JP6615739B2 - Modified conjugated diene polymer and tire rubber composition using the same - Google Patents

Description

  The present invention relates to a conjugated diene polymer having an increased modification rate, and at the time of production of a rubber composite material using a filler and a vulcanizing agent, it balances sheet processability, low hysteresis loss, and wet skid properties. It is intended to provide excellent tire tread materials.

  In the case of styrene butadiene rubber (SSBR) obtained by solution polymerization, generally an organometallic catalyst having carbon anionic property is used as an initiator, and the molecular weight and molecular weight distribution are characteristic of the polymerization method called anionic polymerization. Of course, not only the macro-structure of the polymer but also the macro-structure can be adjusted, and when used for tire treads, it is a rubber material that improves braking performance and fuel ratio on wet road surfaces Can be designed.

  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 modified compound. The synthesized modified conjugated diene polymer uses a technique for improving the compatibility and dispersibility of an amine group present at the terminal and an inorganic additive such as silica in which alkoxysilane has a polar group on the surface. is there. However, since the polymerization is initiated with a carbon-based organometallic catalyst initiator that does not have a functional group, the starting end where polymerization begins cannot be modified, and only the terminal end of the polymer is limited. In addition, when a coupling reaction occurs due to a trivalent or higher-valent modifier that can react with an anion in order to increase molecular weight or improve processability, the functional group moiety exists in the center of the modified conjugated diene polymer. Therefore, there is a limit in effectively improving the compatibility and dispersibility with the inorganic additive. When a tire tread is produced with such a modified conjugated diene system, the fuel ratio is lowered due to the unmodified polymer starting end, or the balance between the braking performance and the fuel ratio is lowered.

  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, there is a limit to effectively improving it for the reasons described above. In the case of a solution-polymerized conjugated diene polymer produced using a trivalent coupling agent, the molecular weight is 200,000 to 600,000 g / mol. When silica and a composite material are produced, the existing ESBR and carbon black composite The results show that the wear characteristics that affect the tire life are significantly lower than the material.

  US 5487848 A (Patent Document 7) and WO 2002008300 A1 (Patent Document 8) introduced the production of polyvalent conjugated diene polymers utilizing a divalent or higher anionic lithium catalyst. As initiators used, 1,3-divinylbenzene (1,3-divinylbenzene), 1,3-diisopropenylbenzene (1,3-diisopropenylbenzene), 1,3,5-trivinylbenzene (1,3 , 5-trivinylbenzene), 1,3,5-triisopropenylbenzene, etc. react with butyl lithium, secondary butyl lithium, divalent or A trivalent anionic initiator was produced, and this was used for polymerization to produce a conjugated diene polymer. While this technique has an effect of increasing the terminal modification rate, a gelation reaction may occur during the coupling reaction, and it is difficult to use commercially.

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 US Pat. No. 5,487,848 International Publication No. 2002/008300 Pamphlet

  The present invention utilizes an amphoteric initiator to produce a styrene-butadiene conjugated diene polymer having both ends activated to anions, and optionally using an additional modifier to form both ends modified linear ( (Hereinafter also referred to as “linear”) conjugated diene polymer is produced and blended in a fixed ratio with a branched chain (hereinafter also referred to as “branch”) conjugated diene polymer polymerized using another reactor. To produce a modified conjugated diene polymer capable of adjusting the modification rate, macromolecular structure and content, and to increase the affinity with the inorganic filler when compounding using the same and the dispersibility thereby A modified conjugated diene polymer material is provided.

In the rubbery form of the inorganic additive, the amphoteric initiator is used to simultaneously have a linear structure having functional groups that can be easily mixed with silica at both ends and a branched structure that is a macromolecule. Modified conjugated diene polymer having improved fuel efficiency, high braking performance, high wear and the like when used in a tire tread by improving dispersion and improving the mechanical performance and wear of the cross-linked specimen, and rubber using the same For providing a composition.

The present invention relates to a mixed conjugate obtained from a solution blend of a linear conjugated diene polymer having functional groups compatible with silica at both ends using an amphoteric initiator and a high molecular weight branched conjugated diene polymer. The present invention relates to a diene polymer and a rubber composition using the same.
Here, the linear polymer modified at both ends means a conjugated diene polymer produced by introducing a terminal modifier in a state where both ends are activated by anions.

  Initiators used include 1,3-divinylbenzene, 1,3-diisopropenylbenzene, 1,3,5-trivinylbenzene (1,3 , 5-trivinylbenzene) and 1,3,5-triisopropenylbenzene, etc. should be used with initiators reacted with butyl lithium and secondary butyl lithium. In the present invention, 1,3-diisopropenylbenzene (1,3-diisopropenylbenzene) is mixed with tertiary-butyllithium (tert-butyllithium (BuLi)) to form an amphoteric initiator (DIB-dianion). Is used to produce a styrene-butadiene polymer having both terminal active anions, and a linear styrene-butadiene copolymer having both ends activated to anions as amine modifiers and alkoxysilanes. , Cyano, hydroxy It means a polymer in which both ends are modified by introducing a series, carboxy, sulfone, phosphate, ether, acrylic, methacrylate or ester modifier.

The conjugated diene polymer used in the production of the rubber composition means one produced through a solution blend of one or more linearly modified ones and a branched one produced in advance.
More specifically, when producing a linear conjugated diene polymer, after filling the reactor with monomers, solvent, and molecular modifier (randomizing agent), an amphoteric initiator is added and both ends are anions. It means a conjugated diene-based linear polymer obtained by polymerizing a conjugated diene polymer having an active terminal and then adding a terminal modifier. Detailed methods can be confirmed from the examples specified below.
The branched high molecular weight conjugated diene polymer is a polyvalent branch produced by adding a coupling agent with the terminal end activated to an anion, and is a star-shaped polymer. means.
Branched conjugated diene polymers use normal butyl lithium as an initiator, and after styrene-butadiene anion polymerization whose terminal ends are activated with anions, the coupling agent is compared with anions according to the number of functional groups. It means the production of a conjugated diene polymer in which 1 equivalent is added and 90% or more is branched.
The conjugated diene polymer used in the production of the rubber composition means a polymer prepared through a solution blend of one or more linearly modified ones and a branched one prepared in advance.

A branched conjugated diene polymer is obtained by using a coupling agent having three or more functional groups capable of reacting with an activated living anion in the conjugated diene polymer having a linear active terminal described above. A branched conjugated diene polymer is produced.
The coupling agent can be any agent that can react with anion in general, and the molecular weight can be increased according to the number of functional groups or the polymer structure can be modified. To obtain a polymer, a trivalent or higher valent coupling agent must be used.

  Generally, a 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, tetrachlorosilane Etc. are 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, an aminosilane derivative containing an ester group such as tertiary butyl acrylate or ((triacryloxypropyl) trimethoxysilane) is used.
The 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 an amphoteric initiator, which is a blend of amphoteric linearity and branch shape (blend), sheet processability during the production of a rubber composite with a filler and a vulcanizing agent, A tire tread material having an excellent balance between low hysteresis loss and wet skid can be provided.

It is a conceptual diagram for manufacture of a modified conjugated diene polymer containing a both-end modified 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 modified conjugated diene polymer presented in the present invention can be produced through polymerization as described below.
In two different reactors, one uses an amphoteric initiator (DIB-dianion) to produce a conjugated diene system in which both ends of the linear structure are active on anions, and then a denaturant is added to modify both ends. Then, after the reaction was completed, a linear conjugated diene polymer modified at both ends was produced, and in other reactors, a conjugated diene system in which the end of the linear structure was activated by an anion was produced, and then a coupling agent To produce a branched conjugated diene polymer. This is a method for producing a modified conjugated diene polymer by blending the two samples thus obtained in the form of a solution, removing the residual solvent using a steam stripper, and then drying.
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 for polymerization, n-hexane, n-heptane, cyclohexane, isooctane, methylcyclopentane, benzene, toluene, xylene, tetrahydrofuran, etc. are used as hydrocarbon solvents, 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 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 with the Mooney viscosity required during the production of the tire composite.

The content of both end-modified linear structures is preferably 10 to 60 parts by weight, but if it is less than 10 parts by weight, the Mooney viscosity of the blend sample is greatly increased, which is not preferable, and if it exceeds 60 parts by weight, the Mooney viscosity becomes too high. In addition, the processability is lowered during the manufacture of the tire composite material, which is not preferable.
In the present invention, the polymer having a both-end modified linear structure has a number average molecular weight of 100,000 to 200,000 g / mol, and the number average of the linear anion active styrene-butadiene copolymer before coupling of the branched polymer. The molecular weight is preferably 100,000 to 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 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.
Depending on the anion reactivity at the end of the polymer before charging the end modifier, to stabilize the bond between the additional modifier and the polymer, or to improve efficiency, conjugated diene monomers and vinyl hydrocarbons The modifier may be added after the additional monomer is added.
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. In particular, when blended, the performance of the modified conjugated diene polymer presented by the present invention is further excellent in an inorganic particle additive having a large number of functional groups on the surface of inorganic particles such as silica.

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 polystyrene 5 μm mixed-C columns 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 packed with silica gel (Zorbax PSM) 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 then injected into a column for measurement.
Denaturation rate (%) = [1- (A2 × A3) / (A1 × A4)] × 100
A1: Total peak area of the sample (excluding the peak area of the polystyrene reference sample) when the total peak area obtained with the styrene gel column is 100
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 Tan δ, which is the viscoelastic properties of the vulcanized specimens, was measured using a DMTA equipment while changing the temperature (temperature sweep) under 10 Hz and 0.1% deformation conditions. When the tan δ value at 0 ° C. is high, the wet skid property, which is a braking property, is excellent, and when the tan δ 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. DIB-diamion was added here, 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 both ends of the polymer with butadiene active anions for 5 minutes. The modifier diethoxydimethylsilane was added at a mole number of 2.2 with respect to the moles of DIB-diamion charged and allowed to react for 10 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 a modified 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. DIB-diamion was added here, 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 both ends of the polymer with butadiene active anions for 5 minutes. Here, a modifier (3-cyanopropyl) dimethylchlorosilane ((3-Cyanopropyl) dimethylchlorosilane) was added at a mole number of 2.2 with respect to the moles of DIB-diamion charged and reacted for 10 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 a 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. DIB-diamion was added here, 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 both ends 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 mole number of 2.2 with respect to the moles of DIB-diamion charged and allowed to react for 10 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 After stirring for a minute to produce a uniform mixed solution, hexane as a solvent was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a 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. DIB-diamion was added here, 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 both ends of the polymer with butadiene active anions for 5 minutes. The modifier diethoxydimethylsilane was added at a mole number of 2.2 with respect to the moles of DIB-diamion charged and allowed to react for 10 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 blended SBR 1) and 2) manufactured in advance are mixed 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 total solids, and 30 minutes After stirring to produce a uniform mixed solution, hexane as a solvent was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a 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. DIB-diamion was added here, 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 both ends of the polymer with butadiene active anions for 5 minutes. Here, a modifier (3-cyanopropyl) dimethylchlorosilane ((3-Cyanopropyl) dimethylchlorosilane) was added at a mole number of 2.2 with respect to the moles of DIB-diamion charged and reacted for 10 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 blended SBR 1) and 2) manufactured in advance are mixed 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 total solids, and 30 minutes After stirring to produce a uniform mixed solution, hexane as a solvent was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a modified 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. DIB-diamion was added here, 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 both ends 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 mole number of 2.2 with respect to the moles of DIB-diamion charged and allowed to react for 10 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 blended SBR 1) and 2) manufactured in advance are mixed 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 total solids, and 30 minutes After stirring to produce a uniform mixed solution, hexane as a solvent was removed using a steam stripper. The obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a modified conjugated diene polymer blend specimen.

Comparative 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. 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 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 a single-terminal modified conjugated diene polymer blend specimen.

Comparative 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 (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 obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a single-terminal modified conjugated diene polymer blend specimen.

Comparative 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 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 obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a single-terminal modified conjugated diene polymer blend specimen.

Comparative 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, 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. 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 obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a single-terminal modified conjugated diene polymer blend specimen.

Comparative 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. 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 obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a single-terminal modified conjugated diene polymer blend specimen.

Comparative 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, 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 obtained solid was dried using a processing roll at 100 ° C. to produce 200 g of a single-terminal modified conjugated diene polymer blend specimen.

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.
Blending 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 produced according to the present invention were analyzed and evaluated for performance and are shown in Tables 2-9.

Claims (5)

Both end-modified linear conjugated diene polymers and branched conjugated diene polymers are solution polymerized using two batch reactors connected in parallel, and the both-end modified linear conjugated diene systems The both-end-modified linear conjugated diene polymer and the branched conjugated diene polymer are in solution so that the polymer content is 10 to 60 parts by weight based on 100 parts by weight of the total solid content after blending. A method for producing a modified conjugated diene polymer blend, which comprises blending to obtain a mixed solution and solidifying the obtained mixed solution.   In the production of the branched conjugated diene polymer, one or more of a tin series, an alkoxysilane, a silyl halide, and a glycidyl group as a coupling agent to a linear styrene-butadiene copolymer whose one end is activated to an anion 2. The method for producing a modified conjugated diene polymer blend according to claim 1, wherein any one or more of the compounds containing is used.   The terminal-modified linear conjugated diene polymer has a number average molecular weight of 100,000 to 200,000 g / mol, and a linear anion active styrene-butadiene copolymer before coupling of the branched conjugated diene polymer. The method for producing a modified conjugated diene polymer blend according to claim 2, wherein the number average molecular weight is from 100,000 to 400,000 g / mol.   The method for producing a modified conjugated diene polymer blend according to claim 1, wherein the modified conjugated diene polymer blend has a Mooney viscosity of 30 to 180.   The manufacturing method of a tire rubber composition including the process of manufacturing a modified conjugated diene polymer blend by the manufacturing method as described in any one of Claims 1 thru | or 4.