaction is facilitated, and the chemical balance is destroyed by the process means of azeotropic evaporation of the solvent and water, and water diversion and backflow, and the reaction is ensured to reach the end point.

2) In the process, the solvent can be reused after being evaporated, theoretically, the consumption is zero, the effluent is only water generated by reaction, the water discharge amount is only 50kg per ton of product, the water discharge amount is about 1/20 of a liquid-phase saponification method, and the reaction water is pure water without subsequent treatment.

The invention has the following beneficial effects:

1. the raw material isooctanoic acid used in the invention is a synthetic acid, colorless, transparent, small in viscosity, high in purity up to above 99%, and its price is less than half of that of naphthenic acid.

2. Compared with naphthenic acid, isooctanoic acid is almost colorless and odorless, and is beneficial to improving the operating environment.

3. Compared with neodecanoic acid, the price of the isooctanoic acid is only about 50 percent of that of the neodecanoic acid.

4. Compared with a liquid-phase saponification method, the synthesis method is more convenient and faster, and has short production period and less energy consumption.

5. In the liquid phase saponification method, the prepared nickel naphthenate needs to be repeatedly washed by water to remove impurities such as sodium sulfate, and rinsing water contains organic matters which can not be completely separated, so that environmental pollution can be caused and the treatment process is troublesome; the synthesis method of the invention is only water produced in the reaction, and the water is pure water and can be returned to a cooling water pool to supplement the consumption of cooling water.

Detailed Description

Example 1

The main raw material for preparing the catalyst is isooctanoic acid, or mixed acid of isooctanoic acid and naphthenic acid/neodecanoic acid, and the preparation methods are the same; the basic nickel carbonate or nickel hydroxide is used as a raw material, the preparation method is the same, and the nickel isooctanoate is prepared by using the isooctanoic acid and the basic nickel carbonate as raw materials in the example.

Preparation of nickel isooctanoate:

preparing nickel isooctanoate in a 2500L reaction kettle by adopting commercially available basic nickel carbonate (the nickel content is more than or equal to 42 percent, and the nickel content is light green powdery solid), isooctanoic acid (the content is more than or equal to 99 percent), D30 environment-friendly solvent oil (D30 environment-friendly solvent) and n-hexane.

The reaction equation is as follows:

the specific process flow is as follows:

1) 596.4kg of isooctanoic acid and 600kg of D30 environment-friendly solvent oil are added into a stainless steel reactor;

2) heating to 60-65 ℃ under the condition of stirring, gradually adding 286kg of basic nickel carbonate, and dispersing for 1 hour;

3) closing the reactor, slowly heating for 1.5 hours until the temperature reaches 95-100 ℃, evaporating the solvent and water by azeotropy, cooling, refluxing the solvent, and separating out reaction water until no reaction water is generated;

4) continuously heating to evaporate the solvent, wherein the reaction end temperature is 170-175 ℃, and the reaction is finished after no solvent is evaporated;

5) cooling the materials to 55-60 ℃, adding 830kg of normal hexane, fully and uniformly stirring, and obtaining the finished product when the nickel content is measured to be 8.0% +/-0.5%.

TABLE 1 preparation of raw materials and product details

The traditional nickel isooctanoate is usually prepared by a liquid-phase saponification method, and compared with the traditional saponification method, the synthesis method process disclosed by the invention has the following advantages:

1. the traditional saponification method can generate a large amount of third-phase wastewater containing sodium chloride and metal hydroxide micelles, and the subsequent processes of third-phase and water-phase separation, third-phase acidification treatment, water-phase oil-water separation treatment and the like are required, and the treated sodium chloride wastewater is also discharged as pollutants.

The synthesis method of the invention can generate a small amount of reaction water in the synthesis reaction, the amount of reaction water generated per ton of product is only 50kg, and the amount of wastewater generated per ton of product by the saponification method is about 1.2 tons. The reaction water produced by the synthesis method is pure water, and the wastewater produced by the saponification method is still the wastewater containing sodium chloride after being treated.

2. The saponification method has long process flow, large equipment investment and complex operation; the synthesis method has the advantages of short process flow, simple and convenient operation, no subsequent treatment process and low energy consumption.

3. The saponification process results in a product containing a relatively large amount of free acid, and the synthesis process is an equimolar reaction and does not contain free acid. Therefore, the product quality is more stable and controllable.

Example 2

Synthesis of nickel-based butadiene rubber:

the catalyst used for polymerization is nickel isooctanoate hexane solution, the concentration is 1 mol/L; triisobutylaluminum hexane solution with a concentration of 1 mol/L; boron trifluoride diethyl etherate in hexane was 0.01mol/L.

The polymerization kettle is a 5L kettle with a jacket, and the jacket is filled with hot water at 50 ℃. All the materials are added and pressed in by nitrogen, 1.9L of hexane and 0.5L of butadiene are added into a polymerization kettle, and stirring is started; mixing 0.12ml of nickel isooctanoate solution with 0.5ml of triisobutylaluminum solution, and then adding into a polymerization kettle; then 100ml boron trifluoride diethyl etherate complex solution is added into a polymerization kettle; reacting for 3 hours, stopping stirring, and pressing the glue solution into a glue boiling barrel by using nitrogen; boiling the glue solution in boiling water for 30 minutes to obtain water glue; extruding and drying the water gel by using an open mill, rolling at the temperature of 120-150 ℃ to obtain dry gel, weighing to obtain the mass m of the dry gel_Glue279 g; calculated conversion was 90%.

Conversion rate 100% m_Glue/(500*0.62)

The cis-structure of the polymer in this and the following examples was tested using infrared spectroscopy.

TABLE 2 Synthesis of Nickel-based cis-butadiene rubber

Example 3

Synthesis of nickel-based butadiene rubber:

the catalyst used for polymerization is nickel isooctanoate hexane solution, the concentration is 1 mol/L; the naphthenic acid nickel hexane solution with the concentration of 1 mol/L; triisobutylaluminum hexane solution with a concentration of 1 mol/L; boron trifluoride diethyl etherate in hexane at a concentration of 0.01mol/L.

The polymerization kettle is a 5L kettle with a jacket, and the jacket is filled with hot water at 50 ℃. All the materials are added and pressed in by nitrogen, 1.9L of hexane and 0.5L of butadiene are added into a polymerization kettle, and stirring is started; 0.06ml of nickel isooctanoate solution, 0.06ml of nickel naphthenate solution and 0.5ml of triisobutyl aluminum solution are mixed and then added into a polymerization kettle; then 100ml boron trifluoride diethyl etherate complex solution is added into a polymerization kettle; reacting for 3 hours, stopping stirring, and pressing the glue solution into a glue boiling barrel by using nitrogen; boiling the glue solution in boiling water for 30 minutes to obtain water glue; extruding and drying the water gel by using an open mill, rolling at the temperature of 120-150 ℃ to obtain dry gel, weighing to obtain the mass m of the dry gel_Glue273 g; calculated conversion was 88%.

Conversion rate 100% m_Glue/(500*0.62)

TABLE 3 Synthesis of Nickel-based cis-butadiene rubber

Example 4

Five formulas of nickel naphthenate, nickel isooctanoate, nickel neodecanoate, nickel naphthenate and nickel isooctanoate mixture and nickel neodecanoate and nickel isooctanoate mixture are respectively used as catalysts for synthesizing nickel-based butadiene rubber, the synthesis method is the same as example 2, and the specific formula and application effect are shown in the following table:

table 4 Nickel isooctanoate and nickel naphthenate are matched according to proportion (mass percentage)

TABLE 5 Nickel isooctanoate and nickel neodecanoate in proportion (mass percent)

TABLE 6 pure nickel isooctanoate, nickel neodecanoate, nickel naphthenate

And (4) conclusion:

1. as can be seen from Table 4, in the formulation of nickel naphthenate and nickel isooctanoate, the catalytic performance relatively decreases with the increase of the amount of nickel naphthenate.

2. As can be seen from Table 5, in the mixed formulation of nickel isooctanoate and nickel neodecanoate, the catalytic performance remained at substantially the same level as that of nickel isooctanoate alone when the amount of nickel neodecanoate used was varied between 1% and 50%. However, the price of the neodecanoic acid is about 2 times of that of the isooctanoic acid, so the use of the isooctanoic acid can reduce the manufacturing cost and the selling price, and has obvious economic benefit and social benefit.

3. It can be seen from table 6 that the catalytic performance of the three formulations of nickel naphthenate, nickel isooctanoate and nickel neodecanoate are compared: the catalytic performance of nickel naphthenate is relatively poor, and nickel isooctanoate and nickel neodecanoate are basically at the same level.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.