KR20170077485A - Method of preparing catalyst for the polymerization of conjugated diene and method of preparing conjugated diene polymer using the same - Google Patents

Abstract

The present invention relates to a process for preparing a catalyst comprising premixing a neodymium compound, a trialkylaluminum compound and a solvent, and allowing the preliminary mixture to stand for 1 to 24 hours, a catalyst produced thereby, A method for producing the conjugated diene polymer can be provided.
According to the process for producing a catalyst of the present invention, the catalyst activity can be improved while using a small amount of catalyst, and in particular, the time for maintaining a high activity for producing a catalytically active species can be increased.
Further, by using the catalyst, the production efficiency of the diene polymerization process can be greatly improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for preparing a conjugated diene-based catalyst, and a conjugated diene-based polymer using the conjugated diene-

The present invention relates to a process for preparing a catalyst for polymerization of conjugated diene, a catalyst produced thereby, and a process for producing a conjugated diene polymer using the same.

The demand for rubber mixtures in various manufacturing sectors such as tires, impact resistant polystyrene, shoe soles, and golf balls is increasing, and the value of butadiene rubber, an intermediate in petrochemical products, is increasing as a substitute for natural rubber, which lacks production.

However, as the price of butadiene rubber has risen due to the recent high oil price situation, the burden of rising costs for synthetic rubber is mounting.

Accordingly, in order to reduce the production cost of butadiene rubber, it is required to expand the butadiene rubber production plant and develop the butadiene rubber process technology.

The butadiene rubber is known to be produced by a polymerization system using a rare earth metal containing catalyst. Particularly, neodymium compounds (Nd (OOCR) ₃ , where R = alkyl group) are proved to be particularly effective among the rare earth metal-containing catalysts (see Patent Document 1).

It has also been reported that a catalyst system in which a neodymium compound and an organoaluminum compound and / or a Lewis acid is added to an aluminoxane-based system can obtain a conjugated diene-based polymer having a high polymerization activity and a narrow molecular weight distribution.

However, when these catalysts are used, it is generally difficult to mix them with other polymer materials such as rubber or various fillers because of the linear structure in which the branched structure is small, and the polymer obtained by the butadiene preforming There is a problem such as clogging of the catalyst input line of the polymerization reactor or difficulty in controlling the molecular weight due to the generation of the polymer.

Thus, by using a neodymium compound, there is a need for a process for preparing a catalyst having uniform catalytic active species homogeneity, high activity and activity retention time, and a conjugated diene polymer using the same, while solving the conventional problems and improving processability .

European Patent Publication No. 1 055 659

In order to solve the above problems, the present invention provides a method for producing a catalyst capable of improving catalytic activity while using a small amount of catalyst.

The present invention also provides a catalyst produced by the above production method.

It is another object of the present invention to provide a method for producing a conjugated diene polymer capable of improving the production efficiency using the catalyst.

Furthermore, the present invention provides a conjugated diene polymer produced by the above production method.

In order to solve the above problems, the present invention provides a process for producing a catalyst, comprising premixing a neodymium compound, a trialkylaluminum compound and a solvent, and allowing the preliminary mixture to stand for 1 to 24 hours to provide.

In addition, the present invention provides a catalyst produced by the above production method.

The present invention also relates to a method for preparing a copolymer comprising the steps of: preparing a mixture of a molecular weight modifier and a conjugated diene monomer; And mixing the mixture with the catalyst, followed by a polymerization reaction. The present invention also provides a method for producing a conjugated diene-based polymer.

Further, the present invention provides the conjugated diene polymer produced by the above production method.

According to the process for preparing a catalyst of the present invention, the catalyst activity can be improved while using a small amount of catalyst, and in particular, it is possible to increase the time for maintaining high activity in producing catalytically active species.

Further, by using the catalyst, the production efficiency of the diene polymerization process can be greatly improved.

Fig. 1 shows the catalytic activity according to the change of the standing time in Examples 1 to 5. Fig.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

A method of preparing a catalyst according to an embodiment of the present invention includes premixing a neodymium compound, a trialkylaluminum compound, and a solvent, and allowing the preliminary mixture to stand for 1 to 24 hours .

Conventional catalyst systems for the production of conjugated diene-based polymers include neodymium compounds, diisobutylaluminum hydride [hereinafter referred to as DIBAH (diisobutyl (hereinafter referred to as " aluminum hydride "), a halogen compound, and butadiene, and the step of preforming the conjugated diene-based monomer using a catalyst derived from the catalyst composition Followed by a polymerization reaction.

However, according to the conventional method for producing a conjugated diene-based polymer, a problem may arise in the process due to the inclusion of an aluminum compound such as DIBAH capable of simultaneously performing the alkylation and the molecular weight regulating function on the catalyst composition. Second, A small amount of butadiene is added in order to reduce the possibility of generating various catalytic active species in the alkylation step using the catalyst. However, the production of the polymer due to the butadiene prepolymerization may cause a problem that the catalyst input line of the polymerization reactor is clogged . Thirdly, there may be a disadvantage that the time required for confirming the molecular weight control change is long and the molecular weight is not easily controlled. Fourth, continuous catalytic processes are inevitable because the time required to make catalytically active species and maintain high activity is very short.

 Thus, in accordance with one embodiment of the present invention, in order to improve the production of uniform catalytically active species, high catalytic activity, and high catalyst activity retention time, the present invention uses (1) trialkyl aluminum instead of DIBAH, (2) premix, and 3) The objective of the present invention was achieved while solving the conventional productivity and process problems by performing the post-mixing and post-mixing step. More preferably, in addition to the above (1) to (3), (4) the aging step after the introduction of the halogen compound can further improve the physical properties such as catalytic activity and conversion of the polymer.

A method for producing a catalyst according to an embodiment of the present invention will be described below.

The process for preparing the catalyst comprises the steps of (i) premixing a neodymium compound, a trialkylaluminum compound and a solvent (step (i)), and leaving the preliminary mixture for 1 to 24 hours (step ii)).

Specifically, the step (i) is a step of producing a catalytically active species by premixing a neodymium compound, a trialkylaluminum compound and a solvent.

By using a trialkylaluminum compound instead of DIBAH, the present invention can perform premixing instead of preliminary polymerization, so that it is very advantageous in the process and can increase the catalyst activation time.

As used herein, the term " preforming " refers to a catalyst system comprising a neodymium compound, an aluminum compound such as DIBAH, and a halogen compound. When DIBAH or the like is included, A small amount of monomers such as butadiene and the like may be added, which may mean that pre-polymerization is carried out in the catalyst system together with butadiene addition.

The term "premix" can also mean a state in which the polymerization is not carried out in the catalyst system and each compound is uniformly mixed.

The premixing may be carried out at a temperature ranging from 10 캜 to 60 캜, specifically from 20 캜 to 50 캜 for about 1 to 24 hours. When premixing is performed in the temperature and time ranges, the optimum catalyst activity can be maintained.

The step (ii) is a step of increasing the catalytic activity and simplifying the production process, and is a step of stocking the preliminary mixture for 1 to 24 hours.

According to one embodiment of the present invention, the setting can be carried out at a temperature ranging from 10 ° C to 60 ° C for a time ranging from 1 hour to 24 hours, more specifically from 20 ° C to 45 ° C, more specifically at room temperature, The leaving time may be preferably performed for 1 hour to 10 hours, more specifically 1 to 5 hours. The conversion and activity of the polymer can be optimized at the above-mentioned incubation temperature and time, and the activity can be decreased as the settling time becomes longer, but the activity can be maintained higher than that in the case of not being left for 24 hours.

If DIBAH is used instead of trialkylaluminum, it is impossible to carry out the negation step due to short activation time and process problems, and it is not preferable to perform the neglecting step because it shows low activity even if it is performed. On the other hand, when trialkylaluminum is used, high activity can be secured for a long time, so that the catalytic activity can be further improved and the catalytic process can be simplified

According to the method of preparing a catalyst according to an embodiment of the present invention, a step of introducing a halogen compound and performing a chlorination reaction may be further included. The step of introducing the halogen compound can be carried out, for example, immediately before premixing, immediately after premixing (premixing), or between the premixing and the leaving step, that is, before the leaving step, or after the leaving step. It may be advantageous to introduce a halogen compound between the preliminary mixing and the neutralization step and to react them, or to introduce them after the neutralization step.

The reaction of the mixture with the halogen compound is carried out at a temperature of 0 ° C to 60 ° C for 1 minute to 5 hours, in particular at a temperature of 10 ° C to 50 ° C for 5 minutes to 1 hour, more specifically 10 ° C to 45 ° C RTI ID = 0.0 > 20 minutes < / RTI > to 1 hour.

According to an embodiment of the present invention, the method may further include a step of charging the halogen compound, reacting the halogen compound, and aging the halogen compound.

For example, when the halogen compound is put in between the preliminary mixing and the leaving step, the aging step may be performed before or after the leaving step, and when the halogen compound is put after the neglecting step, the aging step Can be performed after the neglecting step.

The aging step may be performed at a temperature ranging from 0 캜 to 60 캜 for 1 minute to 240 minutes, specifically 30 minutes to 240 minutes, more specifically, 30 minutes to 60 minutes. The catalyst of the present invention can further improve the conversion rate of the polymer by including the aging step. When the aging is performed for 30 minutes or more, the conversion of the polymer can be ensured to 90% or more.

The neodymium compound usable according to one embodiment of the present invention may comprise a compound of formula 1:

[Chemical Formula 1]

In this formula,

R ₁ to R ₃ independently of one another are hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms.

Specifically, R ₁ is a linear or branched alkyl group having 6 to 10 carbon atoms, and R ₂ and R ₃ are each independently hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms.

Specifically, the neodymium compound may include Nd (2-ethylhexanoate) ₃ , Nd (neodecanoate) ₃ , Nd (2,2-diethyldecanoate) ₃ , Nd decanoate) _3, Nd (2,2- di-butyl decanoate) _3, Nd (2,2- di-hexyl decanoate) _3, Nd (2,2- dioctyl decanoate) _3, Nd (2 -ethyl-2-propyl decanoate) _3, Nd (2- ethyl-2-butyl decanoate) _3, Nd (2- ethyl-2-hexyl decanoate) _3, Nd (2- propyl-2 butyl decanoate) _3, Nd (2- propyl-2-hexyl decanoate) _3, Nd (2- propyl-2-isopropyl decanoate) _3, Nd (2- butyl-2-hexyl decanoate ) _3, Nd (2- cyclohexyl-2-octyl decanoate) _3, Nd (2-t- butyl decanoate) _3, Nd (2,2- diethyl octanoate) _3, Nd (2,2 - dipropyl octanoate) _3, Nd (2,2- dibutyltin octanoate) _3, Nd (2,2- dihexyl octanoate) _3, Nd (2- ethyl-2-propyl-octanoate) ₃ , Nd (2-ethyl-2-hexyl octanoate) _3, Nd (2,2- di titeu ethyl furnace nm) _3, Nd (2,2- dipropyl no nano-benzoate) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2 - dihexyl no nano-benzoate) _3, Nd (2- ethyl-2-propyl-no nano-benzoate) ₃ and Nd (2- ethyl-2-hexyl-no nano-benzoate), two of these, or any one selected from the group consisting of ₃ Or more.

According to an embodiment of the present invention, the neodymium compound may be Nd (2-ethylhexanoate) ₃ , Nd (neodecanoate) ₃ or a mixture thereof.

The neodymium compound represented by Formula 1 may have a weight average molecular weight of 800 to 1400.

The solubility of the neodymium compound represented by the formula (1) means a degree of dissolution without cloudy phenomenon. It is preferable that about 4 g of the neodymium compound is dissolved per 6 g of the nonpolar solvent at room temperature.

The neodymium compound of the present invention as described above contains a carboxylate ligand containing an alkyl group of various lengths as a substituent, thereby inducing a three-dimensional change around the neodymium center metal, thereby hindering entanglement of the compounds. Therefore, oligomerization, which has been a problem of the neodymium compound in the prior art, can be suppressed. As a result, a high solubility in a polymerization solvent can be secured, and therefore, it can be used as a catalyst for diene polymerization requiring high activity.

According to an embodiment of the present invention, the trialkylaluminum compound may be any one selected from the group consisting of triisobutylaluminum, triethylaluminum, trihexylaluminum and trioctylaluminum, or a mixture of two or more thereof . ≪ / RTI > According to one embodiment of the present invention, by using the trialkylaluminum, preliminary mixing is possible, the activity of the catalyst can be improved, and the high activity can be maintained for a long time.

According to an embodiment of the present invention, the solvent may be any one selected from the group consisting of an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, and an aromatic hydrocarbon solvent, or a mixture of two or more thereof. Examples of the solvent include benzene, toluene, pentane, n-hexane, isohexane, heptane and cyclohexane, but are not limited thereto.

According to an embodiment of the present invention, the halogen compound may be any one selected from the group consisting of an elemental halogen, a mixed halogen, a hydrogen halide, an organic halide, an inorganic halide, a metal halide and an organometallic halide or a mixture of two or more thereof But is not limited thereto.

According to one embodiment of the present invention, specifically, any one selected from the group consisting of an organic halide, a metal halide, and an organometallic halide or a mixture of two or more thereof may be included.

Suitable elemental halogens may include fluorine, chlorine, bromine and iodine. Suitable mixed halogens may include iodine monochloride, iodine monobromide, iodine trichloride, iodopentafluoride, iodine monofluoride, and iodotrifluoride.

Suitable hydrogen halides include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

Suitable organic halides include t-amyl chloride, t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenyl methane, bromo- And examples of the organic solvent include chlorine, bromine, bromine, bromine, bromine, chlorine, bromine, chlorine, triphenylmethylbromide, benzylidene chloride, benzylidenebromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, (Also referred to as iodoform), tetraiodomethane, 1-iodopropane, 2-iodo-2-iodo-2-iodo Propane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (neopentyl Benzylidene iodide (also referred to as benzyl iodide), trimethylsilyl (also referred to as benzyl iodide), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, But are not limited to, iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, Phenyl triiodosilane, benzoyl iodide, propionyl iodide, and methyl iodoformate.

Suitable inorganic halides include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, arsenic trichloride, tribromide Arsenic chloride, arsenic chloride, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetrabromide, silicon tetrabromide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorous iodide and selenium iodide.

Suitable metal halides include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony tritiated, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, A metal halide such as indium, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc bromide, zinc fluoride, aluminum triiodide, gallium triiodide, indium triiodide, titaniumiodide, zinc iodide, germanium tetraiodide, Tin sodium iodide, tin iodide, antimony triiodide, and magnesium iodide.

Suitable organometallic halides include dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, But are not limited to, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium Bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, Butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyl Tin dibromide, tri-n-butyltin chloride, tri-n-butyltinbromide, methylmagnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di- For example, isobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum iodide, ethylaluminum iodide, n-butylaluminum iodide, isobutylaluminum iodide, methylaluminum sesquioiodide , Ethyl aluminum sesquioiodide, isobutyl aluminum sesquioiodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl aluminum sesquioiodide, Butylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin iodide And di-t-butyltin iodide.

The halogen compound according to an embodiment of the present invention may specifically be any one selected from the group consisting of t-amyl chloride, t-butyl chloride, silicon tetrachloride, and tin tetrachloride, or a mixture of two or more thereof. Unlike DEAC (Diethylaluminum chloride) or EASC (Ethylaluminum sesquichloride), the halogen compound does not have an aluminum-chloride bond, so that the activity of the catalyst can be maintained longer without any additional reaction.

A method of preparing a catalyst according to an embodiment of the present invention includes: preparing a mixture of the neodymium compound; Trialkylaluminum; And a solvent are added to the reaction mixture to perform premixing in a temperature range of 10 to 60 ° C. A halogen compound is added to the obtained preliminary mixture, and the mixture is allowed to react at a temperature ranging from 0 ° C to 60 ° C. . ≪ / RTI >

A method of preparing a catalyst according to another embodiment of the present invention includes: Trialkylaluminum; And a solvent are mixed to perform premixing in a temperature range of 10 ° C to 60 ° C and allowed to stand for 1 to 24 hours and then a halogen compound is added to the mixture to react and then aged .

The mixing ratio of the neodymium compound: trialkyl aluminum compound may be 1.0: 5.0 to 200, and more preferably 1.0: 5.0 to 100.

According to one embodiment of the present invention, neodymium compound: trialkylaluminum: solvent may be used in an amount of 0.01 to 0.25: 0.05 to 50.0: 10 to 200 molar ratio.

Meanwhile, the present invention can provide a catalyst prepared by the method for producing the catalyst.

Further, the present invention can provide a method for producing a conjugated diene-based polymer using the catalyst.

The method for producing the conjugated diene-based polymer includes the steps of preparing a mixture of the molecular weight modifier and the conjugated diene-based monomer (step (1)); And mixing the mixture with a catalyst of the present invention obtained by preliminarily mixing the neodymium compound, the trialkylaluminum compound and the solvent and allowing the preliminary mixture to stand for 1 to 24 hours, , And a polymerization step (step (2)).

According to one embodiment of the present invention, the neodymium compound may be used in an amount of 0.01 to 0.25 mmol, specifically 0.02 to 0.12 mmol, more specifically 0.02 to 0.08 mmol, based on 100 g of the conjugated diene monomer.

Specifically, according to one embodiment of the present invention, for example, 0.01 to 0.25 mmol of neodymium compound, 0.05 to 50.0 mmol of trialkylaluminum and 10 to 200 mmol of a solvent are contained in 100 g of the conjugated diene monomer can do.

The catalyst may be used in an amount of 0.5 g to 5.0 g per 250 g of the conjugated diene monomer.

According to the method for producing a conjugated diene polymer of the present invention, it is possible to control the molecular weight quickly and easily, and the polymerization activity can be progressed well even at a low temperature since the catalytic activity is very high, have.

Specifically, the method for producing a conjugated diene-based polymer according to an embodiment of the present invention may include preparing a mixture of a molecular weight modifier and a conjugated diene-based monomer (step (1)).

According to the method for producing a conjugated diene-based polymer according to an embodiment of the present invention, the molecular weight modifier is not added during the preparation of the catalyst but is separately introduced together with the conjugated diene-based monomer, whereby the molecular weight can be controlled quickly in the production process, Can be improved.

In the production method according to an embodiment of the present invention, the molecular weight modifier is an organoaluminum compound, which is selected from the group consisting of dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, -Butyl aluminum hydride, diisobutyl aluminum hydride (DIBAH), dit-butyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride and dioctyl aluminum hydride. Or a mixture of two or more thereof. Among these organoaluminum compounds, diethylaluminum hydride, diisobutylaluminum hydride or a mixture thereof is preferable.

Examples of the molecular weight regulator include hydrogen and silane compounds such as trimethylsilane, triethylsilane, tributylsilane, trihexylsilane, dimethylsilane, diethylsilane, dibutylsilane and dioctylsilane. These organoaluminum compounds or silane compounds may be used alone or in combination of two or more. The organoaluminum compound and the silane compound may be used at the same time.

In the production method according to an embodiment of the present invention, the conjugated diene monomer may be 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, Methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, Hexadiene, or a mixture of two or more thereof.

According to one embodiment of the present invention, since the molecular weight modifier can act not only as a molecular weight modifier but also as a scavenger, the amount of the molecular weight modifier may vary depending on the amount of impurities and the amount of water, but is not limited thereto.

In the production method according to one embodiment of the present invention, the molecular weight modifier used in step (1) is preferably used in an amount of 1 to 50 equivalents relative to the neodymium compound as the main catalyst.

The method for producing a conjugated diene-based polymer according to an embodiment of the present invention comprises the steps of premixing a neodymium compound, a trialkylaluminum compound and a solvent, and allowing the preliminary mixture to stand for 1 to 24 hours, (2), after mixing with a catalyst, followed by a polymerization reaction.

In the production method according to an embodiment of the present invention, the polymerization reaction may be carried out at a temperature ranging from 30 ° C to 80 ° C.

The present invention can provide the conjugated diene-based polymer produced by the process for producing the polymer.

The conjugated diene polymer according to an embodiment of the present invention may have a Mooney viscosity at 100 DEG C of from 35 to 75. [

According to one embodiment of the present invention, the Mooney viscosity can be measured using, for example, Monsanto MV2000E at 100 ° C using Rotor Speed 2 0.02 rpm, Large Rotor. The sample used is allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and 27 ± 3 g can be collected, filled in the die cavity, and the platen can be measured.

In addition, the conjugated diene polymer according to an embodiment of the present invention may be a diene polymer having a cis-1,4-bond content of 90% or more, specifically 95% or more.

The conjugated diene polymer according to an embodiment of the present invention may have a PDI (Polydispersity) of 3.7 or less which is a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) Specifically, 1.5 to 3.66. If the PDI exceeds the above range, the abrasion resistance of the polymer may be deteriorated.

The conjugated diene polymer obtained according to one embodiment of the present invention can be obtained by blending the polymer alone or in another synthetic rubber or a natural rubber and adding other additives as required to prepare a conjugated diene polymer for passenger cars, Treads and sidewalls of winter tires such as tires and studless tires. In addition, it can be used in a wide variety of applications requiring mechanical properties such as abrasion resistance, such as various other members, hoses, belts, vibration damping rubbers, and various industrial products. In addition to natural rubber, it is formulated into emulsion polymerized SBR (Styrene Butadiene Rubber), solution polymerization SBR, polyisoprene, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), butyl rubber, hydrogenated BR, And can be advantageously applied to many applications.

For example, the cis-1,4-polybutadiene may be particularly useful in the manufacture of various tire components (including, but not limited to, tire treads, sidewalls, sub treads and bead fillers). The cis-1,4-polybutadiene can be used as a rubber composition useful in the production of all or part of an elastic part of a tire stock, or a tire or parts thereof.

According to one embodiment of the present invention, when the cis-1,4-polybutadiene is used in combination with another rubber to form an elastic part of the tire stock, the other rubber may be natural rubber, synthetic rubber, have.

Examples of the synthetic rubber according to an embodiment of the present invention include polyisoprene, poly (styrene-co-butadiene), polybutadiene having a low cis-1,4-bond content, poly (styrene-co-butadiene- Isoprene) and mixtures thereof.

The cis-1,4-polybutadiene can also be used in the manufacture of hoses, belts, sole windows, window seals and other industrial products.

The rubber composition may comprise fillers, such as inorganic and organic fillers. The organic filler may include carbon black and starch.

The inorganic filler may include silica, aluminum hydroxide, magnesium hydroxide, clay (hydrated aluminum silicate), and mixtures thereof.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example

Production Example 1: Synthesis of Nd (neodecanoate) ₃

100 ml of a round-bottomed flask containing 4.32 g (25 mmol) of neodecanoic acid was added 100 ml of ethanol, and the mixture was stirred at room temperature for 10 minutes. 25 ml of a 1.0 M sodium hydroxide aqueous solution (25 mmol) was added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

3.0 g (8.3 mmol) of neodymium chloride hydrate was added to a 500 ml round-bottomed flask, and 150 ml of hexane and 100 ml of ethanol were added and dissolved to prepare a second mixed solution.

The first mixed solution was put into a dropping funnel and dropped into the two mixed solutions at room temperature to prepare a third mixed solution. After completion of the addition, the mixture was stirred at room temperature for 15 hours.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 100 ml of hexane and 100 ml of distilled water were added to the third mixed solution, and the mixture was put in a separating funnel. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 5.3 g (yield: 96%) of the title compound of the presently used purple solid dissolved in hexane was obtained.

FT-IR: ν 2,956, 2926, 2872, 1512, 1462, 1411, 1375, 1181, 641 cm ^-1

Preparation of conjugated diene polymer

Example 1

Step (1): preparing a mixture of a molecular weight modifier and a conjugated diene monomer

After vacuum and nitrogen were added alternately to the fully dried organic reactor, 12 wt% 1,3-butane diene (0.3328 mol) / hexane mixed solution was added to the glass reactor in the vacuum state, For about 10 minutes to prepare a reaction mixture.

Step (2): Step of polymerization

The neodymium compound of Preparation Example 1 and triisobutylaluminum (TIBA) and 7.6 mmol of hexane were premixed at a temperature of about 40 DEG C for about 24 hours at the amounts shown in Table 1 below, And allowed to stand for 1 hour. After that, t-amyl chloride was added and reacted in a temperature range of about 40 캜 for about 30 minutes and aging at the same temperature for 30 minutes.

The catalyst was poured into the reaction mixture prepared in the step (2), and polymerization reaction was carried out at 70 for about 10 minutes to obtain a conjugated diene polymer.

After completion of the reaction, a portion of the reaction solution was taken to measure the conversion rate, and the catalyst activity was calculated based on the conversion. The results are shown in Tables 1 and 2 below.

Example 2

The conjugated diene polymer was obtained in the same manner as in Example 1, except that the mixture was allowed to stand for about 5 hours after the premixing in the above step (2).

Example 3

The conjugated diene polymer was obtained in the same manner as in Example 1, except that the mixture was allowed to stand for about 24 hours after the premixing in the step (2).

Example 4

The conjugated diene polymer was obtained in the same manner as in Example 1, except that the mixture was allowed to stand for about 48 hours after the premixing in the above step (2).

Example 5

A conjugated diene polymer was obtained in the same manner as in Example 1, except that the mixture was allowed to stand for about 72 hours after the premixing in the above step (2).

Example 6

The conjugated diene polymer was obtained in the same manner as in Example 1 except that the aging was carried out for one minute in the above step (2).

Example 7

The conjugated diene polymer was obtained in the same manner as in Example 1 except that the aging was carried out for 5 minutes in the above step (2).

Example 8

The conjugated diene polymer was obtained in the same manner as in Example 1 except that the aging was carried out for 60 minutes in the above step (2).

Example 9

A conjugated diene polymer was obtained in the same manner as in Example 1, except that the mixture was allowed to stand for about 8 hours in the step (2) after premixing.

Example 10

In the step (2), the conjugated diene polymer was obtained in the same manner as in Example 1, except that t-butyl chloride was used instead of t-amyl chloride after being premixed for about 8 hours.

Example 11

The conjugated diene polymer was obtained in the same manner as in Example 1, except that diethylaluminum chloride (DEAC) was used instead of t-amyl chloride in the step (2), and the mixture was allowed to stand for about 8 hours after premixing.

Example 12

In the above step (2), a conjugated diene polymer was obtained in the same manner as in Example 1 except that DEAC was used instead of t-amyl chloride and aging was not performed.

Example 13

In the same manner as in Example 1 except that DEAC was used instead of t-amyl chloride, t-amyl chloride was added immediately after the premixing, and the aging was not performed in the step (2), the conjugated diene polymer .

Comparative Example 1

Vacuum and nitrogen were alternately added to the completely dried organic reactor, and 150 g of a 12 wt% 1,3-butane diene (0.3328 mol) / hexane mixed solution was added to a glass reactor in a vacuum state. The glass reactor was charged with a mixture of the neodymium compound, 1,3-butane diene, DIBAH and DEAC of Production Example 1 in the amounts shown in the following Table 1, and the polymerization reaction was carried out at 70 for 30 minutes to obtain a conjugated diene- To obtain a polymer.

Comparative Example 2

The neodymium compound of Preparation Example 1, 1,3-butane diene, DIBAH and hexane 7.6 mmol was preliminarily polymerized at a temperature of about 70 캜 for about 24 hours at the amount shown in Table 1 below, And allowed to stand for 1 hour. Thereafter, the conjugated diene polymer was obtained in the same manner as in Example 1, except that DEAC was added and the catalyst obtained was reacted in a temperature range of about 40 캜 for about 30 minutes.

Comparative Example 3

The neodymium compound, 1,3-butane diene, DIBAH and hexane of Preparation Example 1 were preliminarily polymerized at a temperature in the range of about 70 DEG C for about 24 hours at the amount shown in Table 1 below, and DEAC was added immediately after the prepolymerization to give about 1 Of the catalyst was used in place of the catalyst used in Example 1 to obtain a conjugated diene polymer.

Experimental Example 1: Molecular weight measurement and PDI measurement

Weight-Average Molecular Weight and Number-Average Molecular Weight-In order to know the molecular weight and molecular weight distribution of the polymer, the polymer was dissolved in THF at 40 ° C for 30 minutes and then loaded on gel permeation chromatography (GPC).

The column was a PLgel Olexis (Polymer Laboratories) column and two PLgel mixed-C columns were combined. All of the new columns were of mixed bed type. Polystyrene was used as a gel permeation chromatography (GPC) standard material in the calculation of the molecular weight, and number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (PDI) .

Table 1 and FIG. 1 compares the conversion rate, activity, molecular weight and molecular weight distribution of the polymer with respect to the change of the standing time in Examples 1 to 5 and Comparative Example 1.

The incubation time was 1 hour, 5 hours, 24 hours, 48 hours, 72 hours and 0 hours (Comparative Example 1).

First, as can be seen from Table 1 and FIG. 1, it can be seen that the conversion and activity of the polymer gradually decrease with an increase in the standing time. Specifically, the activity was 682 kg / mol.hr or more when the sample was allowed to stand for 1 hour to 24 hours after the alkylation reaction as in Examples 1 to 3. The activity was 1005.0 kg / mol. hr, which is about twice as high as that of Comparative Example 1.

Table 2 compares the conversion, activity, molecular weight, and molecular weight distribution of the polymer after the reaction with the addition of the halogen compound, with the aging time.

The aging time was 1 minute, 5 minutes, 30 minutes, 60 minutes, and 0 hours (Comparative Example 1).

First, as can be seen from Table 2, the conversion and activity of the polymer gradually increase as the aging time becomes longer. Specifically, when aging was performed for 5 minutes, 30 minutes, and 60 minutes after adding a halogen compound as in Examples 1, 7, and 8, the activity was 1.5 Fold or more. Further, it was confirmed that the polymer conversion was 90% or more when the aging time was 30 minutes or more.

Table 3 above compares the conversion rate, activity, molecular weight and molecular weight distribution of the polymer according to the kind of the halogen compound.

The halogen compounds used were t-amyl chloride (t-AmCl), t-butyl chloride (t-BuCl) and diethyl aluminum chloride (DEAC), respectively.

First, as can be seen from Table 3, when t-amyl chloride is used as the halogen compound, the conversion and activity of the polymer gradually increase. Specifically, when t-amyl chloride is used as the halogen compound as in Example 9, the conversion of the polymer is improved by about 50% as compared with Example 10 using t-butyl chloride and Example 11 using diethylaluminum chloride And the activity of the catalyst was improved by about 20% or more.

Table 4 above compares conversion rate, activity, molecular weight and molecular weight distribution of the polymer according to the time of preliminary polymerization and preliminary mixing and halogen compound addition at the time of catalyst preparation.

First, as shown in Table 4, in the case of preliminarily mixing butadiene in the preparation of the catalyst as in Example 12 and Example 13, in the case of preliminary polymerization with butadiene as in Comparative Examples 2 and 3 The conversion and activity of the polymer were improved by about 40% or more.

In addition, in Example 12 in which the halogen compound was added after the preliminary mixing for 20 hours, the conversion of the polymer was about 95% or more, and the halogen compound was increased by about 20% or more as compared with Example 13 added immediately after preliminary mixing , And the activity was remarkably improved to 1070 kg / mol.hr.

In contrast, in Comparative Examples 2 and 3 in which halogenation was added after the prepolymerization, the conversion of the polymer was found to be within about 60% to 80%.

Claims (24)

Pre-mixing a neodymium compound, a trialkylaluminum compound and a solvent, and allowing the preliminary mixture to stand for 1 to 24 hours.
The method according to claim 1,
Wherein said leaving is carried out in a temperature range of 10 ° C to 60 ° C.
The method according to claim 1,
Wherein the premixing is carried out at a temperature in the range of 10 < 0 > C to 60 < 0 > C.
The method according to claim 1,
Further comprising the step of introducing a halogen compound after the step of allowing the catalyst to react.
The method of claim 4,
Wherein the reaction is carried out at a temperature ranging from 0 ° C to 60 ° C.
The method of claim 4,
Further comprising the step of aging the catalyst after the reaction.
The method according to claim 1,
Further comprising introducing a halogen compound between the preliminary mixing and the leaving step.
The method according to claim 1,
Further comprising the step of aging after the step of neglecting.
The method of claim 6 or claim 8,
Wherein the aging is carried out at a temperature ranging from 0 ° C to 60 ° C for 1 minute to 240 minutes.
The method according to claim 1,
Wherein the trialkylaluminum compound is any one selected from the group consisting of triisobutylaluminum, triethylaluminum, trihexylaluminum and trioctylaluminum, or a mixture of two or more thereof.
The method of claim 4,
Wherein the halogen compound is any one selected from the group consisting of an elemental halogen, a mixed halogen, a hydrogen halide, an organic halide, an inorganic halide, a metal halide and an organic metal halide or a mixture of two or more thereof.
The method of claim 11,
Wherein the halogen compound is any one selected from the group consisting of t-amyl chloride, t-butyl chloride, silicon tetrachloride, and tin tetrachloride, or a mixture of two or more thereof.
The method according to claim 1,
Wherein the mixing ratio of the neodymium compound: trialkyl aluminum is in a molar ratio of 1.0: 5.0 to 200.
The method according to claim 1,
Wherein the neodymium compound comprises a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In this formula,
R ₁ to R ₃ independently of one another are hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms.
15. The method of claim 14,
The neodymium compound is Nd (2- ethylhexanoate) _3, Nd (neodecanoate) _3, Nd (2,2- diethyl decanoate) _3, Nd (2,2- dipropyl decanoate) _3, Nd (2,2- di-butyl decanoate) _3, Nd (2,2- di-hexyl decanoate) _3, Nd (2,2- dioctyl decanoate) _3, Nd (2- ethyl- 2-propyl decanoate) _3, Nd (2-ethyl-2-butyl decanoate) _3, Nd (2-ethyl-2-hexyl decanoate) _3, Nd (2-propyl-2-butyl to Kano Eight) _3, Nd (2- propyl-2-hexyl decanoate) _3, Nd (2- propyl-2-isopropyl decanoate) _3, Nd (2- butyl-2-hexyl decanoate) _3, Nd (2- cyclohexyl-2-octyl decanoate) _3, Nd (2-t- butyl decanoate) _3, Nd (2,2- diethyl octanoate) _3, Nd (2,2- dipropyl octanoate) _3, Nd (2,2- dibutyltin octanoate) _3, Nd (2,2- dihexyl octanoate) _3, Nd (2- ethyl-2-propyl-octanoate) _3, Nd (2-ethyl-2-hexyl octanoate) _3, Nd (2,2- di Till the furnace nano titeu) _3, Nd (2,2- dipropyl no nano-benzoate) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2-ethyl-2-propynonanoate) ₃ and Nd (2-ethyl-2-hexylnonanoate) ₃ or a mixture of two or more thereof. Gt;
The method according to claim 1,
Wherein the catalyst does not comprise diisobutyl aluminum hydride (DIBAH).
The method according to claim 1,
Wherein the solvent is any one selected from the group consisting of an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, and an aromatic hydrocarbon solvent, or a mixture of two or more thereof.
A catalyst produced by the process of claim 1.
Preparing a mixture of a molecular weight modifier and a conjugated diene monomer, and
And mixing the mixture with the catalyst of claim 18, followed by a polymerization reaction.
The method of claim 19,
Wherein the catalyst is used in an amount of 0.5 g to 5 g per 100 g of the conjugated diene monomer.
The method of claim 19,
Wherein the molecular weight modifier is used in an amount of 1 to 50 equivalents relative to the neodymium compound.
The method of claim 19,
Wherein the polymerization reaction is carried out at a temperature in the range of 30 to 80 占 폚.
The method of claim 19,
Wherein 0.01 to 0.25 mmol of neodymium compound, 0.05 to 50.0 mmol of trialkylaluminum, and solvent are used in an amount of 10 to 200 mmol based on 100 g of the conjugated diene-based monomer.
A conjugated diene-based polymer produced by the method of claim 19.

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