Solution catalyst composition, solution catalyst, process for the preparation thereof and process for the preparation of conjugated diene polymers

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to a conjugated diene polymerization catalyst, in particular to a solution catalyst composition, a solution catalyst and a preparation method thereof and a conjugated diene polymer preparation method. BACKGROUND

[0002] Rare earth catalyst is a kind of catalyst with rare earth element compound as main catalyst. It is clear that for conjugated diene polymerization, neodymium is the most active element in rare earth. Rare earth catalyst system generally has two kinds of binary or ternary system. The binary catalyst system is composed of main catalyst neodymium chloride and alkylating agent. The alkylating agent can be alkyl aluminum or alkyl magnesium. The ternary catalyst system is generally composed of main catalyst rare earth salt, alkylating agent and halide.

[0003] Rare earth catalyst polymerizes conjugated diene, and the main commercial products are rare earth butadiene rubber and rare earth isoprene rubber. For industrial production, catalyst consumption is crucial to production cost, especially in the case of gradually rising price of rare earth raw materials. At present, the catalyst cost is too high, that is, the catalyst consumption is too high. Therefore, reducing catalyst consumption becomes a research hotspot. According to the public report, neodymium neodecanoate / hydrogenated diisobutyl aluminum / diethyl aluminum chloride catalyst system is used for butadiene polymerization, and the catalyst consumption (in terms of neodymium / monomer molar ratio) is generally 6-8 x 10 -5 mgNd is consumed for producing 1 kg of polybutadiene (see Synthetic Rubber Industry, 2008, 31(5): 358-361). For isoprene, the catalyst consumption increases by more than 3 times, and 420 mgNd is consumed for producing 1 kg of polyisoprene (see Synthetic Rubber Industry, 2006, 29(3): 181-185). CN1840552A discloses a rare earth carboxylate / organic aluminum / chlorinated alkane or chlorinated carboxylate / conjugated olefin or carboxylic acid catalyst. For butadiene polymerization, the catalyst consumption is generally 0.2-1.0 x 10 -3 mgNd is consumed for producing 1 kg of polybutadiene, and more than 3000 mgNd is consumed for producing 1 kg of polyisoprene. SUMMARY

[0004] The present application aims to overcome the problem of high catalyst consumption in the prior art, and provides a solution catalyst composition, a solution catalyst and a preparation method thereof and a conjugated diene polymer preparation method. The solution catalyst provided by the present application has the advantage of high activity, and can significantly reduce catalyst consumption.

[0005] To achieve the above object, the present application provides a solution catalyst composition, wherein the solution catalyst composition comprises component A, component B, component C and component D,

[0006] 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 an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-5:1, and the molar ratio of the alkaline compound to the neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5:1;

[0007] The component B is an alkyl aluminum compound;

[0008] The component C is a halogenated compound;

[0009] The component D is a conjugated diene.

[0010] Preferably, the content of the neodymium chloride in the neodymium chloride aqueous solution is 0.1-0.5 mol / L.

[0011] Preferably, the organic phosphonate is a structure represented by formula (1), wherein R d1 , R d2 and R d3 are each independently hydrogen, hydroxyl, C1-C 20 alkyl or C1-C 20 alkoxy, and at least one of R d1 , R d2 and R d3 is C1-C 20 alkyl or C1-C 20 alkoxy,

[0012]

[0013] Preferably, in formula (1), R d1 is hydroxyl, R d2 and R d3 are each 2-ethylhexyloxy.

[0014] Preferably, in formula (1), R d1 is hydroxyl, R d2 and R d3 are each 2-ethylhexyl.

[0015] Preferably, in formula (1), R d1 is hydroxyl, R d2 is 2-ethylhexyl, and R d3 is 2-ethylhexyloxy.

[0016] Preferably, the organic solvent is C5-C10 alkanes, C5-C 10 cycloalkanes and C6-C 12 aromatic hydrocarbons.

[0017] Preferably, the organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene.

[0018] Preferably, the organic solvent is used in an amount such that the volume of the organic phase to the volume of the aqueous phase is 0.3 to 2:1.

[0019] Preferably, the basic compound is used in the form of an aqueous solution, and the content of the basic compound in the aqueous solution of the basic compound is 0.1 to 5.0 mol / L.

[0020] Preferably, the basic compound is one or more of hydroxides and aqueous ammonia.

[0021] Preferably, the content of water in the neodymium phosphonate solution is less than 300 ug / g.

[0022] Preferably, the molar ratio of the component A to the component B, in terms of neodymium element, is 1:12-30.

[0023] Preferably, the molar ratio of the component A to the component C, in terms of neodymium element, is 1:2-5.

[0024] Preferably, the molar ratio of the component A to the component D, in terms of neodymium element, is 1:10-80, preferably 1:20-60.

[0025] Preferably, the aluminum alkyl compound is one or more of compounds represented by the formula Al(R)3 and compounds represented by the formula Al(R)2H, R being selected from C1-C6 alkyl groups.

[0026] Preferably, the aluminum alkyl compound is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum hydride and diisobutylaluminum hydride.

[0027] Preferably, the halogenated compound is one or more of compounds represented by the formula Al(R 1 )2X, compounds represented by the formula Si(R 1 ) 4-n X n and compounds represented by the formula Al2(R 1 )3X3, each R 1 is independently selected from C1-C6 alkyl groups, benzyl groups and allyl groups, each X is independently selected from halogens, and n is an integer of 1-4.

[0028] Preferably, the halogenated compound is one or more of diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

[0029] Preferably, the conjugated diene is isoprene or butadiene.

[0030] According to a second aspect of the present application, a solution catalyst is provided, which is obtained by mixing the components of the solution catalyst composition of the present application.

[0031] According to a third aspect of the present application, a method for preparing a solution catalyst is provided, wherein the solution catalyst is obtained by mixing the components of the solution catalyst composition of the present application.

[0032] Preferably, the component A is mixed with the component D first, and then the component B and the component C are mixed.

[0033] According to a fourth aspect of the present application, a method for preparing a conjugated diene polymer is provided, which comprises the step of polymerizing a conjugated diene in the presence of an organic solvent and a catalyst to obtain a conjugated diene polymer, wherein the catalyst is the solution catalyst of the present application or the solution catalyst prepared by the method of the third aspect of the present application.

[0034] Preferably, the conjugated diene is butadiene or isoprene.

[0035] Preferably, the conditions of the polymerization reaction include a temperature of 0-90℃ and a time of 1-5h.

[0036] According to a fifth aspect of the present application, the solution catalyst of the present application or the solution catalyst prepared by the method of the third aspect of the present application is used in the preparation of a conjugated diene polymer.

[0037] The rare earth catalyst provided by the present application has the advantage of high activity. When it is used in the polymerization of butadiene, the catalyst consumption for producing 1kg of polybutadiene is less than or equal to 90mg of Nd, and can be as low as 50mg of Nd or less. When it is used in the polymerization of isoprene, the catalyst consumption for producing 1kg of polyisoprene is less than or equal to 160mg of Nd, and can be as low as 100mg of Nd or less. DETAILED DESCRIPTION

[0038] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values from the lower value to the upper value, inclusive of both values, and to sub-ranges falling within the specified range. In this context, individual points within a range should be considered as being included within that range, and individual points included in a range should be considered as being included in the range defined by that individual point and the upper or lower endpoint of the range.

[0039] According to a first aspect of the present invention, there is provided a solution catalyst composition, wherein the solution catalyst composition comprises component A, component B, component C and component D,

[0040] 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 an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-5:1, and the molar ratio of the alkaline compound to the neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5:1.

[0041] The component B is an alkyl aluminum compound;

[0042] The component C is a halogenated compound;

[0043] The component D is a conjugated diene.

[0044] The components A, B, C and D will be described below respectively.

[0045] Component A

[0046] In the present invention, 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 an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-5:1, and the molar ratio of the alkaline compound to the neodymium chloride in the neodymium chloride aqueous solution is 2.8-3.5:1.

[0047] According to the present invention, the neodymium chloride aqueous solution can be obtained by reacting neodymium oxide with hydrochloric acid, or by dissolving anhydrous neodymium chloride or neodymium chloride containing crystal water in water. The concentration of the neodymium chloride is not particularly limited, as long as the neodymium chloride is completely dissolved. For example, the concentration of the neodymium chloride aqueous solution can be 0.1-0.5 mol / L.

[0048] As a specific example of the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous neodymium chloride solution according to the present application, 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 can be given.

[0049] According to the present application, preferably, the organic phosphonate is a structure represented by formula (1) wherein R d1 , R d2 , and R d3 are each independently hydrogen, a hydroxyl group, a C1-C 20 alkyl group, or a C1-C 20 alkoxy group, and at least one of R d1 , R d2 , and R d3 is a C1-C 20 alkyl group or a C1-C 20 alkoxy group; preferably, R d1 , R d2 , and R d3 are each independently a hydroxyl group, a C4-C 12 alkyl group, or a C4-C 12 alkoxy group, and at least one of R d1 , R d2 , and R d3 is a C4-C 12 alkyl group or a C4-C 12 alkoxy group; more preferably, R d1 is a hydroxyl group, at least one of R d2 and R d3 is an alkyl group or an alkoxy group, and R d2 and R d3 are each independently selected from the group consisting of n-butyl, i-butyl, s-butyl, t-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, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, and n-dodecoxy.

[0050]

[0051] As a specific example of the organic phosphonate, for example, one or more of the compounds represented by the following formulae can be selected:

[0052] In formula (1), R d1 is a hydroxyl group, at least one of R d2 and Rd3 each is 2-ethylhexyloxy (i.e., di(2-ethylhexyl)phosphonate) ;

[0053] In formula (1), R d1 is hydroxy, R d2 is 2-ethylhexyl, and R d3 is 2-ethylhexyloxy (i.e., (2-ethylhexyl)phosphonate mono-2-ethylhexyl ester).

[0054] In formula (1), R d1 is hydroxy, R d2 is 2-ethylhexyl, and R d3 is 2-ethylhexyloxy (i.e., (2-ethylhexyl)phosphonate mono-2-ethylhexyl ester).

[0055] According to the present application, the organic phosphonate compound can be obtained in a manner conventional in the art, for example, can be a commercially available product, or can be produced by a method conventional in the art, and the present application is not particularly limited in this regard.

[0056] According to the present application, the organic solvent is a compound capable of dissolving the organic phosphonate neodymium, for example, can be one or more of C5-C 10 alkanes, C5-C 10 cycloalkanes, and C6-C 12 aromatic hydrocarbons, preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene, and cumene.

[0057] The amount of the organic solvent is not particularly limited, and preferably the amount of the organic solvent is such that the concentration of the phosphonate neodymium solution is not higher than 0.5 mol / L (in terms of neodymium element). Further, preferably the amount of the organic solvent is such that the volume of the organic phase to the volume of the aqueous phase is 0.3 to 2: 1, more preferably 0.5 to 1: 1.

[0058] According to the present application, the contacting can be mixing the aqueous neodymium chloride solution, the organic phosphonate, the organic solvent, and the basic compound together, or can be mixing two or more of them together and then mixing the mixture with the other components. In order to obtain a phosphonate neodymium solution having a lower viscosity and a lower impurity content, preferably the contacting includes: first contacting the aqueous neodymium chloride solution with the organic phosphonate and the organic solvent, and then second contacting the first contact product with the basic compound.

[0059] In the present application, the first contacting is for sufficiently dissolving the reaction raw materials, and preferably the temperature of the first contacting is, for example, 5 to 80°C, and from the viewpoint of energy saving, the first contacting is preferably performed at 10 to 50°C. Further, the time of the first contacting is not particularly limited, and can be only a time sufficient to well dissolve the reaction raw materials, and is, for example, 1 minute or more, preferably 1 to 5 minutes.

[0060] According to the present application, the molar ratio of the basic compound to neodymium chloride in the aqueous neodymium chloride solution is 2.8-3.5:1. As specific examples of the molar ratio of the basic compound to neodymium chloride in the aqueous neodymium chloride solution, there can be mentioned 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.

[0061] According to the present application, the basic compound is a substance having a pH value of more than 7 as it is or after being formulated into an aqueous solution, and is preferably one or more of hydroxides and aqueous ammonia, and 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 for use. The concentration of the aqueous solution is not particularly limited, provided that it is sufficiently dissolved, and can be, for example, 0.1-5.0 mol / L.

[0062] Preferably, the basic substance aqueous solution is added in a dropwise manner, and the dropwise addition rate can be 2.0-20.0 mL / min, preferably 5.0-10.0 mL / min. If the dropwise addition rate is too slow, the production efficiency is too low, and if the dropwise addition rate is too fast, the product is generated at a high rate, which is not favorable for the final separation of the oil and water phases and the separation of impurities.

[0063] According to the present application, preferably, the second contact temperature is 30-80°C, more preferably 30-55°C, more preferably 45-55°C, and particularly preferably at 50°C. By performing the reaction at 50°C, both the reaction rate and energy saving can be taken into account.

[0064] Further, as the time for the second contact, it is only required to ensure that the reaction proceeds sufficiently, and can be, for example, 1 hour or more, preferably 1-6 hours, and more preferably 1-2 hours.

[0065] According to the present application, the water removal operation is not particularly limited, and can be a publicly known method such as distillation, rectification, physical adsorption, drying into a solid and then redissolving, provided that the water content in the neodymium phosphonate solution is less than 300 ug / g, preferably less than 200 ug / g, and more preferably less than 100 ug / g.

[0066] Component B

[0067] In the present application, the component B is an alkylaluminum-based compound.

[0068] Preferably, the aluminum alkyl compound is one or more of a compound represented by the formula Al(R)3 and a compound represented by the formula Al(R)2H, R is selected from C1-C6 alkyl; more preferably, the aluminum alkyl compound is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum hydride and diisobutylaluminum hydride.

[0069] As the C1-C6 alkyl group, for example, there can be mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl and the like.

[0070] Component C

[0071] In the present application, the component C is a halogenated compound.

[0072] Preferably, the halogenated compound is one or more of a compound represented by the formula Al(R 1 )2X, a compound represented by the formula Si(R 1 ) 4-n X n a compound represented by the formula Al2(R 1 )3X3, each R 1 is independently selected from C1-C6 alkyl, benzyl and allyl, each X is independently selected from halogen, and n is an integer of 1 to 4; more preferably, the halogenated compound is one or more of diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

[0073] As the C1-C6 alkyl group, the same as recited in the component C.

[0074] Component D

[0075] In the present application, the component D is a conjugated diene which mainly functions to stabilize the active catalyst center and to improve the catalytic activity.

[0076] Preferably, the conjugated diene is isoprene or butadiene.

[0077] Amount of Component A, Component B, Component C and Component D

[0078] According to the present application, the amount of the component B can be selected in accordance with the component A, preferably, the molar ratio of the component A to the component B, based on the neodymium element, is 1:12-30, more preferably 1:15-30. By using the above molar ratio range, the catalytic activity can be further improved.

[0079] According to the present application, the amount of component C can also be selected according to component A, preferably the molar ratio of component A to component C, based on the neodymium element, is 1 : 2-5, more preferably 1 : 3-3.3. By using the above molar ratio range, the catalyst activity and stability can be further improved.

[0080] According to the present application, the amount of component D can also be selected according to component A, preferably the molar ratio of component A to component D, based on the neodymium element, is 1 : 10-80, preferably 1 : 20-60, more preferably 1 : 20-50. By using the above molar ratio range, the catalyst activity can be further improved.

[0081] According to the second aspect of the present application, a solution catalyst is provided, which is obtained by mixing the components of the solution catalyst composition according to the present application.

[0082] According to the third aspect of the present application, a method for preparing a solution catalyst is provided, wherein the solution catalyst is obtained by mixing the components of the solution catalyst composition according to the present application.

[0083] According to the second and third aspects of the present application, the mixing method is not particularly limited, but it is preferred that component A is first mixed with component D, and then component B and component C are mixed.

[0084] In a preferred embodiment of the present application, the mixing is carried out in the following manner: (1) component A and component D are first mixed to obtain component AD, and the mixing conditions are not particularly limited, as long as sufficient mixing is achieved (for example, mixing can be carried out at room temperature); (2) component B is added to component AD, and mixed at 10-50°C for 10-200 min to obtain component ADB; (3) component C is added to component ADB, and mixed at 40-80°C for 30-300 min to obtain the solution catalyst.

[0085] According to the present application, the above catalyst of the present application can be dissolved in an organic solvent to obtain a homogeneous solution. Preferably, the solvent used in the homogeneous solution is a C5-C 10 alkane, C5-C 10 cycloalkane and C6-C 12one or more of alkanes, C5-C8 cycloalkanes, C6-C8 aromatic hydrocarbons, and C6-C8 alicyclic hydrocarbons, preferably one or more of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, and cumene. The amount of the solvent can vary within a wide range, and preferably, the amount of the solvent in the homogeneous solution is such that the concentration of the component A in terms of neodymium element is 0.01-0.5 mmol / mL, preferably 0.01-0.1 mmol / mL, and more preferably 0.01-0.02 mmol / mL.

[0086] According to a fourth aspect of the present application, there is provided a method for preparing a conjugated diene polymer, the method comprising the step of polymerizing a 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-type catalyst according to the present application or the solution-type catalyst prepared by the method according to the third aspect of the present application.

[0087] According to the present application, preferably, the conjugated diene is butadiene or isoprene.

[0088] Further, the solution-type catalyst is as described above, which will not be repeated here.

[0089] According to the present application, the conditions of the polymerization reaction include a temperature of 0-90°C and a time of 1-5 h. Preferably, the conditions of the polymerization reaction include a temperature of 50-90°C and a time of 1-5 h.

[0090] According to the present application, in order to overcome the damage of oxygen to the active centers of the catalyst, the polymerization reaction can be carried out in an inert atmosphere. The method for maintaining the inert atmosphere can be to vacuumize the reaction vessel and then introduce a gas selected from nitrogen, argon, helium, and the like.

[0091] According to the present application, the organic solvent can be any hydrocarbon solvent that is inert to the polymerization reaction, and the organic solvent can be, for example, C5-C 10 alkanes, C5-C 10 cycloalkanes, and C6-C 12 one or more of alkanes, C5-C8 cycloalkanes, C6-C8 aromatic hydrocarbons, and C6-C8 alicyclic hydrocarbons, preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene, and cumene. The amount of the organic solvent can vary within a wide range, and preferably, the amount of the organic solvent is 300-1200 parts by weight with respect to 100 parts by weight of the conjugated diene.

[0092] According to the present application, the amount of the catalyst can be such that the molar ratio of neodymium to monomer is 1.50 x 10 -5 -1.5 x 10 -4 , preferably 2.0 x 10 -5 -8.0 x 10 -5 .

[0093] According to a fifth aspect of the present application, there is provided a use of the solution catalyst according to the present application or the solution catalyst prepared by the method according to the third aspect of the present application in the preparation of a conjugated diene polymer.

[0094] The present application will be described in detail below by way of examples, but the present application is not limited to the following examples.

[0095] In the following examples and comparative examples, the cis-1,4-polymerization structure content is determined by a Nicolet iS5 infrared spectrometer. The Nd consumed in the production of 1 kg of polyisoprene rubber (or polybutadiene rubber) is calculated according to the following method:

[0096]

[0097] Example 1

[0098] In a 500 mL beaker, 100 ml of n-hexane, 48 g of di(2-ethylhexyl) phosphonate and 210 ml of a 0.50 mol / L sodium hydroxide aqueous solution were mixed and reserved. In a 1000 mL three-necked flask, 120 mL of a 0.25 mol / L neodymium chloride aqueous solution and 400 ml of n-hexane were added. The mixture was heated to 50°C in a water bath. The stirring was started, and then the mixture in the beaker was added dropwise to the flask through a constant-pressure funnel. The dropwise addition took 30 min, and after the dropwise addition was completed, the reaction was continued for 30 min. 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 3.5. After the reaction was completed, the stirring was stopped, and the aqueous phase was separated. Then, 200 ml of n-hexane was added for washing three times. Finally, the separated organic phase was distilled to remove water, and a phosphonate neodymium solution with a neodymium concentration of 0.1 mol / L was obtained. The water value was 83 ug / g.

[0099] Under nitrogen protection, 2.4 ml of the above phosphonate neodymium solution, 15 ml of n-hexane and 1.2 ml of isoprene were mixed in a 50 ml dry glass bottle, and then 5.8 ml of a 0.5 mol / L triisobutylaluminum n-hexane solution was added at 30°C. After 30 min of reaction, 1.6 ml of a 0.5 mol / L diethylaluminum monochloride n-hexane solution was added at 60°C. After 2 hours of reaction, the catalyst was obtained. The molar ratio of the phosphonate neodymium solution, isoprene, triisobutylaluminum and diethylaluminum monochloride, in terms of neodymium element, was 1:50:12.1:3.3.

[0100] Under nitrogen protection, 1500 g of hexane and 225 g of isoprene were added to a 5 L stainless steel reaction kettle, and after stirring uniformly, the above catalyst (the molar ratio of neodymium to monomer was 7.3 x 10 -5), and polymerized at 50°C for 5h to obtain the corresponding polyisoprene. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0101] Example 2

[0102] Except that 5.8ml of triisobutylaluminum n-hexane solution with a concentration of 0.5mol / L was added instead of 14.0ml of triisobutylaluminum n-hexane solution with a concentration of 0.5mol / L when the catalyst was prepared, other conditions were the same as in Example 1. The molar ratio of the phosphonate neodymium solution, isoprene, triisobutylaluminum and diethylaluminum chloride, calculated based on the neodymium element, was 1:50:29.2:3.3.

[0103] Under the protection of nitrogen, 2000g of hexane and 360g of isoprene were added into a 5L stainless steel reactor, and after being stirred uniformly, the above-mentioned catalyst (the molar ratio of neodymium to monomer was 4.5x10 -5 ), and polymerized at 50°C for 5h to obtain the corresponding polyisoprene. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0104] Example 3

[0105] In a 500ml beaker, 100ml of n-hexane, 44g of di(2-ethylhexyl)phosphonate and 180ml of sodium hydroxide aqueous solution with a concentration of 0.50mol / L were added, and after being mixed, they were used as prepared. In a 1000ml three-necked flask, 120ml of neodymium chloride aqueous solution with a concentration of 0.25mol / L and 400ml of n-hexane were added. The mixture was heated to 50°C in a water bath. After stirring was started, the contents of the beaker were added dropwise to the flask through a constant-pressure funnel, and the dropping took 30min. After the dropping was completed, the reaction was continued for 30min. The molar ratio of di(2-ethylhexyl)phosphonate to neodymium chloride was 4.5, and the molar ratio of sodium hydroxide to neodymium chloride was 3.0. After the reaction was completed, stirring was stopped, the aqueous phase was separated, and then 200ml of washing liquid was added for three times. Finally, the separated organic phase was dehydrated by distillation to obtain a phosphonate neodymium solution with a neodymium concentration of 0.1mol / L, and the water content was 74ug / g.

[0106] Under the protection of nitrogen, in a 50ml dry glass bottle, 1.8ml of the above-mentioned phosphonate neodymium solution, 15ml of butadiene n-hexane solution with a concentration of 0.3mol / L were mixed, and then 5.6ml of monohydric diisobutylaluminum n-hexane solution with a concentration of 0.5mol / L was added at 50°C. After 30min of reaction, 1.2ml of diethylaluminum chloride n-hexane solution with a concentration of 0.5mol / L was added at 60°C. After 2h of reaction, the catalyst was obtained. The molar ratio of the phosphonate neodymium solution, butadiene, monohydric diisobutylaluminum and diethylaluminum chloride, calculated based on the neodymium element, was 1:25:15.6:3.3.

[0107] Under nitrogen protection, 2000 g of hexane and 365 g of butadiene were added to a 5 L stainless steel reactor, stirred evenly, and then the above catalyst (neodymium / monomer molar ratio was 3.4 × 10 -5 ), and the polymerization reaction was carried out at 50°C for 5h to obtain the corresponding polybutadiene. The monomer conversion rate and the properties of the polybutadiene are shown in Table 2.

[0108] Example 4

[0109] The preparation of neodymium phosphonate solution is the same as that in Example 3.

[0110] Under nitrogen protection, in a 50-ml dry glass bottle, 1.0 ml of the above solution and 8 ml of a 0.3 mol / L butadiene n-hexane solution were added and mixed. Then, 6.0 ml of a 0.5 mol / L diisobutylaluminum monohydrogen n-hexane solution was added at 50°C. After reacting for 30 minutes, 0.6 ml of a 0.5 mol / L diethylaluminum monochloride n-hexane solution was added at 60°C. After reacting for 2 hours, a catalyst was obtained. The molar ratio of the neodymium phosphonate solution, butadiene, diisobutylaluminum monohydrogen, and diethylaluminum monochloride, calculated as neodymium element, was 1:24:30.0:3.0.

[0111] Under nitrogen protection, 2000 g of hexane and 365 g of butadiene were added to a 5 L stainless steel reactor, stirred evenly, and then the above catalyst (neodymium / monomer molar ratio was 1.9 × 10 -5 ), and the polymerization reaction was carried out at 50°C for 5h to obtain the corresponding polybutadiene. The monomer conversion rate and the properties of the polybutadiene are shown in Table 2.

[0112] Example 5

[0113] To a 500mL beaker, add 100mL of n-hexane, 39g of di(2-ethylhexyl)phosphonate, and 170mL of a 0.50mol / L sodium hydroxide aqueous solution, mix, and set aside. To a 1000mL three-necked flask, add 120mL of a 0.25mol / L neodymium chloride aqueous solution and 400mL of n-hexane. Heat to 50°C in a water bath. Stirring is initiated, and the contents of the beaker are then added dropwise to the flask via a constant pressure funnel. The addition takes 30 minutes, and the reaction is continued for 30 minutes after the addition is complete. The molar ratio of di(2-ethylhexyl)phosphonate to neodymium chloride is 4.0, and the molar ratio of sodium hydroxide to neodymium chloride is 2.8. After the reaction is complete, stirring is stopped, the aqueous phase is separated, and then 200mL of water is added and washed three times. The separated organic phase is then distilled to remove water, yielding a phosphonate neodymium solution with a neodymium concentration of 0.1mol / L and a water content of 94ug / g.

[0114] In a 50ml dry glass bottle, 2.4ml of the above neodymium phosphonate solution, 15ml of n-hexane and 1.2ml of isoprene were mixed under nitrogen protection, then 9.0ml of triisobutylaluminum n-hexane solution with a concentration of 0.5mol / L was added at 30°C, and after 30min of reaction, 1.6ml of monochlorodiethylaluminum n-hexane solution with a concentration of 0.5mol / L was added at 60°C, and after 2h of reaction, the catalyst was obtained. The molar ratio of the neodymium phosphonate solution, isoprene, triisobutylaluminum and monochlorodiethylaluminum, calculated based on the neodymium element, was 1:50:18.8:3.3.

[0115] Under nitrogen protection, 1500g of hexane and 270g of isoprene were added to a 5L stainless steel reaction kettle, stirred uniformly, and then the above catalyst (neodymium / monomer molar ratio of 6.0x10 -5 ) was added, and the polymerization reaction was carried out at 50°C for 5h to obtain the corresponding polyisoprene. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0116] Example 6

[0117] Except that 9.0ml of triisobutylaluminum n-hexane solution with a concentration of 0.5mol / L was added instead of 12.0ml of triisobutylaluminum n-hexane solution with a concentration of 0.5mol / L when the catalyst was prepared, the other conditions were the same as in Example 5. The molar ratio of the neodymium phosphonate solution, isoprene, triisobutylaluminum and monochlorodiethylaluminum, calculated based on the neodymium element, was 1:50:25.0:3.3.

[0118] Under nitrogen protection, 1600g of hexane and 320g of isoprene were added to a 5L stainless steel reaction kettle, stirred uniformly, and then the above catalyst (neodymium / monomer molar ratio of 5.1x10 -5 ) was added, and the polymerization reaction was carried out at 50°C for 5h to obtain the corresponding polyisoprene. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0119] Example 7

[0120] In a 500 mL beaker, 100 mL of n-hexane, 46 g of di(2-ethylhexyl)phosphonate and 180 mL of 0.50 mol / L aqueous sodium hydroxide solution were mixed and used as prepared. In a 1000 mL three-necked flask, 120 mL of 0.25 mol / L neodymium chloride aqueous solution and 400 mL of n-hexane were added. The mixture was heated to 50°C in a water bath. The stirring was started and the mixture in the beaker was added dropwise to the flask through a constant pressure funnel. The dropping took 30 min and the reaction was continued for another 30 min after the dropping was completed. The molar ratio of di(2-ethylhexyl)phosphonate to neodymium chloride was 4.8 and the molar ratio of sodium hydroxide to neodymium chloride was 3.0. After the reaction was completed, the stirring was stopped and the aqueous phase was separated. Then 200 mL of n-hexane was added and the separation was repeated three times. Finally, the organic phase was distilled to remove water and a 0.1 mol / L neodymium phosphonate solution was obtained. The water content was 81 ug / g.

[0121] In a 50 mL dry glass bottle, 2.4 mL of the above neodymium phosphonate solution, 15 mL of n-hexane and 1.2 mL of isoprene were mixed under nitrogen protection. Then 10.0 mL of 0.5 mol / L monohydrogen diisobutylaluminum n-hexane solution was added at 30°C. After 30 min of reaction, 1.5 mL of 0.5 mol / L monochlorodiethylaluminum n-hexane solution was added at 60°C. After 2 hours of reaction, the catalyst was obtained. The molar ratio of neodymium phosphonate solution, isoprene, monohydrogen diisobutylaluminum and monochlorodiethylaluminum was 1:50:20.8:3.1 in terms of neodymium element.

[0122] Under nitrogen protection, 1500 g of n-hexane and 360 g of isoprene were added to a 5 L stainless steel reactor. After stirring, the above catalyst (the molar ratio of neodymium to monomer was 4.5 x 10 -5 ) was added. The polymerization reaction was carried out at 50°C for 5 h to obtain the corresponding polyisoprene. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0123] Example 8

[0124] Except that 10.0 mL of 0.5 mol / L monohydrogen diisobutylaluminum n-hexane solution was replaced by 13.0 mL of 0.5 mol / L monohydrogen diisobutylaluminum n-hexane solution when the catalyst was prepared, the other conditions were the same as in Example 7. The molar ratio of neodymium compound, isoprene, monohydrogen diisobutylaluminum and monochlorodiethylaluminum was 1:50:27.1:3.1. The monomer conversion and the properties of the polyisoprene are shown in Table 1.

[0125] Comparative Example 1

[0126] Example 1 except that 48 g of di(2-ethylhexyl)phosphonate was changed to 34 g 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 properties of the polyisoprene obtained are shown in Table 1.

[0127] Comparative Example 2

[0128] Example 1 except that 48 g of di(2-ethylhexyl)phosphonate was changed to 58 g 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 properties of the polyisoprene obtained are shown in Table 1.

[0129] Comparative Example 3

[0130] Example 1 except that 210 ml of an aqueous sodium hydroxide solution having a concentration of 0.50 mol / L was changed to 240 ml of an 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 properties of the polyisoprene obtained are shown in Table 1.

[0131] Table 1

[0132]

[0133] Table 2

[0134]

[0135] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications of the technical solutions of the present application can be made, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A solution-type catalyst composition, characterized in that: The solution-type catalyst composition comprises component A, component B, component C and component D, The component A is a phosphonate neodymium solution obtained by removing water from a reaction product of an aqueous solution of neodymium chloride, an organic phosphonate, an organic solvent, and an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous solution of neodymium chloride is 4 to 5:1, and the molar ratio of the alkaline compound to the neodymium chloride in the aqueous solution of neodymium chloride is 2.8 to 3.5:1; The component B is an alkyl aluminum compound; The component C is a halogenated compound; The component D is a conjugated diene.

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

3. The solution-type catalyst composition according to claim 1, wherein The organic phosphonate has a structure shown in formula (1), wherein R d1 、R d2 and R d3 Each independently is hydrogen, hydroxyl, C1-C 20 Alkyl or C1-C 20 Alkoxy, and R d1 、R d2 and R d3 At least one of them is C1-C 20 Alkyl or C1-C 20 Alkoxy, Formula (1).

4. The solution-type catalyst composition according to claim 3, wherein In formula (1), R d1 is hydroxyl group, R d2 and R d3 All are 2-ethylhexyloxy; Or, in formula (1), R d1 is hydroxyl group, R d2 and R d3 All are 2-ethylhexyl; Or, in formula (1), R d1 is hydroxyl group, R d2 is 2-ethylhexyl, R d3 It is 2-ethylhexyloxy.

5. The solution-type catalyst composition according to claim 1, wherein The organic solvent is C5-C 10 Alkanes, C5-C 10 Cycloalkanes and C6-C 12 One or more aromatic hydrocarbons.

6. The solution-type catalyst composition according to claim 5, wherein The organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene.

7. The solution-type catalyst composition according to claim 1, wherein The amount of the organic solvent used is such that the volume ratio of the organic phase to the aqueous phase is 0.3-2:

1.

8. The solution-type catalyst composition according to claim 1, wherein The alkaline compound is used in the form of an aqueous solution, and the content of the alkaline compound in the aqueous solution is 0.1-5.0 mol / L.

9. The solution-type catalyst composition according to claim 8, wherein The alkaline compound is one or more of hydroxide and ammonia water.

10. The solution-type catalyst composition according to claim 1, wherein The water content in the neodymium phosphonate solution is less than 300 ug / g.

11. The solution-type catalyst composition according to claim 1, wherein The molar ratio of the component A to the component B calculated based on the neodymium element is 1:12-30.

12. The solution-type catalyst composition according to claim 1, wherein The molar ratio of the component A to the component C calculated based on the neodymium element is 1:2-5.

13. The solution-type catalyst composition according to claim 1, wherein The molar ratio of the component A to the component D calculated based on the neodymium element is 1:10-80.

14. The solution-type catalyst composition according to claim 13, wherein The molar ratio of the component A to the component D calculated based on the neodymium element is 1:20-60.

15. The solution-type catalyst composition according to any one of claims 1 to 14, wherein: The alkyl aluminum compound is one or more compounds represented by the formula Al(R)3 and Al(R)2H, and R is selected from a C1-C6 alkyl group.

16. The solution-type catalyst composition according to claim 15, wherein The alkyl aluminum compound is one or more of triethyl aluminum, triisobutyl aluminum, diethyl aluminum monohydrogen and diisobutyl aluminum monohydrogen.

17. The solution-type catalyst composition according to any one of claims 1 to 14, wherein: The halogenated compound is of the formula Al(R 1 )2X represented by the compound of formula Si(R 1 ) 4-n X n The compound shown and the formula Al2(R 1 ) One or more compounds represented by 3X3, each R 1 Each X is independently selected from C1-C6 alkyl, benzyl and allyl, each X is independently selected from halogen, and n is an integer of 1-4.

18. The solution-type catalyst composition according to claim 17, wherein The halogenated compound is one or more of diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

19. The solution-type catalyst composition according to any one of claims 1 to 14, wherein: The conjugated diene is isoprene or butadiene.

20. A solution-type catalyst, characterized in that: The catalyst composition is obtained by mixing the components of the solution-type catalyst composition according to any one of claims 1 to 19.

21. A method for preparing a solution-type catalyst, characterized in that: The solution-type catalyst is obtained by mixing the components of the solution-type catalyst composition according to any one of claims 1 to 19.

22. The method according to claim 21, wherein First, the component A and the component D are mixed, and then the component B and the component C are mixed.

23. A method for preparing a conjugated diene polymer, the method comprising: The step of polymerizing a conjugated diene in the presence of an organic solvent and a catalyst to obtain a conjugated diene polymer is characterized in that the catalyst is the solution-type catalyst according to claim 20 or the solution-type catalyst prepared according to claim 21 or 22.

24. The method according to claim 23, wherein The conjugated diene is butadiene or isoprene.

25. The method according to claim 23, wherein The polymerization reaction conditions include: temperature of 0-90° C. and time of 1-5 h.

26. Use of the solution-type catalyst according to claim 20 or the solution-type catalyst prepared according to claim 21 or 22 in the preparation of conjugated diene polymers.

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