KR20160079323A - Modified conjugated diene polymer and composition comprising the same - Google Patents
Modified conjugated diene polymer and composition comprising the same Download PDFInfo
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- KR20160079323A KR20160079323A KR1020140190537A KR20140190537A KR20160079323A KR 20160079323 A KR20160079323 A KR 20160079323A KR 1020140190537 A KR1020140190537 A KR 1020140190537A KR 20140190537 A KR20140190537 A KR 20140190537A KR 20160079323 A KR20160079323 A KR 20160079323A
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- 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
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- 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
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
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- 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
- C08F2/00—Processes of polymerisation
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- C08F2/00—Processes of polymerisation
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
Description
The present invention relates to a modified conjugated diene polymer comprising a specific styrene-based derivative capable of anionic polymerization and a composition comprising the same.
Recently, as interest in environmentally friendly materials and energy saving materials has increased, modified conjugated diene-based polymer materials in which functional chemicals are introduced into diene-based polymers are used in various applications. Particularly, there is a growing demand for development of material technology capable of improving braking performance and fuel economy by applying such modified conjugated diene polymer to automobile tires. Previously, styrene-butadiene rubber (ESBR) obtained by emulsion polymerization was used as a material used for tire tread, and a material having enhanced elasticity through blending and vulcanization process was used as an inorganic additive such as carbon black and sulfur. However, it is difficult to control the molecular weight and the molecular weight distribution of the ESBR material during the polymerization process, and the control of the microstructure of the polymer is limited.
On the other hand, in the case of styrene butadiene rubber (SSBR) obtained by solution polymerization, an organometallic catalyst such as butyl lithium having carbon anion is generally used as an initiator, and molecular weight and molecular weight distribution Of course, not only the polymer microstructure but also the macro-structure can be freely controlled, so that rubber materials can be designed to improve braking performance and reduce fuel consumption when used in tire treads. Here, in order to improve performance, inorganic particles having a polar group that chemically interacts with the surface of particles such as silica are increasingly used instead of carbon black, and a functional group capable of bonding or interacting with such inorganic particles is added to the end of the polymer It is known that the use of the introduced modified conjugated diene polymer can further improve the tire performance.
In USP 7915349 B2, USP 8426513 B2, USP 8383711 B2 and EP 2045272 B1, the conjugated diene polymer is polymerized using an organometallic catalyst such as butyllithium having carbon anionicity as an initiator, and as the modifying compound, an amine group and an alkoxysilane Was used to synthesize a modified conjugated polymer. The modified conjugated polymer thus synthesized has a role of improving the compatibility and dispersibility of the amine group present at the terminal and the alkoxysilane with an inorganic additive such as silica having a polar group on the surface. However, since the polymerization is initiated with a carbon-based organometallic catalyst initiator having no functional group, only the terminal end of the polymer is denatured. Further, in order to increase the molecular weight or improve the workability, When the coupling reaction is caused by the above modifier, the functional group portion is present at the center of the modified conjugated diene-based polymer chain, so there is a limit to effectively improve the compatibility with the inorganic additive and the dispersibility. When the tire tread is produced using such a modified conjugated diene polymer, the unfiltered polymer starting end may lower the fuel efficiency or lower the balance between braking performance and fuel economy.
On the other hand, in USP 8278395 B2 and KR20045225 B1, a modifier having a multivalent glycidyl group functional group for terminal modification is initiated with an organometallic catalyst such as butyllithium and added to the conjugated diene polymer to obtain a modified conjugated diene polymer The modified conjugated diene polymer having such a functional group was introduced into an inorganic additive such as silica to improve the compatibility and dispersibility. However, for the above reasons, there is a limit to effectively improve the compatibility and dispersibility.
In order to overcome these limitations, US 8729204 B2 and EP 0747405 B1 describe the use of an initiator comprising an amine functional group in the form of an amine anion to prepare a polymer of the starting end modified structure, Were used. However, such a modifier can not be an intermediate modification or an end modification, and is not a monomer type, so there is a limit to increase the modification ratio.
On the other hand, in US 2013/0066008 A1, the modified conjugated diene polymer is polymerized and used by using an initiator containing a silylamine type functional group. However, since it is a technique using a denaturation initiator, there is a limit to increase the modification ratio for the above reason.
SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the prior art described above, and it is an object of the present invention to provide a styrene-based polymer having a specific structure capable of anionic polymerization excellent in affinity with an inorganic additive A modified conjugated diene polymer having a modified structure consisting of a starting end modification, an intermediate modification, an end modification, or a combination thereof is produced by using a monomer. And thereafter selectively using a further modifying agent to provide a modified conjugated diene polymer having a high modifying ratio.
Another object of the present invention is to provide a composition comprising the modified conjugated diene polymer of the present invention and an inorganic filler, wherein the composition of the present invention improves the dispersibility between the inorganic additive and the rubber, It exhibits excellent effects of homogeneity and abrasion resistance.
In order to solve the above problems, the present invention provides a modified conjugated diene polymer comprising a styrene-based functional monomer in at least one of a starting end, a middle and an end of a polymer chain.
The modified conjugated diene polymer of the present invention preferably contains 10% by weight or less, preferably 0.1 to 10% by weight, of the styrene-based functional monomer in the polymer in order to achieve the object of the present invention.
In the modified conjugated diene polymer of the present invention, the styrene-based functional monomer may be contained in the form of a block. In this case, the styrene-based functional monomer block contains 100 or less, preferably 2 to 100, .
In order to achieve the object of the present invention, the modified conjugated diene polymer of the present invention preferably has a vinyl content of 20% by weight or more, preferably 20 to 70% by weight.
In order to achieve the object of the present invention, the modified conjugated diene polymer of the present invention preferably has a Mooney viscosity of 40 or more, preferably 40 to 140.
The modified conjugated diene polymer of the present invention can be produced using at least one method selected from the group consisting of the following polymerization methods (1) to (3):
(1) a method of reacting a styrene-based functional monomer with an anion initiator and then adding a conjugated diene-based monomer to prepare a starting end-modified conjugated diene polymer;
(2) a method in which a conjugated diene-based monomer and a styrene-based functional monomer are added to a solvent and then an anion initiator is added and copolymerized to prepare an intermediate modified conjugated diene polymer; And
(3) In order to produce an end-terminal modified conjugated diene polymer, a conjugated diene monomer is added to a solvent, and an anionic initiator is added to polymerize, followed by addition polymerization with a styrene-based functional monomer.
It is preferable that the method further comprises the step of further modifying by adding a further modifying agent after the polymerization in (1), (2) and (3).
The further modifier is preferably an aminosilane derivative comprising tertiary butyl acrylate or an ester group.
It is preferable that a polar additive is added and polymerized at the time of polymerization in the above (1), (2) and (3).
The present invention also provides a composition comprising 0.1 to 200 parts by weight of an inorganic filler in 100 parts by weight of the modified conjugated diene polymer of the present invention.
The inorganic filler is preferably a carbon black filler, a silica filler, or a mixture thereof.
The composition preferably further comprises a diene rubber.
The diene rubber is preferably at least one selected from the group consisting of natural rubber, isoprene rubber and butadiene rubber.
The composition of the present invention is suitable for use as a tire material.
The modified conjugated diene-based polymer containing the styrene-based functional monomer according to the present invention not only increases the compatibility with the inorganic filler by introducing the styrene-based functional monomer into the polymer, but also increases the compatibility with the inorganic filler when the vulcanization treatment with the vulcanizing agent is performed The hysteresis loss property and the wet skid property are exerted in an excellent effect. Therefore, the composition containing the modified conjugated diene polymer of the present invention can be usefully used as a material for tire tread.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the meaning of the starting terminal, middle terminal, and terminal terminal of the modified conjugated diene polymer of the present invention. Fig.
Hereinafter, the present invention will be described in detail.
The modified conjugated diene polymer of the present invention is characterized in that at least one of the starting end, the middle and the terminal end of the polymer chain contains a styrene-based functional monomer.
Specifically, the modified conjugated diene-based polymer comprising a styrene-based functional monomer capable of anionic polymerization according to the present invention,
1) a styrene-based functional monomer is added to the starting end of the polymer to denature (starting end denature);
2) Modified (intermediate modified) styrene-based functional monomer is added to the main chain of the polymer;
3) a styrene-functional monomer is added to the end of the polymer to denature (end-terminal modification); or
4) a multifunctional conjugated diene polymer containing two or more of the modifications 1) to 3).
The termination end modification refers to the end of polymerization initiated by the anion initiator when the modified conjugated diene polymer is polymerized. The intermediate modification means that the functional monomer is located at the middle of the modified conjugated diene polymer main chain and is polymerized. Terminal modification refers to terminal modification obtained by adding a styrene functional monomer to the terminal of the active anion after all of the polymer has been polymerized to denature or further adding a further denaturant capable of reacting with the active anionic end.
In the present invention, preferred examples of the styrene-based functional monomer include, but are not limited to, styrene-based functional monomers represented by the following formula (1)
[Chemical Formula 1]
here,
R 1 represents hydrogen or a C 1 -C 5 alkyl group;
R 2 is selected from derivatives of the following formulas (2) to (6)
[Chemical Formula 2] Carbonylstyrene derivative
[Chemical Formula 3] Acetal styrene derivative
[Formula 4] Sulfonamido styrene derivative
[Chemical Formula 5] Cyanostyrene derivative
The amine styrene derivative
(7)
here,
R 3 represents C1-C5 alkyl, C1-C5 alkyloxy (-OR), or an amine derivative represented by the following formula (7)
R 4 represents C 1 to C 5 alkyl or C 1 to C 5 alkoxysilane,
R 5 And R < 6 > each independently represents C1-C5 alkyl or C1-C5 alkylsilane,
In the formulas (3) and (7), n represents an integer of 1 to 5.
In the above formula (3), the acetal exhibits polarity, whereby the modified conjugated diene polymer can improve the dispersibility with the inorganic additive, and the braking performance and the fuel economy can be improved when used in a tire. Particularly, in the case of 4-vinyl acetophenone, the anionic polymerization property is excellent, and the dispersibility with the inorganic additive can be further improved by the substituent such as the formula (7). Examples of the compound represented by the formula (3) include 2- (4-vinylphenyl) -1,3-dioxolane and 2- (4-vinylphenyl) 1] to the ortho, meta and para positions. The dispersibility with the inorganic additive is improved by the oxygen atom.
In the formula (4), the dispersibility with the inorganic particles can be improved by the sulfone amino group substituent, and examples thereof include N, N-diethyl-4-vinylbenzenesulfonamide, N, Vinylbenzenesulfonamide, N-methyl-N '- [(4-vinylphenyl) sulfonyl] piperazine and the like.
In the formulas (5) and (6), R 4 represents alkyl or alkoxy silane, R 5 And R 6 represents an alkyl group or an alkylsilane. For this reason, the dispersibility with the inorganic particles can be improved, and the braking performance and the fuel economy can be improved when the tire is used.
In the modified conjugated diene polymer of the present invention, the styrene-based functional monomer may be contained in the form of a block in the polymer. When the styrene-based functional monomer is copolymerized in the form of a block, the repeating unit of the styrene-based functional monomer in the block is preferably 100 or less. When it exceeds 100, the balance of braking / low fuel consumption may be lowered when the resulting modified conjugated diene polymer is applied to a tire material composition, which is not preferable.
The proportion of the styrene-based functional monomer in the total modified conjugated diene polymer of the present invention is preferably 10% by weight or less, more preferably 5% by weight or less. When it is contained in an amount of more than 10% by weight, the viscosity (MV) is high, so that it is difficult to disperse in blending with the inorganic additive and the performance is lowered. Also, the performance is lowered due to the domain when the styrene- Can occur.
The modified conjugated diene polymer (C) according to the present invention has improved dispersibility and compatibility when blended with an inorganic additive having a polar group as compared with the existing end-modified conjugated diene polymer, and is excellent in tire tread material Can be suitably used.
The modified conjugated diene polymer of the present invention as described above can be produced by polymerizing two or more of the following polymerization methods (1) to (3) in combination:
(1) a method in which the styrene-based functional monomer is reacted with an anion initiator and then a conjugated diene-based monomer is added and polymerized;
(2) a method of adding a conjugated diene-based monomer and the styrene-based functional monomer to a solvent followed by copolymerization by adding an anion initiator;
(3) a method in which a conjugated diene-based monomer is added to a solvent, an anion initiator is added to polymerize, and the styrene-based functional monomer is further added to effect further polymerization.
In order to produce the starting end-modified conjugated diene polymer according to the present invention, the styrene-based functional monomer is reacted with the anion initiator in advance in the form of a modified anionic initiator according to the method (1) The conjugated diene-based monomer is added and polymerization is carried out.
In order to produce the intermediate modified conjugated diene polymer according to the present invention, the conjugated diene monomer and styrene-based functional monomer are added to a solvent according to the method described in the above (2), and then copolymerization is initiated as an anion initiator.
In order to produce the end-modified conjugated diene polymer according to the present invention, the conjugated diene-based monomer is added to a solvent according to the above-mentioned method (3), and after the completion of polymerization initiated with an anion initiator, Polymerization is carried out by adding a phenol functional monomer.
In order to produce the multibranched conjugated diene polymer according to the present invention, the polymerization can be carried out by combining two or more of the above-mentioned methods (1) to (3) for starting end modification, intermediate modification and terminal modification have.
After the polymerization in the above polymerization methods, the modified conjugated diene polymer may be polymerized by adding a further denaturant capable of reacting with the active terminal in the presence of the active anion.
Examples of the anion initiator that can be used in the production of the modified conjugated diene polymer according to the present invention include alkyl lithium, alkyl sodium, alkyl potassium and the like. In addition, all kinds of initiators having a specific form of an anion form can be used without limitation .
In the production of the modified conjugated diene polymer according to the present invention, there is no limitation on the type of the additional modifier, and any of those generally available to those skilled in the art can be used. Depending on the number of functional groups, the molecular weight may be increased or the polymer structure may be A modified one can be obtained. As the additional modifier, it is preferable that two or more functional groups capable of reacting with the living anion are used. In general, tin-based, alkoxysilane-based or silyl halide-based ones can be used, and a modification system including a glycidyl group can be used have.
Examples of the tin series modifier include diphenyltin dichloride, dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, tetra Tetraethoxy tin, tetrapropoxy tin, etc. The alkoxysilane series may include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dibutyldimethoxysilane, dibutyldimethoxysilane, Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, tetramethoxysilane, Ethoxy silane, tetraethoxy silane and the like can be used. The silyl halide series may be selected from the group consisting of diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, Silane, methyltrichlorosilane, tetrachlorosilane, and the like can be used. The modifier containing a glycidyl group is exemplified by 4,4'-methylenebis (N, N-diglycidylaniline), N, N-diglycidyl-4-glycidoxyaniline, N, Dianiline, N, N, N ', N'-tetraglycidyl-3,3'-diethyl-4,4'-diaminodiphenylmethane and the like can be used.
In addition, aminosilane derivatives containing an ester group such as tertiary butyl acrylate and (triacryloxypropyl) trimethoxysilane can also be used as further modifiers.
The above-mentioned additional modifying agents may be used alone or in combination of two or more. The additional modifier that can be used in the production of the modified conjugated diene polymer of the present invention is not limited to the above-mentioned types, and may be an end group having an activity such as the tin series, alkoxysilane series, silyl halide series, glycidyl series, Any that can react with the termini can be used.
On the other hand, in the polymerization method for producing the modified conjugated diene polymer of the present invention, a polar additive may be further added at the time of polymerization as occasion demands. The polar additive is added to control the microstructure of the polymer or to improve the polymerization rate or to control the reactivity, and the amount added may vary depending on the purpose or type of additive. Examples of the polar additive that can be used in the present invention include tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), diethylether, cycloalcoholether, dipropylether, ethylene glycol, triethylamine, ethylbutylether, crown ether , Ditetrahydrofuryl propane, ethyl tetrahydrofuryl ether, triethylamine, trimethylamine and derivatives thereof can be used. With such a polar additive, the random structure of the polymer and the content of the vinyl group can be controlled according to the object, and the polymerization reaction rate can be improved.
In the polymerization method for producing the modified conjugated diene-based polymer of the present invention, the solvent used in the polymerization may be n-hexane, n-heptane, cyclohexane, isooctane, methylcyclopentane, benzene, toluene, Xylene, tetrahydrofuran, and the like, which may be used alone or in combination of two or more. In the polymerization, the monomers are added in the hydrocarbon solvent at a level of 5 to 50% by weight, preferably 15 to 35% by weight. When the amount of the monomer is less than 5% by weight, the polymerization time may be long or the reaction may be difficult. When the amount of the monomer is more than 50% by weight, the solution viscosity increases and the molecular weight and reaction heat are difficult to control.
In the polymerization method for producing the modified conjugated diene-based polymer of the present invention, the polymerization temperature at the time of polymerization may vary depending on the solvent, and polymerization is generally possible at 10 to 160 ° C. Depending on the polymerization temperature, the microstructure can be varied, and the polymerization temperature can be controlled according to the purpose.
The modifier may be added after addition of the conjugated diene-based monomer or the vinyl-based hydrocarbon monomer in order to stabilize the binding of the additional modifier to the polymer or improve the efficiency, depending on the anionic reactivity of the end of the polymer before introduction of the additional modifier. A time sufficient for the reaction to proceed sufficiently after the addition of the denaturant is necessary. This can be confirmed by analyzing the modification ratio of the polymer by taking a sample during polymerization. The denaturation ratio refers to the denaturation rate of the modified conjugated diene polymer modified by a styrene-based functional monomer. Experimentally, as described later in the following examples, two columns of silica-based gel (Zorbax PSM) Lt; RTI ID = 0.0 > THF < / RTI > as solvent. The higher the modification ratio, the better the performance by the rubber compounding and the vulcanization process. Therefore, it is preferable to increase the modification ratio to the maximum depending on the purpose. Generally, the modification ratio should be 10% or more, preferably 20% or more.
The present invention also provides a composition comprising the above-mentioned modified conjugated diene polymer of the present invention. The composition of the present invention is characterized by containing 0.1 to 200 parts by weight of an inorganic filler per 100 parts by weight of the modified conjugated diene polymer of the present invention.
As the inorganic filler contained in the composition of the present invention, carbon black, silica, etc. may be used alone or in combination of two or more. Particularly, when an inorganic filler having a large number of functional groups on the surface of inorganic particles such as silica is blended, the performance of the modified conjugated diene polymer of the present invention can be further improved.
The composition of the present invention may further comprise at least one diene rubber selected from the group consisting of natural rubber, isoprene rubber and butadiene rubber.
The composition of the present invention is generally suitable for use as a material for tires, particularly for tire treads, and therefore may further comprise conventional additives usually used in tire compositions.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Is not limited to the following examples.
[ Example ]
Experimental Method
1. Analysis of polymer microstructure
The microstructure of the polymerized polymer was confirmed using 400 MHz < 1 > H-NMR of Bruker.
2. Molecular weight measurement
Molecular weight measurements were made using two polystyrene 5 μm mixed-C columns from PLgel, in series, with a polystyrene reference sample (molecular weight 5000 g / mol) and polymerized polymer with THF as solvent. The detector uses a refractive index detector (RI).
3. Measurement of metamorphic rate
Two columns filled with silica-based gel (Zorbax PSM) were connected in series, and the solvent was measured with a refractive index detector (RI) using THF. A sample of polystyrene standards (molecular weight 5000 g / mol) was dissolved in the solvent together with the polymer and injected into the column for measurement. The denaturation rate was calculated by the following equation.
Modification ratio (%) = [1- (A2 x A3) / (A1 x A4)] x 100
A1: the total peak area of the sample (excluding the peak area of the sample based on polystyrene) and the total peak area of the sample when the area of the entire peak obtained in the styrene gel column is 100;
A2: When the area of the entire peak obtained in the styrene gel column is taken as 100, the peak area of the polystyrene standard sample,
A3: When the area of the entire peak obtained in the silica gel column is taken as 100, the sample peak area not adsorbed to the silica gel gel,
A4: Peak area of the polystyrene-based sample when the area of the entire peak obtained in the silica gel column is taken as 100.
4. Tensile test
The cured specimens were prepared as c-type dumbbells and measured using a universal testing machine (LLOYD UTM) according to the ASTM 412 tensile test method.
5. Viscoelastic properties
The tan δ, the viscoelastic property of the vulcanized specimen, was measured with a temperature sweep at 10 Hz and 0.1% strain conditions using DMTA equipment. When the value of tan? At 0 占 폚 is high, the wet skid property which is braking is excellent, and when the tan? Value at 60 占 폚 is low, low hysteresis is exhibited and the fuel efficiency is excellent.
6. Mineral Particle Dispersibility
The dispersibility of the modified conjugated diene polymer and the inorganic additive particles was confirmed by Payne effect using Alpha Technology's RPA2000 as a sample before vulcanization after blending with Hakke. The Pheny effect is expressed as kPa in the deformation at 0.7% and 14% at 0.1 Hz and 60 ° C, and the smaller the value, the better the dispersion of inorganic particles.
7. Pattern viscosity
The pattern viscosity of the modified conjugated diene polymer itself was measured on the basis of ML (1 + 4) at 100 ° C using a Mooney viscometer manufactured by Alpha technology.
Example One
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 ° C while being turned by a stirrer. 4-vinylpropiophenone, a styrene-functional monomer, was reacted with butyllithium (BuLi) in a tetrahydrofuran solvent to prepare an oligomer-type initiator having an average number of styrene functional monomers of 10 units and a concentration of 0.6M Was prepared, and then this solution was added thereto Polymerization was carried out to polymerize the starting end modified styrene-butadiene rubber polymer (SBR) having a weight average molecular weight (Mw) of 200,000. 10 minutes after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the end of the polymer was replaced with the butadiene active anion for 5 minutes. Thereto, 0.58 mmol of tetramethoxysilane was added and reacted for 20 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Example 2
The procedure of Example 1 was repeated, except that 4-vinylbenzaldehyde diethylacetal was used instead of 4-vinylpropiophenone as a styrene-based modifier.
Example 3
Except that N, N-diisopropyl-4-vinylbenzamide was used instead of 4-vinylpropiophenone as a styrene-based modifier. Respectively.
Example 4
Except that N, N-diethyl-4-vinylbenzenesulfonamide was used instead of 4-vinylpropiophenone as a styrene-based modifier. Respectively.
Example 5
The procedure of Example 1 was repeated, except that 4-cyanostyrene was used instead of 4-vinylpropiophenone as a styrene-based modifier.
Example 6
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 ° C while being turned by an agitator. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. To the reaction mixture was added 13 mmol of 4-vinylacetatophenone as a styrene-based modifier, and then 0.58 mmol of tetrachlorosilane was added thereto, followed by reaction for 10 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Example 7
Except that 4-vinylbenzaldehyde diethyl acetal was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 8
The procedure of Example 6 was repeated, except that N, N-diisopropyl-4-vinylbenzamide was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 9
The procedure of Example 6 was repeated, except that N, N-diethyl-4-vinylbenzenesulfonamide was used in place of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 10
The procedure of Example 6 was repeated, except that 4-cyanostyrene was used instead of 4-vinylacetitophenone as a styrene-based modifier.
Example 11
In a 2 L autoclave reactor, 34 g of styrene, 126 g of 1,3-butadiene, 830 g of hexane and 4-vinylethylacetophenone were added in a predetermined amount, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, The temperature was raised to 40 占 폚. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. Thereto, 0.58 mmol of tetramethoxysilane was added and reacted for 10 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Example 12
Except that 4-vinylbenzaldehyde diethyl acetal was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 13
Except that N, N-diisopropyl-4-vinylbenzamide was used in place of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 14
The procedure of Example 11 was repeated, except that N, N-diethyl-4-vinylbenzenesulfonamide was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 15
The procedure of Example 11 was repeated, except that 4-cyanostyrene was used instead of 4-vinylacetitophenone as a styrene-based modifier.
Example 16
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 캜 while being turned by a stirrer. A solution of 0.6 M of an oligomer type initiator having an average number of styrene functional monomers of 12 units was prepared by reacting 4-vinyl acetethytophenone, a styrene-based functional monomer, with butyllithium (BuLi) in a tetrahydrofuran solvent Thereafter, this solution was added to carry out a polymerization reaction to polymerize the starting terminal modified SBR having Mw of 200,000. 10 minutes after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the end of the polymer was replaced with the butadiene active anion for 5 minutes. 0.58 mmol of tetrachlorosilane was added thereto, and the reaction was carried out for 20 minutes. Then, 0.8 mmol of t-butylacrylate as an additional modifier was added, and after 20 minutes of reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Example 17
Except that 4-vinylbenzaldehyde diethyl acetal was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 18
The procedure of Example 16 was repeated, except that N, N-diisopropyl-4-vinylbenzamide was used in place of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 19
The procedure of Example 16 was repeated, except that N, N-diethyl-4-vinylbenzenesulfonamide was used in place of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 20
The procedure of Example 16 was repeated, except that 4-cyanostyrene was used instead of 4-vinylacetitophenone as a styrene-based modifier.
Example 21
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the mixture was heated to 40 ° C while being turned by a stirrer. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature had reached the maximum temperature, 10 g of butadiene was added and the end of the polymer was replaced with the butadiene active anion for 5 minutes. Then, 13.5 mmol of a styrene-based modifier, 4-vinylacetyltophenone was added and reacted. Then, 1.12 mol of (diaminoethyl) (trimethoxysilylmethyl) ester as a further modifier was added and reacted for 1 hour. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Example 22
The procedure of Example 21 was repeated, except that 4-vinylbenzaldehyde diethyl acetal was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 23
The procedure of Example 21 was repeated, except that N, N-diisopropyl-4-vinylbenzamide was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 24
The procedure of Example 21 was repeated, except that N, N-diethyl-4-vinylbenzenesulfonamide was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Example 25
The procedure of Example 21 was repeated, except that 4-cyanostyrene was used instead of 4-vinyl acetethitophenone as a styrene-based modifier.
Comparative Example One
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the mixture was heated to 40 ° C while being turned by a stirrer. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. Thereto, 0.58 mmol of tetramethoxysilane was added and reacted for 10 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Comparative Example 2
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 캜 while being turned by a stirrer. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. 0.46 mmol of tetrachlorosilane was added thereto, and the reaction was carried out for 10 minutes. Then, 0.8 mmol of t-butyl acrylate was added, and after 20 minutes of reaction, ethanol was added to terminate the polymerization, and I-1076 as an antioxidant was added in an amount of 0.2% by weight based on the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Comparative Example 3
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 캜 while being turned by a stirrer. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. 145 mmol of N, N-diisopropyl-4-vinylbenzamide, a styrene-based modifier, was added and allowed to react for 20 minutes. Then, 0.58 mmol of tetrachlorosilane was added and reacted for 10 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Comparative Example 4
34 g of styrene, 126 g of 1,3-butadiene and 830 g of hexane were placed in a 2 L autoclave reactor, 0.9 ml of tetramethylethylenediamine (TMEDA) was added thereto, and the temperature of the reactor was raised to 40 캜 while being turned by a stirrer. Then, 2.1 mmol of 0.27 M BuLi was added to the mixture to conduct polymerization. After 10 minutes had elapsed after the reaction temperature reached the maximum temperature, 10 g of butadiene was added and the terminal end of the polymer was replaced with the butadiene active anion for 5 minutes. 20 g of a styrene-based modifier N, N-diisopropyl-4-vinylbenzamide was added thereto, and reacted for 20 minutes. Then, 0.58 mmol of tetrachlorosilane was added and reacted for 10 minutes. After the reaction, the polymerization was stopped by adding ethanol, and 0.2 weight% of I-1076 as an antioxidant was added to the polymer. In order to remove the solvent in the polymer, the prepared polymer was placed in heated hot water, stirred and vacuum dried.
Experimental Example : Polymer and Mineral Kneading And physical property measurement experiment
Each of the polymers obtained in the above Examples and Comparative Examples was blended in the composition shown in Table 1 below to prepare a composition. A method of kneading the polymer composition was a Haake Polylab OS Rheodrive manufactured by Thermo Scientific Inc., and a bombarded rotor was used.
The formulation proceeded in two steps. The kneading was carried out in the same manner as in the first kneading, except that the first kneading was performed at a rate of 75% by weight and the rotor was rotated at 60 rpm to prepare a polymer, filler (silica), oil, zinc oxide (ZnO), stearic acid, silane coupling agent -PPD to control the temperature to obtain a first composition at 150-160 占 폚. In the second kneading, the compound obtained in the first kneading is cooled to room temperature, and sulfur is reacted at 90 DEG C or lower with diphenyl guanidine (DPG), N-cyclohexyl-2-benzothiazole sulfonamide (CBS: N-cyclohexyl-2-benzothiazole sulfonamide) was added and kneaded for 5 minutes. The compounded composition was vulcanized at 170 캜 in a T90 + 5 min press to prepare a vulcanized rubber specimen.
[Table 1]
The composition and physical properties of the polymer and polymer composition prepared according to the present invention and their performance were evaluated and shown in the following Tables 2 to 13.
[Table 2]
* Styrene content and vinyl content were calculated by H-NMR (the same applies to the following tables)
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
[Table 13]
Claims (18)
[Chemical Formula 1]
here,
R 1 represents hydrogen or a C 1 -C 5 alkyl group;
R 2 is selected from derivatives of the following formulas (2) to (6)
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
here,
R 3 represents C1-C5 alkyl, C1-C5 alkyloxy (-OR), or an amine derivative represented by the following formula (7)
R 4 represents C 1 to C 5 alkyl or C 1 to C 5 alkoxysilane,
R 5 And R < 6 > each independently represents C1-C5 alkyl or C1-C5 alkylsilane,
In the formulas (3) and (7), n represents an integer of 1 to 5.
(1) a method in which the styrene-based functional monomer is reacted with an anion initiator and then a conjugated diene-based monomer is added and polymerized;
(2) a method of adding a conjugated diene-based monomer and the styrene-based functional monomer to a solvent followed by copolymerization by adding an anion initiator;
(3) a method in which a conjugated diene-based monomer is added to a solvent, an anion initiator is added to polymerize, and the styrene-based functional monomer is further added to effect further polymerization.
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| WO2018021742A1 (en) * | 2016-07-26 | 2018-02-01 | 주식회사 엘지화학 | Method for measuring polymer modification ratio |
| KR20180134328A (en) * | 2016-10-06 | 2018-12-18 | 신도스 에스.에이. | [Bis (trihydrocarbylsilyl) aminosilyl] -functional styrene-based elastomeric copolymers and their use in rubber manufacture |
| WO2019066279A1 (en) * | 2017-09-29 | 2019-04-04 | 주식회사 엘지화학 | Both-end-modified conjugated diene-based polymer and method for producing same |
| KR20190038287A (en) * | 2017-09-29 | 2019-04-08 | 주식회사 엘지화학 | Both ends-modified diene polymer and preparation method thereof |
| WO2019112262A1 (en) * | 2017-12-05 | 2019-06-13 | 주식회사 엘지화학 | Modified conjugated diene-based polymer and rubber composition comprising same |
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