KR20020057922A - Polymerization method of high 1,4-cis polybutadine and its derivatives - Google Patents

Abstract

PURPOSE: Provided is a process for producing high 1,4-cis polybutadiene and derivatives thereof by using a polymerization catalyst containing a novel neodymium carboxylate compound. CONSTITUTION: The high 1,4-cis polybutadiene and derivatives thereof are produced by polymerizing 1,3-butadiene or isoprene in a non-polar solvent in the presence of the catalyst containing the neodymium carboxylate compound(NdHA4, wherein A is C8-C20 carboxylate), a halogen compound, and an organic metal compound. The halogen compound is an aluminum halogen compound or t-alkyl halogen compound, and etc. The organic metal compound is at least one selected from the group consisting of an alkyl aluminum compound, an alkyl magnesium compound, and alkyl lithium compound.

Description

Polymerization method of high 1,4-cis polybutadine and its derivatives

The present invention relates to a method for producing a high 1,4-cis polybutadiene and derivatives thereof using a catalyst for diene polymerization comprising a novel monomolecular niodimium carboxylate compound, more specifically a halogen compound and an organometallic A method for producing a high 1,4-cis polybutadiene and derivatives thereof using a catalyst comprising a novel monomolecular niodymium carboxylate compound which can be used for 1,3-butadiene or isoprene polymerization together with a compound and the like. .

Conventional method for preparing niodymium carboxylate has a number of methods, the general formula is Nd (OOCR) ₃ (where R = alkyl group).

WO 97/36850 and 98/39283, British Patents 2,140,435, European Patents 512,346 and 599,096, US Patents 5,428,119, 5,449,387 and 5,360,898, and Polymer (vol 26,1985) , p 147) discloses a method for producing polybutadiene by reacting a lanthanide carboxylate salt with lanthanide chloride, lanthanide nitrate or lanthanide oxide with an aqueous solution of carboxylate, and then extracting it with an organic solvent.

In addition, U.S. Patent No. 5,220,045 discloses an aqueous solution of niodymium nitrate in an organic solvent dissolved in an organic solvent with ammonia or an organic base, and then removes water using azeotropes to prepare niobium carboxylate.

There is also a method for preparing lanthanite carboxylate by ligand exchange method published by Paul, R. C., Singh, G., Ghota, J. S. (Indian J. Chem. Vol 11, p294, 1973).

Such rare earth-based catalysts are generally prepared from niodymium compounds, organoaluminum cocatalysts and halogen compounds, of which double niodymium carboxylate has proven to be particularly effective.

However, by the above method, the activity of the niobium catalyst is only 7% (Porri. L. et al, Polymer Preprint, 1998, Spring p214), there is a problem in that the gel is formed.

This is because the conventional niodim carboxyl group catalyst is prepared in aqueous solution and then extracted and used as an organic solvent, so that a large amount of niodim carboxyl groups of the oligomer exist, and this oligomer forms a gel and lowers the yield. This is due to the low activity. In particular, salts such as nitrates, chlorides, and sulfates are not easy to remove when they are contained in the product, and water, alcohols (methanol, ethanol, etc.), ethers (tetrahydrofuran, ethyl, etc.) used in synthesizing niodymium compounds. Solvents such as ether) and dimethylformamide promote coordination of catalyst activity and catalyst activity by coordination with niodimium compounds (Polyhedron vol8, No. 17, 1989, p2183; J. Mater. Chem. 8, 1998, p2737) .

On the other hand, a method for producing a polybutadiene having a high 1,4-cis by using a conventional niodymium carboxylate, for example, (1) a niodymium carboxylate compound, (2) alkyl aluminum compound and ( 3) A process for preparing 1,4-cis-polybutadiene in the presence of a catalyst consisting of Lewis acid and a nonpolar solvent is disclosed in European Patent Nos. 11184 and 652240 and US Pat. Nos. 4,260,707 and 5,017,539.

The inventors of the present invention have made efforts to develop a catalyst having a high 1,4-cis content and having high activity and no gel formation. Synthesizing an odymium catalyst and using it together with a halogen compound and an organometallic compound in the preparation of polydiene has completed the present invention.

Accordingly, it is an object of the present invention to provide a novel monomolecular niodymium carboxylate which has high activity and no gel formation in the production of polydienes.

Another object of the present invention is to provide a catalyst for 1,3-butadiene or isoprene polymerization containing such novel monomolecular niodymium carboxylate.

Still another object of the present invention is to provide a method for producing polybutadiene and derivatives thereof having a content of 1,4-cis of 96% or more using the catalyst.

The novel monomolecular niodymium carboxylate of the present invention for achieving this purpose is characterized by being represented by NdHA ₄ (where A is a carboxylate having 8 to 20 carbon atoms).

In addition, the catalyst for diene polymerization of the present invention is (a) NdHA ₄ (where A is a carboxylate having 8 to 20 carbon atoms);

(B) halogen compounds; And

(C) It is composed of an organometallic compound, and high or 1,4-cis polybutadiene and its derivatives can be prepared by aging or reacting the diene compound in the presence of a nonpolar solvent without aging.

The novel niodymium compounds of the invention are represented by NdHA ₄ , where A is a carboxylate having 8 to 20 carbon atoms.

Specific examples of A in the structural formula include neodecanoate (or verstate), octoate or naphthenate.

The compound may be prepared by ligand exchange of niobium acetate or niodim alkoxide with carboxylic acid in an organic solvent such as chlorobenzene. Here, the preferable carboxylic acid includes a bustic acid, 2-ethylhexanoic acid, naphthic acid or styric acid.

The monomolecular niodymium carboxylate compound (NdHA ₄ ) thus prepared is mixed with a halogen compound and an organometallic compound and then activated to be used as a polydiene catalyst.

The compound represented by NdHA ₄ is a compound that satisfies the minimum coordination number 8 of the niodymium compound, and has a monomolecular structure to prevent entanglement of the niodymium compound and has excellent storage stability. It has high niodymium activity and can be used to prevent gel formation of polydienes during polymerization.

In particular, the neodymium neodecanoate obtained by using the non-aqueous solution polymerization method is neutral, water is not coordinated, and sodium neodecanoate salt is not coordinated with impurities, so it is easy to control physical properties, and there is a fear of gel formation. none.

On the other hand, each of the compounds constituting the catalyst used in the polymerization of 1,3-butadiene or isoprene, including the (i) niodymium compound described above is as follows.

(B) halogen compounds

The halogen compound is not particularly limited in kind, but is, for example, an aluminum halogen compound represented by R ¹ _n AlX _n-3 (wherein R ¹ is a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms, and X is Halogen atom, and n is an integer of 3 or less) or an inorganic halogen compound or an organic halogen compound in which aluminum is substituted with boron, silicon, tin or titanium in the aluminum halogen compound, wherein the organic halogen compound is particularly t -alkylhalogen. It is a compound (4-20 carbon atoms).

(C) organic metal compounds

The organometallic compound is also not particularly limited in its kind. For example, it is preferable to use an alkylaluminum compound represented by AlR ² ₃ , an alkylmagnesium compound represented by MgR ² ₂ , or an alkyllithium compound represented by LiR ² . Do. R ² is a hydrogen atom or an alkyl, cycloalkyl, aryl, arylalkyl or alkoxy group having 1 to 10 carbon atoms.

Specifically, as the organometallic compound, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dibutylmagnesium, diethylmagnesium or n-butyllithium Preference is given to using.

The monomolecular niodymium carboxylate compound as described above is mixed with a halogen compound and an organometallic compound, and then activated and used as a catalyst for polydiene polymerization. Specifically, diene is present in the presence of the catalyst and the nonpolar solvent. The polymerization is carried out at a temperature of 20 to 200 ° C. for 30 minutes to 3 hours.

When the polydiene is polymerized using such a catalyst system, polydiene having a content of 1,4-cis is 96% or more, and thus can be produced with high catalytic activity (4.0 × 10 ^-5 mol Nd / 100g BD). It is possible to reduce the formation of gels in the preparation of polydienes.

The catalyst of the present invention is mixed with (a) monomolecular niodimium carboxylate compound, (b) halogen compound, and (c) organometallic compound in a nitrogen atmosphere, and then, at a temperature of -30 to 60 캜 in a nonpolar solvent. Aged for 2 to 2 hours or used in a reactor containing butadiene and solvent (B)-(C)-(A), (C)-(B)-(A) or (A)-(B) -(C) can be added sequentially.

At this time, the molar ratio of the component (b) to the component (a) is preferably 1: 1 to 1:20, and the molar ratio of the component (a) to the component (a) is preferably 1:20 to 1: 200.

The solvent used for the polymerization is preferably a nonpolar solvent which is not reactive with the catalyst components. For example, aliphatic hydrocarbon solvents such as pentane, hexane, isopentane, heptane, octane, isooctane and the like; Cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like; Aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene and the like.

On the other hand, diene may be added when preparing the catalyst of the present invention, the activity of the catalyst can be maintained by the addition of the diene, it is possible to prevent the formation of precipitation, and finally to control the physical properties of the polybutadiene. The amount of diene added is 2 to 10 times the amount of the niobium carboxylate compound (component).

The order of adding each component to prepare the catalyst is to put the niodymium carboxylate solution containing diene into a catalytic reactor in a nitrogen atmosphere, and then to add a halo compound and an organometallic compound. Can be changed.

When the 1,3-butadiene was polymerized in a nonpolar solvent at a temperature of 20 to 200 ° C. for 30 minutes to 3 hours using the catalyst of the present invention, the content of 1,4-cis was 95% or more and the molecular weight was 100,000. Polybutadiene having a Mooney viscosity (ML _{1 + 4,100 ° C} ) of about 10 to 100 can be obtained.

In the preparation of polybutadiene, the ratio of 1,3-butadiene and nonpolar solvent is preferably 1: 1 to 10.

On the other hand, 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 is an antioxidant are added. Finally, polybutadiene can be obtained by precipitating polybutadiene by adding methyl alcohol, ethyl alcohol or steam.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

Example 1 Preparation of Neodcanoate (NdH) ₄

Toluene (80 ml), neodymium acetate (3.2 g), neodecanoic acid (A, NEO ACIDS C10 / Exxon Chemicals, 8.6 g, molecular weight 173.7) was added to a 100 ml round flask, heated to boiling point with stirring and refluxed. The reaction was carried out for 3 hours.

After the reaction, toluene was removed through a rotary-vacuum distillation apparatus (50 ° C.) using a vacuum (10torr), and niobium single molecules were separated using gel chromatography (Bio-RAD, S-X12, and toluene). To give a blue purple product (yield 80%).

The structure was confirmed by mass spectrometry (MALDI Mass Spectroscopy). The product was NdH (neodecanoate) ₄ ([M + 1] = 838.7).

Example 2: Preparation of NdH (C ₈ H ₁₅ COOH) ₄

Toluene (80 mL), niodymium acetate (3.2 g), 2-ethylhexanoic acid (C ₈ H ₁₅ COOH, 7.3 g) were placed in a 100 mL round flask, heated to boiling point with stirring, and then reacted for 3 hours while refluxing. I was. After the reaction, toluene was removed through a rotary-vacuum distillation apparatus (50 ° C.) using a vacuum (10 torr), and after passing through gel chromatography, a blue violet product was obtained (yield 74%).

Polymerization Example 1

After nitrogen was sufficiently blown into a 400 ml pressure glass reactor, cyclohexane (150 ml), 1,3-butadiene (30 g), diethylaluminum chloride and diisobutylaluminum hydride and triisobutylaluminum were added thereto. After aging at 40 ° C. for 30 minutes, the monomolecular niodymium neodecanoate obtained in Example 1 was added and reacted for 2 hours.

At this time, niodymium neodecanoate is 1.0% cyclohexane solution, diethylaluminum chloride and diisobutylaluminum hydride and triisobutylaluminum are 15% n -hexane solution, and the molar ratio of each catalyst component is As shown in Table 1 below, the content of niodymium in monomolecule niodymium neodecanoate is 0.9 × 10 ⁻⁴ mol per 100 g of single molecule.

2,6-di-t-butylparacresol, polyoxyethylene phosphate and ethanol were then added to obtain polybutadiene.

Solution Viscosity of the resulting polybutadiene was measured using a Uberod viscosity meter in 5.3% toluene solution, Mooney Viscosty, cis-content, molecular weight (Mw) and molecular weight distribution (Molecular) Weight Distribution) was measured and the results are shown in Table 1 below.

Polymerization Examples 2-3

Polybutadiene was prepared in the same manner as in Polymerization Example 1 using the monomolecular neodymium neodecanoate obtained in Example 1, and solution viscosity, Mooney viscosity, cis content, molecular weight, and molecular weight distribution were measured. Table 1 shows.

Polymerization example Nd content (10 ^-4 mol / single molecule 100g) Molar ratio S / M SV MV cis content (%) Mw (10 ⁵ ) MWD NdN / DEAC / Al (D / T) One 0.9 1/3/60 (30/30) 5 226 35.3 97.2 3.38 3.92 2 0.6 1/3/90 (20/50) 4 230 44.8 96.3 4.05 3.80 3 0.3 1/3/170 (20/150) 4 297 51.2 97.0 4.42 3.72 NdN: NdH (neodecanoate) ₄ DEAC: Diethylaluminum chloride D: Diisobutylaluminum hydride T: Triisobutylaluminum

Polymerization Examples 6-8

In Example 2 Needle audio di catalyst _{(NdH (8 H 15 COO)} 4) obtained in the polybutadiene was prepared in the same manner as in Polymerization Example 1. Solution viscosity, Mooney viscosity, cis content, molecular weight, molecular weight distribution was measured and the results are shown in Table 2 below.

Polymerization example Nd content (10 ^-4 mol / single molecule 100g) Molar ratio S / M SV MV cis (%) Mw (10 ⁵ ) MWD NdO / DEAC / Al (D / T) 4 1.1 1/3/70 (20/50) 5 277 40.1 96.5 4.13 3.90 5 0.7 1/3/60 (10/70) 5 468 65.8 97.2 5.20 4.20 6 0.4 1/3/140 (40/100) 5 299 54.6 96.5 5.07 4.23 Nd: NdH (octoate) ₄ DEAC: Diethylaluminum chloride D: Diisobutylaluminum hydride T: Triisobutylaluminum

As described above, when monomolecule niodymium carboxylate was used as the diene polymerization catalyst, it showed high activity (4.0 × 10 ^-5 mol Nd / 100g BD) of niodymium, and the cis content was 96% or more. Polybutadiene without gel was obtained.

Claims (13)

(A) a novel single molecule niodymium compound represented by the following formula (1); Formula 1 NdHA ₄ Wherein A is a carboxylate having 8 to 20 carbon atoms. (B) halogen compounds; And (C) A method for producing a high 1,4-cis polybutadiene and its derivatives, characterized in that the catalyst for diene polymerization containing an organometallic compound is aged or reacted with a diene compound in the presence of a nonpolar solvent without aging. 2. The preparation of high 1,4-cis polybutadiene and derivatives thereof according to claim 1, wherein A is a carboxylate having 8 to 20 carbon atoms in the novel monomolecular niodymium compound represented by Chemical Formula 1. Way. The high 1,4-cis polybutadiene and derivatives thereof according to claim 2, wherein A is selected from verstate, octoate, and naphthenate in the novel monomolecular niodymium compound represented by Chemical Formula 1. Manufacturing method. The halogen compound according to claim 1, wherein the halogen compound is an aluminum halogen compound represented by R ¹ _n AlX _n-3 , wherein R ¹ is a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms, and X is a halogen atom N is an integer less than or equal to 3), or, in the aluminum halogen compound, aluminum is an inorganic halogen compound or an organic halogen compound substituted with one selected from the group consisting of boron, silicon, tin, and titanium. A process for producing cis polybutadiene and its derivatives. 5. The process for producing high 1,4-cis polybutadiene and derivatives thereof according to claim 4, wherein the organohalogen compound is a t -alkylhalogen compound. The compound according to claim 1, wherein the (c) organometallic compound is an alkylaluminum compound represented by AlR ² ₃ , wherein R ² is a hydrogen atom or an alkyl, cycloalkyl, aryl, arylalkyl, or alkoxy group having 1 to 10 carbon atoms. ), At least one member selected from the group consisting of alkylmagnesium compounds represented by MgR ² ₂ (wherein R ² is the same as above) and alkyllithium compounds represented by LiR ² (wherein R ² is as defined above). Method for producing high 1,4-cis polybutadiene and derivatives thereof. The organometallic compound according to claim 6, wherein the organometallic compound is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dibutylmagnesium, diethylmagnesium and n A catalyst for diene polymerization, characterized in that at least one member selected from the group consisting of butyllithium. The method of claim 1, wherein the diene is 1,3-butadiene or isoprene. The nonpolar solvent according to claim 1, wherein the nonpolar solvent is butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, ethylbenzene and A method for producing high 1,4-cis polybutadiene and derivatives thereof, characterized by using at least one selected from xylene. The method of claim 1, wherein the catalyst aging is carried out for 5 minutes to 2 hours at a temperature of -30 ~ 60 ℃, the addition amount of the diene compound is 2 to 10 times the amount of the (ni) component of the niodymium carboxylate compound A method for producing a high 1,4-cis polybutadiene and its derivatives, characterized in that the amount. The method of claim 1, wherein the ratio of the monomer to the solvent is 1 to 10 by weight. The method for producing high 1,4-cis polybutadiene and derivatives thereof according to claim 1, wherein the reaction time is 30 minutes to 3 hours. The method for producing high 1,4-cis polybutadiene and derivatives thereof according to claim 1, wherein the reaction temperature is 20 to 200 ° C.