CN114621365A - Rare earth organic matter, preparation method thereof, rare earth catalyst and application - Google Patents

Rare earth organic matter, preparation method thereof, rare earth catalyst and application Download PDF

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CN114621365A
CN114621365A CN202011423821.8A CN202011423821A CN114621365A CN 114621365 A CN114621365 A CN 114621365A CN 202011423821 A CN202011423821 A CN 202011423821A CN 114621365 A CN114621365 A CN 114621365A
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rare earth
catalyst
neodymium
phosphate
reaction
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CN114621365B (en
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李传光
张志强
林曙光
周鹏松
郭中台
李潇
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages

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Abstract

The invention provides a rare earth organic matter, a preparation method thereof, a rare earth catalyst and application. The preparation method comprises the following steps: in the presence of an organic solvent, carrying out coordination reaction on neodymium metal salt and/or neodymium oxide, acidic phosphate ester and an ester compound to obtain a rare earth organic substance; the mole number of the rare earth element neodymium is recorded as M1And the total mole number of the acidic phosphate ester and the ester compound is recorded as M2，M1And M2The ratio of the acid phosphate to the ester compound is 1 (3-4), and the molar ratio of the acid phosphate to the ester compound is 1 (0.001-1). The required rare earth organic matter can be obtained through one-step reaction, so that the synthesis difficulty of the rare earth organic matter can be greatly reduced, and the yield of the rare earth organic matter is improved. Water content in the above synthesisRarely, this can greatly reduce the formation of oligomeric structures of rare earths, which can improve the catalytic activity of the above rare earth organic compounds. The presence of the organic solvent can improve the compatibility of the reaction raw materials, and the presence of the catalyst can improve the reaction rate of the coordination reaction.

Description

Rare earth organic matter, preparation method thereof, rare earth catalyst and application
Technical Field
The invention relates to the field of catalysis, and particularly relates to a rare earth organic matter, a preparation method thereof, a rare earth catalyst and application thereof.
Background
When the rare earth catalyst is used for the synthesis reaction of rare earth butadiene rubber, polybutadiene with high linearity and high cis-structure can be obtained. The rare earth butadiene rubber has a series of advantages of good elasticity, good wear resistance, good low-temperature performance, low heat generation, low rolling resistance and the like, and has better crude rubber strength and vulcanized rubber performance compared with polybutadiene rubber prepared by traditional titanium-based, cobalt-based and nickel-based catalysts.
Currently, Ziegler-Natta type rare earth catalytic systems are classified into binary catalytic systems, ternary catalytic systems, and multi-element catalytic systems according to their components. The binary catalytic system consists of neodymium trichloride nL complex (Nd) and aluminum alkyl (Al), and has the advantages of few components of the binary system, few influencing factors and simple preparation process and method. The ternary catalyst system consists of rare earth carboxylate or rare earth phosphonate compound (Ln), alkyl aluminum (Al) and halogen-containing compound. However, most of these catalysts are heterogeneous systems, and have the disadvantages of poor stability, difficult control of the catalytic process and the polymerization process, large molecular weight of the polymer, wide molecular weight distribution, high viscosity of the polymerization system and the like during the catalysis of the polymerization of the conjugated diene. The literature provides catalysts which are "preformed" in the presence of small amounts of conjugated dienes and which can be converted from heterogeneous systems to homogeneous systems. Another prior art document provides a homogeneous catalyst prepared by adding a small amount of butadiene to a rare earth carboxylate/alkylaluminum/halosilane system to simultaneously reduce polybutadiene molecular weight and molecular weight distribution index.
The activity of the rare earth catalyst is influenced by a coordination structure, a common organic carboxylic acid or phosphoric acid rare earth compound is prepared in an aqueous solution and extracted by an organic solvent, organic carboxylic ester or phosphate exists in a ligand form, and a large amount of rare earth compounds form an oligomeric structure due to the existence of water. The oligomeric structure form of the rare earth compound reduces the number of rare earth active centers participating in polymerization reaction and reduces the activity of the catalyst. By improving the ligand composition of the neodymium active center, the formation of hydrated oligomer is reduced, the utilization rate of the neodymium active center can be effectively improved, and the catalytic efficiency of the catalyst is improved. Another prior document provides a method for preparing neodymium carboxylate by introducing a long-chain organic carboxylic acid with large steric hindrance as a ligand, thereby reducing the formation of rare earth oligomers and improving the activity of the catalyst. Still another prior art document teaches that the utilization of neodymium carboxylate catalysts can be effectively enhanced by preparing a single-structured central neodymium carboxylate in an anhydrous environment.
It can be seen that the ligand composition of the rare earth compound has a large influence on the catalyst activity. However, no report is found on the method of introducing a second ligand into organic carboxylate or organic phosphate rare earth compound to inhibit oligomer formation and improve the activity of rare earth catalyst at present.
Disclosure of Invention
The invention mainly aims to provide a rare earth organic matter, a preparation method thereof, a rare earth catalyst and application thereof, and aims to solve the problem that the existing rare earth catalyst has low catalytic activity when used for the synthesis reaction of rare earth butadiene rubber.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing a rare earth organic material, the method comprising: in the presence of an organic solvent, carrying out coordination reaction on neodymium metal salt and/or neodymium oxide, acidic phosphate ester and an ester compound to obtain a rare earth organic substance; the mole number of the rare earth element neodymium is recorded as M1The total mole number of the acidic phosphate ester and the ester compound is recorded as M2，M1And M2The ratio of the acid phosphate to the ester compound is 1 (3-4), and the molar ratio of the acid phosphate to the ester compound is 1 (0.001-1).
Further, the acidic phosphate ester is selected from di (2-ethylhexyl) phosphate ester of an acidic phosphate ester compound and/or mono 2-ethylhexyl 2-ethylphosphonate ester; the ester compound is selected from one or more of di (2-ethylhexyl) phosphate of the ester compound, mono 2-ethylhexyl 2-phosphonate, diethyl phosphate, trichloroethyl phosphate, diethyl chlorophosphate, ethyl acetate, ethyl dichloroacetate, ethyl trichloroacetate, propyl propionate and methyl methacrylate; the neodymium metal salt is selected from one or more of neodymium chloride, neodymium nitrate, neodymium naphthenate and neodymium isooctanoate.
Further, the temperature of the coordination reaction is 20-70 ℃, and the reaction time is 20-90 min; preferably, the organic solvent is selected from one or more of hexane, cyclohexane and hydrogenated gasoline.
Further, the preparation method also comprises the following steps: the coordination reaction is carried out in the presence of a catalyst, wherein the catalyst is concentrated hydrochloric acid, water or nitric acid; preferably, the molar ratio of concentrated hydrochloric acid to acidic phosphate ester is 1: (20-100).
The other aspect of the application also provides a rare earth organic matter which is prepared by the preparation method provided by the application.
Yet another aspect of the present application also provides a rare earth catalyst comprising: the application provides a rare earth organic matter, a chain transfer agent, a halogen-containing organic matter and a homogeneous phase agent.
Further, the chain transfer agent is selected from trialkylaluminums and/or alkylaluminum hydrides; the halogen-containing organic matter is selected from one or more of diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, tert-butyl chloride, benzyl chloride, allyl chloride, silicon tetrachloride and chloromethylsilane; the homogeneous agent is selected from one or more of butadiene, isoprene and piperylene.
Furthermore, in the rare earth catalyst, the molar ratio of the rare earth organic matter, the chain transfer agent, the halogen-containing organic matter and the homogeneous phase agent is 1 (5-50): (0.5-6.0): 0-200.
In still another aspect, the present application provides an application of the rare earth catalyst provided herein in butadiene rubber synthesis, the application including: under the action of a catalyst, butadiene monomer is taken as a raw material to carry out polymerization reaction, and the catalyst comprises the rare earth catalyst provided by the application.
Further, the temperature of the polymerization reaction is 0-60 ℃, the reaction time is 1-6 h, and neodymium and butadiene in the rare earth catalystThe ratio of the molar number of the monomers is 1X 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL.
Further, the ratio of the mole number of the neodymium element to the butadiene monomer in the rare earth catalyst is 1X 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL; preferably, the ratio of the mole number of the neodymium element to the butadiene monomer in the rare earth catalyst is 0.2 × 10-4～1.2×10-4。
By applying the technical scheme of the invention, two ligands are introduced into the rare earth organic matter, so that two neutral activities are formed in the catalytic reaction process, the catalytic activity of the catalyst in the catalytic process can be improved by introducing the acidic phosphate ester, and the formation of rare earth oligomer can be inhibited by introducing the ester compound, so that the occurrence probability of side reactions can be reduced, and the catalytic activity of the catalyst can be improved. Therefore, the catalyst with the composition can not only improve the catalytic activity of the rare earth catalyst, but also reduce the occurrence of side reactions in the polymerization reaction process.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing rare earth catalyst has the problem of low catalytic activity when being used for the synthesis reaction of rare earth butadiene rubber. In order to solve the above technical problems, the present application provides a method for preparing a rare earth organic compound, including: in the presence of an organic solvent, carrying out coordination reaction on neodymium metal salt and/or neodymium oxide, acidic phosphate ester and an ester compound to obtain a rare earth organic substance; the mole number of the rare earth element neodymium is recorded as M1The total mole number of the acidic phosphate ester and the ester compound is recorded as M2，M1And M2The ratio of the acid phosphate to the ester compound is 1 (3-4), and the molar ratio of the acid phosphate to the ester compound is 1 (0.001-1).
In the preparation method, the required rare earth organic matter can be obtained through one-step reaction. Therefore, the synthesis difficulty of the rare earth organic matters can be greatly reduced, and the yield of the rare earth organic matters can be improved. The synthesis process has low water content, and this can reduce the formation of RE oligomer structure greatly and raise the catalytic activity of the RE organic matter. The presence of the organic solvent can improve the compatibility of the reaction raw materials, and the presence of the catalyst can improve the reaction rate of the coordination reaction. On the basis, the preparation method has the advantages of simple process, low cost, high catalyst activity, high yield and the like.
In a preferred embodiment, the acidic phosphate ester includes, but is not limited to, di (2-ethylhexyl) phosphate and/or mono 2-ethylhexyl phosphonate of the acidic phosphate ester compound. Compared with other acidic phosphate ester ligands, the two acidic phosphate ester ligands have larger steric hindrance, so that the selectivity of the catalyst formed by the two acidic phosphate ester ligands is favorably improved, and the yield of the catalytic product is favorably improved.
In a preferred embodiment, the ester compound includes, but is not limited to, one or more of di (2-ethylhexyl) phosphate, mono 2-ethylhexyl 2-ethylhexylphosphonate, diethyl phosphate, trichloroethyl phosphate, diethyl chlorophosphate, ethyl acetate, ethyl dichloroacetate, ethyl trichloroacetate, propyl propionate, and methyl methacrylate of the ester compound. Compared with other ester compounds, the adoption of the ester compounds is beneficial to further reducing the occurrence probability of side reactions and simultaneously improving the catalytic activity of the catalyst.
The neodymium metal salt used in the above preparation method may be selected from those commonly used in the art, and preferably, the neodymium metal salt includes, but is not limited to, one or more of neodymium chloride, neodymium nitrate, neodymium naphthenate, and neodymium isooctanoate.
In order to further improve the conversion rate of the rare earth organic matter, in a preferred embodiment, the temperature of the coordination reaction is 20-70 ℃, and the reaction time is 20-90 min.
The organic solvent may be selected from those conventionally used in the art. Preferably, the organic solvent includes, but is not limited to, one or more of hexane, cyclohexane, and hydrogenated gasoline.
In a preferred embodiment, the coordination reaction is carried out in the presence of a catalyst, and the catalyst includes, but is not limited to, concentrated hydrochloric acid. The addition of concentrated hydrochloric acid is beneficial to further improving the coordination efficiency of the acidic phosphate and the neodymium element. More preferably, the molar ratio of concentrated hydrochloric acid to acidic phosphate ester is 1: (20-100). The molar ratio of the concentrated hydrochloric acid to the acidic phosphate ester includes, but is not limited to, the above range, and limiting the molar ratio to the acidic phosphate ester is advantageous for further improving the coordination efficiency of the neodymium element to the acidic phosphate ester, and further for improving the catalytic activity of the catalyst.
The other aspect of the application also provides the rare earth organic matter which is prepared by the preparation method provided by the application.
In the preparation method, two ligands are introduced to enable the formed rare earth organic matter to form two active neutrals in the catalytic reaction process, the catalytic activity of the catalyst in the catalytic process can be improved through the introduction of the acidic phosphate ester, and the introduction of the ester compound can inhibit the formation of rare earth oligomer, so that the occurrence probability of side reactions can be reduced, and the catalytic activity can be improved. Therefore, the rare earth organic matter with the composition can not only improve the catalytic activity of the rare earth catalyst, but also reduce the occurrence of side reactions in the polymerization reaction process. Meanwhile, the preparation method can obtain the required rare earth organic matter in one step, thereby greatly reducing the synthesis difficulty of the rare earth organic matter and improving the yield of the rare earth organic matter. Meanwhile, the content of water in the synthesis process is low, so that the formation of the rare earth oligomeric structure can be greatly reduced, and the catalytic activity of the rare earth organic matter can be greatly improved. The presence of the organic solvent can improve the compatibility of the reaction raw materials, and the presence of the catalyst can improve the reaction rate of the coordination reaction. On the basis, the preparation method has the advantages of simple process, low cost, high catalyst activity, high yield and the like.
Yet another aspect of the present application also provides a rare earth catalyst comprising: the rare earth organic matter, the chain transfer agent, the halogen-containing organic matter and the homogeneous phase agent are provided by the application.
The rare earth catalyst prepared by the rare earth organic matter has higher activity, the prepared rare earth butadiene rubber has lower glue solution viscosity, and the production energy consumption and the production difficulty are reduced.
The addition of a chain transfer agent is a substance effective in radical transfer of the chain-propagating radicals, which can adjust the relative molecular weight of the polymer. The chain transfer agent may be selected from those conventionally used in the art. In a preferred embodiment, the chain transfer agent includes, but is not limited to, a trialkyl aluminum and/or an alkyl aluminum hydride. Compared with other chain transfer agents, the chain transfer agents are beneficial to better controlling the polymerization degree of the rare earth butadiene rubber, so that the viscosity of the rare earth butadiene rubber can be better controlled.
In a preferred embodiment, the halogen-containing organic compound includes, but is not limited to, one or more of diisobutylaluminum monochloride, diethylaluminum monochloride, ethylaluminum sesquichloride (also known as ethylaluminum sesquichloride), t-butyl chloride, benzyl chloride, allyl chloride, silicon tetrachloride, chloromethylsilane.
The addition of the homogeneous agent enables the synthesis reaction of the rare earth butadiene rubber to be carried out in a homogeneous environment. The above-mentioned homogeneous agents may be selected from those commonly used in the art. In order to further improve the reaction effect and the yield of the target product, preferably, the homogeneous agent includes, but is not limited to, one or more of butadiene, isoprene and piperylene.
In a preferred embodiment, the ratio of the mole numbers of the rare earth organic, the chain transfer agent, the halogen-containing organic and the homogeneous agent in the rare earth catalyst is 1 (5-50): (0.5-6.0): 0-200. The ratio of the number of moles of the rare earth organic, the chain transfer agent, the halogen-containing organic, and the homogenizing agent includes, but is not limited to, the above range, and it is preferable to further improve the catalytic activity of the rare earth catalyst by limiting the ratio to the above range.
In yet another aspect, the present application provides a use of the rare earth catalyst provided herein in butadiene rubber synthesis, the use comprising: under the action of catalyst, butadiene monomer is used as raw material to make polymerization reaction, and the catalyst includes the above-mentioned rare earth catalyst. The rare earth catalyst has high catalytic activity, so that the yield of the rare earth butadiene rubber can be greatly improved by selecting the catalyst.
In order to further increase the reaction rate of the polymerization reaction and the yield of the rare earth maleic rubber, in a preferred embodiment, the polymerization reaction temperature is 0-60 ℃, the reaction time is 1-6 h, the mole ratio of neodymium element to butadiene monomer in the rare earth catalyst is 1 × 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL.
To further increase the reaction rate of butadiene during the polymerization reaction, in a preferred embodiment, the ratio of the mole number of the neodymium element to the butadiene monomer in the rare earth catalyst is 1 × 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL. More preferably, the ratio of the mole number of the neodymium element to the butadiene monomer in the rare earth catalyst is 0.2 × 10-4～1.2×10-4。
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
20g of di (2-ethylhexyl) phosphate (0.062mmol) and 200ml of hexane were mixed and added to a three-necked flask, and stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of saturated neodymium chloride solution is added dropwise, 1g (0.004mmol) of trichloroethyl phosphate is added, and the mixture reacts for 2 hours at the temperature of 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C1 hexane solution, wherein M1And M2The ratio of the acidic phosphate to the ester compound (hereinafter referred to as the first ligand L1 and the second ligand L2) is 1:3.01, and the molar ratio of the acidic phosphate to the ester compound is 1: 0.065.
Example 2
18.1g of di (2-ethylhexyl) phosphate (0.056mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of neodymium nitrate saturated solution is added dropwise, 2.5g (0.014mmol) of diethyl chlorophosphate is added, and the mixture reacts for 2 hours at 50-55 ℃ until the product is clear; the product is poured into a tubeA liquid funnel is used for discharging the lower water phase after standing and layering; collecting the product to obtain the final product of rare earth compound C2 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1:3.21, and the molar ratio was 1: 0.25.
Example 3
17.3g of di (2-ethylhexyl) phosphate (0.053mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of neodymium chloride solution is dripped, after 3min of reaction, 3.2g (0.017mmol) of ethyl trichloroacetate is added, and the reaction is carried out for 2h at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C3 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1: 0.32.
Example 4
16.8g of di (2-ethylhexyl) phosphate (0.052mmol), 2.8g of ethyl trichloroacetate (0.015mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of neodymium chloride solution is dripped, and the reaction is carried out for 2 hours at the temperature of 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C4 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1: 0.29.
Example 5
19.8g of di (2-ethylhexyl) phosphate (0.061mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 0.5ml of hydrochloric acid solution and 2ml of neodymium chloride solution are dripped, after 15min of reaction, 0.8g of diethyl phosphate (0.006mmol) is added, and the reaction is carried out for 2h at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C5 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 is 1: 0.098.
Example 6
18.1g of di (2-ethylhexyl) phosphate (0.056mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 0.5ml of hydrochloric acid solution is dripped, after 5min of reaction, 2.8g of ethyl dichloroacetate (0.017mmol) is added, and the reaction is carried out for 2h at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C6 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1:3.36, and the molar ratio was 1: 0.3.
Example 7
15.1g of di (2-ethylhexyl) phosphate (0.047mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 1.8ml of neodymium chloride solution and 0.3ml of concentrated hydrochloric acid are sequentially dripped, after 15min of reaction, 2.6 methyl methacrylate (0.026mmol) is added, and the reaction is carried out for 2h at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C7 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1:3.31, and the molar ratio was 1: 0.55.
The rare earth compounds C1, C2 and C3 have absorption peaks of P ═ O bonds relative to the common phosphate compound Nd (P507) measured by a Vertex-70FTIR type infrared spectrometer of Bruker, Germany3Offset of 50-70cm-1The absorption peaks of the P ═ O bonds of the rare earth compounds C4, C5, C6 and C7 are relative to those of the common phosphate compound Nd (P204)3Offset of 60-80cm-1Indicating that the ligand structure around Nd is changed.
Example 8
The differences from example 1 are: m1And M2The ratio of the first ligand L1 to the second ligand L2 was 1: 0.001. The final product is rare earth compound C8 hexane solution.
28.3g of di (2-ethylhexyl) phosphate (0.088mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when 50 ℃ is reached, 3ml of saturated neodymium chloride solution is added dropwise, 0.001g (0.0000062mmol) of trichloroethyl phosphate is added, and the mixture is reacted for 2 hours at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C9 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 was 1: 0.001.
Example 9
The differences from example 1 are: m1And M2The ratio of the first ligand L1 to the second ligand L2 is 1:3, and the molar ratio of the first ligand L1 to the second ligand L2 is 1: 1. The final product is rare earth compound C9 hexane solution.
10g of di (2-ethylhexyl) phosphate (0.031mmol) and 200ml of hexane are mixed and added into a three-neck flask, and the mixture is stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of saturated neodymium chloride solution is added dropwise, 7.18g (0.031mmol) of trichloroethyl phosphate is added, and the mixture reacts for 2 hours at 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product of rare earth compound C9 hexane solution, wherein M1And M2The ratio of the first ligand L1 to the second ligand L2 is 1:3, and the molar ratio of the first ligand L1 to the second ligand L2 is 1: 1.
Example 10
The differences from example 1 are: no hydrochloric acid was added. The final product is rare earth compound C10 hexane solution.
20g of di (2-ethylhexyl) phosphate (0.062mmol) and 200ml of hexane were mixed and added to a three-necked flask, and stirred uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of saturated neodymium chloride solution is added dropwise, 1g (0.004mmol) of trichloroethyl phosphate is added, and the mixture reacts for 2 hours at 70 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining a lower-layer water phase; collecting the product to obtain the final product rare earth compound C9 Hexane solution of M1And M2The ratio of the first ligand L1 to the second ligand L2 is 1: 0.065.
Comparative example 1
The differences from example 1 are: m1And M2The ratio of the first ligand L1 to the second ligand L2 is 1:5, and the molar ratio of the first ligand L1 to the second ligand L2 is 1: 2.
The final product is rare earth compound D1 hexane solution.
Mixing 11.9g of di (2-ethylhexyl) phosphate (0.037mmol) and 200ml of hexane, adding into a three-neck flask, and stirring uniformly; then 3.7g of neodymium oxide (0.011mmol) is added into the flask, stirred evenly and heated; when the temperature reaches 50 ℃, 3ml of saturated neodymium chloride solution is added dropwise, 17g (0.074mmol) of trichloroethyl phosphate is added, and the mixture reacts for 2 hours at the temperature of 50-55 ℃ until the product is clear; pouring the product into a separating funnel, standing for layering, and draining the lower-layer water phase; collecting the product to obtain the final product, namely a rare earth compound D1 hexane solution, wherein M is1And M2The ratio of the first ligand L1 to the second ligand L2 is 1:5, and the molar ratio of the first ligand L1 to the second ligand L2 is 1: 2.
Examples 1 to 10 rare earth compounds were measured by means of a Vertex-70FTIR type infrared spectrometer from Bruker, Germany, having an absorption peak for the P ═ O bond relative to the ordinary phosphoric acid compound Nd (P507)3Offset 70cm-1-100cm-1Shows that the ligand structure is changed, and the structural composition can be qualitatively expressed as Nd (L)1)X(L2)Y。
Preparation of rare earth catalyst:
examples 11 to 14 the rare earth compounds C1, C2 and C3 synthesized in examples 1 to 3 were used as main catalysts, and a common rare earth compound Nd (P507) was used3As comparative examples 2 and 3, the catalyst prepared in comparative example 1 was used as comparative example 4 to compare the catalyst activities.
Example 11
The rare earth catalyst was prepared using the rare earth compound prepared in example 1 and subjected to butadiene polymerization as follows:
30mL of n-hexane and 3mL of a rare earth compound C1 solution (0.33mmol) containing0.23g of butadiene (4.25mmol) in hexane, 9.01mL of diisobutylaluminum hydride Al (i-Bu)2After H (1.0mol/L), the reaction mixture was reacted at 50 ℃ for 20min, and then 2.53mL of ethylaluminum sesquichloride (1.0mol/L) was added thereto and the reaction mixture was reacted for 20 min.
Into a 1000mL polymerization reactor was charged 500mL of a butadiene-hexane solution (monomer concentration: 0.10g/mL), followed by 2.01mL of the rare earth catalyst prepared above (molar ratio of Nd/butadiene: 1.0X 10)-3) The mixture was stirred to mix well and reacted at 50 ℃ for 4 hours. After the reaction, an ethanol solution containing 1% of 2, 6-di-tert-butyl-p-methylphenol is added, a polymer is precipitated in excess ethanol, washed and extruded with ethanol, and dried in a vacuum oven at 40 ℃ to constant weight.
The product results are that the product conversion rate is 88 percent; the cis-1, 4-polybutadiene content is 97% by mass, the trans-1, 4-polybutadiene content is 2% by mass, and the 1, 2-polybutadiene content is 1% by mass; the weight average molecular weight is 4.1X 104Molecular weight distribution 2.330; mooney (ML1+4, 100 ℃): 43 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 189 cps.
Example 12
20mL of n-hexane, 4.3mL of a rare earth compound C2(0.33mmol), a hexane solution containing 0.31g of butadiene, and 9.01mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, and then reacted at 50 ℃ for 20min, followed by addition of 2.55mL of ethylaluminum sesquichloride (1.0mol/L) and further reaction for 20 min.
Polymerization As in example 11
The product result is that the product conversion rate is 90 percent; the cis-1, 4-polybutadiene content is 96 mass percent, the trans-1, 4-polybutadiene content is 3 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 3.9X 104Molecular weight distribution 2.370; mooney (ML1+4, 100 ℃): 40 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 207 cps.
Example 13
20mL of n-hexane, 4.8mL of a rare earth compound C3(0.33mmol), a hexane solution containing 0.27 butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, and then reacted at 50 ℃ for 20min, followed by addition of 2.49mL of ethylaluminum sesquichloride (1.0mol/L) and further reaction for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 89%; the cis-1, 4-polybutadiene content is 98 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.2X 104Molecular weight distribution 2.330; mooney (ML1+4, 100 ℃): 48 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 168 cps.
Example 14
20mL of n-hexane, 4.8mL of a rare earth compound C1, (0.498mmol), a hexane solution containing 0.27 butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, and then reacted at 50 ℃ for 20min, followed by addition of 2.49mL of ethylaluminum sesquichloride (1.0mol/L) and further reaction for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 97 percent; the cis-1, 4-polybutadiene content is 98 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.2X 104The molecular weight distribution was 2.470; mooney (ML1+4, 100 ℃): 52 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 178 cps.
Comparative example 2
At room temperature, 30mL of n-hexane, 0.528gNd (P507) were added sequentially to a 100mL catalyst aging bottle3(0.498mmol), a hexane solution containing 0.27g of butadiene, a hexane solution containing 0.23g of butadiene, 9.01mL of diisobutylaluminum hydride (1.0mol/L) was reacted at 50 ℃ for 20min, and then 2.53mL of ethylaluminum sesquichloride (1.0mol/L) was added and reacted for 20 min.
The polymerization was as in example 11.
The product has the following resultThe conversion rate was 82%; the cis-1, 4-polybutadiene content is 97% by mass, the trans-1, 4-polybutadiene content is 1% by mass, and the 1, 2-polybutadiene content is 1% by mass; the weight average molecular weight is 4.1X 104Molecular weight distribution 2.360; mooney (ML1+4, 100 ℃): 42 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 223 cps.
Comparative example 3
At room temperature, 30mL of n-hexane, 0.35Nd (P507) were added in this order to a 100mL catalyst aging flask3(0.33mmol), a hexane solution containing 0.27g of butadiene, a hexane solution containing 0.23g of butadiene, 9.01mL of diisobutylaluminum hydride (1.0mol/L) was reacted at 50 ℃ for 20min, and then 2.53mL of ethylaluminum sesquichloride (1.0mol/L) was added thereto and reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 63 percent; the mass percent of the cis-1, 4-polybutadiene content is 98%, the mass percent of the trans-1, 4-polybutadiene content is 1%, and the mass percent of the 1, 2-polybutadiene content is 1%; the weight average molecular weight is 4.1X 104Molecular weight distribution 2.230; mooney (ML1+4, 100 ℃): 31 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 196 cps.
Comparative example 4
20mL of n-hexane, 4.8mL of a rare earth compound D1, (0.498mmol), a hexane solution containing 0.27 butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, and then reacted at 50 ℃ for 20min, followed by addition of 2.49mL of ethylaluminum sesquichloride (1.0mol/L) and further reaction for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 17 percent; the cis-1, 4-polybutadiene content is 97 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 2 mass percent; the weight average molecular weight is 4.2X 103Molecular weight distribution 3.470; mooney (ML1+4, 100 ℃): 12 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 228 cps.
By comparing examples 11-14 with comparative examples 2-3, the rare earth butadiene rubber synthesized by the catalyst prepared from the rare earth compound C1-C3 (examples 11-14) has less catalyst usage, which is 60% -80% of the common rare earth compound system, and the glue solution viscosity is reduced by about 20% -50% compared with the common rare earth butadiene rubber (comparative examples 2 and 3). Whereas the catalyst prepared from the rare earth compound D1 was low in activity (comparative example 4).
Examples 15 to 20 the rare earth compounds C4, C5, C6, C7 and C8 synthesized in examples 4 to 7 were used as main catalysts, and a common rare earth compound Nd (P204) was used3Comparative examples 5 and 6 were used to compare the catalyst activities.
Example 15
20mL of n-hexane, 4.6mL of a rare earth compound C4(0.38mmol), a hexane solution containing 0.27g of butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, followed by reaction at 50 ℃ for 20min, and then 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) was added thereto and further reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 81 percent; the cis-1, 4-polybutadiene content is 98 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.2X 104Molecular weight distribution 2.130; mooney (ML1+4, 100 ℃): 43 MU; gum viscosity (5.02% mass content toluene solution, room temperature): 203 cps.
Example 16
20mL of n-hexane, 4.01mL of a rare earth compound C5(0.38mmol), a hexane solution containing 0.27g of butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, followed by reaction at 50 ℃ for 20min, and then 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) was added thereto and further reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 83 percent; the cis-1, 4-polybutadiene content is 97% by mass, and the trans-1, 4-polybutadiene content is hundred by massThe fraction is 2 percent, and the content of 1, 2-polybutadiene is 1 percent by mass; the weight average molecular weight is 4.0X 104The molecular weight distribution was 2.430; mooney (ML1+4, 100 ℃): 39 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 189 cps.
Example 17
20mL of n-hexane, 4.38mL of a rare earth compound C6(0.38mmol) and a hexane solution containing 0.27g of butadiene were sequentially charged into a 50mL catalyst aging bottle at room temperature, 0.034g (0.19mmol) of diethyl chlorophosphate and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were added, and then the mixture was reacted at 50 ℃ for 20min, and 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) was added and the reaction was further reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 87 percent; the cis-1, 4-polybutadiene content is 98 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.2X 104Molecular weight distribution 2.230; mooney (ML1+4, 100 ℃): 41 MU; gum viscosity (5.02% mass content toluene solution, room temperature): 193 cps.
Example 18
20mL of n-hexane, 4.01mL of a rare earth compound C7(0.38mmol), a hexane solution containing 0.27g of butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, followed by reaction at 50 ℃ for 20min, and then 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) was added thereto and further reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 81 percent; the cis-1, 4-polybutadiene content is 97 mass percent, the trans-1, 4-polybutadiene content is 2 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.5X 104Molecular weight distribution 2.370; mooney (ML1+4, 100 ℃): 43 MU; gum viscosity (5.02% mass content toluene solution, room temperature): 199 cps.
Example 19
20mL of n-hexane, 4.01mL of a rare earth compound C4(0.498mmol), a hexane solution containing 0.27g of butadiene, and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, and then reacted at 50 ℃ for 20min, followed by addition of 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) and further reaction for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 93 percent; the cis-1, 4-polybutadiene content is 97% by mass, the trans-1, 4-polybutadiene content is 2% by mass, and the 1, 2-polybutadiene content is 1% by mass; the weight average molecular weight is 4.5X 104Molecular weight distribution 2.370; mooney (ML1+4, 100 ℃): 43 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 199 cps.
Example 20
20mL of n-hexane, 4.01mL of a rare earth compound C8(0.38mmol), a hexane solution containing 0.27g of butadiene (5mmol), and 8.96mL of diisobutylaluminum hydride (1.0mol/L) were sequentially added to a 50mL catalyst aging bottle at room temperature, followed by reaction at 50 ℃ for 20min, and then 2.49mL of aluminum sesquiethylate chloride (1.0mol/L) was added thereto and further reacted for 20 min.
The polymerization was carried out as in example 11.
The product result is that the product conversion rate is 82 percent; the cis-1, 4-polybutadiene content is 98 mass percent, the trans-1, 4-polybutadiene content is 1 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight was 3.7X 104A molecular weight distribution of 2.213; mooney (ML1+4, 100 ℃): 43 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 253 cps.
Comparative example 5
20mL of n-hexane, 0.552gNd (P204) were added sequentially to a 50mL catalyst aging bottle at room temperature3(0.498mmol), 0.32g of butadiene in hexane, 9.96mL of diisobutylaluminum hydride (1.0mol/L), reaction at 50 ℃ for 20min, and addition of 2.98mL of ethylaluminum sesquichloride (1.0mol/L) for another 20 min.
The polymerization was as in example 11.
The product has the following resultThe chemical conversion rate is 79 percent; the cis-1, 4-polybutadiene content is 97 mass percent, the trans-1, 4-polybutadiene content is 2 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.5X 104Molecular weight distribution 2.330; mooney (ML1+4, 100 ℃): 37 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 273 cps.
Comparative example 6
20mL of n-hexane, 0.39gNd (P204) were added sequentially to a 50mL catalyst aging bottle at room temperature3(0.38mmol), a hexane solution containing 0.32g of butadiene, 9.96mL of diisobutylaluminum hydride (1.0mol/L), followed by reaction at 50 ℃ for 20min, and then 2.98mL of ethylaluminum sesquichloride (1.0mol/L) was added thereto and reacted for 20 min.
The polymerization was as in example 11.
The product result is that the product conversion rate is 69%; the cis-1, 4-polybutadiene content is 97 mass percent, the trans-1, 4-polybutadiene content is 2 mass percent, and the 1, 2-polybutadiene content is 1 mass percent; the weight average molecular weight is 4.5X 104Molecular weight distribution 2.370; mooney (ML1+4, 100 ℃): 46 MU; glue viscosity (5.02% mass content toluene solution, room temperature): 255 cps.
By comparing examples 15-20 with comparative examples 5 to 6, the rare earth butadiene rubber synthesized by the catalyst prepared from the rare earth compound C4-C8 (examples 15-20) has less catalyst amount and lower viscosity of the dope compared with the common rare earth butadiene rubber (comparative examples 5 and 6).
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: two ligands are introduced into the rare earth organic matter, so that two neutral activities are formed in the catalytic reaction process, the catalytic activity of the catalyst in the catalytic process can be improved by introducing acidic phosphate, and the formation of rare earth oligomers can be inhibited by introducing ester compounds, so that the occurrence probability of side reactions can be reduced, and the catalytic activity of the catalyst can be improved. Therefore, the catalyst with the composition can not only improve the catalytic activity of the rare earth catalyst, but also reduce the occurrence of side reactions in the polymerization reaction process.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. The preparation method of the rare earth organic matter is characterized by comprising the following steps: in the presence of an organic solvent, carrying out coordination reaction on neodymium metal salt and/or neodymium oxide, acidic phosphate ester and an ester compound to obtain the rare earth organic matter; the mole number of the rare earth element neodymium is recorded as M1The total mole number of the acidic phosphate ester and the ester compound is recorded as M2Said M is1And said M2The ratio of the acid phosphate to the ester compound is 1 (3-4), and the molar ratio of the acid phosphate to the ester compound is 1 (0.001-1).
2. The method for producing a rare earth organic compound according to claim 1, wherein the acidic phosphate is selected from di (2-ethylhexyl) phosphate and/or mono 2-ethylhexyl phosphonate of an acidic phosphate compound;
the ester compound is selected from one or more of di (2-ethylhexyl) phosphate of the ester compound, mono 2-ethylhexyl 2-ethylphosphonate, diethyl phosphate, trichloroethyl phosphate, diethyl chlorophosphate, ethyl acetate, ethyl dichloroacetate, ethyl trichloroacetate, propyl propionate and methyl methacrylate;
the neodymium metal salt is selected from one or more of neodymium chloride, neodymium nitrate, neodymium naphthenate and neodymium isooctanoate.
3. The preparation method according to claim 1 or 2, wherein the temperature of the coordination reaction is 20 to 70 ℃, and the reaction time is 20 to 90 min; preferably, the organic solvent is selected from one or more of hexane, cyclohexane and hydrogenated gasoline.
4. The method of manufacturing according to claim 3, further comprising: the coordination reaction is carried out in the presence of a catalyst, wherein the catalyst is concentrated hydrochloric acid, water or nitric acid;
preferably, the molar ratio of the concentrated hydrochloric acid to the acidic phosphate ester is 1: (20-100).
5. A rare earth organic compound produced by the production method according to any one of claims 1 to 4.
6. A rare earth catalyst, wherein the rare earth catalyst comprises: the rare earth organic compound of claim 5, a chain transfer agent, a halogen-containing organic compound, and a homogeneous agent.
7. The rare earth catalyst according to claim 6, wherein the chain transfer agent is selected from trialkylaluminums and/or alkylaluminum hydrides;
the halogen-containing organic matter is selected from one or more of diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, tert-butyl chloride, benzyl chloride, allyl chloride, silicon tetrachloride and chloromethylsilane;
the homogeneous agent is selected from one or more of butadiene, isoprene and piperylene.
8. The rare earth catalyst as claimed in claim 6 or 7, wherein the ratio of the mole numbers of the rare earth organic substance, the chain transfer agent, the halogen-containing organic substance and the homogeneous agent in the rare earth catalyst is 1 (5-50): (0.5-6.0): 0-200.
9. Use of a rare earth catalyst according to any of claims 6 to 8 in the synthesis of butadiene rubber, wherein the use comprises: polymerizing butadiene monomer under the action of catalyst, which contains rare-earth catalyst as defined in any one of claims 6-8.
10. The method of claim 9, wherein the polymerization temperature is 0-60 ℃, the reaction time is 1-6 h, and the molar ratio of the neodymium element in the rare earth catalyst to the butadiene monomer is 1 x 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL.
11. Use according to claim 9 or 10, characterized in that the ratio of the molar amount of neodymium element in the rare earth catalyst to the butadiene monomer is 1 x 10-5～3.0×10-4The concentration of the butadiene monomer is 8-20 g/100 mL;
preferably, the ratio of the mole number of the neodymium element to the butadiene monomer in the rare earth catalyst is 0.2 × 10-4～1.2×10-4。
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