WO2016076549A1 - Modified conjugated diene polymer, method for preparing same, and rubber composition containing same - Google Patents

Modified conjugated diene polymer, method for preparing same, and rubber composition containing same Download PDF

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Publication number
WO2016076549A1
WO2016076549A1 PCT/KR2015/011230 KR2015011230W WO2016076549A1 WO 2016076549 A1 WO2016076549 A1 WO 2016076549A1 KR 2015011230 W KR2015011230 W KR 2015011230W WO 2016076549 A1 WO2016076549 A1 WO 2016076549A1
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Prior art keywords
conjugated diene
formula
modified conjugated
independently
based polymer
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PCT/KR2015/011230
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French (fr)
Korean (ko)
Inventor
이로미
김노마
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020150140480A external-priority patent/KR101668567B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201580010973.6A priority Critical patent/CN106068289B/en
Priority to JP2016568781A priority patent/JP6307633B2/en
Priority to EP15859197.4A priority patent/EP3093297B1/en
Priority to US15/119,933 priority patent/US9725527B2/en
Publication of WO2016076549A1 publication Critical patent/WO2016076549A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/26—Incorporating metal atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. More specifically, the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. It relates to a modified conjugated diene-based polymer having a resistance, a preparation method thereof, and a rubber composition comprising the same.
  • the tire tread was used in combination with an inorganic filler in order to reinforce the above properties in the conjugated diene rubber, but there is still much room for improvement in terms of physical properties.
  • the problem to be solved by the present invention is to provide a modified conjugated diene-based polymer and a method for producing the same having excellent exothermicity when included in the rubber composition, and exhibits tensile strength, wear resistance, and wet road resistance.
  • Another object of the present invention is to provide a modifier used in the preparation of the modified conjugated diene-based polymer.
  • Another object of the present invention is to provide a rubber composition and a tire including the same having excellent exothermicity, tensile strength, wear resistance, and wet road resistance including the modified conjugated diene-based polymer.
  • the present invention provides a modified conjugated diene-based polymer represented by the following formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms
  • P is a conjugated diene polymer chain
  • n and m are each independently 1 to 10
  • a And b are each independently 0, 1 or 2
  • c and d are each independently 0, 1, 2 or 3
  • c and d cannot both be 0,
  • a + c and b + d are each independently 1, 2 or 3.
  • the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the present invention provides a modifier represented by the following formula (2).
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the present invention also provides a modified conjugated diene-based polymer rubber composition comprising the modified conjugated diene-based polymer.
  • the present invention also provides a tire or tire tread comprising the modified conjugated diene-based polymer rubber composition.
  • a modified conjugated diene-based polymer having excellent exothermicity and exhibiting tensile strength, abrasion resistance, wet road resistance, and the like when blending silica as a reinforcing agent can be prepared and used in a rubber composition for tires.
  • the present invention provides a modified conjugated diene-based polymer represented by Formula 1:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms
  • P is a conjugated diene polymer chain
  • n and m are each independently 1 to 10
  • a And b are each independently 0, 1 or 2
  • c and d are each independently 0, 1, 2 or 3
  • c and d cannot both be 0,
  • a + c and b + d are each independently 1, 2 or 3.
  • the conjugated diene polymer chain represented by P in Formula 1 may be derived from a homopolymer of conjugated diene monomer or a copolymer of conjugated diene monomer and vinyl aromatic monomer.
  • the conjugated diene polymer chain is a homopolymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in a batch or continuous manner in a hydrocarbon solvent in the presence of an organic alkali metal compound.
  • a copolymer may be formed by reaction with a silyl group substituted with one or more alkoxy groups.
  • the conjugated diene-based polymer chain is a conjugated diene-based monomer.
  • the polymer chain may include 0.0001 to 50% by weight, 10 to 40% by weight, or 20 to 40% by weight of the aromatic vinylic monomer based on a total of 100% by weight of the conjugated diene monomer and the vinyl aromatic monomer.
  • the polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
  • the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
  • the vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be at least one selected from the group consisting of -vinyl-5-hexyl naphthalene, and as another example, may be styrene or ⁇ -methylstyrene.
  • the modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 90, more preferably 50 to 80.
  • the modified conjugated diene-based polymer has, for example, a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 1,000,000 g / mol, most preferably 100,000 to 500,000 g / mol or 200,000 to 700,000 g / mol.
  • Mn number average molecular weight
  • the modified conjugated diene-based polymer may be, for example, a vinyl content of 18% or more, preferably 25% or more, and more preferably 30 to 70%, and the glass transition temperature of the polymer is increased within this range to be applied to a tire. In addition to satisfying the properties required for tires such as driving resistance and braking force, the fuel consumption is reduced.
  • the vinyl content means the content of the monomer having a vinyl group, or the content of the 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene monomer.
  • the modified conjugated diene-based polymer may have a PDI of 1 to 10, preferably 1 to 5, and more preferably 1 to 2.
  • the compound represented by Chemical Formula 1 may be, for example, a compound represented by Chemical Formula 1a.
  • c and d are each independently 0, 1, 2 or 3, and c and d may not be all 0, and n and m are each independently 1 to 10.
  • the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organoalkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the organoalkali metal compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyllithium, It may be at least one selected from the group consisting of n-eicosillithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.
  • the organic alkali metal compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
  • the organoalkali metal compound consists of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, and potassium amide It may be one or more selected from the group, and may also be used in combination with other organic alkali metal compounds.
  • the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, It may be one or more selected from the group consisting of 1-vinyl-5-hexyl naphthalene, and may be styrene or ⁇ -methylstyrene as another example.
  • the organoalkali metal compound is used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, or 0.1 to 1 mmol, based on the total molar ratio of the monomer.
  • the above 'activation molar ratio criteria' means that the organoalkali metal compound used in the present invention may be deactivated depending on the water content, so that the use content is defined based on the activation.
  • an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer can be made.
  • the molar ratio of the organic alkali metal compound and the compound represented by Chemical Formula 2 is, for example, 1: 0.1 to 1:10, preferably 1: 0.3 to 1: 2. When the molar ratio satisfies this range, it is possible to give a modified reaction of optimum performance to the conjugated diene-based polymer.
  • the active polymer having the alkali metal terminal means a polymer in which a polymer anion and an alkali metal cation are bonded.
  • the modified conjugated diene-based polymer production method may be carried out by further adding a polar additive during the polymerization in the step (a).
  • the reason why the polar additive is further added is that the polar additive controls the reaction rate of the conjugated diene monomer and the aromatic vinyl monomer.
  • the polar additive may be a base or an ether, an amine or a mixture thereof, and specifically, tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether With diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine It may be selected from the group consisting of, preferably ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
  • the polar additive may be used in 0.001 to 50 g, 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 100 g of the monomer to be added.
  • the polar additive may be used in 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 1 mmol of the organoalkali metal compound.
  • block copolymers are generally easy to be produced due to their difference in reaction rate, but when the polar additive is added, the reaction rate of the aromatic vinyl monomer having a slow reaction rate is increased. This has the effect of inducing a microstructure of the corresponding copolymer, for example a random copolymer.
  • the polymerization of (a) may be, for example, anionic polymerization, and specifically, the polymerization of (a) may be a living anion polymerization that obtains active ends by growth reaction by anions.
  • polymerization of (a) may be, for example, elevated temperature polymerization or constant temperature polymerization.
  • the elevated temperature polymerization refers to a polymerization method including a step of raising the reaction temperature by adding heat optionally after adding the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after adding the organometallic compound. .
  • the polymerization temperature of (a) may be, for example, -20 to 200 °C, 0 to 150 °C or 10 to 120 °C.
  • the preparation method of the present invention includes the step of modifying the compound represented by the following formula (2) to the active polymer having the alkali metal terminal.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the compound represented by Chemical Formula 2 may be, for example, a compound represented by Chemical Formula 2a.
  • n and m are each independently 1 to 10.
  • the step (b) may be a step of injecting one or more, or two to three kinds of compounds represented by Formula 1, for example.
  • step (b) may be a step of reacting for 1 minute to 5 hours at 0 to 90 °C, for example.
  • the modified conjugated diene-based polymer production method may be a batch polymerization (batch), or a continuous polymerization method including one or more reactors, for example.
  • a denaturing agent is provided, which is a compound represented by the following formula (2).
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the compound represented by Formula 2 may be, for example, a compound represented by Formula 2a.
  • n and m are each independently 1 to 10.
  • a modified conjugated diene-based polymer rubber composition comprising 10 to 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of an inorganic filler based on 100 parts by weight of the modified conjugated diene-based polymer.
  • the inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.
  • the inorganic filler may be at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof.
  • silica-based fillers When the inorganic filler is a silica-based filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles with the terminal of the modified conjugated diene-based polymer of the present invention.
  • the modified conjugated diene-based polymer rubber composition may further include another conjugated diene-based polymer.
  • the other conjugated diene-based polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof.
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • natural rubber or a mixture thereof.
  • SBR may be, for example, solution styrene-butadiene rubber (SSBR).
  • the modified conjugated diene-based polymer rubber composition may include, for example, 20 to 100 parts by weight of the modified conjugated diene-based polymer and 0 to 80 parts by weight of the other conjugated diene-based polymer. have.
  • the modified conjugated diene-based polymer rubber composition of the present invention may include 20 to 99 parts by weight of the modified conjugated diene-based polymer and 1 to 80 parts by weight of the other conjugated diene-based polymer.
  • the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent.
  • the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 2 to 20 parts by weight and 2 to 20 parts by weight of the silane coupling agent, and the sum of the weights of the modified conjugated diene-based polymer and other conjugated diene-based polymer may be 100 parts by weight.
  • the modified conjugated diene-based polymer rubber composition of the present invention is 100 parts by weight of the polymer mixture comprising 10 to 99% by weight of the modified conjugated diene-based polymer and 1 to 90% by weight of the conjugated diene-based polymer It may include 1 to 100 parts by weight of black, 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent.
  • the modified conjugated diene-based polymer rubber composition may further include 1 to 100 parts by weight of oil.
  • the oil may be, for example, a mineral oil or a softener.
  • the oil may be used in an amount of 10 to 100 parts by weight or 20 to 80 parts by weight based on 100 parts by weight of the conjugated diene-based copolymer, and exhibits good physical properties within this range. Excellent effect.
  • the modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 100, more preferably 45 to 90.
  • Mooney viscosity has such a range, a modified conjugated diene polymer having excellent workability, compatibility, exothermicity, tensile strength, abrasion resistance, low fuel consumption, and wet road surface resistance can be prepared.
  • the modified conjugated diene-based polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, the Tan ⁇ value at 0 ° C. (Tan ⁇ at 0 ° C.) is, for example, 0.4 to 1 or 0.5 to 1 In this range, there is an effect that the road surface resistance or wetting resistance is significantly improved compared to the conventional invention.
  • Tan ⁇ value (Tan ⁇ at 60 ° C.) at 60 ° C. may be, for example, 0.3 to 0.2, or 0.15 to 0.1, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved as compared with the conventional invention. Effect.
  • the tire or tire tread is manufactured using a rubber composition including a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby being excellent in exothermicity, tensile strength, wear resistance, and wet road resistance. It has the advantage of low rolling resistance.
  • the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried by roll to remove residual solvent and water to prepare a modified conjugated diene-based polymer.
  • the analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
  • a sample was prepared in the same manner as in Example 1 except that 1.5 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
  • a sample was prepared in the same manner as in Example 1 except that 2 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
  • a sample was prepared in the same manner as in Example 1 except that 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was not added.
  • a sample was prepared in the same manner as in Example 1 except that 1.8 g of 1,4-bis (3- (triethoxysilyl) propyl) piperazine was added.
  • Mooney Viscosity ALPHA Technologies Inc. MV-2000 was used to preheat for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 °C.
  • Mw Weight average molecular weight
  • Mn number average molecular weight
  • PDI molecular weight distribution
  • Example 1 Example 2
  • Example 3 Comparative Example 1 Comparative Example 2 sample A B C D E Denaturant a - b Denaturant equivalent eq / [NBL] 0.5 1.0 1.5 - 1.5 Mooney 78 70 69 63 68 Styrene (%) 26 27 27 27 26 vinyl(%) 42 41 42 41 41 GPC ( ⁇ 10 4 ) Mn 40 38 36 34 37 Mw 62 58 50 41 50 PDI 1.6 1.5 1.4 1.2 1.3
  • the conjugated diene-based polymer rubber composition was prepared by blending A to E in the samples shown in Table 1 as raw material rubbers under the blending conditions shown in Table 2 below.
  • the unit of raw material in Table 2 is phr based on 100 parts by weight of rubber.
  • the rubber composition of the conjugated diene-based polymer is kneaded through a total of first stage kneading and second stage kneading.
  • the raw rubber (conjugated diene-based polymer), filler, organosilane coupling agent, oil, galvanizing agent, stearic acid antioxidant, antioxidant, wax and accelerator are prepared using a half-variety mixer with temperature control device. Kneaded. At this time, the temperature of the kneader was controlled, and the primary blend was obtained at the discharge temperature of 145-155 degreeC.
  • Tan ⁇ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (-60 to 60 ° C.) in the torsion mode.
  • the Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain.
  • the smaller the Faye effect the better the dispersibility of the filler such as silica.
  • the higher the low temperature 0 [deg.] C. Tan ⁇ the better the wet road surface resistance.
  • the lower the high temperature 60 [deg.] C. Tan ⁇ the lower the hysteresis loss and the lower the rolling resistance of the tire, that is, the lower the fuel efficiency.
  • Table 3 shows the physical properties of the vulcanized rubber.
  • the tan ⁇ value at 0 ° C. was higher than that of Comparative Preparation Example 2, and the modified conjugated diene-based polymer of the present invention was applied to a tire.
  • the rubber composition is included, it was confirmed that the resistance on the wet road surface was high.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a modifying agent having a 1,4-bis (alkoxysilyl alkylene oxyalkylene) piperazine structure, a modified conjugated diene polymer which is modified by using the same, and a method for manufacturing the same.

Description

변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물Modified conjugated diene-based polymer, preparation method thereof, and rubber composition comprising same
본 출원은 2014년 11월 13일자 한국 특허 출원 제10-2014-0158077호 및 2015년 10월 6일자 한국 특허 출원 제10-2015-0140480호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0158077 filed on November 13, 2014 and Korean Patent Application No. 10-2015-0140480 filed on October 6, 2015. All content disclosed in the literature is included as part of this specification.
본 발명은 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물에 관한 것으로서, 보다 상세하게는 보강제로 실리카를 배합하는 경우에 우수한 발열성을 갖는 것과 동시에, 인장강도, 내마모성, 젖은 노면 저항성을 갖는 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물에 관한 것이다.The present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. More specifically, the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. It relates to a modified conjugated diene-based polymer having a resistance, a preparation method thereof, and a rubber composition comprising the same.
자동차에 대한 안정성, 및 내구성의 요구가 갈수록 커져가고 있다. 이에 따라, 자동차용 타이어, 특히 지면과 접하는 타이어 트레드의 재료로서, 젖은 노면 저항성 및 기계적 강도가 뛰어나면서도, 구름 저항(rolling resistance)이 낮은 고무의 개발이 필요한 실정이다.There is an increasing demand for stability and durability for automobiles. Accordingly, the development of automotive tires, particularly tire treads in contact with the ground, requires the development of rubber having excellent rolling resistance and low rolling resistance while providing excellent wet road resistance and mechanical strength.
종래 타이어 트레드는 공역디엔계 고무에 상기와 같은 물성을 보강하기 위해 무기 충진제 등을 배합하여 사용하였으나, 여전히 물성 측면에서 개선의 여지가 많은 실정이다.Conventionally, the tire tread was used in combination with an inorganic filler in order to reinforce the above properties in the conjugated diene rubber, but there is still much room for improvement in terms of physical properties.
본 발명이 해결하려는 과제는 고무 조성물에 포함시 우수한 발열성을 갖는 것과 동시에, 인장강도, 내마모성, 및 젖은 노면 저항성을 나타내는 변성 공역디엔계 중합체 및 이의 제조방법을 제공하는 것이다.The problem to be solved by the present invention is to provide a modified conjugated diene-based polymer and a method for producing the same having excellent exothermicity when included in the rubber composition, and exhibits tensile strength, wear resistance, and wet road resistance.
본 발명이 해결하려는 다른 과제는 상기 변성 공역디엔계 중합체의 제조에 사용되는 변성제를 제공하는 것이다.Another object of the present invention is to provide a modifier used in the preparation of the modified conjugated diene-based polymer.
본 발명이 해결하려는 다른 과제는 상기 변성 공역디엔계 중합체를 포함하는 발열성, 인장강도, 내마모성, 및 젖은 노면 저항성 등이 우수한 고무 조성물 및 이를 포함하는 타이어를 제공하는 것이다.Another object of the present invention is to provide a rubber composition and a tire including the same having excellent exothermicity, tensile strength, wear resistance, and wet road resistance including the modified conjugated diene-based polymer.
이러한 과제를 해결하기 위하여, 본 발명은, 하기 화학식 1로 표시되는 변성 공역디엔계 중합체를 제공한다:In order to solve this problem, the present invention provides a modified conjugated diene-based polymer represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2015011230-appb-I000001
Figure PCTKR2015011230-appb-I000001
상기 화학식 1에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공역디엔계 중합체 사슬이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이고, c 및 d는 각각 독립적으로 0, 1, 2 또는 3 이고, c 및 d는 모두 0일 수 없으며, a+c 및 b+d는 각각 독립적으로 1, 2 또는 3이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, P is a conjugated diene polymer chain, n and m are each independently 1 to 10, a And b are each independently 0, 1 or 2, c and d are each independently 0, 1, 2 or 3, c and d cannot both be 0, and a + c and b + d are each independently 1, 2 or 3.
또한, 본 발명은 (a) 유기 알칼리 금속 화합물의 존재 하에 탄화수소 용매 중에서 공역디엔계 단량체, 또는 공역디엔계 단량체와 방향족 비닐계 단량체를 중합시켜 알칼리 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및 (b) 상기 알칼리 금속 말단을 갖는 활성 중합체에 하기 화학식 2로 표시되는 화합물을 결합시켜 변성시키는 단계를 포함하는 변성 공역디엔계 중합체의 제조방법을 제공한다:In addition, the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
[화학식 2][Formula 2]
Figure PCTKR2015011230-appb-I000002
Figure PCTKR2015011230-appb-I000002
상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
또한, 본 발명은 하기 화학식 2로 표시되는 변성제를 제공한다.In addition, the present invention provides a modifier represented by the following formula (2).
[화학식 2][Formula 2]
Figure PCTKR2015011230-appb-I000003
Figure PCTKR2015011230-appb-I000003
상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
또한, 본 발명은 상기 변성 공역디엔계 중합체를 포함하는 변성 공역디엔계 중합체 고무 조성물을 제공한다.The present invention also provides a modified conjugated diene-based polymer rubber composition comprising the modified conjugated diene-based polymer.
또한, 본 발명은 상기 변성 공역디엔계 중합체 고무 조성물을 포함하는 타이어 또는 타이어 트레드를 제공한다.The present invention also provides a tire or tire tread comprising the modified conjugated diene-based polymer rubber composition.
본 발명에 따르면, 보강제로 실리카를 배합하는 경우에 우수한 발열성을 갖는 것과 동시에 인장강도, 내마모성, 젖은 노면 저항성 등을 나타내는 변성 공역디엔계 중합체를 제조하여 타이어용 고무 조성물에 이용할 수 있다.According to the present invention, a modified conjugated diene-based polymer having excellent exothermicity and exhibiting tensile strength, abrasion resistance, wet road resistance, and the like when blending silica as a reinforcing agent can be prepared and used in a rubber composition for tires.
이하, 본 발명을 상세히 설명하기로 한다. Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 1로 표시되는 변성 공역디엔계 중합체를 제공한다:The present invention provides a modified conjugated diene-based polymer represented by Formula 1:
[화학식 1][Formula 1]
Figure PCTKR2015011230-appb-I000004
Figure PCTKR2015011230-appb-I000004
상기 화학식 1에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공역디엔계 중합체 사슬이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이고, c 및 d는 각각 독립적으로 0, 1, 2 또는 3 이고, c 및 d는 모두 0일 수 없으며, a+c 및 b+d는 각각 독립적으로 1, 2 또는 3이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, P is a conjugated diene polymer chain, n and m are each independently 1 to 10, a And b are each independently 0, 1 or 2, c and d are each independently 0, 1, 2 or 3, c and d cannot both be 0, and a + c and b + d are each independently 1, 2 or 3.
상기 화학식 1에서 P로 표시되는 공역디엔계 중합체 사슬은 공역디엔계 단량체의 단독 중합체 또는 공역디엔계 단량체와 비닐 방향족 단량체의 공중합체로부터 유래될 수 있다.The conjugated diene polymer chain represented by P in Formula 1 may be derived from a homopolymer of conjugated diene monomer or a copolymer of conjugated diene monomer and vinyl aromatic monomer.
구체적으로, 상기 공역디엔계 중합체 사슬은 유기 알칼리 금속 화합물의 존재 하에 탄화수소 용매 중에서 공역디엔계 단량체 또는 공역 디엔계 단량체와 비닐 방향족 단량체를 배치 또는 연속적인 방법으로 중합함으로써 얻어진 알칼리 금속 말단을 가진 단독 중합체 또는 공중합체가 하나 이상의 알콕시기로 치환된 실릴기와 반응하여서 형성될 수 있다.Specifically, the conjugated diene polymer chain is a homopolymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in a batch or continuous manner in a hydrocarbon solvent in the presence of an organic alkali metal compound. Or a copolymer may be formed by reaction with a silyl group substituted with one or more alkoxy groups.
이때, 상기 공역디엔계 중합체 사슬은 공역디엔계 단량체와. 공역디엔계 단량체와 비닐 방향족 단량체를 합한 총 100 중량%를 기준으로 방향족 비닐계 단량체 0.0001 내지 50 중량%, 10 내지 40 중량% 또는 20 내지 40 중량%를 포함하여 이루어진 폴리머 사슬일 수 있다.In this case, the conjugated diene-based polymer chain is a conjugated diene-based monomer. The polymer chain may include 0.0001 to 50% by weight, 10 to 40% by weight, or 20 to 40% by weight of the aromatic vinylic monomer based on a total of 100% by weight of the conjugated diene monomer and the vinyl aromatic monomer.
상기 공역디엔계 단량체와 비닐 방향족 단량체로 이루어진 폴리머 사슬은 일례로 랜덤 폴리머 사슬일 수 있다.The polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
상기 공역디엔계 단량체는 일례로 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 피페릴렌, 3-부틸-1,3-옥타디엔, 이소프렌 및 2-페닐-1,3-부타디엔으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
상기 비닐 방향족 단량체는 일례로 스티렌, α-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, 4-프로필스티렌, 1-비닐나프탈렌, 4-사이클로헥실스티렌, 4-(p-메틸페닐)스티렌 및 1-비닐-5-헥실나프탈렌으로 이루어진 군으로부터 선택된 1종 이상일수 있고, 또 다른 일례로 스티렌 또는 α-메틸스티렌일 수 있다.The vinyl aromatic monomers are, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be at least one selected from the group consisting of -vinyl-5-hexyl naphthalene, and as another example, may be styrene or α-methylstyrene.
상기 변성 공역디엔계 중합체는 무니점도가 40 이상, 바람직하게는 40 내지 90, 보다 바람직하게는 50 내지 80일 수 있다.The modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 90, more preferably 50 to 80.
상기 변성 공역디엔계 중합체는 일례로 수평균분자량(Mn)이 1,000 내지 2,000,000 g/mol, 바람직하게는 10,000 내지 1,000,000 g/mol, 보다 바람직하게는 100,000 내지 1,000,000 g/mol, 가장 바람직하게는 100,000 내지 500,000 g/mol 또는 200,000 내지 700,000 g/mol 일 수 있다.The modified conjugated diene-based polymer has, for example, a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 1,000,000 g / mol, most preferably 100,000 to 500,000 g / mol or 200,000 to 700,000 g / mol.
상기 변성 공역디엔계 중합체는 일례로 비닐 함량이 18% 이상, 바람직하게는 25 % 이상, 보다 바람직하게는 30 내지 70 %일 수 있고, 이 범위 내에서 중합체의 유리전이온도가 상승되어 타이어에 적용시 주행저항 및 제동력과 같은 타이어에 요구되는 물성을 만족시킬 수 있을 뿐만 아니라, 연료소모를 줄이는 효과가 있다.The modified conjugated diene-based polymer may be, for example, a vinyl content of 18% or more, preferably 25% or more, and more preferably 30 to 70%, and the glass transition temperature of the polymer is increased within this range to be applied to a tire. In addition to satisfying the properties required for tires such as driving resistance and braking force, the fuel consumption is reduced.
이때 비닐 함량은 비닐기를 갖는 단위체의 함량, 혹은 공역디엔계 단량체 100 중량%에 대하여 1,4-첨가가 아닌 1,2-첨가된 공역디엔계 단량체의 함량을 의미한다.In this case, the vinyl content means the content of the monomer having a vinyl group, or the content of the 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene monomer.
상기 변성 공역디엔계 중합체는 일례로 PDI가 1 내지 10, 바람직하게는 1 내지 5, 보다 바람직하게는 1 내지 2일 수 있다.For example, the modified conjugated diene-based polymer may have a PDI of 1 to 10, preferably 1 to 5, and more preferably 1 to 2.
상기 화학식 1로 표시되는 화합물은 일례로 하기 화학식 1a로 표시되는 화합물일 수 있다.The compound represented by Chemical Formula 1 may be, for example, a compound represented by Chemical Formula 1a.
[화학식 1a][Formula 1a]
Figure PCTKR2015011230-appb-I000005
Figure PCTKR2015011230-appb-I000005
상기 화학식 1a에서, c 및 d는 각각 독립적으로 0, 1, 2 또는 3이고, c 및 d는 모두 0일 수 없으며, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 1a, c and d are each independently 0, 1, 2 or 3, and c and d may not be all 0, and n and m are each independently 1 to 10.
또한, 본 발명은, (a) 유기 알칼리 금속 화합물의 존재 하에 탄화수소 용매 중에서 공역디엔계 단량체, 또는 공역디엔계 단량체와 방향족 비닐계 단량체를 중합시켜 알칼리 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및 (b) 상기 알칼리 금속 말단을 갖는 활성 중합체에 하기 화학식 2로 표시되는 화합물을 결합시켜 변성시키는 단계를 포함하는 변성 공역디엔계 중합체의 제조방법을 제공한다:In addition, the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organoalkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
[화학식 2][Formula 2]
Figure PCTKR2015011230-appb-I000006
Figure PCTKR2015011230-appb-I000006
상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
상기 유기 알칼리 금속 화합물은 메틸리튬, 에틸리튬, 이소프로필리튬, n-부틸리튬, sec-부틸리튬, tert-부틸리튬, n-데실리튬, tert-옥틸리튬, 페닐리튬, 1-나프틸리튬, n-에이코실리튬, 4-부틸페닐리튬, 4-톨릴리튬, 사이클로헥실리튬, 3,5-디-n-헵틸사이클로헥실리튬 및 4-사이클로펜틸리튬으로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 바람직하게는, 상기 유기 알칼리 금속 화합물은 n-부틸리튬, sec-부틸리튬 또는 이들의 혼합일 수 있다.The organoalkali metal compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyllithium, It may be at least one selected from the group consisting of n-eicosillithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium. Preferably, the organic alkali metal compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
다른 일례로, 상기 유기 알칼리 금속 화합물은 나프틸나트륨, 나프틸칼륨, 리튬 알콕사이드, 나트륨 알콕사이드, 칼륨 알콕시드, 리튬 술포네이트, 나트륨 술포네이트, 칼륨 술포네이트, 리튬 아미드, 나트륨 아미드 및 칼륨 아미드로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 또한 다른 유기 알칼리 금속 화합물과 병용하여 사용될 수도 있다.In another example, the organoalkali metal compound consists of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, and potassium amide It may be one or more selected from the group, and may also be used in combination with other organic alkali metal compounds.
상기 공역디엔계 단량체는 일례로 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 피페릴렌, 3-부틸-1,3-옥타디엔, 이소프렌 및 2-페닐-1,3-부타디엔으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
상기 방향족 비닐계 단량체는 일례로 스티렌, α-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, 4-프로필스티렌, 1-비닐나프탈렌, 4-사이클로헥실스티렌, 4-(p-메틸페닐)스티렌 및 1-비닐-5-헥실나프탈렌으로 이루어진 군으로부터 선택된 1종 이상일수 있고, 또 다른 일례로 스티렌 또는 α-메틸스티렌일 수 있다.Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, It may be one or more selected from the group consisting of 1-vinyl-5-hexyl naphthalene, and may be styrene or α-methylstyrene as another example.
본 발명의 일 실시예에 따르면, 상기 유기 알칼리 금속 화합물은 상기 단량체 총 100g을 기준으로 할 때, 활성화 몰비 기준으로 0.01 내지 10 mmol, 0.05 내지 5 mmol, 0.1 내지 2 mmol 또는 0.1 내지 1 mmol로 사용될 수 있다. 상기의 '활성화 몰비 기준'이라 함은, 본 발명에서 사용하는 유기 알칼리 금속 화합물이 수분의 함유에 따라서, 비활성화되는 경우가 있기 때문에 활성화를 기준으로 사용 함량을 정의하는 것을 뜻한다. 상기 유기 알칼리 금속 화합물의 함량이 이러한 범위를 만족하는 경우 변성 공역디엔계 중합체를 제조하기 위한 최적의 공역디엔계 중합체를 만들 수 있다.According to an embodiment of the present invention, the organoalkali metal compound is used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, or 0.1 to 1 mmol, based on the total molar ratio of the monomer. Can be. The above 'activation molar ratio criteria' means that the organoalkali metal compound used in the present invention may be deactivated depending on the water content, so that the use content is defined based on the activation. When the content of the organoalkali metal compound satisfies this range, an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer can be made.
상기 유기 알칼리 금속 화합물과 상기 화학식 2로 표시되는 화합물의 몰비는 예를 들면 1:0.1 내지 1:10, 바람직하게는 1:0.3 내지 1:2이다. 상기 몰비가 이러한 범위를 만족하는 경우 공역디엔계 중합체에 최적 성능의 변성 반응을 부여할 수 있다.The molar ratio of the organic alkali metal compound and the compound represented by Chemical Formula 2 is, for example, 1: 0.1 to 1:10, preferably 1: 0.3 to 1: 2. When the molar ratio satisfies this range, it is possible to give a modified reaction of optimum performance to the conjugated diene-based polymer.
상기 알칼리 금속 말단을 갖는 활성 중합체는 중합체 음이온과 알칼리 금속 양이온이 결합된 중합체를 의미한다.The active polymer having the alkali metal terminal means a polymer in which a polymer anion and an alkali metal cation are bonded.
본 발명의 일 실시예에 따르면, 상기 변성 공역디엔계 중합체의 제조방법은 상기 (a) 단계에서 중합 시 극성첨가제를 더 첨가하여 실시될 수 있다. 이와 같이 극성 첨가제를 더 첨가하는 이유는 극성첨가제가 공역디엔계 단량체와 방향족 비닐계 단량체의 반응속도를 조절하기 때문이다. According to one embodiment of the invention, the modified conjugated diene-based polymer production method may be carried out by further adding a polar additive during the polymerization in the step (a). The reason why the polar additive is further added is that the polar additive controls the reaction rate of the conjugated diene monomer and the aromatic vinyl monomer.
상기 극성첨가제는 염기이거나, 또는 에테르, 아민 또는 이들의 혼합물일 수 있으며, 구체적으로 테트라히드로퓨란, 디테트라히드로프릴프로판, 디에틸에테르, 시클로아밀에테르, 디프로필에테르, 에틸렌디메틸에테르, 에틸렌디메틸에테르, 디에틸렌글리콜, 디메틸에테르, 3차 부톡시에톡시에탄 비스(2-디메틸아미노에틸)에테르, (디메틸아미노에틸) 에틸에테르, 트리메틸아민, 트리에틸아민, 트리프로필아민, 및 테트라메틸에틸렌디아민으로 이루어진 그룹으로부터 선택된 것일 수 있으며, 바람직하게는 디테트라히드로프로필프로판, 트리에틸아민 또는 테트라메틸에틸렌디아민일 수 있다.The polar additive may be a base or an ether, an amine or a mixture thereof, and specifically, tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether With diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine It may be selected from the group consisting of, preferably ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
상기 극성첨가제는 투입되는 단량체 총 100 g을 기준으로 0.001 내지 50 g, 0.001 내지 10 g, 0.005 내지 1 g, 또는 0.005 내지 0.1 g으로 사용될 수 있다.The polar additive may be used in 0.001 to 50 g, 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 100 g of the monomer to be added.
또한, 상기 극성첨가제는 투입되는 유기 알칼리 금속 화합물 총 1 mmol을 기준으로 0.001 내지 10 g, 0.005 내지 1 g, 또는 0.005 내지 0.1 g으로 사용될 수 있다.In addition, the polar additive may be used in 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 1 mmol of the organoalkali metal compound.
상기 공역디엔계 단량체와 방향족 비닐계 단량체를 공중합시키는 경우 이들의 반응 속도 차이로 인해 대체로 블록 공중합체가 제조되기 쉬우나, 상기 극성첨가제를 첨가하는 경우 반응 속도가 느린 방향족 비닐계 단량체의 반응 속도를 증가시켜 이에 상응하는 공중합체의 미세구조, 예를 들어 랜덤 공중합체를 유도하는 효과가 있다.When copolymerizing the conjugated diene monomer and the aromatic vinyl monomer, block copolymers are generally easy to be produced due to their difference in reaction rate, but when the polar additive is added, the reaction rate of the aromatic vinyl monomer having a slow reaction rate is increased. This has the effect of inducing a microstructure of the corresponding copolymer, for example a random copolymer.
상기 (a)의 중합은 일례로 음이온 중합일 수 있고, 구체적으로는 상기 (a)의 중합은 음이온에 의한 성장반응에 의해 활성 말단을 얻는 리빙 음이온 중합일 수 있다.The polymerization of (a) may be, for example, anionic polymerization, and specifically, the polymerization of (a) may be a living anion polymerization that obtains active ends by growth reaction by anions.
또한, 상기 (a)의 중합은 일례로 승온 중합 또는 정온 중합일 수 있다.In addition, the polymerization of (a) may be, for example, elevated temperature polymerization or constant temperature polymerization.
상기 승온 중합은 유기금속 화합물을 투입한 이후 임의로 열을 가해 반응 온도를 높이는 단계를 포함하는 중합방법을 의미하고, 상기 정온 중합은 유기금속 화합물을 투입한 이후 임의로 열을 가하지 않는 중합방법을 의미한다.The elevated temperature polymerization refers to a polymerization method including a step of raising the reaction temperature by adding heat optionally after adding the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after adding the organometallic compound. .
상기 (a)의 중합 온도는 일례로 -20 내지 200 ℃, 0 내지 150 ℃ 또는 10 내지 120 ℃일 수 있다.The polymerization temperature of (a) may be, for example, -20 to 200 ℃, 0 to 150 ℃ or 10 to 120 ℃.
본 발명의 제조방법은 (b) 상기 알칼리 금속 말단을 갖는 활성 중합체에 하기 화학식 2로 표시되는 화합물을 결합시켜 변성시키는 단계를 포함한다.The preparation method of the present invention includes the step of modifying the compound represented by the following formula (2) to the active polymer having the alkali metal terminal.
[화학식 2][Formula 2]
Figure PCTKR2015011230-appb-I000007
Figure PCTKR2015011230-appb-I000007
상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
상기 화학식 2로 표시되는 화합물은 일례로 하기 화학식 2a로 표시되는 화합물일 수 있다.The compound represented by Chemical Formula 2 may be, for example, a compound represented by Chemical Formula 2a.
[화학식 2a][Formula 2a]
Figure PCTKR2015011230-appb-I000008
Figure PCTKR2015011230-appb-I000008
상기 화학식 2a에서, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 2a, n and m are each independently 1 to 10.
상기 (b) 단계는 일례로 상기 화학식 1로 표시되는 화합물을 1종 이상, 또는 2 내지 3종 투입하는 단계일 수 있다.The step (b) may be a step of injecting one or more, or two to three kinds of compounds represented by Formula 1, for example.
또한, 상기 (b) 단계는 일례로 0 내지 90 ℃에서 1분 내지 5 시간 동안 반응시키는 단계일 수 있다.In addition, the step (b) may be a step of reacting for 1 minute to 5 hours at 0 to 90 ℃, for example.
본 발명의 일 실시예에 따르면, 상기 변성 공역디엔계 중합체의 제조방법은 일례로 회분식(배치식), 또는 1종 이상의 반응기를 포함하는 연속식 중합방법일 수 있다.According to one embodiment of the invention, the modified conjugated diene-based polymer production method may be a batch polymerization (batch), or a continuous polymerization method including one or more reactors, for example.
본 발명의 다른 측면에 따르면, 하기 화학식 2로 표시되는 화합물인 것을 특징으로 하는 변성제가 제공된다.According to another aspect of the present invention, a denaturing agent is provided, which is a compound represented by the following formula (2).
[화학식 2][Formula 2]
Figure PCTKR2015011230-appb-I000009
Figure PCTKR2015011230-appb-I000009
상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
상기 화학식 2으로 표시되는 화합물은 일례로 하기 화학식 2a로 표시되는 화합물일 수 있다.The compound represented by Formula 2 may be, for example, a compound represented by Formula 2a.
[화학식 2a][Formula 2a]
Figure PCTKR2015011230-appb-I000010
Figure PCTKR2015011230-appb-I000010
상기 화학식 2a에서, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 2a, n and m are each independently 1 to 10.
또한, 본 발명의 다른 측면에 따르면, 상기 변성 공역디엔계 중합체 10 내지 100중량부, 및 상기 변성 공역디엔계 중합체 100 중량부에 대하여 무기 충진제 0.1 내지 200 중량부를 포함하는 변성 공역디엔계 중합체 고무 조성물이 제공된다.According to another aspect of the present invention, a modified conjugated diene-based polymer rubber composition comprising 10 to 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of an inorganic filler based on 100 parts by weight of the modified conjugated diene-based polymer. This is provided.
상기 무기 충진제는 일례로 10 내지 150 중량부, 또는 50 내지 100 중량부일 수 있다.The inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.
상기 무기 충진제는 실리카계 충진제, 카본블랙, 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 무기 충진제가 실리카계 충진제인 경우, 분산성이 크게 개선되고, 또한 실리카 입자가 본 발명의 변성 공역디엔계 중합체의 말단과 결합함으로써 히스테리시스 손실이 크게 감소되는 효과가 있다.The inorganic filler may be at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof. When the inorganic filler is a silica-based filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles with the terminal of the modified conjugated diene-based polymer of the present invention.
상기 변성 공역디엔계 중합체 고무 조성물은 다른 공역디엔계 중합체를 더 포함할 수 있다.The modified conjugated diene-based polymer rubber composition may further include another conjugated diene-based polymer.
상기 다른 공역디엔계 중합체는 SBR(styrene-butadiene rubber), BR(butadiene rubber), 천연고무 또는 이들의 혼합일 수 있다. 상기 SBR은 일례로 SSBR(solution styrene-butadiene rubber)일 수 있다.The other conjugated diene-based polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof. The SBR may be, for example, solution styrene-butadiene rubber (SSBR).
만일, 상기 다른 공역디엔계 중합체를 더 포함한다면, 변성 공역디엔계 중합체 고무 조성물은 일례로 상기 변성 공역디엔계 중합체 20 내지 100 중량부 및 이와 다른 공역디엔계 중합체 0 내지 80 중량부를 포함하는 것일 수 있다.If the other conjugated diene-based polymer is further included, the modified conjugated diene-based polymer rubber composition may include, for example, 20 to 100 parts by weight of the modified conjugated diene-based polymer and 0 to 80 parts by weight of the other conjugated diene-based polymer. have.
또 다른 일례로, 본 발명의 변성 공역디엔계 중합체 고무 조성물은 상기 변성 공역디엔계 중합체 20 내지 99 중량부 및 이와 다른 공역디엔계 중합체 1 내지 80 중량부를 포함하는 것일 수 있다.As another example, the modified conjugated diene-based polymer rubber composition of the present invention may include 20 to 99 parts by weight of the modified conjugated diene-based polymer and 1 to 80 parts by weight of the other conjugated diene-based polymer.
또 다른 일례로, 본 발명의 변성 공역디엔계 중합체 고무 조성물은 상기 변성 공역디엔계 중합체 10 내지 100 중량부, 이와 다른 공역디엔계 중합체 0 내지 90 중량부, 카본블랙 0 내지 100중량부, 실리카 5 내지 200 중량부 및 실란 커플링제 2 내지 20 중량부를 포함하는 것일 수 있다.In another example, the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent.
또 다른 일례로, 본 발명의 변성 공역디엔계 중합체 고무 조성물은 상기 변성 공역디엔계 중합체 10 내지 100 중량부, 이와 다른 공역디엔계 중합체 0 내지 90 중량부, 카본블랙 0 내지 100 중량부, 실리카 5 내지 200 중량부 및 실란 커플링제 2 내지 20 중량부를 포함하되, 상기 변성 공역디엔계 중합체 및 이와 다른 공역디엔계 중합체의 중량의 합은 100 중량부인 것일 수 있다.In another example, the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 2 to 20 parts by weight and 2 to 20 parts by weight of the silane coupling agent, and the sum of the weights of the modified conjugated diene-based polymer and other conjugated diene-based polymer may be 100 parts by weight.
또 다른 일례로, 본 발명의 변성 공역디엔계 중합체 고무 조성물은 상기 변성 공역디엔계 중합체 10 내지 99 중량%와 이와 다른 공역디엔계 중합체 1 내지 90 중량%를 포함하는 중합체 혼합물 100 중량부에, 카본블랙 1 내지 100 중량부, 실리카 5 내지 200 중량부 및 실란 커플링제 2 내지 20 중량부를 포함하는 것일 수 있다.As another example, the modified conjugated diene-based polymer rubber composition of the present invention is 100 parts by weight of the polymer mixture comprising 10 to 99% by weight of the modified conjugated diene-based polymer and 1 to 90% by weight of the conjugated diene-based polymer It may include 1 to 100 parts by weight of black, 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent.
또한, 상기 변성 공역디엔계 중합체 고무 조성물은 일례로 오일 1 내지 100 중량부를 더 포함할 수 있다. 상기 오일은 일례로 광물유나 연화제 등일 수 있다.In addition, the modified conjugated diene-based polymer rubber composition may further include 1 to 100 parts by weight of oil. The oil may be, for example, a mineral oil or a softener.
상기 오일은 예를 들면 공역디엔계 공중합체 100 중량부에 대하여 10 내지 100 중량부 또는 20 내지 80 중량부로 사용될 수 있고, 이 범위 내에서 물성 발현이 잘되며, 또한 고무 조성물을 적당히 연화시켜 가공성이 우수한 효과가 있다.For example, the oil may be used in an amount of 10 to 100 parts by weight or 20 to 80 parts by weight based on 100 parts by weight of the conjugated diene-based copolymer, and exhibits good physical properties within this range. Excellent effect.
상기 변성 공역디엔계 중합체는 40 이상, 바람직하게는 40 내지 100, 더 바람직하게는 45 내지 90의 무니점도를 가질 수 있다. 상기 무니 점도가 이러한 범위를 갖는 경우, 가공성, 상용성, 발열성, 인장강도, 내마모성, 저연비성 및 젖은 노면 저항성이 뛰어난 변성 공역디엔계 중합체를 제조할 수 있다.The modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 100, more preferably 45 to 90. When the Mooney viscosity has such a range, a modified conjugated diene polymer having excellent workability, compatibility, exothermicity, tensile strength, abrasion resistance, low fuel consumption, and wet road surface resistance can be prepared.
상기 변성 공역디엔계 중합체는 점탄성의 특징에 있어서, 실리카 배합 후 DMA를 통하여 10 Hz로 측정하는 경우, 0℃에서의 Tan δ값(Tanδ at 0℃)은 일례로 0.4 내지 1 또는 0.5 내지 1이고, 이 범위 내에서 종래 발명에 비해 노면 저항 또는 습윤 저항이 크게 향상되는 효과가 있다.The modified conjugated diene-based polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, the Tan δ value at 0 ° C. (Tanδ at 0 ° C.) is, for example, 0.4 to 1 or 0.5 to 1 In this range, there is an effect that the road surface resistance or wetting resistance is significantly improved compared to the conventional invention.
또한, 60℃에서의 Tan δ값(Tanδ at 60℃)은 일례로 0.3 내지 0.2, 또는 0.15 내지 0.1일 수 있고, 이 범위 내에서 종래 발명에 비하여 구름저항 또는 회전저항(RR)이 크게 향상되는 효과를 보인다.In addition, the Tan δ value (Tan δ at 60 ° C.) at 60 ° C. may be, for example, 0.3 to 0.2, or 0.15 to 0.1, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved as compared with the conventional invention. Effect.
본 발명의 다른 측면에 따르면, 전술한 변성 공역디엔계 중합체 고무 조성물을 이용한 타이어 또는 타이어 트레드가 제공된다.According to another aspect of the present invention, there is provided a tire or tire tread using the modified conjugated diene-based polymer rubber composition described above.
상기 타이어 또는 타이어 트레드는 무기 충진제와의 상용성이 우수하고, 가공성이 개선된 변성 공역디엔계 중합체를 포함하는 고무 조성물을 이용하여 제조됨으로써, 발열성, 인장강도, 내마모성, 젖은 노면 저항성 등이 뛰어나면서도 구름 저항이 낮은 장점이 있다.The tire or tire tread is manufactured using a rubber composition including a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby being excellent in exothermicity, tensile strength, wear resistance, and wet road resistance. It has the advantage of low rolling resistance.
이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 하기 실시예에 한정되는 것으로 해석되어져서는 안 된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.
실시예 1Example 1
20L 오토클레이브 반응기에 스티렌 270g, 1,3-부타디엔 710g 및 노말헥산 5000g, 극성첨가제로 2,2-비스(2-옥소라닐)프로판 0.86g을 넣은 후 반응기 내부온도를 40℃로 승온하였다. 반응기 내부 온도가 40℃에 도달했을 때, n-부틸리튬 2.5g을 반응기에 투입하여 단열 승온 반응을 진행시켰다. 20여분 경과 후 1,3-부타디엔 20g을 투입하였다. 5분 후 1,4-비스(3-(3-(트리에톡시실릴)프로폭시)프로필)피페라진 0.7g 투입하고 15분간 반응시켰다. 이후 에탄올을 이용하여 중합반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔)가 헥산에 0.3 중량% 녹아있는 용액 45ml를 첨가하였다.270 g of styrene, 710 g of 1,3-butadiene, 5000 g of normal hexane, and 0.86 g of 2,2-bis (2-oxoranyl) propane were added to the 20 L autoclave reactor, and the temperature of the reactor was raised to 40 ° C. When the internal temperature of the reactor reached 40 ° C, 2.5 g of n-butyllithium was added to the reactor to proceed with the adiabatic heating reaction. After 20 minutes, 20 g of 1,3-butadiene was added thereto. After 5 minutes, 0.7 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added and reacted for 15 minutes. Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
그 결과 얻어진 중합물을 스팀으로 가열된 온수에 넣고 교반하여 용매를 제거한 다음, 롤 건조하여 잔량의 용매와 물을 제거하여, 변성 공역디엔계 중합체를 제조하였다. 이렇게 제조된 변성 공역디엔계 중합체에 대한 분석결과는 하기 표 1에 나타내었다.The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried by roll to remove residual solvent and water to prepare a modified conjugated diene-based polymer. The analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
실시예 2Example 2
실시예 1에서 1,4-비스(3-(3-(트리에톡시실릴)프로폭시)프로필)피페라진 을 1.5g 투입한 것을 제외하고는 동일하게 샘플을 제조 하였다.A sample was prepared in the same manner as in Example 1 except that 1.5 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
실시예 3Example 3
실시예 1에서 1,4-비스(3-(3-(트리에톡시실릴)프로폭시)프로필)피페라진 을 2g 투입한 것을 제외하고는 동일하게 샘플을 제조 하였다.A sample was prepared in the same manner as in Example 1 except that 2 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
비교예 1Comparative Example 1
실시예 1에서 1,4-비스(3-(3-(트리에톡시실릴)프로폭시)프로필)피페라진 을 투입하지 않은것을 제외하고는 동일하게 샘플을 제조 하였다.A sample was prepared in the same manner as in Example 1 except that 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was not added.
비교예 2Comparative Example 2
실시예 1에서 1,4-비스(3-(트리에톡시실릴)프로필)피페라진을 1.8g 투입한것을 제외하고는 동일하게 샘플을 제조 하였다.A sample was prepared in the same manner as in Example 1 except that 1.8 g of 1,4-bis (3- (triethoxysilyl) propyl) piperazine was added.
상기 실시예 1 내지 3 및 비교예 1 내지 2에서 제조된 공역디엔계 중합체의 분석은 하기의 방법으로 측정하여 이루어졌다.Analysis of the conjugated diene-based polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was measured by the following method.
ㄱ) 무니점도: ALPHA Technologies사의 MV-2000을 이용하여 시편 무게 15g 이상 2개를 이용하여 1분 동안 예열한 후 100 ℃에서 4분 동안 측정하였다.Mooney Viscosity: ALPHA Technologies Inc. MV-2000 was used to preheat for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 ℃.
ㄴ) 스티렌 모노머 (SM) 및 비닐(Vinyl) 함량: NMR을 이용하여 측정하였다.B) Styrene monomer (SM) and vinyl (Vinyl) content: measured using NMR.
ㄷ) 중량평균분자량(Mw), 수평균분자량(Mn) 및 분자량분포도(PDI): 40 ℃ 조건하에서 GPC 분석으로 측정하였다. 이때 컬럼(Column)은 Polymer Laboratories사의 PLgel Olexis 컬럼 두 자루와 PLgel mixed-C 컬럼 한 자루를 조합하였고, 새로 교체한 컬럼은 모두 mixed bed 타입의 컬럼을 사용하였다. 또한, 분자량 계산시 GPC 기준물질(Standard material)로서 PS(Polystyrene)를 사용하였다.C) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (PDI): measured by GPC analysis under 40 ° C. The column was a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories, and all of the newly replaced columns were mixed bed type columns. In addition, polystyrene (PS) was used as a GPC standard material for molecular weight calculation.
표 1
실시예 1 실시예 2 실시예 3 비교예 1 비교예 2
시료 A B C D E
변성제 a - b
변성제 당량 eq/[NBL] 0.5 1.0 1.5 - 1.5
무니 78 70 69 63 68
스타이렌(%) 26 27 27 27 26
비닐(%) 42 41 42 41 41
GPC(×104) Mn 40 38 36 34 37
Mw 62 58 50 41 50
PDI 1.6 1.5 1.4 1.2 1.3
Table 1
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2
sample A B C D E
Denaturant a - b
Denaturant equivalent eq / [NBL] 0.5 1.0 1.5 - 1.5
Mooney 78 70 69 63 68
Styrene (%) 26 27 27 27 26
vinyl(%) 42 41 42 41 41
GPC (× 10 4 ) Mn 40 38 36 34 37
Mw 62 58 50 41 50
PDI 1.6 1.5 1.4 1.2 1.3
a: 1,4-비스(3-(3-(트리에톡시실릴)프로폭시)프로필)피페라진a: 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine
b: 1,4-비스(3-(트리에톡시실릴)프로필)피페라진b: 1,4-bis (3- (triethoxysilyl) propyl) piperazine
상기 표 1에 나타낸 시료 중 A 내지 E를 원료 고무로 하여, 하기 표 2에 나타낸 배합 조건으로 배합하여 공역디엔계 중합체 고무 조성물을 제조하였다. 표 2 내 원료의 단위는 고무 100중량부 기준 phr이다.The conjugated diene-based polymer rubber composition was prepared by blending A to E in the samples shown in Table 1 as raw material rubbers under the blending conditions shown in Table 2 below. The unit of raw material in Table 2 is phr based on 100 parts by weight of rubber.
구체적으로 상기 공역디엔계 중합체의 고무 조성물은 총 제1 단 혼련과 제2 단 혼련을 거쳐 혼련된다. 제1 단 혼련에서는 온도제어장치를 부속한 반바리 믹서를 사용하여 원료고무(공역디엔계 중합체), 충진제, 유기실란 커플링제, 오일, 아연화제, 스테아르산 산화방지제, 노화방지제, 왁스 및 촉진제를 혼련하였다. 이때 혼련기의 온도를 제어하고, 145 내지 155℃의 배출온도에서 1차 배합물을 얻었다. 제 2단 혼련에서는 상기 1차 배합물을 실온까지 냉각한 후 혼련기에 고무, 황 및 가황촉진제를 가하고, 100℃이하의 온도에서 믹싱을 하여 2차 배합물을 얻었다. 마지막으로 100℃에서 20분간 큐어링 공정을 거쳐 실시예 1 내지 3의 중합체를 원료 고무로 하는 제조예 1 내지 3, 및 비교예 1 내지 2의 중합체를 원료 고무로 하는 비교제조예 1 내지 2의 공역디엔계 중합체 고무 조성물을 제조하였다.Specifically, the rubber composition of the conjugated diene-based polymer is kneaded through a total of first stage kneading and second stage kneading. In the first stage kneading, the raw rubber (conjugated diene-based polymer), filler, organosilane coupling agent, oil, galvanizing agent, stearic acid antioxidant, antioxidant, wax and accelerator are prepared using a half-variety mixer with temperature control device. Kneaded. At this time, the temperature of the kneader was controlled, and the primary blend was obtained at the discharge temperature of 145-155 degreeC. In the second stage kneading, after cooling the primary blend to room temperature, rubber, sulfur and a vulcanization accelerator were added to the kneader, and the mixture was mixed at a temperature of 100 ° C. or lower to obtain a secondary blend. Finally, after the curing process at 100 ° C. for 20 minutes, Preparation Examples 1 to 3 using the polymers of Examples 1 to 3 as raw material rubbers and Comparative Production Examples 1 to 2 using the polymers of Comparative Examples 1 to 2 as raw rubbers A conjugated diene-based polymer rubber composition was prepared.
표 2
구분 물질 함량(단위 : phr)
제1 단 혼련 고무 100
실리카 70.0
커플링제 11.2
오일 37.5
아연화제 3.0
스테아르산 2.0
산화방지제 2.0
노화방지제 2.0
왁스 1.0
제2 단 혼련 고무촉진제 1.75
황 1.5
가황촉진제 2.0
총 중량 233.95
TABLE 2
division matter Content (unit: phr)
1st stage kneading Rubber 100
Silica 70.0
Coupling agent 11.2
oil 37.5
Galvanizing agent 3.0
Stearic acid 2.0
Antioxidant 2.0
Anti-aging 2.0
Wax 1.0
2nd stage kneading Rubber accelerator 1.75
sulfur 1.5
Vulcanization accelerator 2.0
Total weight 233.95
상기 각 제조된 고무 조성물의 물성은 이하의 방법으로 측정하였다.The physical properties of the rubber compositions prepared above were measured by the following method.
1) 인장실험1) Tensile test
ASTM 412의 인장시험법에 의해 시험편의 절단시의 인장강도 및 300% 신장시의 인장응력(300% 모듈러스)을 측정하였다. 이를 위해 Instron사의 Universal Test Machine 4204 인장 시험기를 이용하였으며 실온에서 50cm/min의 인장속도로 측정하여 인장강도, Modulus, 신장율 등의 측정값을 얻었다. Tensile strength at the time of cutting the specimen and tensile stress at 300% elongation (300% modulus) were measured by the tensile test method of ASTM 412. For this purpose, Instron's Universal Test Machine 4204 tensile tester was used, and the tensile strength, modulus, and elongation were measured by measuring a tensile speed of 50 cm / min at room temperature.
2) 점탄성 특성2) viscoelastic properties
TA 사의 동적 기계 분석기를 사용하였다. 비틀림 모드로 주파수 10Hz, 각 측정 온도(-60~60℃)에서 변형을 변화시켜서 Tan δ 를 측정하였다. 페이니 효과는 변형 0.28% 내지 40%에서의 최소값과 최대값의 차이로 나타내었다. 페이니 효과가 작을수록 실리카 등 충전제의 분산성이 좋다. 저온 0℃ Tan δ 가 높은 것일수록 젖은 노면저항성이 우수하고, 고온 60℃의 Tan δ 가 낮을수록 히스테리시스 손실이 적고, 타이어의 저구름저항성, 즉 저연비성이 우수하다. 표 3에 가황 고무의 물성을 나타내었다.A dynamic mechanical analyzer from TA was used. Tan δ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (-60 to 60 ° C.) in the torsion mode. The Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain. The smaller the Faye effect, the better the dispersibility of the filler such as silica. The higher the low temperature 0 [deg.] C. Tan δ, the better the wet road surface resistance. The lower the high temperature 60 [deg.] C. Tan δ, the lower the hysteresis loss and the lower the rolling resistance of the tire, that is, the lower the fuel efficiency. Table 3 shows the physical properties of the vulcanized rubber.
표 3
구분 시험예 1 시험예 2 시험예 3 비교시험예 1 비교시험예 2
시료 A B C D E
300% 모듈러스(㎏f/㎠) 110 118 119 95 115
인장강도(㎏f/㎠) 183 185 181 192 168
Tan δ at 0℃ 114 118 119 100 115
Tan δ at 60℃ 117 118 120 100 118
TABLE 3
division Test Example 1 Test Example 2 Test Example 3 Comparative Test Example 1 Comparative Test Example 2
sample A B C D E
300% modulus (㎏f / ㎠) 110 118 119 95 115
Tensile Strength (㎏f / ㎠) 183 185 181 192 168
Tan δ at 0 ℃ 114 118 119 100 115
Tan δ at 60 ℃ 117 118 120 100 118
상기 표 3의 결과에서와 같이, 본 발명에 따른 제조예 1 내지 3의 변성 공역디엔계 중합체 고무 조성물의 경우, 비교제조예 1 및 2에 비하여 300% 모듈러스(인장응력) 및 인장강도가 크게 향상이 되었고, 또한 60℃에서의 Tan δ값이 낮게 나타나 타이어에 본 발명의 변성 공역디엔계 중합체 고무 조성물이 포함되는 경우 구름 저항이 종래 기술에 비하여 낮은 값을 가져, 연비효율이 좋음을 확인할 수 있었다. As shown in the results of Table 3, in the modified conjugated diene-based polymer rubber composition of Preparation Examples 1 to 3 according to the present invention, 300% modulus (tensile stress) and tensile strength significantly improved compared to Comparative Preparation Examples 1 and 2 In addition, when the value of Tan δ at 60 ° C. was low, and the modified conjugated diene-based polymer rubber composition of the present invention was included in the tire, the rolling resistance had a lower value than that of the prior art, and it was confirmed that fuel efficiency was good. .
또한, 본 발명에 따른 제조예 1 내지 3의 변성 공역디엔계 중합체 고무 조성물의 경우, 0 ℃에서의 Tan δ 값이 비교제조예 2 에 비하여 더 높게 나타나, 타이어에 본 발명의 변성 공역디엔계 중합체 고무 조성물이 포함되는 경우 젖은 노면에서의 저항성이 높음을 확인할 수 있었다.In addition, in the modified conjugated diene-based polymer rubber compositions of Preparation Examples 1 to 3 according to the present invention, the tan δ value at 0 ° C. was higher than that of Comparative Preparation Example 2, and the modified conjugated diene-based polymer of the present invention was applied to a tire. When the rubber composition is included, it was confirmed that the resistance on the wet road surface was high.

Claims (14)

  1. 하기 화학식 1로 표시되는 변성 공역디엔계 중합체:Modified conjugated diene polymer represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2015011230-appb-I000011
    Figure PCTKR2015011230-appb-I000011
    상기 화학식 1에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공역디엔계 중합체 사슬이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이고, c 및 d는 각각 독립적으로 0, 1, 2 또는 3이고, c 및 d는 모두 0일 수 없으며, a+c 및 b+d는 각각 독립적으로 1, 2 또는 3이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, P is a conjugated diene polymer chain, n and m are each independently 1 to 10, a And b are each independently 0, 1 or 2, c and d are each independently 0, 1, 2 or 3, c and d cannot both be 0, and a + c and b + d are each independently 1, 2 or 3.
  2. 하기 화학식 1a로 표시되는 변성 공역디엔계 중합체:Modified conjugated diene polymer represented by the general formula (1a):
    [화학식 1a][Formula 1a]
    Figure PCTKR2015011230-appb-I000012
    Figure PCTKR2015011230-appb-I000012
    상기 화학식 1a에서, c 및 d는 각각 독립적으로 0, 1, 2 또는 3이고, c 및 d는 모두 0일 수 없으며, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 1a, c and d are each independently 0, 1, 2 or 3, and c and d may not be all 0, and n and m are each independently 1 to 10.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 변성 공역디엔계 중합체는 1,000 내지 2,000,000 g/mol의 수평균분자량(Mn)을 가지는 것을 특징으로 하는 변성 공역디엔계 중합체.The modified conjugated diene-based polymer is a modified conjugated diene-based polymer, characterized in that it has a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol.
  4. (a) 유기 알칼리 금속 화합물의 존재 하에 탄화수소 용매 중에서 공역디엔계 단량체, 또는 공역디엔계 단량체와 방향족 비닐계 단량체를 중합시켜 알칼리 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및(a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And
    (b) 상기 알칼리 금속 말단을 갖는 활성 중합체에 하기 화학식 2로 표시되는 화합물을 결합시켜 변성시키는 단계를 포함하는 변성 공역디엔계 중합체의 제조방법:(b) a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the following formula (2) to the active polymer having an alkali metal terminal:
    [화학식 2][Formula 2]
    Figure PCTKR2015011230-appb-I000013
    Figure PCTKR2015011230-appb-I000013
    상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  5. 청구항 4에 있어서, 상기 화학식 2로 표시되는 화합물은 하기 화학식 2a로 표시되는 화합물인 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법:The method of claim 4, wherein the compound represented by Chemical Formula 2 is a compound represented by Chemical Formula 2a.
    [화학식 2a][Formula 2a]
    Figure PCTKR2015011230-appb-I000014
    Figure PCTKR2015011230-appb-I000014
    상기 화학식 2a에서, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 2a, n and m are each independently 1 to 10.
  6. 청구항 4에 있어서,The method according to claim 4,
    상기 유기 알칼리 금속 화합물은, 상기 단량체 총 100 g을 기준으로 할 때, 활성화 몰비 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법. The organoalkali metal compound, based on a total of 100 g of the monomer, a method for producing a modified conjugated diene-based polymer, characterized in that used in 0.01 to 10 mmol on the basis of the activation molar ratio.
  7. 청구항 4에 있어서,The method according to claim 4,
    상기 유기 알칼리 금속 화합물과 상기 화학식 2로 표시되는 화합물의 몰비는 1: 0.1 내지 1: 10인 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법. The molar ratio of the organic alkali metal compound and the compound represented by the formula (2) is 1: 0.1 to 1: 10 method for producing a modified conjugated diene polymer.
  8. 청구항 4에 있어서,The method according to claim 4,
    상기 (a) 단계에서 극성첨가제가 더 투입되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.Method of producing a modified conjugated diene-based polymer, characterized in that further added to the polar additive in step (a).
  9. 청구항 8에 있어서,The method according to claim 8,
    상기 극성첨가제는 상기 유기 알칼리 금속 화합물 총 1 mmol을 기준으로 0.001 내지 10 g으로 투입되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.The polar additive is a method for producing a modified conjugated diene-based polymer, characterized in that added to 0.001 to 10 g based on a total of 1 mmol of the organic alkali metal compound.
  10. 하기 화학식 2로 표시되는 화합물인 것을 특징으로 하는 변성제:Modifier characterized in that the compound represented by the formula (2):
    [화학식 2][Formula 2]
    Figure PCTKR2015011230-appb-I000015
    Figure PCTKR2015011230-appb-I000015
    상기 화학식 2에서, R1, R2, R3 및 R4 는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, n 및 m은 각각 독립적으로 1 내지 10이고, a 및 b는 각각 독립적으로 0, 1 또는 2이다.In Formula 2, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  11. 청구항 10에 있어서,The method according to claim 10,
    상기 화학식 2로 표시되는 화합물은 하기 화학식 2a로 표시되는 화합물인 것을 특징으로 하는 변성제:The compound represented by the formula (2) is a modifier, characterized in that the compound represented by the formula (2a):
    [화학식 2a][Formula 2a]
    Figure PCTKR2015011230-appb-I000016
    Figure PCTKR2015011230-appb-I000016
    상기 화학식 2a에서, n 및 m은 각각 독립적으로 1 내지 10이다.In Formula 2a, n and m are each independently 1 to 10.
  12. 청구항 1의 변성 공역디엔계 중합체 10 내지 100 중량부, 상기 변성 공역디엔계 중합체 100 중량부에 대하여 무기 충진제 0.1 내지 200 중량부를 포함하는 변성 공역디엔계 중합체 고무 조성물. A modified conjugated diene-based polymer rubber composition comprising 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0.1 to 200 parts by weight of the inorganic filler with respect to 100 parts by weight of the modified conjugated diene-based polymer.
  13. 청구항 12에 있어서,The method according to claim 12,
    상기 무기 충진제는 실리카계 충진제, 카본 블랙 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 변성 공역디엔계 중합체 고무 조성물.The inorganic filler is a modified conjugated diene-based polymer rubber composition, characterized in that at least one selected from the group consisting of silica-based filler, carbon black and mixtures thereof.
  14. 청구항 12의 변성 공역디엔계 중합체 고무 조성물을 포함하는 타이어 또는 타이어 트레드.A tire or tire tread comprising the modified conjugated diene-based polymer rubber composition of claim 12.
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