KR101873932B1 - A method for manufacturing a functionalized high-cis polydiene - Google Patents

Abstract

The present invention provides a method for producing functional high-cis polydiene, comprising the following steps of: (a) making a diene monomer react with one or more compounds represented by chemical formulas 1-3 in the presence of a catalyst; and (b) further polymerizing a diene monomer with the product in the step (a). In the chemical formulas 1-3, R_1 to R_3 are as described in the present invention. According to one aspect of the present invention, the method can improve affinity to and compatibility with fillers.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a functionalized polydiene,

The present invention relates to a process for the production of functional gossypolyadiene.

As the demand for rubber compositions increases in various manufacturing fields such as tires, shoe soles, golf balls, etc., the value of conjugated diene-based polymers, especially butadiene-based polymers, which are synthetic rubbers as substitutes for natural rubber, .

Generally, the structure of the conjugated diene polymer greatly affects the physical properties of the polymer. Specifically, the lower the linearity and the larger the branching, the higher the dissolution rate and viscosity characteristics of the polymer, and as a result, the processability of the polymer is improved. However, when the branching of the polymer is large, the molecular weight distribution is widened, so that the mechanical properties of the polymer, which affects the abrasion resistance, cracking resistance or rebound characteristics of the rubber composition, are rather deteriorated.

Further, the linearity or degree of branching of the conjugated diene-based polymer, particularly the butadiene-based polymer, largely depends on the content of the cis 1,4-bond contained in the polymer. The higher the content of the cis 1,4-bond in the conjugated diene polymer is, the more the linearity is increased. As a result, the polymer has excellent mechanical properties, so that the abrasion resistance, crack resistance and rebound characteristics of the rubber composition can be improved.

Accordingly, a variety of methods for producing conjugated diene-based polymers for increasing the linearity and imparting appropriate processability by increasing the content of cis-1,4 bond in the conjugated diene polymer have been researched and developed. For example, a method of producing a conjugated diene polymer having a high degree of linearity by using a polymerization system containing a lanthanide-based rare earth element-containing compound, particularly a nioiodide-based compound, or using a polymerization system containing a nickel- It was proposed.

Typically, gossyp 1,4-polybutadiene having a high content of cis 1,4-bonds, for example, at least 90% by weight, has a linear structure, and the gossy 1,4-polybutadiene The product thus obtained is excellent in physical properties, but has a high viscosity and low cold flow, resulting in poor processability, compatibility with fillers, and poor storage stability.

It is an object of the present invention to provide a method for producing a gossypolyadiene which is excellent in affinity and compatibility with a filler and can improve formability upon compounding .

(A) reacting at least one of a diene monomer and a compound represented by the following general formula (1) to (3) in the presence of a catalyst; And (b) further polymerizing a diene monomer to the product of step (a). The present invention also provides a process for producing a functional gossypolyadiene.

≪ Formula 1 >

(2)

(3)

Wherein R ₁ to R ₃ are each a C ₁ to C ₂₀ alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''',R''' are each a C ₁ to an alkyl group, an aryl group, an alkoxy group or a hydrogen of the C _20, Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus, carbon or hydrogen, a ₁ is C ₁ To C ₂₀ alkylene or arylene group, and n is an integer of 1 to 20.

In one embodiment, the catalyst may be a niodiesel-based catalyst prepared from a monomolecular niobium salt compound.

In one embodiment, the monomolecular niobium salt compound is selected from the group consisting of niodium hexanoate, neodymium heptanoate, neodymium octanoate, nioodimium octoate, neodymium naphthenate, (Mono-2-ethylhexyl-2-ethylhexyl) phosphate, niobium (2-ethylhexyl) phosphate, niobium Phonate) and niobium (2-ethylhexyl) phosphite.

In one embodiment, in step (a), the molar ratio of the monomolecular niodite salt compound to the diene monomer may be 1: 5 to 30, respectively.

In one embodiment, in step (a), the molar ratio of the monomolecular niodite salt compound to the compound represented by any one of Chemical Formulas 1 to 3 may be 1: 1 to 10, respectively.

In one embodiment, the diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethylbutadiene, 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl- -Hexadiene, 2-ethyl-1,3-butadiene, 2,4-hexadiene, and cyclo 1,3-hexadiene.

In one embodiment, the method may further include the step of (c) after the step (b), reacting the product of step (b) with at least one compound represented by any one of the following general formulas (1) to (5)

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

≪ Formula 5 >

Wherein R ₁ to R ₄ are each a C ₁ to C ₂₀ alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''',R''' are each a C ₁ to an alkyl group, an aryl group, an alkoxy group or a hydrogen of the C _20, Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus, carbon or hydrogen, a ₁ is C ₁ and to C ₂₀ alkylene group or arylene group, n is one of integers of 1 to 20, S is sulfur, X ₁ and X ₂ is one or more hydrogen as equal to or different from each other, oxygen, a halogen atom, C ₁ to alkyl group of C _20, an aryl group, an alkyl phenol group, an aryl phenol group, a is any of integers from 1 to 10, Y is silicon, tin, germanium, lead, X ₃ is a halogen atom, m is from 0 to Lt; / RTI >

In one embodiment, in step (c), 0.01 to 2.0 parts by weight of the compound represented by any one of the above formulas (1) to (5) may be used relative to 100 parts by weight of the diene monomer.

The method for producing a functionalized polystyrene according to one aspect of the present invention can easily control the branching and the molecular structure of the gossypolyadiene and can form a compound having the same or different ends at both ends of the gossypolyidene, For example, it can be modified and functionalized with an alkyne compound and a sulfur compound to improve affinity and compatibility with a filler.

According to another aspect of the present invention, the processability, mechanical properties, and dynamic properties of a product produced using the gossypolyadiene can be improved.

It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.

Fig. 1 shows gel permeation chromatogram (GPC) analysis results of gossyp 1,4-polybutadiene according to the examples and comparative examples of the present invention.
Figure 2 shows an infrared spectroscopy (IR) spectrum of gossyp 1,4-polybutadiene according to examples and comparative examples of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

(A) reacting at least one of a diene monomer and a compound represented by the following general formula (1) to (3) in the presence of a catalyst; And (b) further polymerizing a diene monomer to the product of step (a). The present invention also provides a process for producing a functional gossypolyadiene.

≪ Formula 1 >

(2)

(3)

Wherein R ₁ to R ₃ are each a C ₁ to C ₂₀ alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''',R''' are each a C ₁ to an alkyl group, an aryl group, an alkoxy group or a hydrogen of the C _20, Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus, carbon or hydrogen, a ₁ is C ₁ To C ₂₀ alkylene or arylene group, and n is an integer of 1 to 20.

In the step (a), the diene monomer and at least one of the compounds represented by the following formulas (1) to (3) are reacted in the presence of a catalyst to induce the bonding of a small amount of a diene monomer and an arbitrary alkyne compound have. Since the alkyne compound is bonded to the diene monomer at the initial stage of polymerization of the diene monomer, one end of the gossypolyadiene can be functionalized (head functionalization).

The compounds represented by Chemical Formulas 1 to 3 are alkyne compounds bonded with silicon, tin, nitrogen, oxygen, sulfur, phosphorus, or the like.

When n = 1, the compound of the above formula (1) is, for example, selected from the group consisting of bis (trialkylstannyl) acetylene, bis (trioctyltentanyl) acetylene, bis (tributylstannyl) acetylene, bis Acetylenes such as acetylenes, bis (triethylstannyl) acetylenes, bis (trimethylstannyl) acetylenes, bis (dialkylamino) acetylenes, bis (dioctylamino) acetylenes, bis (dibutylamino) acetylenes, bis ) Acetylene, bis (diethylamino) acetylene, bis (dimethylamino) acetylene, bis (N, N-bis (trimethylsilyl) amino) acetylene, bis (alkyloxy) acetylene, bis (Trialkylsilyl) acetylene, bis (trimethylsilyloxy) acetylene, bis (trimethylsilyloxy) acetylene, bis (trimethylsilyloxy) acetylene, bis (isopropyloxy) acetylene, bis (diethoxy) acetylene, bis Bis (tributylsilane ) Acetylene, bis (tributylsilyl) acetylene, bis (triisopropylsilyl) acetylene, bis (triethylsilyl) acetylene, bis (trimethylsilyl) acetylene, bis Silyl) acetylene, bis (triethoxysilyl) acetylene, bis (trimethylsilyl) acetylene, and the like.

In the case of n = 2, the compound of the formula (1) is, for example, 1,4-bis (trialkylstannyl) butadiene, 1,4- Butadiene, 1,4-bis (triisopropylstannyl) butadiene, 1,4-bis (triethylstannyl) butadiene, 1,4-bis 1,4-bis (dialkylamino) butadiene, 1,4-bis (dibutylamino) butadiene, 1,4-bis (1,4-bis (diethylamino)) butadiene, 1,4-bis (dimethylamino) butadiene, 1,4-bis (Butoxy) butadiene, 1,4-bis (octyloxy) butadiene, 1,4-bis (Diethoxy) butadiene, 1,4-bis (dimethoxy) butadiene, 1,4-bis (trimethylsilyloxy) ) Butadiene, 1,4-bis (tri (Triisopropylsilyl) butadiene, 1,4-bis (triisopropylsilyl) butadiene, 1,4-bis Bis (trimethylsilyl) butadiene, 1,4-bis (trialkylsilyl) butadiene, 1,4-bis Butadiene, 1,4-bis (trimethylsilyl) butadiene, 1,4-bis (triethoxysilyl) butadiene, 1,4-bis However, the present invention is not limited thereto.

When Z ₁ is hydrogen (H), the compound of formula (1) is, for example, trialkylstannyl acetylenes, trioctylstannyl acetylenes, tributylstannyl acetylenes, triisopropylstannyl acetylenes, triethyl (Trimethylsilyl) aminoacetylene, N, N-bis (trimethylsilyl) aminoacetylene, diethylaminoacetylene, isopropylaminoacetylene, diethylaminoacetylene, dimethylaminoacetylene, But are not limited to, alkyloxyacetylene, octyloxyacetylene, butoxyacetylene, isopropyoxyacetylene, diethoxyacetylene, dimethoxyacetylene, trimethylsilyloxyacetylene, trialkylsilylacetylene, trioctylsilylacetylene, tributylsilylacetylene, , Triethylsilyl acetylene, trimethylsilylacetylene, trialkoxysilyl acetylene, tri Butoxysilyl acetylene, triisopropyloxysilyl acetylene, triethoxysilyl acetylene, trimethylsilylacetylene, acetylene, and the like, but is not limited thereto.

The compound of Formula 2 may be, for example, trialkylstannyl-2-propyne, trioctylstannyl-2-propyne, tributylstannyl-2-propyne, triisopropylstannyl- 2-propyne, diethylamino-2-propyne, dibutylamino-2-propyne, isopropyl Amino-2-propyne, diethylamino-2-propyne, dimethylamino-2-propyne, N, N-bis (trimethylsilyl) Propane, butoxy-2-propyne, butoxy-2-propyne, isopropoxyxy-2-propyne, diethoxy- 2-propyne, triethylsilyl-2-propyne, triethylsilyl-2-propyne, Pin, trialkoxysilyl-2-propyne, tributoxysilyl-2-propyne, tri Isopropyl-2-oxy-silyl propyne, or the like, but-2-ethoxy-silyl propyne, trimethylsilyl-2-propyne in the tree, and the like.

The compound of formula (3) may be, for example, 1,4-bis (trialkylstannyl) -2-butyne, 1,4- Bis (triethylpropyl) -2-butyne, 1,4-bis (triisopropylstannyl) Bis (dibutylamino) -2-butyne, 1,4-bis (dialkylamino) Butene, 1,4-bis (isopropyl) amino-2-butyne, 1,4-bis Bis (octyloxy) -2-butyne, 1,4-bis (alkyloxy) Bis (isopropoxy) -2-butyne, 1,4-bis (diethoxy) Butene, 1,4-bis (trimethylsilyloxy) butyne, 1,4-bis (trialkylsilyl) (Tree portion (Triethylsilyl) -2-butyne, 1,4-bis (trimethylsilyl) -2-butyne, Butene, 1,4-bis (trialkoxysilyl) -2-butyne, 1,4-bis (tributoxysilyl) Bis (trimethylsilyl) -2-butyne and the like. In particular, when n = 2, 1,4-bis (triethoxysilyl) Butadiene, 1,4-bis (triisopropylstannyl) butadiene, 1,4-bis (tributylstannyl) 1,4-bis (trimethylstannyl) butadiene, 1,4-bis (dialkylamino) butadiene, 1,4- Bis (diethylamino) butadiene, 1,4-bis (dibutylamino) butadiene, 1,4-bis 1,4-bis (dimethylamino) butadiene, 1,4-bis (N, N- Bis (butoxy) butadiene, 1,4-bis (octyloxy) butadiene, 1,4-bis (Diethoxy) butadiene, 1,4-bis (dimethoxy) butadiene, 1,4-bis (trimethylsilyloxy) Butadiene, 1,4-bis (trialkylsilyl) butadiene, 1,4-bis (trioctylsilyl) Bis (trimethylsilyl) butadiene, 1,4-bis (trimethylsilyl) butadiene, 1,4-bis (trialkylsilyl) (Triethoxysilyl) butadiene, 1,4-bis (triethoxysilyl) butadiene, 1,4-bis 4-bis (trimethylsilyl) butadiene, and the like, but the present invention is not limited thereto.

The catalyst may be a niodiesel-based catalyst prepared from a niobium salt compound. As used herein, the niodiesel-based catalyst refers to a compound in a form prepared by coordinating a central metal element and a ligand. The monomolecular niobium salt compound may be at least one selected from the group consisting of nioium hexanoate, nioium heptanoate, nioodimentanoate, nioodimioctoate, niohumidnaphthenate, nioodium stearate, (Mono-2-ethylhexyl-2-ethylhexyl) phosphonate) and niobium (niobium phosphate) Bis (2-ethylhexyl) phosphite, and preferably, it is not limited to niobium butoxide.

Specifically, the niodinium-based catalyst is prepared by mixing the niobium salt compound, the chlorinated organoaluminum compound and the at least one organoaluminum compound at a predetermined molar ratio, for example, in a molar ratio of 1: 1 to 5:20 to 30, Lt; / RTI > may be an aged catalyst system.

The solvent for producing the catalyst system is not particularly limited and may be a nonpolar solvent that is not reactive with the catalyst, an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, benzene, ethylbenzene, toluene, xylene, Isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane.

The chlorinated organoaluminum compound is selected from the group consisting of diethylaluminum chloride, dimethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, dioctylaluminum chloride, ethylaluminum dichloride, methylaluminum dichloride, , Isobutyl aluminum dichloride, hexyl aluminum dichloride, octyl aluminum dichloride, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, propyl aluminum sesquichloride, isobutyl aluminum sesquichloride, hexyl aluminum sesquichloride, octyl aluminum And the organoaluminum compound or organic aluminoxane may be trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and diisobutylaluminum hydra Diethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, dioctyl aluminum hydride, methyl aluminoxane (MAO) , Modified methylaluminoxane (MMAO), ethylaluminoxane, propylaluminoxane, isobutylaluminoxane, isobutylaluminoxane, hexylaluminoxane, and octylaluminoxane, but the present invention is not limited thereto.

In the step (a), the molar ratio of the monomolecular niodite salt compound to the diene monomer may be 1: 5 to 30, and the ratio of the monomolecular niodite salt compound to the compound represented by any one of the formulas The molar ratio may be 1: 1 to 10, respectively.

If the molar ratio of each reactant used in the step (a) is out of the above range, it is difficult to introduce and substitute the alkyne compound at a specific site of the gossypolyadiene, specifically at one end, to make it functional.

The diene monomer may be 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethylbutadiene, Butadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2 -Ethyl-1,3-butadiene, 2,4-hexadiene, and cyclo 1,3-hexadiene, preferably 1,3-butadiene or isoprene, But is not limited thereto.

In the step (b), when the diene monomer such as 1,3-butadiene is further polymerized in the product of step (a), the content of cis-1,4-butadiene is 90% by weight, A so-called 95% by weight or more of gossyc 1,4-polybutadiene is produced. The gossyp 1,4-polybutadiene may have a linear structure composed of molecular chains.

In general, gossypolyadiene is excellent in mechanical properties of a product produced therefrom, but has low productivity and storage stability because of high viscosity and low-temperature flowability, affinity for a filler when mixed with a filler, compatibility, And the mechanical properties and dynamic properties of the final product are deteriorated.

On the other hand, in the case of the gossypolyadiene produced in the step (b), since one end of the gossypolyadiene is functionalized with the alkyne compound of the above Chemical Formulas 1 to 3, compatibility with the filler, compatibility with the filler, And the dispersibility of the filler can be improved and the mechanical properties and dynamic properties of the final product can be balanced.

In addition, since the gossypolyadiene produced in the step (b) is only functionalized at its one end by the alkyne compound added at the beginning of the polymerization, the end of the gossypolyadiene is further functionalized, The effect of mixing and the physical properties of the final product can be further improved. Specifically, the method may further include the step of (c) after the step (b), reacting at least one of compounds represented by the following Chemical Formulas 1 to 5 with the product of the step (b).

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

≪ Formula 5 >

Wherein R ₁ to R ₄ are each a C ₁ to C ₂₀ alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''',R''' are each a C ₁ to an alkyl group, an aryl group, an alkoxy group or a hydrogen of the C _20, Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus, carbon or hydrogen, a ₁ is C ₁ and to C ₂₀ alkylene group or arylene group, n is one of integers of 1 to 20, S is sulfur, X ₁ and X ₂ is a halogen atom, C ₁ to C ₂₀ hydrogen, oxygen, equal to or different from each other as A is an integer of 1 to 10, Y is silicon, tin, germanium or lead, X ₃ is a halogen element, m is an integer of 0 to 4, It is one of the integers.

In the step (c), the terminal of the gossypolyidene molecular chain is added by reacting at least one of the gossypolyprene molecular chains prepared in the step (b) and the compounds represented by the following formulas (1) to (5) (End functionalization).

The compound of Formula 4 is an oligomer or polymer comprising an alkylphenol disulfide or an arylphenol disulfide. In Formula 4, R ₄ may be, for example, methyl, ethyl, isopropyl, isobutyl, n-butyl, t-butyl, octyl, .

The compound of formula (4) may be, for example, dimethyl disulfide, diethyl disulfide, diphenyl disulfide, p-tolyl disulfide, bis (4- methoxyphenyl) disulfide, bis Benzyltrisulfide, methylphenylsulfide, ethylphenylsulfide, diphenylsulfide, dibenzylsulfide, 2-aminophenyldisulfide, 4-aminophenyldisulfide, dibenzyldisulfide, benzyltrisulfide, Dithiobis (4-methylphenol), 2,2'-dithiobis [4-propylphenol], 2,2'-dithiobis [4-isopropylphenol], 2,2'- 4-butylphenol], 2,2'-dithiobis [4-tert-butylphenol], and the like, but are not limited thereto.

In formula (4), a may be any one of integers from 1 to 10, preferably one of integers from 1 to 4, more preferably 1 or 2. The compound of Formula 4 may be, for example, S ₂ Cl ₂ , SCl ₂ , SOCl ₂ , S ₂ Br ₂ , SOBr ₂ , and the like, but is not limited thereto.

In particular, the sulfur compound of Formula 4 may react with the gossypolyprene molecular chain prepared in the step (b) to increase the molecular weight of the gossypolyidene molecular chain.

The compound of formula (5) is, for example, selected from the group consisting of tin tetrachloride, tin dichloride, tin tetrabromide, tributyl tin chloride, dibutyl tin dichloride, butyl tin trichloride, triethyl tin chloride, diethyl tin dichloride, But are not limited to, chloride, trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, bistrichlorotranyl ethane, tributyltin hydride, triethyltin hydride, trimethyltin hydride, silicon tetrachloride, silicon tetrabromide, A silane coupling agent such as triethylchlorosilane, triethylchlorosilane, butyltrichlorosilane, dibutyldichlorosilane, tributylchlorosilane, bis (trimethylsilyl) silane, bis Trichlorosilyl ethane, Butyl silicon hydride, triethyl silicon hydride, trimethyl silicon hydride, or the like, but germanium tetrachloride, lead dichloride, and the like.

In the step (c), 0.01 to 2.0 parts by weight of the compound represented by the general formulas (1) to (5) may be used per 100 parts by weight of the diene monomer.

If the amount of the compound represented by any one of Chemical Formulas 1 to 5 used in the step (c) is out of the above range, the alkyne compound is introduced into a specific site, specifically, the terminal end of the gossypolyadiene, It is difficult to substitute for functionalization. Specifically, when the amount of the compound represented by any one of Chemical Formulas 1 to 5 is less than 0.01 part by weight, the viscosity of the gossypolyphene and the combination thereof may be high and the processability may be deteriorated. If the amount is more than 2.0 parts by weight, The mechanical properties of the resulting product may be deteriorated.

On the other hand, by adding a reaction terminator, an antioxidant, or the like after the step (b) or (c) to terminate the polymerization reaction, a gossypolyadiene whose one end of the molecular chain is functionalized with an alkyne compound, Can be obtained by functionalizing a gossypolyadiene at both ends with an alkyne compound and / or a sulfur compound.

Hereinafter, embodiments of the present invention will be described in detail.

Example  One

1,3-butadiene (15.6 mmole) and bis (tributylstannyl) acetylene (2.9 mmole) were mixed with a solution of diisobutylaluminum hydride (15.9 mmole), triisobutylaluminum hydride Butyl aluminum (16.2 mmole) and diethyl aluminum chloride (3.2 mmole) are added. At this time, the monomolecular you Audi 1.5 × 10 per amount of your audio di of di bus Tate is 100g monomolecular ^- a ⁴ mol. The polymerization reaction is carried out by blowing nitrogen sufficiently in a 5 L pressure glass reactor and then adding a cyclohexane polymerization solvent 5 times the monomer content.

The catalyst was transferred under nitrogen purging, followed by addition of butadiene (400 g) as a monomer, followed by polymerization at 70 ° C for 2 hours. After the polymerization reaction, the reaction terminator and antioxidant were added to terminate the reaction to obtain functionalized 1,4-polybutadiene.

Example  2

The procedure of Example 1 was repeated except that bis (tributylstannyl) acetylene (2.9 mmole) was changed to bis (triethylsilyl) acetylene (2.7 mmole) Polybutadiene was obtained.

Example  3

The procedure of Example 1 was repeated except that bis (tributylstannyl) acetylene (2.9 mmole) was changed to bis (trimethylsilyl) aminopropyne (3.4 mmole) - polybutadiene. ≪ / RTI >

Example  4

The procedure of Example 1 was repeated except that bis (tributylstannyl) acetylene (2.9 mmole) was changed to trimethylsiloxy-2-propyne (3.2 mmole) - polybutadiene. ≪ / RTI >

Example  5

1,3-butadiene (15.6 mmole) and bis (tributylstannyl) acetylene (2.8 mmole) were mixed with a solution of diisobutylaluminum hydride (15.9 mmole), triisobutylaluminum hydride Butyl aluminum (16.2 mmole) and diethyl aluminum chloride (3.2 mmole) are added. At this time, the monomolecular you Audi 1.5 × 10 per amount of your audio di of di bus Tate is 100g monomolecular ^- a ⁴ mol. The polymerization reaction is carried out by blowing nitrogen sufficiently in a 5 L pressure glass reactor and then adding a cyclohexane polymerization solvent 5 times the monomer content.

The catalyst was transferred under nitrogen purging, followed by addition of butadiene (400 g) as a monomer, followed by polymerization at 70 ° C for 2 hours. After the polymerization reaction, bis (tributylstannyl) acetylene (0.5 phm) was gradually added thereto and reacted for 50 minutes. Then, the reaction was stopped by adding a reaction terminator and an antioxidant to obtain functionalized 1,4-polybutadiene.

Example  6

Bis (triethylsilyl) acetylene (2.7 mmole) and bis (triethylsilyl) acetylene (2.9 mmole) and bis (tributylstannyl) acetylene 1,4-polybutadiene functionalized in the same manner as in Example 5 was obtained except that acetylene (0.5 phm) was used.

Example  7

Bis (trimethylsilyl) aminopropyne (3.4 mmole) and bis (trimethylsilyl) acetylene (2.9 mmole) and bis (tributylstannyl) acetylene 1,4-polybutadiene functionalized in the same manner as in Example 5 was obtained except that aminopropyne (0.5 phm) was used.

Example  8

Bis (tributylstannyl) acetylene (2.9 mmole) and bis (tributylstannyl) acetylene (0.5 phm) were added to trimethylsiloxy-2-propyne (3.2 mmole) and trimethylsiloxy- -Propyne (0.5 phm), the functionalized 1,4-polybutadiene was obtained in the same manner as in Example 5.

Example  9

The same procedure as in Example 5 was carried out except that bis (tributylstannyl) acetylene (0.5 phm) was changed to 2,2'-dithiobis [4-tert-butylphenol] Lt; RTI ID = 0.0 > 1,4-polybutadiene < / RTI >

Example  10

The same procedure as in Example 5 was carried out except that bis (tributylstannyl) acetylene (0.5 phm) was changed to disulfide dichloride (S ₂ Cl ₂ , 0.5 phm) - polybutadiene. ≪ / RTI >

Example  11

Polybutadiene functionalized in the same manner as in Example 5, except that bis (tributylstannyl) acetylene (0.5 phm) was changed to tin tetrachloride (SnCl ₄ , 0.5 phm) ≪ / RTI >

Example  12

Polybutadiene functionalized in the same manner as in Example 5, except that bis (tributylstannyl) acetylene (0.5 phm) was changed to dibutyl tin dichloride (0.5 phm) in Example 5, .

Example  13

The same procedure as in Example 5 was carried out except that bis (tributylstannyl) acetylene (0.5 phm) was changed to triethoxysilylpropyltetrasulfide (0.5 phm) Polybutadiene was obtained.

Comparative Example

1,3-butadiene (15.6 mmole) was mixed with a solution of diiodobutyl aluminum hydride (15.9 mmole), triisobutyl aluminum (16.2 mmole) and diethyl aluminum chloride (3.2 mmole) mmole) is added. At this time, 1.5 x 10 <" ⁴ > mol of neodymium catalyst per 100 g of monomolecular was used as a catalyst. In the polymerization reaction, a nitrogen gas is sufficiently blown into a 5 L pressure glass reactor, and then a cyclohexane polymerization solvent is added in an amount of 5 times the monomer content. The catalyst was transferred under nitrogen purging, followed by addition of butadiene (400 g) as a monomer, followed by polymerization at 70 ° C for 2 hours. After the polymerization reaction, a reaction terminator and an antioxidant were added to terminate the reaction to obtain 1,4-polybutadiene.

Experimental Example 1: 1 , The properties of 4-polybutadiene

The molecular weight (Mn, Mw) and the molecular weight distribution (Mw / Mn) of 1,4-polybutadiene prepared in Examples 1 to 13 and Comparative Example were measured by GPC and the solution viscosity, Mooney viscosity, linearity, The results are shown in Table 1 below.

division Mn Mw Mw / Mn Solution viscosity
(SV, cps) Mooney viscosity
(MV, ML _{1 + 4} , 100 ° C) Linearity
(MV / SV) * 10 Low temperature flowability
(mg / min) Example 1 279 624 2.2 195 42 2.15 0.6 Example 2 288 627 2.2 189 44 2.33 0.3 Example 3 261 614 2.4 199 40 2.01 0.3 Example 4 245 545 2.2 183 41 2.24 0.4 Example 5 253 590 2.3 191 42 2.2 0.4 Example 6 238 567 2.4 179 41 2.3 0.4 Example 7 275 668 2.4 198 42 2.12 0.8 Example 8 249 593 2.4 189 40 2.11 0.7 Example 9 258 573 2.2 170 41 2.41 0.4 Example 10 263 637 2.4 183 44 2.4 0.2 Example 11 285 630 2.2 179 43 2.4 0.3 Example 12 236 659 2.3 185 43 2.32 0.3 Example 13 239 532 2.3 183 42 2.29 0.3 Comparative Example 252 580 2.4 219 43 1.96 1.2

Examples 1 to 4, wherein one terminal of the gossyp 1,4-polybutadiene molecular chain was functionalized with an alkyne compound, Examples 5 to 8, wherein both terminals were functionalized with an alkyne compound, In Examples 9 to 13 in which both ends were functionalized with an alkene compound and a sulfur compound, the solution viscosity and low-temperature flowability were significantly lower than those in Comparative Example 1 in which no functionalization with a specific compound was made at all, . In particular, the effects are remarkably realized in Examples 9 to 13 in which both terminals of the gossyhex 1,4-polybutadiene molecular chain are functionalized with an alkene compound and a sulfur compound, respectively.

1 shows gel permeation chromatogram (GPC) analysis results of gossyp 1,4-polybutadiene according to Example 3 and Comparative Example. Referring to FIG. 1, it can be seen that, in Example 3 (red), the alkenyl compound-bound polymer is eluted widely over the retention time of the eluent, that is, 20 to 23 minutes, compared with the comparative example (blue).

Figure 2 shows an infrared spectroscopy (IR) spectrum of gossyp 1,4-polybutadiene according to Example 3 and comparative example. Referring to FIG. 2, in the case of Example 3 (red), the CH stretching peak change was remarkable at 2,800 to 3,000 cm ^-1 compared with the comparative example (black), and thus the molecular weight of the 1,4-polybutadiene molecular chain It was confirmed that the terminal was functionalized by an alkyne compound having multiple bonds.

Manufacturing example  And Comparative Manufacturing Example

40 parts by weight of natural rubber, zinc oxide, stearic acid, carbon black, and process oil were blended in a 500-cc brabender at 120 占 폚 with respect to 60 parts by weight of 1,4-polybutadiene in Examples and Comparative Examples, The blend was prepared by mixing and stirring the accelerator. The blends containing the 1,4-polybutadiene of Examples 1 to 13 and Comparative Examples were named Production Examples 1 to 13 and Comparative Production Examples, respectively, and the compositions of the respective blends are shown in Tables 2 and 3 below.

division Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Manufacturing Example Natural rubber 40 40 40 40 40 Example 1 60 Example 2 60 Example 3 60 Example 4 60 Comparative Example 60 Zinc oxide 3 3 3 3 3 Stearic acid 2 2 2 2 2 Carbon black 60 60 60 60 60 Process oil 1.5 1.5 1.5 1.5 1.5 sulfur 1.5 1.5 1.5 1.5 1.5 Vulcanization accelerator 1.5 1.5 1.5 1.5 1.5

(Unit: parts by weight)

division Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Production Example 11 Production Example 12 Production Example 13 Comparative Manufacturing Example natural
Rubber 40 40 40 40 40 40 40 40 40 40 Example 5 60 Example 6 60 Example 7 60 Example 8 60 Example 9 60 Example 10 60 Example 11 60 Example 12 60 Example 13 60 Comparative Example 60 Oxidation
zinc 3 3 3 3 3 3 3 3 3 3 Stearic acid 2 2 2 2 2 2 2 2 2 2 Carbon
black 60 60 60 60 60 60 60 60 60 60 Process oil 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 cure
accelerant 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5

(Unit: parts by weight)

Experimental Example  2: Physical properties of rubber specimens 1

One. Mooney viscosity

30 g each of the formulations of Production Examples 1 to 13 and Comparative Production Example were taken in each case and two specimens having a thickness of 8 mm and an area of 5 cm x 5 cm were produced using a roller. Attach the specimen to the front and back of the rotor and use a rotary viscometer (ALPHA Technologies, MOONEY MV2000). When the rotor was mounted on a rotary viscometer, the rotor was pre-heated to 100 ° C for 1 minute, and then the viscosity change of the blend was measured for 4 minutes to measure the Mooney viscosity, expressed as ML _{1 + 4} (100 ° C) .

2. Other properties

The blends of Production Examples 1 to 13 and Comparative Production Examples were kneaded at 80 DEG C on a roll mill, processed into a flat sheet form on a roll having a thickness of 2 mm, and left for 24 hours. Then, vulcanization was carried out at the crosslinking time measured by RPA (Rubber Process Analyzer) using a press at 160 캜 to prepare a 2 mm-thick sheet specimen.

The mechanical and dynamic properties of the sheet specimens were measured and compared. The results are shown in Tables 4 and 5 below. The method of measuring the physical properties is as follows.

- Hardness: measured by ASTM shore-A method

100%, 300% modulus: measured the stress acting in the specimen to the specimen 25 ℃ when 100%, 300% elongation (unit: kgf / cm ²⁾

- Tensile strength: Measured according to ASTM D 790 (unit: kgf / cm ² )

- Elongation: strain is measured in% until the specimen is broken using a tensile tester.

-Tanδ: Using DMTA (Dynamic Mechanical Thermal Analyzer), temperature sweep is performed to measure the values at 0 ° C and 60 ° C

-DIN Loss (g): Measures the amount of shattering through mechanical repetition of specimen surface

division Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Manufacturing Example Mooney viscosity 85 84 84.9 83.6 89.2 Hardness 74 73 73 73 73 100% modulus 44.3 43.5 46.8 48.5 43.5 300% modulus 206.6 214.7 199.8 203 190.4 The tensile strength 215.2 217.5 216.4 208.9 200.5 Elongation 312 324 315 309 301 Tanδ (0 C) 0.111 0.121 0.115 0.113 0.089 Tanδ (60 DEG C) 0.091 0.082 0.08 0.088 0.105 DIN Loss 0.0808 0.0799 0.081 0.0805 0.0824

division Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Production Example 11 Production Example 12 Production Example 13 Comparative Manufacturing Example Mooney viscosity 86 85.9 85 86 85.5 83.7 84.2 83 83.5 89.2 Hardness 74 73 73 73 74 74 74 74 73 73 100% modulus 49.2 45.5 45.2 48.1 51.5 49.9 47.1 50.7 49.2 43.5 300% modulus 170.9 181.2 200.5 199.5 172.5 178.1 199.7 198.5 205.2 190.4 The tensile strength 219.6 220.5 221 208.2 222.2 210.8 237.1 221.4 240.4 200.5 Elongation 305 308 300 309 299 301 325 331 290 301 Tanδ (0 C) 0.113 0.108 0.09 0.085 0.111 0.109 0.119 0.099 0.088 0.089 Tanδ (60 DEG C) 0.088 0.081 0.98 0.95 0.072 0.077 0.07 0.081 0.08 0.105 DIN Loss 0.0795 0.0803 0.0809 0.0818 0.0804 0.0789 0.0801 0.0799 0.081 0.0824

Referring to Tables 4 and 5, the sheet specimens of Production Examples 1 to 13 had low workability due to a low Mooney viscosity as compared with Comparative Production Examples, and had excellent mechanical properties such as 100% modulus, 300% modulus, tensile strength and elongation And has low tan δ at 60 캜, which is also excellent in dynamic physical properties.

In particular, the sheet specimens of Production Examples 9 to 13 had lower Mooney viscosities than those of Comparative Examples 1 to 8, superior mechanical properties such as 100% modulus, tensile strength and elongation, And the dynamic properties are also excellent. When both ends of the 1,4-polybutadiene molecular chain of gossypse are functionalized with an alkene compound and a sulfur compound, respectively, affinity to the filler, compatibility, and filler content It can be understood that the mechanical properties and the dynamic properties of the final product can be most balancedly implemented while improving the acidity.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (8)

(a) reacting at least one of a diene monomer and a compound represented by the following formula 1 or 3, trimethylsiloxy-2-propyne, bis (trimethylsilyl) aminopropyne in the presence of a catalyst; And
(b) further polymerizing a diene monomer to the product of step (a).
≪ Formula 1 >

(3)

In this formula,
R ₁ is an alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''or hydrogen, each of C ₁ to C ₂₀ ,
R ', R "and R'" are each a C ₁ to C ₂₀ alkyl, aryl, alkoxy or hydrogen,
Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus or carbon,
A ₁ is a C ₁ to C ₂₀ alkylene group or an arylene group,
n is an integer of 1 to 20,
b is one of an integer of 1 to 3; The method according to claim 1,
Wherein the catalyst is a nickel-based catalyst produced from a monomolecular niobium salt compound. 3. The method of claim 2,
The monomolecular niobium salt compound may be at least one selected from the group consisting of nioium hexanoate, nioium heptanoate, nioodimentanoate, nioodimioctoate, niohumidnaphthenate, nioodium stearate, (Mono-2-ethylhexyl-2-ethylhexyl) phosphonate) and niobium (niobium phosphate) Bis (2-ethylhexyl) phosphite, and at least one selected from the group consisting of bis (2-ethylhexyl) phosphite. 3. The method of claim 2,
Wherein the molar ratio of the monomolecular nioome salt compound to the diene monomer in the step (a) is 1: 5 to 30, respectively. 3. The method of claim 2,
Wherein the molar ratio of the monomolecular niodite salt compound to the compound represented by the formula (1) or (3) is 1: 1 to 10 in the step (a), respectively. The method according to claim 1,
The diene monomer may be 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethylbutadiene, Butadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2 -Ethyl-1,3-butadiene, 2,4-hexadiene, and cyclo-1,3-hexadiene. The method according to claim 1,
After the step (b)
(c) reacting the product of step (b) with at least one compound represented by one of the following general formulas (1) and (3) to (5)
≪ Formula 1 >

(3)

≪ Formula 4 >

≪ Formula 5 >

In this formula,
R ₁ and R ₄ are each a C ₁ to C ₂₀ alkyl group, an aryl group, an alkoxy group, -NR'R '', -SiR'R '' R '''
R ', R "and R'" are each a C ₁ to C ₂₀ alkyl, aryl, alkoxy or hydrogen,
Z ₁ is silicon, tin, nitrogen, oxygen, sulfur, phosphorus or carbon,
A ₁ is a C ₁ to C ₂₀ alkylene group or an arylene group,
n is an integer of 1 to 20,
S is sulfur,
X ₁ and X ₂ are the same or different from each other and are hydrogen, oxygen, a halogen element, a C ₁ to C ₂₀ alkyl group, an aryl group, an alkylphenol group or an arylphenol group,
a is an integer of 1 to 10,
b is one of integers from 1 to 3,
Y is silicon, tin, germanium or lead,
X ₃ is a halogen element,
m is an integer of 0 to 4; 8. The method of claim 7,
, Wherein 0.01 to 2.0 parts by weight of a compound represented by one of the general formulas (1) and (5) in the step (c) is used relative to 100 parts by weight of the total amount of the diene monomer charged up to the step (c) Gt;

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