CN117242104A

CN117242104A - Liquid butadiene compound modified at both ends, preparation method and application thereof

Info

Publication number: CN117242104A
Application number: CN202280033083.7A
Authority: CN
Inventors: 白贤钟; 金元浩; 廉暻东; 金铜赫; 崔夏恩; 宋尚勋
Original assignee: Pusan National University Industry University Cooperation Group
Current assignee: Pusan National University Industry University Cooperation Group
Priority date: 2021-04-06
Filing date: 2022-04-05
Publication date: 2023-12-15

Abstract

The present invention relates to a liquid butadiene compound having both ends modified, a method for producing the same, and a use thereof, and more particularly, to a liquid butadiene rubber compound having both ends modified, synthesized using a chain transfer agent having a triethoxysilyl group and a tetrasulfide group and a 1, 3-butadiene monomer, a rubber composition for a tire comprising the same, a method for producing the same, and the like. According to the present invention, silica affinity functional groups are introduced to both ends of a chain, so that various properties affecting fuel economy characteristics can be improved by adjusting hysteresis (hysteresis) or the like generated from the chain ends of the existing liquid butadiene rubber.

Description

Liquid butadiene compound modified at both ends, preparation method and application thereof

Technical Field

The present invention relates to a both-end modified liquid butadiene compound, a method for producing the same, and use thereof, and more particularly, to a both-end modified liquid butadiene rubber compound synthesized using a chain transfer agent having triethoxysilyl functional groups and tetrasulfide functional groups and a 1, 3-butadiene monomer, a rubber composition containing the same, a tire produced using the same, and methods for producing the same.

Background

At present, as regulations on greenhouse gas emissions are strengthened in countries around the world, there is an increasing demand for improving fuel economy of automobiles. Therefore, the biggest factor affecting the transformation of the automobile industry paradigm is environmental protection, and electric automobiles have become an environmental protection core technology for reducing greenhouse gases. The European Union (EU) has proposed regulations that the carbon dioxide emissions per car should not exceed 95g/km based on average car sales since 2020, and similar fuel economy regulations will be implemented in major automobile consumer countries such as the United states, japan, etc.

As such, with the shift of the trend of automobiles from internal combustion automobiles to electric automobiles, tires are also required to have performances suitable for electric automobiles. Due to the limited battery capacity, electric vehicles are required to greatly reduce the tire rolling resistance to ensure a long driving distance. Moreover, due to the characteristics of the electric motor, it is necessary to improve wear resistance to withstand high torque output from acceleration and high load of the motor/battery.

In 1993, tire manufacturers, beginning with Michelin (Michelin), conducted research using silica as a reinforcing agent in place of existing carbon black to reduce greenhouse gas emissions. Unlike hydrophobic carbon black, silica has hydrophilic surface properties, so traction (traction) and rolling resistance (rolling resistance) of a tire compound are improved by using a silane coupling agent, and the conversion of this filler technology (filler technology) becomes a trigger for introducing functional groups into a polymer chain.

On the other hand, tires are sulfides filled with various additives including reinforcing agents. In the preparation process, a large amount of processing oil such as a treated distilled aromatic extract (treated distil late aromatic extracts, TDAE) or the like is added as a processing aid to facilitate the process. Because of the greater or lesser deformation of the tire at high temperatures during running and braking, the injected process oil gradually migrates (scales) and emerges from the compound as the distance travelled and the time increases. The compound that emerges from the process oil hardens and its physical properties are worse than those of the original. In particular, the smaller deformation of the hardened tread during braking results in a reduced contact area with the road surface and reduced braking performance. The liquid butadiene rubber can be used as a processing aid and can form cross-linking with the rubber main chain of the sizing material in the vulcanization process, so that the migration phenomenon is hardly generated after the tire is prepared, and the original physical properties can be maintained for a long time. And the glass transition temperature (T) of the compound can be adjusted according to the microstructure of the liquid butadiene rubber _g ) Thus when a low T is applied _g Excellent snow braking performance and wear resistance are obtained when the liquid butadiene rubber is used.

However, rolling resistance affecting fuel economy characteristics is adversely affected due to large hysteresis (hysteresis) generated from the chain ends of the liquid butadiene rubber. Thus, there is a need for a liquid butadiene rubber synthesis technique that chemically fixes the chain ends to the filler.

Disclosure of Invention

Technical problem

The object of the present invention is to provide a novel liquid butadiene compound modified at both ends, which enables the chain ends to be chemically fixed to a filler to impart excellent fuel economy performance, wear performance, and the like, and a method for producing the same.

Another object of the present invention is to provide a rubber composition for manufacturing a tire using a both end-modified liquid butadiene compound and a method of manufacturing a tire using the same, which enable a chain end to be chemically fixed to a filler to impart excellent fuel economy performance, wear performance, and the like to the tire.

Solution to the problem

In order to achieve the above object, the present invention provides a compound represented by the following chemical formula 1.

Chemical formula 1:

R’ _x (RO) _3-x -Si-(CH ₂ ) _a -S _c -(M)-S _d -(CH ₂ ) _b -Si-(OR) _3-x R’ _x

in the above chemical formula 1, R and R' can be the same or different, respectively, selected from hydrogen or C1-C6 alkyl, x is an integer selected from 0 to 2, a and b are each independently an integer selected from 1 to 5, C and d are each independently an integer selected from 1 to 9, and M is a polymerized chain comprising one or two or more diene (diene) monomers.

The M may be one or more selected from the compounds represented by the following chemical formula 2-1, chemical formula 2-2, or chemical formula 2-3, may be composed of 20 to 25 mole (mol) percent of the compound represented by the above chemical formula 2-1, and 75 to 80 mole percent of the compounds represented by the above chemical formula 2-2 and chemical formula 2-3, and may have a number average molecular weight of 500 to 50000g/mol.

Chemical formula 2-1:

chemical formula 2-2:

chemical formula 2-3:

the M may be a copolymer of one or more monomers selected from the group consisting of butadiene, styrene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2-phenyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-chloro-1, 3-butadiene, 3-butyl-1, 3-octadiene, acrylate monomers, and acrylonitrile monomers.

The above compound may be a butadiene rubber modified at both ends.

The vinyl (vinyl) content in the above-mentioned compounds may be 15 to 30 parts by weight, and each of the above-mentioned compounds may contain 1 to 3 silyl (silyl group) functional groups, relative to 100 parts by weight of the total amount of the above-mentioned compounds.

The invention provides a preparation method of a compound, which comprises the following steps: a first step of preparing a radical compound by reacting an initiator with a monomer; a second step of preparing a chain transfer agent radical by reacting the prepared radical compound with a chain transfer agent represented by the following chemical formula 3; a third step of forming a single-end modified intermediate radical compound by polymerizing the prepared chain transfer agent radical with the monomer; and a fourth step of forming a compound having both ends modified by reacting the formed intermediate radical compound with a chain transfer agent represented by the following chemical formula 3.

Chemical formula 3:

R’ _x (RO) _3-x -Si-(CH ₂ ) _a -S _c -(CH ₂ ) _b -Si-(OR) _3-x R’ _x

in the above chemical formula 3, R and R' may be the same or different, respectively, and are selected from hydrogen or C1-C6 alkyl, x is an integer selected from 0 to 2, a and b are each independently an integer selected from 1 to 5, and C is an integer selected from 1 to 9.

In the second step and the fourth step, the chain transfer agent is supplied with-S _c The bond may be cleaved by the radical compound described above and reacted.

The first to fourth steps described above may be performed at a temperature of 130 to 150 ℃.

The initiator, the chain transfer agent, and the monomer may be added at a molar ratio of 1:5 to 20:500 to 2000.

The present invention provides a rubber composition for a tire, the composition comprising a rubber polymer and a compound represented by the above chemical formula 1 as an active ingredient.

The above compound may be a butadiene rubber modified at both ends.

The rubber polymer may be selected from natural rubber; more than one butadiene-based rubber selected from the group consisting of butadiene rubber, styrene-butadiene rubber, and nitrile rubber; or a mixed rubber thereof.

The content of the above compound may be 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the above rubber polymer.

The present invention provides a tire prepared by comprising the rubber composition for a tire described above.

The above tire may be prepared by further comprising one or more selected from the group consisting of silica, a coupling agent, a softening agent, a vulcanizing agent, a vulcanization accelerator, a crosslinking agent, a crosslinking activator, an antioxidant, an accelerator, and a super accelerator.

Moreover, the present invention provides a method for manufacturing a tire, comprising: a first step of preparing a rubber mixture by mixing the rubber composition for a tire described above with silica; a second step of molding the prepared rubber mixture into a tire shape; and a third step of performing a vulcanization reaction by heating the rubber mixture in the tire shape.

The rubber mixture may be formed by mixing butadiene rubber and styrene-butadiene rubber in a weight ratio of 1:3-5.

ADVANTAGEOUS EFFECTS OF INVENTION

The compound of the present invention is a liquid butadiene rubber modified at both ends with a chain transfer agent having a triethoxysilyl (triethysilyl) functional group and a tetrasulfide (tetra sulfide) functional group and a 1, 3-butadiene (1, 3-butadiene) monomer, and a silica affinity functional group is introduced at both ends of the chain, whereby various performances affecting fuel economy characteristics can be improved by adjusting hysteresis (hysteresis) or the like generated from the chain ends of the existing liquid butadiene rubber, deterioration of physical properties with time can be prevented, and deterioration of glass transition temperature (T) of the liquid butadiene rubber can be reduced _g ) To improve wear resistance.

Drawings

FIG. 1 shows a process for preparing a compound according to an embodiment of the present invention.

FIG. 2 is a schematic diagram showing Compound A prepared according to example 1-1 of the present invention ¹ Graph of H-NMR results.

FIG. 3 is a schematic diagram showing Compound B prepared according to examples 1-2 of the present invention ¹ Graph of H-NMR results.

FIG. 4 is a schematic diagram showing Compound C prepared according to examples 1-3 of the present invention ¹ Graph of H-NMR results.

FIG. 5 is a schematic diagram showing Compound D prepared according to examples 1 to 4 of the present invention ¹ Graph of H-NMR results.

FIG. 6 is a schematic diagram showing Compound E prepared according to examples 1-5 of the present invention ¹ Graph of H-NMR results.

FIG. 7 is a schematic diagram showing Compound F prepared according to examples 1 to 6 of the present invention ¹ Graph of H-NMR results.

Fig. 8 is a graph showing the results of size exclusion chromatography (Size exclusion chromatography, SEC) analysis of compounds C, D, E and F prepared according to examples 1-3 to 1-6 of the present invention.

FIG. 9 is a graph showing the 1H-NMR results of compound G prepared according to examples 1 to 7 of the invention.

FIG. 10 is a graph showing the 1H-NMR results of compound H prepared according to examples 1 to 8 of the invention.

Fig. 11 is a graph showing SEC analysis results of compound G and compound H prepared according to examples 1 to 7 and examples 1 to 8 of the present invention.

Best mode for carrying out the invention

Hereinafter, the present invention will be described in detail.

The terms used in the present invention select general terms widely used at present as much as possible in view of functions in the present invention, but this may vary according to the intention or precedent of those skilled in the art, the appearance of new technologies, etc. Accordingly, the terms used in the present invention should be defined based on the meanings of the terms and the entire contents of the present invention, not the names of the terms themselves.

Throughout the specification, when a portion "comprises" a certain structural element, unless specifically stated to the contrary, it is meant that other structural elements may also be included, rather than excluded.

The present invention provides a compound represented by the following chemical formula 1.

Chemical formula 1:

Preferably, M may be one or more selected from the compounds represented by the following chemical formula 2-1, chemical formula 2-2, or chemical formula 2-3.

Chemical formula 2-1:

chemical formula 2-2:

chemical formula 2-3:

preferably, the M may be composed of 20 to 25 mole percent of the compound of the chemical formula 2-1 and 75 to 80 mole percent of the compounds of the chemical formulas 2-2 and 2-3, but is not limited thereto.

Preferably, the number average molecular weight of M may be 500g/mol to 50000g/mol, more preferably 1000g/mol to 10000g/mol, but is not limited thereto.

Alternatively, the above M may be a copolymer of one or two or more monomers selected from the group consisting of butadiene, styrene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2-phenyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-chloro-1, 3-butadiene, 3-butyl-1, 3-octadiene, acrylic monomers and acrylonitrile monomers, but is not limited thereto.

The compound of the present invention may contain a unit structure derived from the above-mentioned M, and preferably may be a butadiene polymer, i.e., a butadiene rubber modified at both ends, but is not limited thereto.

Preferably, the vinyl (vinyl) content of the above-mentioned compound may be 15 to 30 parts by weight, more preferably, 18 to 25 parts by weight, relative to 100 parts by weight of the total amount of the above-mentioned compound, but is not limited thereto.

Preferably, each of the above compounds may contain 1 to 3 silyl functional groups, but is not limited thereto.

The invention provides a preparation method of the compound.

The preparation method of the compounds of the invention can comprise the following steps: a first step of preparing a radical compound by reacting an initiator with a monomer; a second step of preparing a chain transfer agent radical by reacting the prepared radical compound with a chain transfer agent represented by the following chemical formula 3; a third step of forming a single-end modified intermediate radical compound by polymerizing the prepared chain transfer agent radical with the monomer; and a fourth step of forming a compound having both ends modified by reacting the formed intermediate radical compound with a chain transfer agent represented by the following chemical formula 3.

Chemical formula 3:

R’ _x (RO) _3-x -Si-(CH ₂ ) _a -S _c -(CH ₂ ) _b -Si-(OR) _3-x R’ _x

in the above chemical formula 3, R and R' may be the same or different, and are selected from hydrogen or C1-C6 alkyl, x is an integer selected from 0 to 2, a and b are each independently an integer selected from 1 to 5, and C is an integer selected from 1 to 9.

The first step of preparing the radical compound may be performed by reacting an initiator with a monomer, and the initiator and the monomer may be added at a molar ratio of 1:500 to 2000, preferably at a molar ratio of 1:500 to 1000.

The initiator may be selected from di-tert-butyl peroxide (di-tert-butyl peroxide), benzoyl peroxide (benzoyl peroxide), diacetyl peroxide (diacetyl peroxide), tert-butyl acetate (tert-butyl acetate), tert-butyl hydroperoxide (tert-butyl hydrop eroxide), dicumyl peroxide (dicumyl peroxide) or Azobisisobutyronitrile (AIBN), but is not limited thereto.

The second step of preparing the above chain transfer agent radical may be performed by reacting the radical compound prepared in the first step with the chain transfer agent represented by the above chemical formula 3, and the chain transfer agent represented by the above chemical formula 3 may be selected from the group consisting of bis [3- (triethoxysilyl) propyl ] tetrasulfide (TESPT), bis [3- (triethoxysilyl) propyl ] tetrasulfide (TMSPT), and a mixture thereof, but is not limited thereto.

The third step of forming the one-terminal modified intermediate radical compound may be performed by polymerizing the chain transfer agent radical prepared in the second step with the monomer, and the chain transfer agent and the monomer may be added in a molar ratio of 1:50 to 500 to perform the reaction.

The fourth step of forming the above both end modified compound may be performed by reacting the one end modified intermediate radical compound formed in the third step with a chain transfer agent as shown in the above chemical formula 3.

In the second and fourth steps, the chain transfer agent is supplied with-S _c The bond may be cleaved by the radical compound and thenAnd (3) carrying out reaction.

The first to fourth steps described above may be performed at a temperature of 130 to 150 ℃, but are not limited thereto.

Preferably, the initiator, the chain transfer agent, and the monomer may be added in a molar ratio of 1:5 to 20:500 to 2000, but is not limited thereto.

The present invention provides a rubber composition for a tire, the composition comprising a rubber polymer; and a compound represented by the following chemical formula 1 as an active ingredient.

Chemical formula 1:

Chemical formula 2-1:

chemical formula 2-2:

chemical formula 2-3:

preferably, the above M may be composed of 20 to 25 mole percent of the compound represented by the above chemical formula 2-1 and 75 to 80 mole percent of the compounds represented by the above chemical formulas 2-2 and 2-3, but is not limited thereto.

The both end-modified butadiene rubber has a very small molecular weight and is liquid at room temperature as compared with the conventional solid butadiene, and thus can be used as a processing aid like processing oil to smoothly mix rubber and silica.

The present invention provides a tire prepared by comprising a rubber composition for a tire, comprising the above rubber polymer; and a compound represented by the following chemical formula 1 as an active ingredient.

In more detail, the tire may be prepared by crosslinking the rubber polymer and the silica with the compound.

Preferably, the rubber polymer may include a solution polymerized styrene-butadiene prepared by a continuous process of styrene and butadiene, in which case the content of the styrene may be 20 to 30 parts by weight with respect to 100 parts by weight of the total styrene-butadiene, and the content of the vinyl group in the butadiene may be 20 to 30 parts by weight with respect to 100 parts by weight of the total butadiene, but is not limited thereto.

Preferably, the above rubber polymer may comprise a solution polymerized butadiene rubber having a cis (cis) content of 90 weight percent or more and prepared from a neodymium (neodymium) catalyst, which has excellent abrasion resistance due to a high cis (cis) content.

Preferably, the rubber polymer may be mixed with the butadiene rubber and the styrene-butadiene rubber in a weight ratio of 1:3 to 5, but is not limited thereto.

The content of the silica may be 90 to 130 parts by weight, and preferably may be 110 to 120 parts by weight, relative to 100 parts by weight of the rubber polymer. The above range is preferable because the braking performance on a wet road surface may be lowered with a decrease in the content of silica when the content of the silica is less than 90 parts by weight relative to 100 parts by weight of the above rubber polymer, and the processing difficulty in mixing may be caused by an excessive content of silica when it is more than 130 parts by weight.

Preferably, the silica may have a CTAB surface area of 180m ² /g to 220m ² Precipitated silica/g. In this case, the abrasion resistance is facilitated by easy dispersion, and further improvement can be madeBraking performance on a high wet road surface.

The content of the above compound may be 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the above rubber polymer. When the content of the above compound is less than 5 parts by weight relative to 100 parts by weight of the above rubber polymer, the mixing of the rubber polymer and silica may not proceed smoothly, and the effect of improving the abrasion and fuel economy performance may not be significant. Also, when the content of the above-mentioned compound is more than 50 parts by weight with respect to 100 parts by weight of the above-mentioned rubber polymer, there is a possibility that a negative effect against braking performance on a wet road surface may be generated due to a significant decrease in the glass transition temperature of the tire.

The above tire may be prepared by further comprising one or more selected from the group consisting of a coupling agent, a softening agent, a vulcanizing agent, a vulcanization accelerator, a crosslinking agent, a crosslinking activator, an antioxidant, an accelerator, and a super accelerator, but is not limited thereto.

Preferably, a sulfur vulcanizing agent may be contained as the vulcanizing agent. As the sulfur vulcanizing agent, elemental sulfur such as amine disulfide (amine disulfide) or polymer sulfur or a sulfur-generating vulcanizing agent may be used, and preferably elemental sulfur may be used.

The amount of the vulcanizing agent may be 1.0 part by weight to 1.5 parts by weight relative to 100 parts by weight of the rubber polymer, and the above range is preferable since the rubber can be made less heat-sensitive and chemically stable as an appropriate vulcanizing effect.

And, as the vulcanization accelerator, 1.0 to 3.0 parts by weight of one selected from the group consisting of Amine (Amine), disulfide, guanidine (guanidine), thio (thio), urea, thiazole (thiazole), thiuram (thium), sulfenamide (sulfenamide), and combinations thereof may be further contained with respect to 100 parts by weight of the rubber polymer.

The above tire may further comprise 1 to 5 parts by weight of any one selected from the group consisting of N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine (6 PP D), N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine (3 PPD), 2, 4-trimethyl-1, 2-dihydroquinoline (RD), and combinations thereof as an antioxidant with respect to 100 parts by weight of the above rubber polymer.

Of course, in addition to this, the above-mentioned tire may be optionally used with various additives used in conventional tire production, such as zinc oxide, stearic acid, a coupling agent, a processing aid, or the like, as required.

The tire of the present invention may be, but is not limited to, a car tire, a racing tire, an aircraft tire, an agricultural tire, an off-the-road tire, a truck tire, or a bus tire, etc.

The tire may be a radial (radial) tire or a bias (bias) tire, and is preferably a radial tire.

The invention provides a preparation method of a tire, which comprises the following steps: a first step of preparing a rubber mixture by mixing a rubber composition for a tire containing the above rubber polymer and a compound represented by the following chemical formula 1 as effective ingredients with silica; a second step of molding the prepared rubber mixture into a tire shape; and a third step of performing a vulcanization reaction by heating the rubber mixture in the tire shape.

Features corresponding thereto may be substituted in the above-described sections.

In the method for producing a tire of the present invention, the first step of producing the above-mentioned rubber mixture may be carried out by further comprising an existing processing oil, but is not limited thereto.

The above-mentioned compound may be added as a processing aid to replace part or all of the existing processing oil, and preferably the above-mentioned compound may replace part of the above-mentioned oil, and thus the above-mentioned compound and the above-mentioned processing oil may be contained at the same time.

As described above, when a tire is produced, a rubber composition for a tire containing the above-described compound is used, so that it is possible to significantly improve fuel economy performance as well as wear performance and prevent deterioration of physical properties with time.

The present invention also provides a rubber composition containing the compound represented by the following chemical formula 1 as an active ingredient.

Chemical formula 1:

The above-mentioned rubber composition may further contain one or two or more selected from the group consisting of natural rubber, synthetic rubber, coupling agent, softener, vulcanizing agent, vulcanization accelerator, crosslinking agent, crosslinking activator, antioxidant, accelerator and ultra accelerator.

The rubber composition can be used for preparing tires, profiles, cable jackets, hoses, transmission belts, conveyor belts, tire treads, soles, sealing rings or damping elements.

Detailed Description

Hereinafter, the present invention will be described in detail by way of examples to aid understanding. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples. Embodiments of the present invention are provided to more fully illustrate the invention to those of ordinary skill in the art.

< example 1> preparation of Compound (liquid butadiene modified at both ends)

1. Material

Cyclohexane (99%, korean Samchun Chemical Co., ltd., (Seoul, south Korea)), bis- [3- (triethoxysilyl) propyl ] tetrasulfide (Bis- [3- (triethoxysilyl) propyl ] tetr asulfide, TESPT, si-69, korean winning Co., ltd., (Korea)), di-tert-Butyl peroxide (Sigma-tert-Butyl peroxide, korean Sigma-Aldrich Corp., (Seoul), korea), azobisisobutyronitrile (2, 2' -azobissibutyronitrile, AIBN, korean Sigma Aldrich corp., seoul, korea), 1,3-butadiene (1, 3-butadiene, korean large Tian Jinhu petrochemical company (Kumho Petrochemical co., dajeon, korea)), styrene (Styrene, korean Samchun Chemical co., seul, korea), and Butyl acrylate (Butyl acrylate, korean Sigma Aldrich corp., seoul, korea).

2. Synthesis

TESPT (Si-69), di-t-butyl peroxide (I) and cyclohexane were each added to a stainless steel high-temperature high-pressure stirred reactor (1L) at room temperature, and then replaced with nitrogen gas. 1, 3-butadiene (monomer) (BD) was injected through the gas line of the above reactor. Then, the temperature was raised to 135℃and polymerization was carried out at a predetermined pressure for a corresponding period of time. Then, the temperature was lowered to a temperature of 15 ℃ to terminate the reaction, and unreacted 1, 3-butadiene was removed through a vent line after reaching a temperature of 15 ℃. In the case of cyclohexane, 1, 3-butadiene was removed by distillation under reduced pressure. After precipitation of the polymer in ethanol, the remaining initiator and chain transfer agent are removed using a centrifuge (fig. 1).

< example 1-1> preparation of Compound A

Compound a was prepared according to the procedure of example 1 above using 18g of TESPT, 0.49g of di-tert-butyl peroxide, 180g of cyclohexane, 180g of 1, 3-butadiene and polymerizing at a pressure of 18bar for 4 hours.

< example 1-2> preparation of Compound B

Compound B was prepared by polymerization at 18bar for 4 hours using 9g of TESPT, 0.49g of di-tert-butyl peroxide, 180g of cyclohexane, 180g of 1, 3-butadiene, as in example 1 above.

< examples 1-3> preparation of Compound C

Compound C was prepared by polymerization at 40bar for 4 hours using 9g of TESPT, 0.49g of di-tert-butyl peroxide, 180g of cyclohexane, 180g of 1, 3-butadiene, as in example 1 above.

< examples 1-4> preparation of Compound D

Compound D was prepared by polymerization at 40bar for 8 hours using 9g of TESPT, 0.49g of di-tert-butyl peroxide, 180g of cyclohexane, 180g of 1, 3-butadiene, as in example 1 above.

< examples 1 to 5> preparation of Compound E

Compound E was prepared according to the procedure of example 1 above using 21.6g TESPT, 0.73g di-tert-butyl peroxide, 180g cyclohexane, 180g 1, 3-butadiene and polymerizing at a pressure of 40bar for 8 hours.

< examples 1-6> preparation of Compounds

Compound F was prepared by polymerization at 40bar for 8 hours using 18g of TESPT, 0.97g of di-tert-butyl peroxide, 180g of cyclohexane, 180g of 1, 3-butadiene according to the procedure of example 1 above.

< examples 1 to 7> preparation of Compound G

Compound G was prepared by bulk polymerization at 70 ℃ for 8 hours under normal pressure, using 0.78G of TESPT, 0.047G of azobisisobutyronitrile instead of di-tert-butyl peroxide, and 15G of styrene instead of 1, 3-butadiene, as in example 1 above.

< examples 1 to 8> preparation of Compound H

Compound H was prepared by bulk polymerization at 70 ℃ for 8 hours under normal pressure using 0.394g of TESPT, 0.019g of azobisisobutyronitrile instead of di-tert-butyl peroxide, and 15g of butyl acrylate instead of 1, 3-butadiene according to the method of example 1 described above.

< Experimental example 1> analysis of physical Properties of Compounds

1-1 analytical methods

1) Analysis of molecular weight

Molecular weight correction was performed by size exclusion chromatography (Size exclusion chromatography, SEC) consisting of a solution delivery unit (solvent delivery unit), a refractive index detector (refractive index detector) and 3 polystyrene type crosslinked copolymer columns (styragel column) [ HT 6E (10 μm,7.8mm×300 mm), HMW 7column (HMW 7 column) (15-20 μm,7.8mm×300 mm), HMW6E column (HMW 6E column) (15-20 μm,7.8mm×300 mm) ] using polybutadiene (polybutadiene) standard samples (Waters corp., germany).

2) Confirmation of vinyl content

Vinyl (vinyl) content of the compound prepared according to example 1 above was confirmed by proton nuclear magnetic resonance (Proton nuclear magnetic resonance,1h nmr, varian, unity Plus 300spectrometer, garden science (Garden State Scientific), new jersey cymoston, NJ, USA). Deuterated chloroform (CDCl 3, an Duofu cambridge isotope laboratories, inc. Cambridge Isotope Laboratories, inc., andover, MA, USA) was dissolved as a solvent in a 5mm NMR tube at a concentration of 15 mg/mL.

3) Confirmation of glass transition temperature

Determination of the glass transition temperature (T) of the above Compounds by differential scanning calorimeter (DSC-Q10, new Castle, DE, USA) using differential scanning calorimeter (Differential scanning calorimetry, DSC) _g ). Thermograms of samples (3-6 mg) were obtained by heating the samples from-120 ℃ to-20 ℃ at a heating rate of 10 ℃/min under nitrogen atmosphere.

1-2 analysis results

When the polymerization degree (degree of polymerization, dp) of the liquid butadiene (LqBR) is 100 or less, it exists in a liquid state having viscosity (viscous) at normal temperature, and the physical properties are changed according to the chain length (chain length) and microstructure (microstructure) thereof. Thus, in this experiment the synthesis molecular weight was attempted to beD _p And (2) liquid butadiene (DF-LqBR) modified at two ends less than or equal to 100.

Table 1 below analyzes physical properties of the compounds prepared according to example 1 above.

TABLE 1

* I: initiator (Initiator)/Si-69: chain transfer agent (TESPT)/M: monomer(s)

< example 2> preparation of rubber composition

Table 2 below shows the compositions of the respective substances used for preparing the rubber compositions for tire treads comprising the compounds a to F prepared according to example 1 above.

TABLE 2

Details of the substances contained in table 2 above are as follows.

1) The S-SBR (Solution-polymerized styrene-butadiene rubber (Solution-Styrene Butadiene Rubb er)) is a Solution-polymerized styrene-butadiene rubber (5220M, korean brocade lake petrochemical company (Kumho Petrochemical co., ltd., korea)) prepared by a continuous method, which has a styrene content of 26.5 weight percent, a vinyl content in butadiene of 26 weight percent, a mooney viscosity of 54, and a glass transition temperature of-48 ℃.

2) BR is a solution polymerized butadiene rubber (CB 24, colophony chemical industries, inc. (Lanxess Chemic al Industry Co., ltd., cologne, germany)) prepared by a neodymium catalyst (neodymium catalyst) having a cis (cis) content of 96 weight percent in butadiene and a Mooney viscosity of 44.

3) Use of hexadecane for silicaTrimethyl ammonium bromide (Cetyl trimethyl ammon ium bromide, CTAB) surface area of 180m ² /g to 220m ² Microbead (micropearl) precipitated silica (ZEOSIL 195MP, sonaver silica korean limited of the korean mountain city (Solvay Silica Korea co., ltd., gunsan, korea)).

4) The coupling agent was Bis- [3- (triethoxysilyl) propyl ] tetrasulfide (Bis- [3- (triethox ysilyl) propyl ] tetrasulfide, TESPT) in an amount of 50 weight percent and carbon black (carbon black) N330 in an amount of 50 weight percent, and was designated as X50S (Germany, eisen-win Industrial group (Evonik Industries AG, essen, germany)).

5) As the softener (processing Oil), a treated distilled aromatic extract (treated distilled aromatic extr acted, TDAE) Oil (Vivatec 500, kukdo ng Oil & Chemicals co., yangsan, korea) was used, which had a total content of polycyclic aromatic hydrocarbon (Polycyclic Aromatic Hydocarbon, PAH) components of 3 weight percent or less, an kinematic viscosity of 95 (210°f SUS), an aromatic component content of 25 weight percent, a naphthene component content of 32.5 weight percent, and a paraffin component content of 47.5 weight percent.

6) Comparative example 2 is an unmodified liquid butadiene rubber, specifically, a liquid polybutadiene rubber having a number average molecular weight of 4400g/mol, a vinyl content of 15 weight percent, and synthesized at a glass transition temperature of 95 ℃ (LBR 307, japan cola (kuraray, japan)).

7) Zinc oxide was used as a crosslinking activator, and Zinc oxide No.2 (Sigma-Aldrich Corp., seoul, korea) was used.

8) Stearic acid was used as a crosslinking activator (Sigma-Aldrich Corp., seoul, korea) of Korea.

9) N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine [ N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenyl-end-amine, 6PPD, korea large Tian Jinhu petrochemical Co., ltd. (Kumho Petrochemical Co., daejeon, korea) ] was used as the antioxidant.

10 Sulfur was used as a crosslinking agent, and sulfur powder (elemental sulfur), large positive chemical Metals limited of Korea, inc. (Daejung Chemicals & Metals co., siheung, korea) was used.

11 CBS [ N-cyclohexyl-2-benzothiazole sulfenamide (N-cycloxyl-2-be nzothiazolylsulfenamide,98%, tokyo chemical industry co., japan) (Tokyo Chemical Industry co.ltd., tokyo, japan)) ] was used as the accelerator.

12 DPG (1, 3-biphenylguanidine (1, 3-diphenyguanidine), 98%, tokyo chemical industry Co., ltd., (Tokyo Chemical Industry Co., ltd., tokyo, japan))

13 Zinc dibenzyldithiocarbamate (zinc dibenzyl dithiocarbamat e, ZBEC; korea Cynoma Sigma Aldrich Corp., seo ul, korea) as an ultra-accelerator.

The above rubber composition was prepared according to the preparation method of the rubber composition shown in the following table 3.

TABLE 3 Table 3

As shown in table 3 above, the above rubber composition for tire tread was prepared by a two-step continuous preparation process. That is, it can be prepared in a suitable mixer by a first step (non-production phase) of thermomechanically treating or mixing at a maximum temperature up to 100 ℃ to 180 ℃, preferably at a high temperature of 130 ℃ to 160 ℃, and a second step (production phase) of mechanically treating at a temperature lower than 110 ℃, for example at a low temperature of 40 ℃ to 100 ℃, at the final stage of the hybrid crosslinking system.

< Experimental example 2> analysis of physical Properties of rubber composition

2-1 analytical methods

1)Mooney viscosity (Mooney viscosity, ML1+4@100deg.C)

The measurement was performed according to ASTM D-1646 with a Mooney viscometer (Mooney viscometer, korea Vluchem IND Co., korea).

2)Mechanical physical Properties

Modulus at 100% extension (Module, M100%), modulus at 300% extension (M300%) and elongation (elongation) were measured according to ASTM D412 using a Universal tester (Universal testing machine, UTM, KSU-05M-C, korean KSU Co., ltd.).

3) Wear resistance

Cylindrical test pieces having a diameter of 16mm and a thickness of 8mm were prepared in accordance with DIN 53516. The test pieces were ground at 40rpm for 40m using a German industry standard (Deutsche Industrie Normen, DIN) abrasion tester and the amount of mass loss was determined.

4) Dynamic viscoelasticity (dynamic viscoelasticity)

Temperature scan (temperature sweep) storage modulus (G'), loss modulus (G "), tan δ from-60 ℃ to 70 ℃ were measured using an ARES gauge in torsion mode (torsion mode) at a frequency of 10Hz with a strain of 0.5%.

Strain sweep (strain sweep) dynamic strain (dynamic strain) from 0.5% to 10% was measured using a dynamic material thermal spectrometer (dynamic materia l thermal spectrometer, DMTS, eplexor 500N, GABO limited responsibilities, germany (GABO GmbH & co.kg, germany)) at a temperature of 60 ℃ in tension mode (tension mode) at a frequency of 10 Hz.

2-2 analysis results

Table 4 below shows the results of analyzing the physical properties of the rubber composition according to Experimental example 2.

TABLE 4 Table 4

Referring to Table 4 above, the Payne effect (Payne effect) represents the filler-filler interaction of the unvulcanized compound (filer-filler interaction). The decrease in storage modulus (G ') with increasing strain amplitude is a result of the disruption of the filler network (filler network), with a larger Δg' value indicating a stronger filler-filler interaction. The compound prepared according to example 1 above improved the dispersion of silica by hydrophobizing the silica surface, thus exhibiting a low Payne effect (Payne effect) value.

The Mooney viscosity is an index of compound processability, and the above compound not only improves dispersion of silica, but also serves as a lubricating oil (lubricating) between raw rubber to make chain slip (chain slip) easier, thereby reducing the Mooney viscosity of the rubber composition.

The extraction weight loss (extraction weight loss) value is an experimental result in which migration (migration) of the processing aid can be predicted from sulfide, and the lower the value, the higher the extraction resistance.

The compound prepared according to example 1 above may be fixed on the rubber network by co-vulcanization (co-vulcabonification) with the raw rubber at the time of vulcanization, and the terminal functional group may be fixed on the silica surface by a silylation reaction, thus exhibiting a lower extraction amount than that of comparative example 1. That is, since the migration phenomenon is reduced, deterioration due to a change in physical properties with time can be prevented.

The total crosslink density (total crosslink density) is defined as the number of crosslink points (cross-links) of the sulfide. A high crosslink density means that the molecular weight between the crosslinking points decreases and the number of crosslinking points increases. In the swelling test (swelling test), the higher the crosslinking density, the smaller the number of solvent molecules that can penetrate between the crosslinked rubber chains, thereby reducing swelling.

The three-dimensional network structure formed by self-condensation (self-condensation) reaction of the compound prepared according to example 1 above has swelling resistance (swollening) and thus exhibits a higher chemical crosslink density (chemical crosslink density) than comparative examples 1 and 2. Moreover, the filler-rubber interaction (filler-rubber interaction) can be increased by the coupling reaction of-Si-with the raw rubber, and as a result, the total crosslink density is shown to be higher than that of comparative examples 1, 2.

The above compound forms a three-dimensional network structure by self-condensation reaction, and thus increases the initial modulus (30% modulus) of the low tensile region as compared with comparative example 1.

The above compound increases filler-rubber interaction through coupling reaction, and thus exhibits a high modulus value of 300% compared with comparative example 2.

The abrasion resistance is largely determined by the glass transition temperature (T _g ) And the effect of filler-rubber interactions.

The compound prepared according to example 1 above not only lowers the glass transition temperature of the rubber composition but also increases filler-rubber interactions through coupling reactions to improve abrasion resistance.

The viscoelasticity of the rubber composition is a laboratory measurement that can predict the performance of a tire, with a very high correlation between the two. In table 4, the storage modulus (G') value at a temperature of-30 ℃ is an index indicating braking performance (snow traction) on an icy or snowy road surface, and the lower the value, the higher the snow traction (snow traction). This is because the lower the G' value under low temperature conditions, the more easily the tire tread is deformed on an icy road surface, and the contact area (contact area) can be increased.

The loss modulus (G ") value at a temperature of 0 ℃ is an index of the braking performance (wet traction) of a tire on a wet road surface, and the higher the value, the more excellent the wet traction performance. Moreover, the higher the effective filler volume fraction (effective filler vol ume fraction), the higher the G "value is exhibited. The tan δ value at 60 ℃ is an index indicating the rolling resistance (rolling resistance, RR) of the tire, and it is known that the lower the tan δ value is, the more fuel economy performance is improved. It is well known that the main energy dissipation at this temperature (main energy dissipation) is caused by the disruption and regeneration of the filler-filler network and the free chain ends of the rubber.

The glass transition temperature (T) _g ) Lower than the processing oil, thus reducing the flexibility (flexibility) and modulus of the rubber at low temperatures by lowering the glass transition temperature of the rubber composition, thereby making it possible to showThe braking performance (snow traction) on ice and snow road is significantly improved.

The above compound lowers the glass transition temperature of the rubber composition and lowers the effective filler volume fraction (effective filler volume fracti on) with the improvement of silica dispersion, and thus can exhibit a G "value at a temperature of 0 ℃ lower than that of the rubber composition to which the processing oil is applied (comparative example 1).

Since the terminal of the above compound is fixed on the silica surface, the number of free chain terminals is reduced and hysteresis is reduced, and therefore fuel economy characteristics can be improved as compared with the rubber composition using processing oil (comparative example 1) and the rubber composition using unmodified liquid butadiene rubber (comparative example 2).

Accordingly, referring to the results of table 4 above, the rubber composition for tire tread prepared in the examples contains both end-modified liquid butadiene rubber as the above compound, so that it is possible to improve both wear performance and fuel economy performance and prevent deterioration of physical properties with time. Therefore, it is known that the above-mentioned compounds can be used as a rubber composition for a tire tread.

While specific embodiments of the invention have been described in detail above, it will be apparent to those skilled in the art that such specific descriptions are merely preferred examples, and the scope of the invention is not limited thereto. Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof. The scope of the present invention is shown by the following claims of the present invention, and it should be construed that all modifications or variations suggested from the meaning of the claimed scope of the invention, the scope and equivalents thereof are included in the scope of the present invention.

Claims

1. A compound represented by the following chemical formula 1, characterized in that,

chemical formula 1:

R’ _x (RO) _3-x -Si-(CH ₂ ) _a -S _c -(M)-S _d -(CH ₂ ) _b -Si-(OR) _3-x R’ _x ，

in the above-mentioned chemical formula 1,

r and R' can be identical or different and are selected from hydrogen or C1-C6-alkyl,

x is an integer selected from 0 to 2,

a and b are each independently an integer selected from 1 to 5,

c and d are each independently an integer selected from 1 to 9,

m is a polymerized chain comprising one or more diene monomers.

2. The compound according to claim 1, wherein M is one or more selected from the group consisting of compounds represented by the following chemical formula 2-1, chemical formula 2-2, and chemical formula 2-3:

chemical formula 2-1:

chemical formula 2-2:

chemical formula 2-3:

3. the compound according to claim 2, wherein M is composed of 20 to 25 mole percent of the compound represented by the chemical formula 2-1 and 75 to 80 mole percent of the compounds represented by the chemical formulas 2-2 and 2-3.

4. The compound of claim 1, wherein M has a number average molecular weight of 500g/mol to 50000g/mol.

5. The compound according to claim 1, wherein M is a copolymer of one or more monomers selected from the group consisting of butadiene, styrene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2-phenyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-chloro-1, 3-butadiene, 3-butyl-1, 3-octadiene, acrylate monomers, and acrylonitrile monomers.

6. The compound of claim 1, wherein said compound is a butadiene rubber modified at both ends.

7. The compound according to claim 1, wherein the vinyl group content in the compound is 15 to 30 parts by weight relative to 100 parts by weight of the total amount of the compound.

8. A compound according to claim 1, wherein each of said compounds comprises 1 to 3 silyl functional groups.

9. A preparation method of a compound is characterized in that,

comprising the following steps:

a first step of preparing a radical compound by reacting an initiator with a monomer;

a second step of preparing a chain transfer agent radical by reacting the prepared radical compound with a chain transfer agent represented by the following chemical formula 3;

a third step of forming a single-end modified intermediate radical compound by polymerizing the prepared chain transfer agent radical with the monomer; and

a fourth step of forming a compound having both ends modified by reacting the formed intermediate radical compound with a chain transfer agent represented by the following chemical formula 3,

chemical formula 3:

R’ _x (RO) _3-x -Si-(CH ₂ ) _a -S _c -(CH ₂ ) _b -Si-(OR) _3-x R’ _x ，

In the above-mentioned chemical formula 3, a compound represented by formula 1,

x is an integer selected from 0 to 2,

a and b are each independently an integer selected from 1 to 5,

c is an integer selected from 1 to 9.

10. The process for producing a compound according to claim 9, wherein in the second step and the fourth step, -S is supplied to the chain transfer agent _c The bond is cleaved by the radical compound and the reaction proceeds.

11. The method for producing a compound according to claim 9, wherein the first to fourth steps are performed at a temperature of 130 ℃ to 150 ℃.

12. The method for producing a compound according to claim 9, wherein the initiator, the chain transfer agent and the monomer are added in a molar ratio of 1:5 to 20:500 to 2000.

13. A rubber composition for a tire, characterized in that,

comprising a rubber polymer and a compound represented by the following chemical formula 1 as an active ingredient,

chemical formula 1:

in the above-mentioned chemical formula 1,

x is an integer selected from 0 to 2,

a and b are each independently an integer selected from 1 to 5,

c and d are each independently an integer selected from 1 to 9,

m is a polymerized chain comprising one or more diene monomers.

14. The rubber composition for a tire according to claim 13, wherein M is one or more selected from the group consisting of compounds represented by the following chemical formula 2-1, chemical formula 2-2, and chemical formula 2-3:

chemical formula 2-1:

chemical formula 2-2:

chemical formula 2-3:

15. the rubber composition for a tire according to claim 14, wherein the M is composed of 20 to 25 mole percent of the compound represented by the above chemical formula 2-1 and 75 to 80 mole percent of the compounds represented by the above chemical formulas 2-2 and 2-3.

16. The rubber composition for tires according to claim 13, wherein said M has a number average molecular weight of 500g/mol to 50000g/mol.

17. The rubber composition for a tire according to claim 13, wherein M is a copolymer of one or two or more monomers selected from the group consisting of butadiene, styrene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2-phenyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-chloro-1, 3-butadiene, 3-butyl-1, 3-octadiene, acrylate monomers and acrylonitrile monomers.

18. The rubber composition for a tire according to claim 13, wherein said compound is a butadiene rubber modified at both ends.

19. The rubber composition for a tire according to claim 13, wherein the vinyl group content in the above-mentioned compound is 15 to 30 parts by weight with respect to 100 parts by weight of the total amount of the above-mentioned compound.

20. A rubber composition for a tire according to claim 13, wherein each of said compounds contains 1 to 3 silyl functional groups.

21. A rubber composition for a tire according to claim 13, wherein said rubber polymer is selected from the group consisting of natural rubber; more than one butadiene-based rubber selected from the group consisting of butadiene rubber, styrene-butadiene rubber, and nitrile rubber; or a mixed rubber thereof.

22. The rubber composition for a tire according to claim 13, wherein the content of the above-mentioned compound is 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the above-mentioned rubber polymer.

23. A tire, characterized by being prepared by comprising the rubber composition for a tire as claimed in any one of claims 13 to 22.

24. The tire of claim 23, wherein said tire is prepared by further comprising one or more selected from the group consisting of silica, coupling agents, softeners, vulcanizing agents, vulcanization accelerators, crosslinking agents, crosslinking activators, antioxidants, accelerators, and ultra accelerators.

25. A method of manufacturing a tire, comprising:

a first step of preparing a rubber mixture by mixing the rubber composition for a tire of any one of claims 13 to 22 with silica;

a second step of molding the prepared rubber mixture into a tire shape; and

and a third step of heating the rubber mixture in the tire shape to perform a vulcanization reaction.

26. A method of producing a tire according to claim 25 wherein said rubber polymer is selected from the group consisting of natural rubber; more than one butadiene-based rubber selected from the group consisting of butadiene rubber, styrene-butadiene rubber, and nitrile rubber; or a mixed rubber thereof.

27. The method of producing a tire according to claim 25, wherein the rubber mixture is formed by mixing butadiene rubber and styrene-butadiene rubber in a weight ratio of 1:3 to 5.