CN116023558A - Solution catalyst composition, solution catalyst, preparation method thereof and preparation method of conjugated diene polymer - Google Patents

Abstract

The invention relates to the field of conjugated diene polymerization catalysts, and discloses a solution type catalyst composition, a solution type catalyst, a preparation method thereof and a preparation method of a conjugated diene polymer. The solution-type catalyst composition of the present invention comprises a component a, a component B, a component C and a component D, wherein the component a is a neodymium phosphonate solution obtained by removing water from a reaction product of a neodymium chloride aqueous solution, an organic phosphonate, an organic solvent and a basic compound, wherein the molar ratio of the organic phosphonate to neodymium chloride in the neodymium chloride aqueous solution is 4 to 5:1, wherein the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5: 1, a step of; the component B is an alkyl aluminum compound; the component C is a halogenated compound; the component D is conjugated diene. The solution type catalyst provided by the invention has the advantage of high activity, and the dosage of the catalyst can be obviously reduced.

Description

Solution catalyst composition, solution catalyst, preparation method thereof and preparation method of conjugated diene polymer

Technical Field

The invention relates to a conjugated diene polymerization catalyst, in particular to a solution catalyst composition, a solution catalyst, a preparation method thereof and a preparation method of a conjugated diene polymer.

Background

Rare earth catalysts are catalysts which use rare earth element compounds as main catalysts. It is clear that neodymium is the most catalytically active element of rare earths for the polymerization of conjugated dienes. The rare earth catalytic system is generally two binary or ternary systems, the binary catalytic system consists of a main catalyst neodymium chloride and an alkylating agent, and the alkylating agent can be aluminum alkyl or magnesium alkyl. Ternary catalytic systems generally consist of three types of main catalyst rare earth salts, alkylating agents and halides.

Rare earth catalysts polymerize conjugated dienes and are currently commercialized mainly by two products. The first is rare earth butadiene rubber and the second is rare earth isoprene rubber. For industrial production, the catalyst dosage is critical to the production cost, especially in the case of the current rising price of rare earth raw materials. At present, the cost of the catalyst is too high, namely, the catalyst dosage is too high, so that the reduction of the catalyst dosage is a research hot spot. It has been reported that using neodecanoic acid neodymium/diisobutylaluminum hydride/diethylaluminum chloride catalyst system for butadiene polymerization, the catalyst amount (calculated as neodymium/monomer mole ratio) is generally 6 to 8X 10 ^-5 120-170 mgNd is required to be consumed per 1kg of polybutadiene produced (see synthetic rubber industry, 2008,31 (5): 358-361). When the catalyst is used for isoprene, the catalyst consumption is increased by more than 3 times, and 420mgNd is required to be consumed per 1kg of polyisoprene produced (see synthetic rubber industry, 2006,29 (3): 181-185). CN1840552A discloses rare earth carboxylate/organoaluminium/chloroalkane or chlorocarboxylate/conjugated olefin or carboxylic acid catalyst, when used in butadiene polymerization, the catalyst is usually used in an amount of 0.2-1.0X10 ^-3 That is, when 420 to 2100mgNd and isoprene are consumed per 1kg of polybutadiene, 1kg of polyisoprene is consumedConsumption exceeds 3000mgNd.

Disclosure of Invention

The invention aims to solve the problem of excessive catalyst dosage in the prior art, and provides a solution catalyst composition, a solution catalyst, a preparation method thereof and a preparation method of conjugated diene polymer.

In order to achieve the above object, the present invention provides, in a first aspect, a solution-type catalyst composition, wherein the solution-type catalyst composition comprises a component A, a component B, a component C and a component D,

the component A is a neodymium phosphonate solution obtained by removing water from a reaction product of an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and a basic compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous neodymium chloride solution is 4-5: 1, wherein the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5: 1, a step of;

the component B is an alkyl aluminum compound;

the component C is a halogenated compound;

the component D is conjugated diene.

Preferably, the content of neodymium chloride in the neodymium chloride aqueous solution is 0.1-0.5 mol/L.

Preferably, the organic phosphonate is of the structure shown in formula (1), wherein R ^d1 、R ^d2 And R is ^d3 Each independently is hydrogen, hydroxy, C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Alkoxy, and R ^d1 、R ^d2 And R is ^d3 At least one of which is C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Is a group consisting of an alkoxy group,

preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 Are all 2-ethylhexyloxy groups.

Preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 All are 2-ethylhexyl groups.

Preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 Is 2-ethylhexyl, R ^d3 Is 2-ethylhexyl oxy.

Preferably, the organic solvent is C ₅ -C ₁₀ Alkanes, C ₅ -C ₁₀ Cycloalkanes and C ₆ -C ₁₂ One or more of the aromatic hydrocarbons of (a).

Preferably, the organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene, and cumene.

Preferably, the organic solvent is used in an amount such that the volume of the organic phase and the volume of the aqueous phase are between 0.3 and 2:1.

preferably, the alkaline compound is used in the form of an aqueous solution, and the content of the alkaline compound in the aqueous solution of the alkaline compound is 0.1 to 5.0mol/L.

Preferably, the basic compound is one or more of hydroxide and ammonia.

Preferably, the water content of the neodymium phosphonate solution is less than 300ug/g.

Preferably, the molar ratio of said component a to said component B, calculated as neodymium element, is 1:12-30.

Preferably, the molar ratio of said component a to said component C, calculated as neodymium element, is 1:2-5.

Preferably, the molar ratio of said component a to said component D, calculated as neodymium element, is 1:10-80, preferably 1:20-60.

Preferably, the alkyl aluminum compound is of formula Al (R) ₃ The compound and Al (R) ₂ One or more of the compounds shown in H, R is selected from C ₁ -C ₆ Is a hydrocarbon group.

Preferably, the alkyl aluminum compound is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monohydride and diisobutylaluminum monohydride.

Preferably, the halogenated compound is of formula Al (R ¹ ) ₂ X is a compound of formula Si (R) ¹ ) _4-n X _n The compounds and formula Al ₂ (R ¹ ) ₃ X ₃ One or more of the compounds shown, each R ¹ Each independently selected from C ₁ -C ₆ Each X is independently selected from the group consisting of halogen, and n is an integer of 1 to 4.

Preferably, the halogenated compound is one or more of diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

Preferably, the conjugated diene is isoprene or butadiene.

According to a second aspect of the present invention, there is provided a solution-type catalyst obtained by mixing the components of the solution-type catalyst composition of the present invention.

According to a third aspect of the present invention, there is provided a method for producing a solution-type catalyst, characterized in that the solution-type catalyst is obtained by mixing the components of the solution-type catalyst composition of the present invention.

Preferably, the component B and the component C are mixed after the component a and the component D are mixed.

According to a fourth aspect of the present invention, there is provided a process for producing a conjugated diene polymer, the process comprising: and polymerizing the conjugated diene in the presence of an organic solvent and a catalyst to obtain a conjugated diene polymer, wherein the catalyst is a solution catalyst according to the present invention or a solution catalyst prepared by the preparation method according to the third aspect of the present invention.

Preferably, the conjugated diene is butadiene or isoprene.

Preferably, the polymerization conditions include: the temperature is 0-90 ℃ and the time is 1-5h.

According to a fifth aspect of the present invention there is provided the use of a solution catalyst according to the present invention or prepared by a method of preparation according to the third aspect of the present invention in the preparation of a conjugated diene polymer.

The rare earth catalyst provided by the invention has the advantage of high activity, and when the rare earth catalyst is used for butadiene polymerization, the catalyst consumed for producing 1kg of polybutadiene is less than or equal to 90mgNd and can be as low as below 50 mgNd; when it is used for isoprene polymerization, the catalyst consumed for producing 1kg of polyisoprene is 160mgNd or less and can be as low as 100mgNd or less.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a solution-type catalyst composition, wherein the solution-type catalyst composition comprises a component A, a component B, a component C and a component D,

the component A is a neodymium phosphonate solution obtained by removing water from a reaction product of an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and a basic compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous neodymium chloride solution is 4-5: 1, wherein the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5: 1, a step of;

the component B is an alkyl aluminum compound;

the component C is a halogenated compound;

the component D is conjugated diene.

The following describes component A, component B, component C and component D, respectively.

Component A

In the present invention, the component a is a neodymium phosphonate solution obtained by removing water from a reaction product of an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent, and a basic compound, wherein a molar ratio of the organic phosphonate to neodymium chloride in the aqueous neodymium chloride solution is 4 to 5:1, wherein the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5: 1.

according to the invention, the aqueous solution of neodymium chloride can be obtained by reacting neodymium oxide with hydrochloric acid, or can be obtained by adopting a mode of dissolving anhydrous neodymium chloride or neodymium chloride containing crystal water in water. The concentration of neodymium chloride is not particularly limited as long as the neodymium chloride is ensured to be completely dissolved. For example, the concentration of the aqueous solution of neodymium chloride may be 0.1 to 0.5mol/L.

According to the present invention, specific examples of the molar ratio of the organophosphonate to neodymium chloride in the neodymium chloride aqueous solution include, for example, 4: 1. 4.1: 1. 4.2: 1. 4.3: 1. 4.4: 1. 4.5: 1. 4.6: 1. 4.7: 1. 4.8: 1. 4.9: 1. 5:1.

according to the present invention, preferably, the organic phosphonate is of the structure represented by formula (1), wherein R ^d1 、R ^d2 And R is ^d3 Each independently is hydrogen, hydroxy, C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Alkoxy, and R ^d1 、R ^d2 And R is ^d3 At least one of which is C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Alkoxy groups of (a); preferably R ^d1 、R ^d2 And R is ^d3 Each independently is hydroxy, C ₄ -C ₁₂ Alkyl or C of (2) ₄ -C ₁₂ Alkoxy, and R ^d1 、R ^d2 And R is ^d3 At least one of which is C ₄ -C ₁₂ Alkyl or C of (2) ₄ -C ₁₂ Alkoxy groups of (a); more preferably, R ^d1 Is hydroxy, R ^d2 And R is ^d3 At least one of which is alkyl or alkoxy, and R ^d2 And R is ^d3 Each independently selected from the group consisting of n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-Undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decyloxy, n-undecoxy or n-dodecoxy.

Specific examples of the organic phosphonate may be selected from, for example, one or more of the compounds shown in the following formulas:

in the formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 Are all 2-ethylhexyl oxy groups (namely, di (2-ethylhexyl) phosphonate);

in the formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 Are all 2-ethylhexyl (i.e., di (2-ethylhexyl) phosphinate);

in the formula (1), R ^d1 Is hydroxy, R ^d2 Is 2-ethylhexyl, R ^d3 Is 2-ethylhexyl oxy (namely, is (2-ethylhexyl) phosphoric acid mono-2-ethylhexyl ester).

The organic phosphonate compound according to the present invention may be obtained in a conventional manner in the art, for example, may be commercially available, or may be prepared by a conventional method in the art, and the present invention is not particularly limited thereto.

According to the invention, the organic solvent is a compound capable of dissolving neodymium organophosphonate, for example C ₅ -C ₁₀ Alkanes, C ₅ -C ₁₀ Cycloalkanes and C ₆ -C ₁₂ Preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene.

The amount of the above-mentioned organic solvent is not particularly limited, and it is preferable that the amount of the organic solvent is such that the concentration of the neodymium phosphonate solution is not higher than 0.5mol/L (calculated as neodymium element). Furthermore, the organic solvent is preferably used in such an amount that the volume of the organic phase and the volume of the aqueous phase are 0.3 to 2:1, more preferably 0.5 to 1:1.

according to the present invention, the above-mentioned contact may be performed by mixing an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and a basic compound together, or by mixing two or more kinds of the above-mentioned components and then mixing the above-mentioned components with each other. In order to provide the resulting neodymium phosphonate solution with a lower viscosity and lower impurity content, preferably, the contacting comprises: after the aqueous solution of neodymium chloride is subjected to the first contact with the organic phosphonate and the organic solvent, the first contact product is subjected to the second contact with the alkaline compound.

In the present invention, the first contact is for sufficiently dissolving the reaction raw material, and preferably, the temperature of the first contact may be, for example, 5 to 80 ℃, and from the viewpoint of energy saving, the first contact is preferably performed at 10 to 50 ℃. The time for the first contact is not particularly limited, and may be, for example, 1 minute or more, preferably 1 to 5 minutes, as long as the reaction raw materials can be dissolved well.

According to the invention, the molar ratio of the alkaline compound to neodymium chloride in the aqueous solution of neodymium chloride is 2.8-3.5: 1. specific examples of the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution include: 2.8: 1. 2.9: 1. 3.0: 1. 3.1: 1. 3.2: 1. 3.3: 1. 3.4: 1. 3.5:1, etc.

According to the present invention, the alkaline compound is a substance having a pH of more than 7 by itself or after being formulated into an aqueous solution, preferably one or more of hydroxide and aqueous ammonia, more preferably one or more of sodium hydroxide, potassium hydroxide and aqueous ammonia. For the basic compound in solid form, it is usually formulated into an aqueous solution. The concentration of the aqueous solution is not particularly limited as long as sufficient dissolution is ensured, and may be, for example, 0.1 to 5.0mol/L.

Preferably, the aqueous alkaline substance solution is added dropwise, and the dropping speed can be 2.0-20.0 mL/min, preferably 5.0-10.0 mL/min. And if the dropping speed is too low, the production efficiency is too low, the dropping speed is too high, the product generation rate is high, and the layering and impurity separation of the final oil-water phase are not facilitated.

According to the present invention, preferably, the second contact temperature is 30 to 80 ℃, more preferably 30 to 55 ℃, still more preferably 45 to 55 ℃, particularly preferably at 50 ℃, and both the reaction rate and the energy saving can be achieved by performing at 50 ℃.

The time for the second contact may be, for example, 1 hour or more, preferably 1 to 6 hours, and more preferably 1 to 2 hours, as long as the reaction is sufficiently performed.

According to the present invention, the water removal operation is not particularly limited, and may be a known method of distillation, rectification, physical adsorption, drying to a solid, then redissolution, etc., as long as the water content in the neodymium phosphonate solution is ensured to be less than 300ug/g, preferably less than 200ug/g, more preferably less than 100ug/g.

Component B

In the present invention, the component B is an alkyl aluminum compound.

Preferably, the alkyl aluminum compound is of formula Al (R) ₃ The compound and Al (R) ₂ One or more of the compounds shown in H, R is selected from C ₁ -C ₆ Alkyl of (a); more preferably, the alkyl aluminum compound is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monohydride and diisobutylaluminum monohydride.

As the above C ₁ -C ₆ Examples of the alkyl group of (a) include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl and the like.

Component C

In the present invention, the component C is a halogenated compound.

Preferably, the halogenated compound is of formula Al (R ¹ ) ₂ X is a compound of formula Si (R) ¹ ) _4-n X _n The compounds and formula Al ₂ (R ¹ ) ₃ X ₃ One or more of the compounds shown, each R ¹ Each independently selected from C ₁ -C ₆ Each X is independently selected from halogen, n is an integer from 1 to 4; more preferably, the halogenated compound is one or more of diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

As the above C ₁ -C ₆ The alkyl groups of (a) are identical to those listed in component C.

Component D

In the present invention, the component D is conjugated diene, which mainly plays roles of stabilizing the active center of the catalyst and improving the catalytic activity.

Preferably, the conjugated diene is isoprene or butadiene.

The amounts of component A, component B, component C and component D

According to the invention, the amount of said component B may be chosen according to said component a, preferably the molar ratio of said component a to said component B, calculated as neodymium element, is 1:12-30, more preferably 1:15-30. By adopting the proportion within the above molar ratio range, the catalyst activity can be further improved.

According to the invention, the amount of component C can also be chosen according to component A, preferably the molar ratio of component A to component C, calculated as neodymium element, is 1:2-5, more preferably 1:3-3.3. By adopting the proportion in the molar ratio range, the activity and stability of the catalyst can be further improved.

According to the invention, the amount of component D can also be chosen according to component A, preferably the molar ratio of component A to component D, calculated as neodymium element, is 1:10-80, preferably 1:20-60, more preferably 1:20-50. By adopting the proportion within the above molar ratio range, the catalyst activity can be further improved.

According to a second aspect of the present invention, there is provided a solution-type catalyst obtained by mixing the components of the solution-type catalyst composition of the present invention.

According to a third aspect of the present invention, there is provided a method for producing a solution-type catalyst, characterized in that the solution-type catalyst is obtained by mixing the components of the solution-type catalyst composition of the present invention.

According to the second and third aspects of the present invention, the mode of mixing is not particularly limited, but it is preferable that the component B and the component C are mixed after the component a and the component D are mixed.

In a preferred embodiment of the invention, the mixing is carried out in the following manner: (1) Firstly, mixing the component A and the component D to obtain the component AD, wherein the mixing condition is not particularly required, and the components A and D can be fully mixed (for example, the components A and D can be mixed at room temperature); (2) Adding component B into component AD, mixing at 10-50deg.C for 10-200min to obtain component ADB; (3) Adding component C into component ADB, mixing at 40-80deg.C for 30-300min to obtain solution catalyst.

According to the invention, the above catalyst of the invention can be dissolved in an organic solvent to obtain a solution in a homogeneous state. Wherein, preferably, the solvent used in the homogeneous solution is C ₅ -C ₁₀ Alkanes, C ₅ -C ₁₀ Cycloalkanes and C ₆ -C ₁₂ Preferably one or more of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene and cumene. The amount of solvent used may vary within wide limits, and is preferably such that in the homogeneous solution the concentration of component A, calculated as neodymium element, is from 0.01 to 0.5mmol/mL, preferably from 0.01 to 0.1mmol/mL, more preferably from 0.01 to 0.02mmol/mL.

According to a fourth aspect of the present invention, there is provided a process for producing a conjugated diene polymer, which comprises: and polymerizing the conjugated diene in the presence of an organic solvent and a catalyst to obtain a conjugated diene polymer, wherein the catalyst is a solution catalyst according to the present invention or a solution catalyst prepared by the preparation method according to the third aspect of the present invention.

According to the present invention, preferably, the conjugated diene is butadiene or isoprene.

In addition, the solution-type catalyst is as described above and will not be described in detail herein.

According to the invention, the polymerization conditions include: the temperature is 0-90 ℃ and the time is 1-5h. Preferably, the polymerization conditions include: the temperature is 50-90 ℃ and the time is 1-5h.

According to the present invention, the polymerization reaction may be performed in an inert atmosphere in order to overcome the damage of the catalyst active center by oxygen. The inert atmosphere may be maintained by evacuating the reaction vessel and then introducing a gas selected from the group consisting of nitrogen, argon, helium, and the like.

According to the invention, the organic solvent may be any hydrocarbon solvent inert to the polymerization reaction, and may be, for example, C ₅ -C ₁₀ Alkanes, C ₅ -C ₁₀ Cycloalkanes and C ₆ -C ₁₂ Preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene. Wherein the amount of the organic solvent may vary within a wide range, preferably, the amount of the organic solvent is 300 to 1200 parts by weight with respect to 100 parts by weight of the conjugated diene.

According to the invention, the catalyst may be used in an amount of: neodymium to monomer molar ratio of 1.50X10 ^-5 -1.5×10 ^-4 Preferably 2.0X10 ^-5 -8.0×10 ^-5 。

According to a fifth aspect of the present invention there is provided the use of a solution catalyst according to the present invention or prepared by a method of preparation according to the third aspect of the present invention in the preparation of a conjugated diene polymer.

The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.

In the following examples and comparative examples, the cis 1, 4-polymeric structure content was determined using a Nicolet iS5 mid-IR spectrometer. The Nd consumption for producing 1kg of polyisoprene rubber (or polybutadiene rubber) was calculated as follows:

example 1

100mL of n-hexane, 48g of di (2-ethylhexyl) phosphonate and 210mL of aqueous sodium hydroxide solution with a concentration of 0.50mol/L were added to a 500mL beaker and mixed for further use. Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L and 400mL of n-hexane were charged. Heating to 50 ℃ in a water bath. Stirring was started, then the material in the beaker was added dropwise to the flask through a constant pressure funnel, the dropwise addition took 30min, and the reaction was continued for 30min after the dropwise addition was completed. The molar ratio of the di (2-ethylhexyl) phosphonate to the neodymium chloride was 5.0, and the molar ratio of the sodium hydroxide to the neodymium chloride was 3.5. After the reaction, stirring is stopped, the water phase is separated, 200ml of washing solution is added for three times, and finally, the separated organic phase is distilled to remove water to obtain a neodymium phosphonate solution with neodymium concentration of 0.1mol/L, and the water value is 83ug/g.

2.4ml of the above-mentioned neodymium phosphonate solution, 15ml of n-hexane and 1.2ml of isoprene are added into a 50ml dry glass bottle under the protection of nitrogen, then 5.8ml of triisobutylaluminum n-hexane solution with the concentration of 0.5mol/L is added at 30 ℃ for reaction for 30min, and after the reaction is carried out, 1.6ml of diethylaluminum chloride n-hexane solution with the concentration of 0.5mol/L is added at 60 ℃ for reaction for 2 hours, the catalyst is obtained. Wherein, the mole ratio of the phosphonate neodymium solution, isoprene, triisobutyl aluminum and diethyl aluminum chloride calculated by neodymium element is 1:50:12.1:3.3.

under the protection of nitrogen, 1500g of hexane and 225g of isoprene are added into a stainless steel reaction kettle with 5L scale, and after being stirred uniformly, the catalyst (the molar ratio of neodymium to monomer is 7.3X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polyisoprenes, and the monomer conversions and properties of the polyisoprenes obtained are shown in Table 1.

Example 2

The procedure of example 1 was repeated except that 5.8ml of a 0.5mol/L triisobutylaluminum n-hexane solution was added thereto in order to prepare a catalyst, and 14.0ml of a 0.5mol/L triisobutylaluminum n-hexane solution was added thereto. Wherein, the mole ratio of the phosphonate neodymium solution, isoprene, triisobutyl aluminum and diethyl aluminum chloride calculated by neodymium element is 1:50:29.2:3.3.

under the protection of nitrogen, 2000g of hexane and 360g of isoprene are added into a stainless steel reaction kettle with 5L scale, and after being stirred uniformly, the catalyst (the molar ratio of neodymium to monomer is 4.5X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polyisoprenes, and the monomer conversions and properties of the polyisoprenes obtained are shown in Table 1.

Example 3

100mL of n-hexane, 44g of di (2-ethylhexyl) phosphonate and 180mL of aqueous sodium hydroxide solution with a concentration of 0.50mol/L were added to a 500mL beaker and mixed for further use. Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L and 400mL of n-hexane were charged. Heating to 50 ℃ in a water bath. Stirring was started, then the material in the beaker was added dropwise to the flask through a constant pressure funnel, the dropwise addition took 30min, and the reaction was continued for 30min after the dropwise addition was completed. The molar ratio of the di (2-ethylhexyl) phosphonate to the neodymium chloride was 4.5, and the molar ratio of the sodium hydroxide to the neodymium chloride was 3.0. After the reaction is finished, stirring is stopped, the water phase is separated, 200ml of washing solution is added for three times, and finally, the separated organic phase is distilled to remove water to obtain the neodymium phosphonate solution with the neodymium concentration of 0.1mol/L, and the water value content is 74ug/g.

Under the protection of nitrogen, 1.8ml of the neodymium phosphonate solution and 15ml of 0.3mol/L butadiene normal hexane solution are added into a 50ml dry glass bottle to be mixed, then 5.6ml of 0.5mol/L diisobutylaluminum hydride normal hexane solution is added into the mixture at 50 ℃ to react for 30min, and after the reaction, 1.2ml of 0.5mol/L diethylaluminum chloride normal hexane solution is added into the mixture at 60 ℃, and the catalyst is obtained after the reaction for 2 hours. Wherein, the mole ratio of the neodymium phosphonate solution, butadiene, diisobutyl aluminum monohydrogen and diethyl aluminum monochloride calculated by neodymium element is 1:25:15.6:3.3.

2000g of hexane and 365g of butadiene are added into a stainless steel reaction kettle with 5L scale under the protection of nitrogen, and stirredAfter homogenization, the catalyst was added (neodymium/monomer molar ratio 3.4X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polybutadiene, and the monomer conversions and properties of the polybutadiene obtained are shown in Table 2.

Example 4

The neodymium phosphonate solution was prepared as in example 3.

Under the protection of nitrogen, 1.0ml of the solution and 8ml of 0.3mol/L butadiene normal hexane solution are added into a 50ml dry glass bottle to be mixed, then 6.0ml of 0.5mol/L diisobutyl aluminum normal hexane solution is added at 50 ℃ to react for 30min, and after the reaction, 0.6ml of 0.5mol/L diethyl aluminum normal hexane solution is added at 60 ℃, and the catalyst is obtained after the reaction for 2 h. Wherein, the mole ratio of the neodymium phosphonate solution, butadiene, diisobutyl aluminum monohydrogen and diethyl aluminum monochloride calculated by neodymium element is 1:24:30.0:3.0.

2000g of hexane and 365g of butadiene are added into a stainless steel reaction kettle with 5L scale under the protection of nitrogen, and the catalyst (the molar ratio of neodymium to monomer is 1.9X10) is added after being stirred evenly ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polybutadiene, and the monomer conversions and properties of the polybutadiene obtained are shown in Table 2.

Example 5

100mL of n-hexane, 39g of di (2-ethylhexyl) phosphonate and 170mL of aqueous sodium hydroxide solution with a concentration of 0.50mol/L were added to a 500mL beaker and mixed for further use. Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L and 400mL of n-hexane were charged. Heating to 50 ℃ in a water bath. Stirring was started, then the material in the beaker was added dropwise to the flask through a constant pressure funnel, the dropwise addition took 30min, and the reaction was continued for 30min after the dropwise addition was completed. The molar ratio of the di (2-ethylhexyl) phosphonate to the neodymium chloride was 4.0, and the molar ratio of the sodium hydroxide to the neodymium chloride was 2.8. After the reaction is finished, stirring is stopped, the water phase is separated, 200ml of washing solution is added for three times, and finally, the separated organic phase is distilled to remove water to obtain a neodymium phosphonate solution with neodymium concentration of 0.1mol/L, and the water value is 94ug/g.

2.4ml of the above-mentioned neodymium phosphonate solution, 15ml of n-hexane and 1.2ml of isoprene are added into a 50ml dry glass bottle under the protection of nitrogen, then 9.0ml of triisobutylaluminum n-hexane solution with the concentration of 0.5mol/L is added at 30 ℃ for reaction for 30min, and after the reaction is carried out, 1.6ml of diethylaluminum chloride n-hexane solution with the concentration of 0.5mol/L is added at 60 ℃ for reaction for 2 hours, the catalyst is obtained. Wherein, the mole ratio of the phosphonate neodymium solution, isoprene, triisobutyl aluminum and diethyl aluminum chloride calculated by neodymium element is 1:50:18.8:3.3.

under the protection of nitrogen, 1500g of hexane and 270g of isoprene are added into a stainless steel reaction kettle with 5L scale, and after being stirred uniformly, the catalyst (the molar ratio of neodymium to monomer is 6.0X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polyisoprenes, and the monomer conversions and properties of the polyisoprenes obtained are shown in Table 1.

Example 6

The procedure of example 5 was repeated except that 9.0ml of a 0.5mol/L triisobutylaluminum n-hexane solution was added thereto in order to prepare a catalyst, and 12.0ml of a 0.5mol/L triisobutylaluminum n-hexane solution was added thereto. Wherein, the mole ratio of the phosphonate neodymium solution, isoprene, triisobutyl aluminum and diethyl aluminum chloride calculated by neodymium element is 1:50:25.0:3.3.

under the protection of nitrogen, 1600g of hexane and 320g of isoprene are added into a stainless steel reaction kettle with 5L of scale, and after being stirred uniformly, the catalyst (the molar ratio of neodymium to monomer is 5.1X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polyisoprenes, and the monomer conversions and properties of the polyisoprenes obtained are shown in Table 1.

Example 7

100mL of n-hexane, 46g of di (2-ethylhexyl) phosphonate and 180mL of aqueous sodium hydroxide solution with a concentration of 0.50mol/L were added to a 500mL beaker and mixed for further use. Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L and 400mL of n-hexane were charged. Heating to 50 ℃ in a water bath. Stirring was started, then the material in the beaker was added dropwise to the flask through a constant pressure funnel, the dropwise addition took 30min, and the reaction was continued for 30min after the dropwise addition was completed. The molar ratio of the di (2-ethylhexyl) phosphonate to the neodymium chloride was 4.8, and the molar ratio of the sodium hydroxide to the neodymium chloride was 3.0. After the reaction, stirring is stopped, the water phase is separated, 200ml of washing solution is added for three times, and finally, the separated organic phase is distilled to remove water to obtain a neodymium phosphonate solution with neodymium concentration of 0.1mol/L, and the water value is 81ug/g.

2.4ml of the above-mentioned neodymium phosphonate solution, 15ml of n-hexane and 1.2ml of isoprene are added into a 50ml dry glass bottle under the protection of nitrogen, then 10.0ml of diisobutylaluminum hydride n-hexane solution with the concentration of 0.5mol/L is added at 30 ℃ for reaction for 30min, and after the reaction is carried out, 1.5ml of diethylaluminum chloride n-hexane solution with the concentration of 0.5mol/L is added at 60 ℃ for reaction for 2 hours, the catalyst is obtained. The molar ratio of the neodymium phosphonate solution, isoprene, diisobutylaluminum monohydrogen and diethylaluminum monochloride calculated as neodymium element is 1:50:20.8:3.1.

under the protection of nitrogen, 1500g of hexane and 360g of isoprene are added into a stainless steel reaction kettle with 5L scale, and after being stirred uniformly, the catalyst (the molar ratio of neodymium to monomer is 4.5X10) ^-5 ) Polymerization was carried out at 50℃for 5 hours to give the corresponding polyisoprenes, and the monomer conversions and properties of the polyisoprenes obtained are shown in Table 1.

Example 8

The procedure of example 7 was repeated except that 10.0ml of 0.5 mol/L-diisobutylaluminum-n-hexane solution was added in the preparation of the catalyst, and 13.0ml of 0.5 mol/L-diisobutylaluminum-n-hexane solution was added instead. Wherein, the mole ratio of the neodymium compound, isoprene, diisobutylaluminum monohydride and diethylaluminum monochloride is 1:50:27.1:3.1. the monomer conversion and the properties of polyisoprene obtained are shown in Table 1.

Comparative example 1

The conditions were the same as in example 1 except that 48g of di (2-ethylhexyl) phosphonate was added instead of 34g of di (2-ethylhexyl) phosphonate. The molar ratio of di (2-ethylhexyl) phosphonate to neodymium chloride was 3.5 and the molar ratio of sodium hydroxide to neodymium chloride was 3.5. The monomer conversion and the properties of polyisoprene obtained are shown in Table 1.

Comparative example 2

The conditions were the same as in example 1 except that 48g of di (2-ethylhexyl) phosphonate was added instead of 58g of di (2-ethylhexyl) phosphonate. The molar ratio of di (2-ethylhexyl) phosphonate to neodymium chloride was 6.0 and the molar ratio of sodium hydroxide to neodymium chloride was 3.5. The monomer conversion and the properties of polyisoprene obtained are shown in Table 1.

Comparative example 3

The same conditions as in example 1 were followed except that the addition of 210ml of the aqueous sodium hydroxide solution having a concentration of 0.50mol/L was changed to the addition of 240ml of the aqueous sodium hydroxide solution having a concentration of 0.50 mol/L. The molar ratio of di (2-ethylhexyl) phosphonate to neodymium chloride was 5.0 and the molar ratio of sodium hydroxide to neodymium chloride was 4.0. The monomer conversion and the properties of polyisoprene obtained are shown in Table 1.

TABLE 1

TABLE 2

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A solution-type catalyst composition, characterized in that the solution-type catalyst composition comprises a component A, a component B, a component C and a component D,

the component A is a neodymium phosphonate solution obtained by removing water from a reaction product of an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and a basic compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous neodymium chloride solution is 4-5: 1, wherein the molar ratio of the alkaline compound to neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5: 1, a step of;

the component B is an alkyl aluminum compound;

the component C is a halogenated compound;

the component D is conjugated diene.

2. The solution-type catalyst composition according to claim 1, wherein the content of neodymium chloride in the aqueous solution of neodymium chloride is 0.1 to 0.5mol/L;

preferably, the organic phosphonate is of the structure shown in formula (1), wherein R ^d1 、R ^d2 And R is ^d3 Each independently is hydrogen, hydroxy, C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Alkoxy, and R ^d1 、R ^d2 And R is ^d3 At least one of which is C ₁ -C ₂₀ Alkyl or C of (2) ₁ -C ₂₀ Is a group consisting of an alkoxy group,

preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 All are 2-ethylhexyl oxy groups;

preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 And R is ^d3 All are 2-ethylhexyl groups;

preferably, in formula (1), R ^d1 Is hydroxy, R ^d2 Is 2-ethylhexyl, R ^d3 Is 2-ethylhexyloxy;

preferably, the organic solvent is C ₅ -C ₁₀ Alkanes, C ₅ -C ₁₀ Cycloalkanes and C ₆ -C ₁₂ One or more of the aromatic hydrocarbons of (a);

preferably, the organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene, and cumene;

preferably, the organic solvent is used in an amount such that the volume of the organic phase and the volume of the aqueous phase are between 0.3 and 2:1, a step of;

preferably, the alkaline compound is used in the form of an aqueous solution, and the content of the alkaline compound in the aqueous solution of the alkaline compound is 0.1-5.0 mol/L;

preferably, the alkaline compound is one or more of hydroxide and ammonia water;

preferably, the water content of the neodymium phosphonate solution is less than 300ug/g.

3. The solution catalyst composition according to claim 1, wherein the molar ratio of component a and component B, calculated as neodymium element, is 1:12-30 parts;

preferably, the molar ratio of said component a to said component C, calculated as neodymium element, is 1:2-5;

preferably, the molar ratio of said component a to said component D, calculated as neodymium element, is 1:10-80, preferably 1:20-60.

4. The solution-type catalyst composition according to any one of claims 1 to 3, wherein the alkylaluminum-based compound is of formula Al (R) ₃ The compound and Al (R) ₂ One or more of the compounds shown in H, R is selected from C ₁ -C ₆ Alkyl of (a);

preferably, the alkyl aluminum compound is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monohydride and diisobutylaluminum monohydride;

preferably, the halogenated compound is of formula Al (R ¹ ) ₂ X is a compound of formula Si (R) ¹ ) _4-n X _n The compounds and formula Al ₂ (R ¹ ) ₃ X ₃ One or more of the compounds shown, each R ¹ Each independently selected from C ₁ -C ₆ Each X is independently selected from halogen, n is an integer from 1 to 4;

preferably, the halogenated compound is one or more of diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride;

preferably, the conjugated diene is isoprene or butadiene.

5. A solution catalyst obtained by mixing the components of the solution catalyst composition according to any one of claims 1 to 4.

6. A method for producing a solution catalyst, characterized in that the solution catalyst is obtained by mixing the components of the solution catalyst composition according to any one of claims 1 to 4.

7. The method of claim 6, wherein component B and component C are mixed after component a is mixed with component D.

8. A process for preparing a conjugated diene polymer, the process comprising: a step of polymerizing conjugated diene in the presence of an organic solvent and a catalyst to obtain a conjugated diene polymer, characterized in that the catalyst is the solution catalyst according to claim 5 or the solution catalyst prepared according to claim 6 or 7.

9. The method of claim 8, wherein the conjugated diene is butadiene or isoprene;

preferably, the polymerization conditions include: the temperature is 0-90 ℃ and the time is 1-5h.

10. Use of the solution catalyst according to claim 5 or the solution catalyst prepared according to claim 6 or 7 for the preparation of conjugated diene polymers.