KR100729433B1 - Highly soluble and monomeric nickel carboxylate and polymerization of conjugated dienes using it as catalyst - Google Patents

Abstract

A monomeric nickel carboxylate is provided to have high activity and solubility. And a diene polymerizing catalyst comprising the same is provided to have narrow molecular weight distribution, low solution viscosity and more than 94% of a cis content without gel formation. The nickel carboxylate compound is represented by the formula(1) of NiA2X2, wherein A is C8-20 carboxylate, and X is H2O or C1-20 alkyl alcohol. The diene polymerizing catalyst comprising a fluorine complex compound such as a complex compound of HF or BF3 and an organometallic compound includes the nickel carboxylate compound of the formula(1). In the catalyst, the organometallic compound is at least one selected from the group consisting of an alkyl aluminum represented by the formula(2) of AI(R^2)3, an alkyl magnesium represented by the formula(3) of Mg(R^2)2, and an alkyl lithium represented by the formula(4) of LiR^2, wherein the R^2 is H, C1-10 alkyl, C1-10 alkoxy, C5-10 cycloalkyl, aryl and C5-15 aryl alkyl.

Description

Highly Soluble and Monomeric Nickel Carboxylate and Polymerization of Conjugated Dienes Using it as Catalyst}

1 shows mass spectrometry data of Ni (C ₇ H ₁₅ COO) _2. (H ₂ O) ₂ prepared in Example 1 of the present invention.

2 shows infrared spectroscopy data of Ni (C ₇ H ₁₅ COO) _2. (H ₂ O) ₂ prepared in Example 1 of the present invention.

Figure 3 shows the mass spectrometry data of the multimeric nickel naphthenate prepared in Comparative Example 1.

Figure 4 shows the infrared spectroscopy data of the multimeric nickel naphthenate prepared in Comparative Example 1.

Figure 5 shows the mass spectrometry data of the multimeric nickel octoate prepared in Comparative Example 2.

FIG. 6 shows infrared spectroscopy data of multimer nickel octoate prepared in Comparative Example 2.

The present invention relates to a nickel carboxylate having a high solubility and a catalyst for diene polymerization using the same, more particularly, to prepare a single molecule nickel carboxylate compound by ligand exchange in a non-aqueous solution, the nickel carboxylate compound When the diene polymerization is carried out using a catalyst containing a halogen compound and an organometallic compound in a certain ratio, the activity of nickel can be increased, the content of 1,4-cis is 94% or more, The present invention relates to a catalyst for diene polymerization that can be easily used as a polystyrene modifier such as tires, golf balls, industrial rubber articles, as well as high-impact polystyrene (HIPS).

The method for preparing the nickel carboxylate compound generally occurs by reacting an alkali metal carboxylate salt with an aqueous nickel chloride solution in an aqueous solution or an alcohol solution [US Pat. No. 4,424,482; Mehrotra, RC; Bohra, R. "Metal Carboxylates" Academic Press, 1983]. Due to the reaction under these conditions, nickel carboxylate is mainly produced in oligomeric form. When these compounds are used for butadiene or isoprene polymerization, they cause gel formation and yield deterioration and have low activity. Kinds of nickel salts, especially nitrates, chlorides and sulphates, are difficult to remove when contained in the product [ Macromolecules 2002 , 35 , 4875-9].

 Conventionally, a method for producing a polybutadiene having a high 1,4-cis using nickel carboxylate is made of, for example, (1) a nickel carboxylate compound, (2) a fluorine compound, and (3) an alkylaluminum compound. A method for producing 1,4-cis-polybutadiene in the presence of a catalyst and a nonpolar solvent is described next.

In general, a method for preparing a polybutadiene having a high cis-1,4 content is a method of contacting butadiene with a catalyst in a liquid phase as disclosed in US Pat. No. 3,170,905. In this case, the catalyst may include at least one compound selected from nickel salts of carboxylic acids and organic complex compounds of nickel, at least one compound selected from fluorine boron compounds and complexes thereof, and organometallic metals of the metals of the periodic table II to III and alkali metals. One consisting of at least one compound selected from the compounds is used.

However, while this method is effective in producing butadiene polymers having high cis-1,4 content in high yield, the catalysts are not completely dissolved in hydrocarbon solvents, and they act as impurities to reduce the degree of polymerization. there was.

In addition, US Patent No. 3,725,492 discloses a method for preparing 1,4-cis-polybutadiene having a very low molecular weight from a 1,3-butadiene polymerization using a nickel compound, a halogen compound, and an organoaluminum as a catalyst. have. In this case, however, the cis content is not high.

U.S. Pat.No. 6727330 discloses polymerization of inorganic bases with amine compounds or carboxylic acids to prevent gelation from butadiene polymerization using catalysts consisting of nickel salts of carboxylic acids, fluorine boron compounds and alkali metal organometallic compounds. Terminators were used to inhibit gel formation.

Thus, the present inventors have tried to develop novel catalysts that can be used to prepare polydienes with high 1,4-cis content, have high activity, and no gel formation. As a result, it was found that the above-mentioned disadvantages were formed from oligomers of dimers or more, and produced novel nickel carboxylate compounds in monomolecular form, containing the nickel carboxylate compounds, halogen compounds and organometallic compounds. When applied to the diene polymerization, the nickel carboxylate compound is a compound that satisfies the coordination number 6 to exhibit a monomolecular structure, thereby preventing entanglement of the nickel compound, high activity, and from this It has been found that the gel formation of the formed polydiene can be suppressed to complete the present invention.

Accordingly, the present invention is a catalyst for diene polymerization in which a monomolecular nickel carboxylate compound having high activity and solubility, containing it, having a narrow molecular weight distribution, low solution viscosity, and a cis content of 94% or more without formation of a gel. The purpose is to provide.

The present invention is characterized by the nickel carboxylate compound represented by the following formula (1).

NiA ₂ X ₂

In Chemical Formula 1, A is a carboxylate having 8 to 20 carbon atoms, preferably A is selected from verstate (neodecanate), octoate and naphthenate, and X is H ₂ O or C 1 to C It is preferable to use 20 alkyl alcohols, preferably selected from methanol, ethanol, isopropyl alcohol and octanol.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a catalyst comprising a nickel carboxylate compound having a monomolecular structure and a nickel carboxylate compound, a halogen compound, and an organometallic compound, wherein the compound satisfies the coordination number of 6; Applied to the polymerization, it is possible to prevent the entanglement of the nickel compound, high activity of 2 × 10 ⁷ g / Nimol or more, it is possible to suppress the gel formation of the polydiene formed therefrom, especially high 1,4-cis content It is suitable for the production of polydiene having.

Looking at the nickel carboxylate compound according to the present invention in more detail.

The nickel carboxylate compound represented by Chemical Formula 1 is a compound having a monomolecular structure satisfying the coordination number 6.

A method for preparing such a compound is generally used in the art, and the present invention is not particularly limited. However, the present invention is a ligand of nickel carboxylate (NiA ₂ X ₂ ) or nickel alkoxide and carboxylic acid in an organic solvent such as chlorobenzene. Manufactured by exchange method. The amount used in the preparation is preferably controlled within the equivalent range, the ratio of nickel ion to carboxylic acid in the reaction conditions is preferably maintained from 1: 1 to 1: 5.

On the other hand, 1) 1 mol of NiA ₂ X ₂ nickel carboxylate compound of Formula 1, 2) 3 to 30 mol of fluorine complex; And 3) a diene polymerization catalyst comprising 2 to 20 moles of an organometallic compound.

The fluorine complex is generally used in the art, and preferably, hydrogen fluoride or boron trifluoride complex is used. The fluorine complex compound is preferably contained in the range of 3 to 30 moles with respect to 1 mole of the nickel carboxylate compound. When the content is less than 3 moles, the reaction rate is lowered and the molecular weight becomes very large. It is preferable to maintain the above range because a problem arises in that mainly produced or low molecular weight polymers are produced.

In addition, the organometallic compound is preferably selected from the following alkyl aluminum of formula (2), alkyl magnesium of formula (3) and alkyl lithium of formula (4), specifically trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum , Triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dibutylmagnesium, diethylmagnesium and n -butyllithium can be used.

[Formula 2]

AlR ² ₃

[Formula 3]

MgR ² ₂

[Formula 4]

LiR ²

In said Formula (2), 3 or 4, R <^2> represents a hydrogen atom or a C1-C10 alkyl, a C1-C10 alkoxy group, a C5-C10 cycloalkyl, aryl, and a C5-C15 arylalkyl.

The organometallic compound is contained in a range of 2 to 20 moles per 1 mole. When the content is less than 2 moles, an oligomer or a low molecular weight polymer is formed, and when the molar exceeds 20 moles, the reaction rate is very low and the molecular weight is very low. It is desirable to maintain the above range because of the problem of high polymer production.

Such a catalyst is carried out by a method of preparing a conventional catalyst containing the above components, and aged in a nonpolar solvent at a temperature of −30 to 60 ° C. for 5 minutes to 2 hours, or in a reactor containing butadiene and a solvent. The catalyst component can be added sequentially and used. The order does not have a special meaning when used sequentially.

When the diene polymerization is carried out using the catalyst prepared above, the present invention prepares polybutadiene as a specific example, but is not limited thereto.

First, the diene is polymerized at a temperature of 20 to 200 ° C. for 30 minutes to 3 hours in the presence of the catalyst prepared above and a nonpolar solvent. The polymerization temperature and time is in a range for forming a typical diene polymerization, and when the temperature is out of the above conditions, polymerization is not formed, or adverse effects due to excessive polymerization are feared, so it is preferable to maintain the above range. The nonpolar solvent is generally used in the art, and specifically, pentane, hexane, heptane, carbon tetrachloride, benzene, toluene, and a nonpolar mixed solvent may be used. In the preparation of polybutadiene, the ratio of 1,3-butadiene and nonpolar solvent used as a reaction raw material is preferably maintained at a weight ratio of 1 to 2 to 10. When the amount of the nonpolar solvent is less than 2 weight ratio, the reaction temperature and molecular weight can be controlled. It is difficult to maintain the above range because it is difficult and a problem arises in transporting the polymer solution, and when it exceeds 10 weight ratio, the reaction rate is lowered.

  In addition, the present invention may be added to the diene during the preparation of the catalyst, by the addition of the diene can maintain the activity of the catalyst, prevent the formation of precipitation, it is possible to control the final polybutadiene physical properties. When the diene is used in a molar ratio of 2 to 10 with respect to 1 mole of the nickel carboxylate compound, if the amount of use is less than 2 molar ratio, precipitation of the catalyst is likely to occur, and when the molar ratio exceeds 10 molar ratio, a polymer may be formed. It is preferable to maintain the above range.

In addition, in order to complete the polymerization reaction of 1,3-butadiene, polyoxyethylene glycol phosphate which is a commonly used reaction terminator and 2,6-di- t -butyl paracresol which are antioxidants may be added and used. The reaction terminator and the antioxidant may be used in the range of 0.1 to 0.5 wt% and 0.3 to 1.0 wt%, respectively, based on 1,3-butadiene.

The polybutadiene prepared by the polymerization has a content of 94% or more of 1,4-cis, a molecular weight of 100,000 to 2,000,000, and a polybutadiene having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of about 10 to 100. have.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Preparation of Ni (C ₇ H ₁₅ COO) _2. (H ₂ O) ₂

Chlorobenzene (80 mL), nickel acetate (3.2 g), water (0.5 g), and octanoic acid (C ₇ H ₁₅ COOH, 8.6 g) were placed in a 250-mL round flask and heated to the boiling point with stirring to react for 3 hours. Let. At this time, the reaction by-products were removed using a Dean-Stark distiller. After the reaction, chlorobenzene was removed through a rotary-vacuum distillation apparatus (50 ° C), and gel permeation chromatography was used to obtain a green product as a monomer. The structure was confirmed by mass, infrared and ultraviolet-visible light spectroscopy, and the results are shown in FIGS. 1 and 2, respectively.

MS-MALDI m / z : calcd for C ₁₆ H ₃₄ O ₆ Ni (M) &lt; + &gt;,380.7; found 380. UV-Visible (λ max, CH ₂ Cl ₂ ): 680 nm.

Example 2 Preparation of Catalyst

The Ziegler-Natta catalysts used in the reaction were monomolecular nickel octoate (0.05% toluene solution), boron trifluoride ethyl ether (1.5% toluene solution) and triethylaluminum (0.8% toluene solution) prepared in Example 1 above. , 7.0 x 10 ^-5 mol of nickel catalyst per 100 g of single molecule was used.

Maturation of the reaction catalyst was performed by sufficiently adding nitrogen, and then adding nickel octoate, boron trifluoride ethyl ether and triethylaluminum in a 1: 10: 6 molar ratio sequentially to a 100 mL round flask sealed with a rubber stopper, and then at 1 ° C at 20 ° C. Aged for hours before use.

In the polymerization process, nitrogen was sufficiently blown into a 2 L pressure reactor, heptane, the Ziegler-Natta catalyst and the monomer butadiene (100 g) were added thereto, and reacted at 60 ° C. for 2 hours.

In this case, the polymerization solvent is 5 times the monomer content, and after the reaction, 2,6-di- t -butylparacresol (0.5 g) as an antioxidant, polyoxyethylene phosphate (0.2 g) and ethanol (3 mL) as a terminator Was added to terminate the reaction.

Example 3

The Ziegler-Natta catalysts used in the reaction were monomolecular nickel octoate (0.05% toluene solution), boron trifluoride ethyl ether (1.5% toluene solution) and triethylaluminum (0.8% toluene solution) prepared in Example 1 above. , 4.0 x 10 ^-5 mol of nickel catalyst per 100 g of single molecule was used.

Maturation of the reaction catalyst was performed by sufficiently adding nitrogen, and then adding nickel octoate, boron trifluoride ethyl ether and triethylaluminum in a 1: 10: 6 molar ratio sequentially to a 100 mL round flask sealed with a rubber stopper, and then at 1 ° C at 20 ° C. Aged for hours before use.

In the polymerization process, a hexane polymerization solvent in which nitrogen was sufficiently blown into a 2 L pressure reactor, a Ziegler-Natta catalyst aged above, and a butadiene monomer (100 g) were added thereto and reacted at 60 ° C. for 2 hours.

At this time, the polymerization solvent is 5 times the monomer content, and after the reaction, 2,6-di- t -butylparacresol (0.5 g) as an antioxidant, polyoxyethylene phosphate (0.2 g) and ethanol (3 mL) as a terminator ) Was added to terminate the reaction.

Comparative Example 1: Multimer Nickel Naphthenate

The sodium naphthonic salt (ca.mw 463, 9.26 g) is dissolved in water (50 g), and then slowly added to an aqueous nickel chloride solution (50 mL, 0.2 M) at room temperature, followed by stirring for 1 hour. The green product was extracted using toluene (100 mL). After the extraction solution was dried through a rotary-vacuum distillation apparatus (50 ° C.), structural analysis was performed by mass, infrared and ultraviolet-visible spectroscopy, and the results are shown in FIGS. 3 and 4, respectively.

MS-MALDI m / z : 1269.2, 1205.54, 1057.7, 844.3, 785.6, 576.4; UV-Visible (λ max, CH ₂ Cl ₂ ): 670 nm.

Comparative Example 2: Multimer Nickel Octoate

The sodium octanoate salt (ca.mw 339, 6.18 g) is dissolved in water (50 g), and then slowly added to an aqueous nickel chloride solution (50 mL, 0.2 M) at room temperature, followed by stirring for 1 hour. The green product was extracted using toluene (100 mL). The extract solution was dried through a rotary-vacuum distillation apparatus (50 ° C.) and then subjected to structural analysis by mass, infrared and ultraviolet-visible spectroscopy.

MS-MALDI m / z : 997.5, 783.3, 577.6, 387.5, 365.7; UV-Visible (λ max, CH ₂ Cl ₂ ): 670 nm.

Comparative Example 3

The Ziegler-Natta catalyst used in the reaction was Ni (naphthenate) ₂ (0.05% toluene solution) containing a small amount of 1,3-butadiene prepared in Comparative Example 1, BF ₃ OEt ₂ (1.5% toluene Solution) and AlEt ₃ (0.8% toluene solution), and 7.0 x 10 ^-5 mol of nickel catalyst per 100 g of monomer was used. After the aging of the reaction catalyst was sufficiently blown with nitrogen, 100 ml round flasks sealed with rubber stoppers were sequentially added in a 1: 10: 6 molar ratio of Ni (naphthenate) ₂ , BF ₃ OEt ₂ and AlEt ₃ . It was used after aging for 1 hour at 20 ℃.

In the polymerization process, the 2L-pressure reactor was sufficiently blown with nitrogen, followed by the addition of a hexane polymerization solvent, the Ziegler-Natta catalyst and monomer 1,3-butadiene (100 g) as described above, followed by 2 hours at 60 ° C. Reacted.

At this time, the ratio of the polymerization solvent and the monomer was 5, 2,6-di- t -butyl paracresol (0.5 g) as an antioxidant after the reaction, polyoxyethylene phosphate (0.2 g) and ethanol (3 mL) as a terminator Was added to terminate the reaction.

Comparative Example 4

The Ziegler-Natta catalysts used in the reaction were Ni (naphthenate) ₂ (0.05% toluene solution), BF ₃ OEt ₂ (1.5% toluene solution) containing a small amount of 1,3-butadiene prepared in Comparative Example 1 And AlEt ₃ (0.8% toluene solution), 5.0 × 10 ⁻⁵ mol of nickel catalyst per 100 g of monomer was used. Aging of the reaction catalyst was sufficiently blown with nitrogen, and then sequentially added Ni (naphthenate) ₂ , BF ₃ OEt ₂ and AlEt ₃ in a 1: 10: 6 molar ratio to a 100 ml round flask sealed with a rubber stopper. It was used after aging for 1 hour at 20 ℃.

In the polymerization process, the 2L-pressure reactor was sufficiently blown with nitrogen, followed by the addition of a hexane polymerization solvent, the Ziegler-Natta catalyst and monomer 1,3-butadiene (100 g) as described above, followed by 2 hours at 60 ° C. Reacted.

At this time, the ratio of the polymerization solvent and the monomer was 5, 2,6-di- t -butyl paracresol (0.5 g) as an antioxidant after the reaction, polyoxyethylene phosphate (0.2 g) and ethanol (3 mL) as a terminator Was added to terminate the reaction.

Comparative Example 5

Ziegler-Natta catalysts used in the reaction were nickel octoate (0.05% toluene solution), boron trifluoride ethyl ether (1.5% toluene solution) and triethylaluminum (0.8% toluene solution) prepared in Comparative Example 2 7.0 x 10 ^-5 mol of nickel catalyst per 100 g was used.

Maturation of the reaction catalyst was carried out by adding nitrogen octoate, boron trifluoride ethyl ether and triethylaluminum in a 1: 10: 6 molar ratio sequentially to a round flask (100 mL) sealed with a rubber stopper after sufficiently blowing nitrogen, and then at 20 ° C. Aged for 1 hour at and then used.

In the polymerization process, nitrogen was sufficiently blown into a 2 L pressure reactor, a heptane polymerization solvent, the Ziegler-Natta catalyst aged above, and a butadiene (100 g) monomer were added thereto, and reacted at 60 ° C. for 2 hours.

At this time, the polymerization solvent is 5 times the monomer content, and after the reaction, 2,6-di- t -butylparacresol (0.5 g) as an antioxidant, polyoxyethylene phosphate (0.2 g) and ethanol (3 mL) as a terminator ) Was added to terminate the reaction.

The following Table 1 shows the composition, nickel concentration and yield of the catalysts used in Examples 2 to 3 and Comparative Examples 3 to 5, and the following Table 2 shows the pattern viscosity, the solution viscosity, and the 1,4-cis content. Physical properties such as weight average molecular weight and molecular weight distribution were measured and shown in Table 2 below.

division Catalyst composition Ni concentration (mol) Yield (%) Example 2 Nickel Octoate / Boron Trifluoride Ethyl Ether / TEA 7.0 × 10 ^-5 100 Example 3 Nickel Octoate / Boron Trifluoride Ethyl Ether / TEA 4.0 × 10 ^-5 93 Comparative Example 3 Nickel Naphthenate / Boron Trifluoride Ethyl Ether / TEA 7.0 × 10 ^-5 87 Comparative Example 4 Nickel Naphthenate / Boron Trifluoride Ethyl Ether / TEA 5.0 × 10 ^-5 65 Comparative Example 5 Nickel octoate / boron trifluoride ethyl ether / 7.0 × 10 ^-5 85 TEA: triethylaluminum

division Pattern viscosity ML (1 + 4,100 degrees Celsius) Solution viscosity (cps) Sheath Content (%) Weight average molecular weight (Mw) Molecular Weight Distribution (MWD) Example 2 38 158 96.1 405000 3.60 Example 3 58 250 96.5 452000 3.12 Comparative Example 3 39 282 95.9 501000 4.60 Comparative Example 4 65 546 96.3 683000 4.26 Comparative Example 5 48 370 96.0 567000 4.37

As described in Table 2, Examples 2 to 3 using monomolecular nickel carboxylate according to the present invention polymerize 1,3-butadiene compared to Comparative Examples 3 to 5 using multimer nickel carboxylate. In addition, it showed a high catalytic activity, 1,4-cis content is 94% or more, the resulting solution of the polybutadiene is low, it was confirmed that the molecular weight distribution shows a narrow range.

As described above, according to the present invention, when a specific monomolecular nickel carboxylate compound is applied as a diene polymerization catalyst, the activity is increased by 30% or more, the cis content is 94% or more, the molecular weight distribution is narrow, and the gel is It was confirmed that a polybutadiene having no solution viscosity was obtained.

Claims (9)

Nickel carboxylate compound represented by the following formula (1): [Formula 1] NiA ₂ X ₂ In Formula 1, A represents a carboxylate having 8 to 20 carbon atoms, and X represents H ₂ O or an alkyl alcohol having 1 to 20 carbon atoms. The nickel carboxylate compound according to claim 1, wherein A is selected from neodecanoate, octoate and naphthenate. The nickel carboxylate compound according to claim 1, wherein X is selected from methanol, ethanol, isopropyl alcohol and octanol. In the diene polymerization catalyst comprising a fluorine complex compound and an organometallic compound, A catalyst for diene polymerization, comprising: a nickel carboxylate compound represented by Formula 1 in the catalyst: [Formula 1] NiA ₂ X ₂ In Formula 1, A represents a carboxylate having 8 to 20 carbon atoms, and X represents H ₂ O or an alkyl alcohol having 1 to 20 carbon atoms. The diene polymerization of claim 4, comprising 1) 1 mol of nickel carboxylate compound of formula 1, 2) 3-30 mol of fluorine complex compound, and 2-20 mol of organometallic compound. catalyst. The catalyst for diene polymerization according to claim 4, wherein the fluorine complex is hydrogen fluoride or boron trifluoride complex. The catalyst for diene polymerization according to claim 4, wherein the organometallic compound is selected from alkyl aluminum of formula 2, alkyl magnesium of formula 3 and alkyl lithium of formula 4. [Formula 2] AlR ² ₃ [Formula 3] MgR ² ₂ [Formula 4] LiR ² In the above formulas (2), (3) and (4), R ² represents a hydrogen atom or an alkyl having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, aryl and an arylalkyl having 5 to 15 carbon atoms. The method of claim 7, wherein the organometallic compound is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dibutylmagnesium, diethylmagnesium and Catalyst for diene polymerization, characterized in that selected from n -butyllithium. The catalyst for diene polymerization according to claim 4, wherein the diene is 1,3-butadiene or isoprene.

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