JP2017128713A - Manufacturing method of modified conjugated diene polymer and rubber composition using polymer manufactured by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a modified conjugated diene polymer excellent in affinity for an inorganic additive during a polymerization of a conjugated diene polymer containing an inorganic filler and containing a structure consisting of a linear initiation terminal modification and final terminal modification for enhancing mechanical performances and abrasion performances of the composite and branch macro molecule at same time and a rubber composition obtained therefrom.SOLUTION: There is provided a manufacturing method of a styrene-butadiene copolymer by solution blending an anion solution polymerization reaction product by polymerizing a styrene monomer and a butadiene monomer to linear and branch structures respectively by using two or more batch type reactors, wherein 1) the content of the linear structure is 10-60 pts.wt. and 2) the content of the branch structure is 40-90 pts.wt.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a multi-modal conjugated diene polymer, which not only increases the storage stability of the product and the compatibility with inorganic fillers, but also depends on fillers and vulcanizing agents. An object of the present invention is to provide a tire tread material having an excellent balance of sheet processability, low hysteresis loss property, and wet skid property when a rubber composite material is manufactured.

  Recently, as interest in environmentally friendly materials and energy-saving materials has increased, modified conjugated diene polymer materials obtained by introducing functional chemicals into diene polymers have been used in various applications. In particular, there is an increasing demand for the development of material technologies that can improve the braking performance and fuel ratio on wet road surfaces by applying such modified conjugated diene polymers to automobile tires. As an existing tire tread material, composites with styrene-butadiene rubber (ESBR) obtained from emulsion polymerization and inorganic additives such as carbon black and additives such as sulfur are increased in elasticity through blending and vulcanization processes. The material is used. However, in the case of ESBR materials, it is difficult not only to control the molecular weight and molecular weight distribution during the polymerization process, but also to limit the fine structure of the polymer. The performance could not be expressed.

  On the other hand, in the case of styrene butadiene rubber (SSBR) obtained using solution polymerization, generally an organometallic catalyst having carbon anionic property is used as an initiator, and the molecular weight as a characteristic of the polymerization method called anionic polymerization, Not only the molecular weight distribution but also the macro-structure of the polymer as well as the macro-structure can be adjusted, and when used in a tire tread, the braking performance on wet roads and the fuel ratio can be improved. Rubber material can be designed. However, the rubber composite manufactured by SSBR has lower molecular weight than ESBR, and showed poor performance in terms of mechanical strength and wear. In recent years, not only the fuel ratio and braking performance on wet road surfaces, but also the performance with respect to tire life has become important, and the SSBR that was once used is now being supplemented. In recent years, reinforcing agents are changing from carbon black to precipitated silica due to fuel ratio and braking performance on wet road surfaces. Unlike conventional carbon black, precipitated silica is a modified conjugated diene system in which the particle surface is composed of hydroxy groups and carboxyl groups, and functional groups capable of having such functional groups and interactions are introduced at the polymer ends. It is known that tire performance can be further improved by using a polymer.

  In USP 7915349 B2 (patent document 1), USP 8426513 B2 (patent document 2), USP 8383711 B2 (patent document 3), and EP 2045272 B1 (patent document 4), an organic metal such as alkyllithium having carbon anionic property is used. A conjugated diene polymer was polymerized using a catalyst as an initiator, and a modified conjugated diene polymer was synthesized using a compound containing an amine group and alkoxysilane as a modifying compound. The synthesized modified conjugated diene polymer uses a technology in which the amine group present at the terminal and the alkoxysilane improve the compatibility and dispersibility with inorganic additives such as silica having a polar group on the surface. Is.

  In USP 8278395 B2 (Patent Document 5) and KR20045225 B1 (Patent Document 6), a modifier having a polyvalent glycidyl group functional group is initiated with an organometallic catalyst such as butyllithium for terminal modification. It is manufactured by adding to the polymerized conjugated diene polymer, and by introducing a modified conjugated diene polymer having such a functional group into an inorganic additive such as silica, compatibility and dispersibility However, when coupling an active linear (hereinafter also referred to as “linear”) polymer, a tri- or higher-valent branched (hereinafter also referred to as “branch”) structure may be realized. It is difficult and the adjustment of the content is not easy, so it is difficult to adjust the microstructure of the polymer. For these reasons, there is a limit to effectively improving the physical properties.

US Pat. No. 7,915,349 U.S. Pat. No. 8,426,513 U.S. Pat. No. 8,383,711 European Patent No. 2045272 US Pat. No. 8,278,395 Korean Patent No. 20045225 Specification

The present invention selectively blends linear and branched conjugated diene polymers polymerized with other reactive groups, using an additional modifier, at a fixed ratio, thereby allowing a modification rate and a macromolecular structure. A modified conjugated diene polymer material capable of increasing the affinity with an inorganic filler and improving the dispersibility when compounded using the method for producing a modified conjugated diene polymer capable of adjusting provide.
As described above, the present invention is excellent in affinity with an inorganic additive during polymerization of a conjugated diene polymer containing an inorganic filler, and improves the mechanical performance and wear performance of the composite material. For providing a modified conjugated diene polymer and a rubber composition using the same, comprising a linear macromolecular structure having a terminal end modification, a terminal terminal modification or a combination thereof, and a branched macromolecule It is.

The present invention relates to a method for producing a mixed conjugated diene polymer obtained from a solution blend of a linear terminal-modified conjugated diene polymer and a high molecular weight branched conjugated diene polymer, and a polymer produced by this method. The present invention relates to the rubber composition used. Here, the linear terminal-modified modified conjugated diene polymer means a conjugated diene polymer produced by introducing a terminal modifier in a state where the terminal terminal is activated by an anion.
The branched high molecular weight conjugated diene polymer is a multivalent branched polymer produced by adding a coupling agent with the terminal end activated to an anion, and is a star polymer. Means.
The terminal modification presented in the linear terminal-modified conjugated diene polymer uses alkyl lithium as an initiator. The polymerization initiator is a polymerization initiator represented by the following chemical formula 1.

      R (Li) x Formula 1

In the chemical formula, R is a hydrocarbyl group having 2 to 8 carbon atoms per R group, and x is an integer of 1 to 4. The linear terminal modified conjugated diene polymer is a linear styrene-butadiene copolymer having one or both ends activated to an anion at the time of production of a linear structure by producing a styrene-butadiene polymer active anion using the initiator. Amines, alkoxysilanes, cyanos, hydroxys, carboxys, sulfones, phosphates, ethers, acrylics, methacrylates, and ester modifiers are added to the coalescence as terminal modifiers, and one end is modified. It means the one that produced the polymer.
A branched conjugated diene polymer is prepared by polymerizing a styrene-butadiene anion whose terminal end is activated to an anion using normal butyl lithium as an initiator, and then coupling the coupling agent according to the number of functional groups. One equivalent is charged, and 80% or more means that a branched conjugated diene polymer is produced.

The conjugated diene polymer used in the production of the rubber composition means one produced through a solution brand of one or more of the previously produced linear shapes and a branch shape.
In order to produce a modified conjugated diene polymer using the blend presented in the present invention, not only anionic initiators alkyllithium, alkylsodium and alkylpotassium in two reactors, but also a specific form of anion. The conjugated diene polymers having different linear and branched shapes are prepared using an initiator having an ionic form, and then mixed at a constant ratio in a mixing tank, and then manufactured through a steam stripping and drying process.
More specifically, when producing a linear conjugated diene polymer, after filling the reactor with a monomer, a solvent, and a molecular modifier (randomizing agent), an anionic initiator is added to terminate the anion. This means a modified conjugated diene-based linear polymer obtained by performing a conjugated diene-based polymer polymerization having an active terminal and then adding a terminal modifier. Detailed methods can be confirmed from the examples specified below.

  The branched conjugated diene polymer is a branched conjugated diene polymer having a linear active terminal as described above by using a coupling agent having three or more functional groups capable of reacting with the activated living anion. A conjugated diene polymer is produced.

  The additional terminal modifier is a compound intended for terminal modification, and the coupling agent is a compound for adjusting the mechanical properties of the conjugated diene polymer and has three functional groups capable of reacting with the active anion. That means the above. In general, any substance capable of reacting with an anion is possible, and a substance having an increased molecular weight or a modified polymer structure depending on the number of functional groups can be obtained. In general, tin series, alkoxysilane, or silyl halide can be used, and a compound containing a glycidyl group can also be used. For example, the tin series includes diphenyltin dichloride, dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, tetrachlorotin, tetramethoxytin, tetraethoxytin, tetrapropoxytin The alkoxysilane series is dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane , Ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, etc. It is.

The silyl halide series is diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, tetra Chlorosilane or the like is used.
Compounds containing a glycidyl group include 4,4′-methylenebis (N, N-diglycidylaniline), N, N-diglycidyl-4-glycidoxyaniline, N, N-diglycidylaniline, N, N, N′-N′-tetraglycidyl-3,3′-diethyl-4,4′-diaminodiphenylmethane and the like are used.

In addition, tertiary butyl acrylate, aminosilane derivatives containing ester groups such as ((triacryloxypropyl) trimethoxysilane), and bis (3-methylamino) propyl) trimethoxysilane (Bis (3- Derivatives having both an amino group and an alkoxysilane can also be used, such as methylamino) propyl) trimethoxysilane).
The terminal modifiers and coupling agents exemplified above can be used alone or in admixture of two or more. Exemplifying compounds is not intended to limit the structure, but any compound capable of reacting with a terminal end having an anion activity such as tin series, alkoxysilane series, silyl halide series, and glycidyl series is used. Is possible.

  The present invention relates to a conjugated diene polymer utilizing linearity and branch shape, and not only increases the storage stability of products and compatibility with inorganic fillers, but also rubber composites with fillers and vulcanizing agents. A tire tread material having an excellent balance of sheet processability, low hysteresis loss property, and wet skid property during material cross-linking can be provided.

1 is a gel permeation chromatography (GPC) of a blend conjugated diene polymer.

While the present invention can be modified in various ways and can have various embodiments, preferred embodiments are presented to assist in understanding the present invention, but the following embodiments illustrate the present invention. However, the scope of the present invention is not limited to the following examples.
The present invention is a polymerization method of a modified conjugated diene polymer polymerized into a copolymerized form using a functional styrene monomer and a conjugated diene monomer capable of anionic polymerization using a solution polymerization method, Is excellent in storage stability, and is compounded and crosslinked with an inorganic additive to provide a composition excellent in mechanical strength and dispersibility.
The modified conjugated diene polymer presented in the present invention can be produced through polymerization as described below.

  In two different reactors, one uses the anion initiators alkyllithium, alkylsodium, and alkylpotassium to produce a conjugated diene system with one end of the linear structure active at the anion, and then the modifier is added. One end is modified to terminate the reaction, and a terminal mono-modified linear conjugated diene polymer is produced. In the other reactor, the end of the linear structure is an anion-activated conjugated diene polymer. After the production, a coupling agent is added to produce a branched conjugated diene polymer. In this method, the two samples thus obtained are blended in the form of a solution, the residual solvent is removed using a steam stripper, and then dried to produce a modified conjugated diene polymer.

  In the above, a polar additive may be optionally added during the polymerization. The polar additive is added to control the microstructure of the polymer, to improve the polymerization rate, or to adjust the reactivity, and the addition amount varies depending on the purpose and type of the additive. Examples of polar additives include tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), diethyl ether, cycloamal ether, dipropyl ether, ethylene glycol, triethylamine, ethyl butyl ether, crown ether, ditetrahydrofurylpropane, ethyltetrahydrofuryl. Ether, triethylamine, trimethylamine and their derivatives are used. With such a polar additive, the random structure of the polymer and the content of the vinyl group can be adjusted according to the purpose, and the polymerization reaction rate may be improved.

As the solvent used in the polymerization, n-hexane, n-heptane, cyclohexane, isooctane, methylcyclopentane, benzene, toluene, xylene, tetrahydrofuran, or the like is used as a hydrocarbon solvent, and these are used alone or in combination of two or more. be able to. A monomer is added so that it may become 5 to 50 weight% in the said hydrocarbon solvent. Preferably, it is added at a level of 15 to 35% by weight. If it is less than 5% by weight, the polymerization time may be long or the reaction may be difficult. If it is 50% by weight or more, the viscosity of the solution will increase and it will be difficult to control the molecular weight and reaction heat, and uniform stirring during polymerization will be difficult.
The polymerization temperature during the polymerization varies depending on the solvent, and the polymerization is generally possible at 10 to 160 ° C. The fine structure varies depending on the polymerization temperature, and the polymerization temperature can be adjusted according to the purpose.
The microstructure of the conjugated diene polymer produced is preferably a structure having a vinyl content of 20 to 60 wt% and a styrene content of 15 to 45 wt%. The reason is that if the vinyl content or styrene content is too low, the glass transition temperature of the polymer will be low, the glass transition temperature of the tire composite will be low as well, and the grip performance on wet road surfaces (wet-grip performance, If the value is too high, the rolling resistance (Tan σ 60 ° C. value) may increase, and the fuel ratio characteristics may deteriorate.

Before introducing the terminal modifier, a conjugated diene monomer or vinyl hydrocarbon monomer is added depending on the anion reactivity of the polymer terminal or in order to improve the stability or efficiency of the bond between the additional modifier and the polymer. A modifier may be added after the addition.
In addition to the proposed styrene-butadiene conjugated diene polymer, other rubber components can be blended together, and other rubber components include natural rubber (NR), isoprene rubber (IR), butadiene rubber ( BR) and a rubber composition containing a diene rubber such as neodymium butadiene rubber (NdBR) can be used together. Moreover, the present invention can be applied not only to blends between products produced in a batch system, but also to conjugated diene polymers produced in a continuous system.
The reason for adjusting the content of the linear structure and the number average molecular weight of the linear / branched polymer in the production of the blend sample is to produce the blend sample at the Mooney viscosity required during the production of the tire composite.

The content of the linear structure is preferably 10 to 60 parts by weight, but if it is less than 10 parts by weight, it is not preferable because the Mooney viscosity of the blend sample greatly increases, and if it exceeds 60 parts by weight, the Mooney viscosity becomes too high and the tire composite This is not preferable because the workability deteriorates during the manufacture of the material.
The content of the branch structure is preferably 40 to 90 parts by weight. However, if the content is less than 40 parts by weight, the workability is improved, but the physical properties of the final tire composite are deteriorated. The physical properties of the composite material are good, but the workability is lowered, which is not preferable.
In the present invention, the polymer having a linear structure has a number average molecular weight of 100,000 to 200,000 g / mol, and the linear anion active styrene-butadiene copolymer before coupling of the branched polymer has a number average molecular weight of 100,000. It is preferably ˜400,000 g / mol.
When producing a tire composite using carbon black or silica, the Mooney viscosity of the rubber used is produced using rubber having a Mooney viscosity of 30 to 180 depending on the compounding application. If the content of the linear structure is too high or the number average molecular weight is produced too low, the Mooney viscosity may be produced to 30 or less, and conversely the content of the linear structure is too low or the number average molecular weight is too low. This is because the Mooney viscosity may exceed 180 at higher levels.

  The rubber compounding can be generally used for tires, and the inorganic particle additive can be used alone or in combination of two or more of carbon black, silica and the like. At this time, the amount of the inorganic filler to be used is preferably added to 200 parts by weight or less of the raw rubber in consideration of processability, and there are a large number of functional groups on the surface of the inorganic particles such as silica particularly at the time of compounding. When the modified conjugated diene polymer presented by the present invention is added to the inorganic particle additive, the performance is further improved.

1． Analysis of polymer microstructure The microstructure of the polymerized polymer was confirmed using Bruker's 400 MHz 1H-NMR.
2． Measurement of molecular weight The molecular weight was measured by connecting two 5 μm mixed-C column polystyrenes from PLgel in series, a polystyrene standard sample (molecular weight 5000 g / mol) together with the polymer, and the solvent using THF. A refractive index detector (RI) was used as a detector. In the method, two columns filled with silica-based gel (Zorbax OSM) are connected in series, THF is used as the solvent, and the modification rate means the modification rate of the modified conjugated diene polymer. Two columns packed with silica gel are connected in series, and the solvent is a value calculated using THF, which can be analyzed by the experimental method presented in the present invention.

3． Measurement of Denaturation Rate Two columns packed with silica gel (Zorbax PSM) were connected in series, THF was used as a solvent, and a detector was measured with a refractive index detector (RI). A polystyrene reference sample (molecular weight 5000 g / mol) was dissolved together with the polymer and injected into a column for measurement.
Denaturation rate (%) = [1- (A2 × A3) / (A1 × A4)] × 100
A1: When the total peak area obtained with the styrene gel column is 100, the total peak area of the sample (excluding the peak area of the polystyrene reference sample)
A2: When the area of the total peak obtained on the styrene gel column is 100, the peak area of the polystyrene reference sample
A3: When the total peak area obtained with a silica gel column is 100, the peak area of the sample not adsorbed on the silica gel
A4: When the total peak area obtained with a silica gel column is 100, the higher the peak area modification rate of the polystyrene reference sample, the better the performance due to the rubber compounding and vulcanization process. It is preferable to maximize the modification rate. In general, the modification rate should be 10% or more, preferably 20% or more.

Four. Tensile experiment Vulcanized specimens were manufactured as c-type dumbbells and measured using a universal testing machine (LLOYD UTM) according to the ASTM 412 tensile test method.
Five. Viscoelastic properties The tanσ, which is the viscoelastic properties of the vulcanized test piece, was measured using a DMTA equipment while changing the temperature (temperature sweep) under 10 Hz and 0.1% deformation conditions. When the tan σ value at 0 ° C. is high, the wet skid property, which is a braking property, is excellent, and when the tan σ value at 60 ° C. is low, low hysteresis property is exhibited and the fuel ratio is good.

6． Dispersibility of the inorganic particles The dispersibility of the modified conjugated diene system and the inorganic particles was confirmed by the Payne effect using RPA2000 of Alpha Technology Co., Ltd., after blending with Hakke and before vulcanization.
The Payne effect indicates the difference between 0.7% and 14% deformation at 0.1 Hz and 60 ° C. in kPa, and the smaller the value, the better the dispersibility of the inorganic particles.
7． Mooney Viscosity The Mooney viscosity of the modified conjugated diene polymer itself was measured using an Moon Technology Mooney viscometer at 100 ° C. based on ML (1 + 4).

Example 1
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 150,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Thereafter, ethanol as a reaction terminator was added to terminate the polymerization, and 0.2 wt% of an antioxidant I-1076 was added to the polymer to produce a linear SBR solution.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 300,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 20 parts by weight (40 g) and 2) 80 parts by weight (160 g) based on 100 parts by weight of total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of an unmodified conjugated diene polymer blend specimen.

Example 2
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 150,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, the modifier diethoxydimethylsilane was added in a mole number of 1.2 with respect to the mole number of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. Thereafter, ethanol as a reaction terminator was added to stop the polymerization, and 0.2 wt% of antioxidant I-1076 was added to the polymer to produce an SBR solution modified at one end with ethoxysilane. did.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 300,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blended SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 20 parts by weight (40 g) and 2) 80 parts by weight (160 g) based on 100 parts by weight of total solids. The mixture was stirred for 30 minutes to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Example 3
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 150,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, the modifier (3-cyanopropyl) dimethylchlorosilane ((3-Cyanopropyl) dimethylchlorosilane) was charged in a mole ratio of 1.2 with respect to the moles of butyl lithium (BuLi) charged, and reacted for 10 minutes. I let you. Thereafter, ethanol as a reaction terminator was added to terminate the polymerization, and I-1076, an antioxidant, was added at 0.2 wt% to the polymer to produce an SBR solution modified at one end with a cyano group. did.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 300,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 20 parts by weight (40 g) and 2) 80 parts by weight (160 g) based on 100 parts by weight of total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Example 4
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 150,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, the modifier 1- (2-chloroethyl) -2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane (1- (2-chloroethyl) -2,2,5 , 5-tetramethyl-1-aza-2,5-disilacyclopentane) was added at a ratio of 1.2 moles to the moles of butyllithium (BuLi) charged and allowed to react for 10 minutes. Thereafter, the reaction termination agent ethanol was added to stop the polymerization, and the antioxidant I-1076 was added 0.2 wt% to the polymer, and one end was modified with nitrogen and a silicon compound. Manufactured.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 300,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 20 parts by weight (40 g) and 2) 80 parts by weight (160 g) based on 100 parts by weight of total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Example 5
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 120,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Thereafter, ethanol as a reaction terminator was added to terminate the polymerization, and 0.2 wt% of an antioxidant I-1076 was added to the polymer to produce a linear SBR solution.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 350,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 40 parts by weight (80 g), 2) 60 parts by weight (120 g), based on 100 parts by weight of the total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of an unmodified conjugated diene polymer blend specimen.

Example 6
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 120,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. The modifier diethoxydimethylsilane was added at a mole number of 1.2 with respect to the moles of butyllithium (BuLi) charged and allowed to react for 10 minutes. Thereafter, ethanol as a reaction terminator was added to stop the polymerization, and 0.2 wt% of antioxidant I-1076 was added to the polymer to produce an SBR solution modified at one end with ethoxysilane. did.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 350,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.
3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 40 parts by weight (80 g), 2) 60 parts by weight (120 g), based on 100 parts by weight of the total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Example 7
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 120,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, the modifier (3-cyanopropyl) dimethylchlorosilane ((3-Cyanopropyl) dimethylchlorosilane) was charged in a mole ratio of 1.2 with respect to the moles of butyl lithium (BuLi) charged, and reacted for 10 minutes. I let you. Thereafter, ethanol as a reaction terminator was added to terminate the polymerization, and I-1076, an antioxidant, was added at 0.2 wt% to the polymer to produce an SBR solution modified at one end with a cyano group. did.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 350,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.

3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 40 parts by weight (80 g), 2) 60 parts by weight (120 g), based on 100 parts by weight of the total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Example 8
1) Manufacture of linear SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, 10 ml of tetramethylethylenediamine (TMEDA) was added, and the temperature of the reactor was increased to 50 ° C. while rotating with a stirrer. Butyl lithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 120,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, the modifier 1- (2-chloroethyl) -2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane (1- (2-chloroethyl) -2,2,5 , 5-tetramethyl-1-aza-2,5-disilacyclopentane) was added at a ratio of 1.2 moles to the moles of butyllithium (BuLi) charged and allowed to react for 10 minutes. Thereafter, the reaction termination agent ethanol was added to stop the polymerization, and the antioxidant I-1076 was added 0.2 wt% to the polymer, and one end was modified with nitrogen and a silicon compound. Manufactured.

2) Manufacture of branch SBR
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Butyllithium (BuLi) was added thereto, and a linear SBR having a weight average molecular weight (Mw) of about 350,000 g / mol was polymerized through a polymerization reaction. After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to replace the terminal end of the polymer with butadiene active anions for 5 minutes. Here, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added at a mole number of 1/3 with respect to the moles of butyl lithium (BuLi) charged, and allowed to react for 10 minutes. . After the reaction, ethanol was added to terminate the polymerization, and an antioxidant I-1076 was added in an amount of 0.2 wt% to the polymer to produce a branched SBR solution.
3) Manufacture of blend SBR After mixing 1) and 2) prepared in advance at a ratio of 1) 40 parts by weight (80 g), 2) 60 parts by weight (120 g), based on 100 parts by weight of the total solids, 30 The mixture was stirred for a minute to produce a uniform mixed solution, and the solvent hexane was removed using a steam stripper. The water content of the obtained solid was dried using a processing roll at 100 ° C. to produce a 200 g terminal mono-modified conjugated diene polymer blend specimen.

Comparative Example 1
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Here, 10.5 mmol of 0.3M butyl lithium (BuLi) was added to cause a polymerization reaction, and after 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to end the polymer for 5 minutes. Substituted with butadiene active anion. Here, 2.9 mmol of tetramethoxysilane was added and allowed to react for 10 minutes. After the reaction, ethanol was added to terminate the polymerization, and 0.2 wt% of the antioxidant I-1076 was added to the polymer. Thereafter, hexane as a solvent was removed using a steam stripper. The moisture of the obtained solid was dried using a processing roll at 100 ° C. to produce a sample.

Comparative Example 2
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Here, 10.5 mmol of 0.3M butyl lithium (BuLi) was added to cause a polymerization reaction, and after 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added to end the polymer for 5 minutes. Substituted with butadiene active anion. Here, 2.9 mmol of tetraethoxysilane was added and allowed to react for 10 minutes. After the reaction, ethanol was added to terminate the polymerization, and 0.2 wt% of the antioxidant I-1076 was added to the polymer. Thereafter, hexane as a solvent was removed using a steam stripper. The moisture of the obtained solid was dried using a processing roll at 100 ° C. to produce a sample.

Comparative Example 3
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, and 10 ml of tetramethylethylenediamine (TMEDA) was added. Here, 10.5 mmol of 0.3 M butyllithium (BuLi) was added and allowed to undergo a polymerization reaction.After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added and the terminal end of the polymer was placed for 5 minutes. Substituted with butadiene active anion.
To this, 2.9 mmol of 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) was added and allowed to react for 10 minutes. After the reaction, ethanol was added to terminate the polymerization, and 0.2 wt% of the antioxidant I-1076 was added to the polymer. Thereafter, hexane as a solvent was removed using a steam stripper. The moisture of the obtained solid was dried using a processing roll at 100 ° C. to produce a sample.

Comparative Example 4
In a 10 L autoclave reactor, 170 g of styrene, 630 g of 1,3-butadiene and 4150 g of hexane were added, 10 ml of tetramethylethylenediamine (TMEDA) was added, and the temperature of the reactor was increased to 50 ° C. while rotating with a stirrer. Here, 10.5 mmol of 0.3 M butyllithium (BuLi) was added and allowed to undergo a polymerization reaction.After 10 minutes had passed since the reaction temperature reached the maximum temperature, 50 g of butadiene was added and the terminal end of the polymer was placed for 5 minutes. Substituted with butadiene active anion. To this, 2.9 mmol of bis (methyldimethoxysilylpropyl) -N-methylamine (Bis (methyldimethoxysilylpropyl) -N-methylamine) was added and reacted for 10 minutes. After the reaction, ethanol was added to terminate the polymerization, and 0.2 wt% of the antioxidant I-1076 was added to the polymer. Thereafter, hexane as a solvent was removed using a steam stripper. The moisture of the obtained solid was dried using a processing roll at 100 ° C. to produce a sample.

Experimental Example Kneading of Polymer and Inorganic Material and Physical Property Measurement Experiment The rubber composition of the polymer obtained above was kneaded using Thermo Scientific's Haake Polylab OS Rheodrive, and a Banbury rotor was used. The polymers obtained in the examples and comparative examples were blended in the compositions shown in the following table.
Formulation proceeded in two stages. In the first kneading, 75% is filled in the first kneading, and the polymer, filler (silica), oil, zinc oxide (ZnO), stearic acid, silane coupling agent (Si-69) at a rotor speed of 60 rpm. ), An antioxidant (6-PPD) is added to control the temperature, and a primary rubber composition is obtained at 150 to 160 ° C. In the second kneading, the blend was cooled to room temperature, and sulfur, DPG (Diphenyl Guanidine) and CBS (N-cyclohexyl-2-benzothiazole sulfonamide) were added and kneaded at 90 ° C. or lower for 5 minutes.
The compounded rubber is vulcanized at 160 ° C with a T90 + 5min press to produce a vulcanized rubber.

  The polymers and polymer blends prepared according to the present invention were analyzed and evaluated for performance and are shown in Tables 2-7.

  The solution styrene butadiene rubber produced by polymerizing the linear and branched structures independently and mixing them into a solution form is colder than the solution styrene butadiene rubber produced in the batch system. It was confirmed that the flow was low, the storage stability was excellent, the trivalent branch shape was included, and the mechanical strength (tensile strength, modulus) and wear performance were improved. In addition to providing various functional groups at the end of the linear structure to improve the dispersibility of the reinforcing material, it also shows improved viscoelasticity and exhibits excellent physical properties when used as a tire tread material I was able to confirm.

Claims (8)

After the solution blending of anionic solution polymerization reaction products polymerized into a linear and branched structure from two or more batch type reactors using a styrene monomer and a butadiene monomer, A styrene-butadiene copolymer from which
1) The content of linear structure is 10-60 parts by weight,
2) A method for producing a styrene-butadiene copolymer having a branch structure content of 40 to 90 parts by weight.   The linear structure polymer has a number average molecular weight of 100,000 to 200,000 g / mol, and the linear anion active styrene-butadiene copolymer has a number average molecular weight of 100,000 to 400,000 before coupling of the branched structure polymer. It is g / mol, The manufacturing method of the styrene-butadiene-type copolymer of Claim 1 characterized by the above-mentioned.   The method for producing a styrene-butadiene copolymer according to claim 1, wherein the end of the linear polymer is at least one of alkoxysilane, amine, cyano, and amine-silane.   Any one of compounds containing tin series, alkoxysilane, silyl halide, and glycidyl group as a coupling agent to a linear styrene-butadiene copolymer whose one end is activated to an anion at the time of manufacturing the branched structure The method for producing a styrene-butadiene copolymer according to claim 1, wherein the above is used.   The styrene-butadiene copolymer according to claim 1, wherein the styrene-butadiene copolymer having a linear structure and a branched structure has a styrene content of 15 to 45 wt% and a vinyl content of 20 to 60 wt%. A method for producing a polymer.   The method for producing a styrene-butadiene copolymer according to claim 1, wherein the Mooney viscosity of the styrene-butadiene copolymer is 30 to 180.   In the production of the rubber composite material, 0.1 to 200 parts by weight of an inorganic filler is included with respect to 100 parts by weight of the styrene-butadiene copolymer produced by the production method according to claims 1 to 6. A rubber composition for a tire tread characterized by comprising:   The rubber composition for a tire tread according to claim 7, wherein the inorganic filler is carbon black or a silica-based filler used alone or in combination.