KR20150016688A - Modified conjugated diene based polymer with heat-resistance, method for preparing and modified asphalt composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer with heat resistance, a manufacturing method thereof and modified asphalt compositions including the same. A specific modified conjugated diene-based polymer is used as an asphalt modifying agent which improves the retention of physical properties by slowing the aging speed of the modified asphalt down and is used for manufacturing modified asphalt to minimize the decline of softening point and elongation at high temperatures, thereby providing improved heat stability to maintain the quality of modified asphalt when moved to an area where the modified asphalt is laid.

Description

TECHNICAL FIELD The present invention relates to a thermostable denatured conjugated diene polymer, a process for producing the same, and a modified asphaltic composition comprising the modified denatured conjugated diene based polymer,

The present invention relates to a heat-resistant modified conjugated diene polymer, a process for producing the same, and a modified asphalt composition containing the modified heat-denatured conjugated diene polymer. More particularly, the present invention relates to an asphalt modifier for retarding the aging speed of a modified asphalt, And a heat-resistant modified conjugated diene polymer improved in thermal stability to maintain the quality immediately after the production of the modified asphalt even in the transportation to the road-installed area by minimizing the softening point and the decrease in the elongation at the high temperature after the manufacture of the modified asphalt And a modified asphalt composition comprising the same.

Unmodified asphalt is limited in its use due to the problem of sintering at high temperature and cracking at low temperature. In order to solve such a problem, research has been conducted to improve physical properties by adding various polymers.

The vinyl aromatic hydrocarbon-conjugated diene block copolymer such as styrene-butadiene-styrene block copolymer exhibits the effect of improving the high temperature and low temperature properties of the asphalt composition. Therefore, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is contained in the asphalt, Widely used.

In the modified asphalt manufacturing plant, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is dissolved in the asphalt to prepare the modified asphalt, and then it is transported to the actual road installation area at a temperature of 160 ° C or higher. At this time, if the distance between the modified asphalt manufacturing plant and the road installation area is long or the shipment of the modified asphalt is delayed due to the weather change, it will stay in the modified asphalt transportation vehicle or the manufacturing tank for a long time. Even when the initial modified asphalt is produced with excellent physical properties, the aging proceeds at a temperature of 160 ° C or higher, and when the modified asphalt is paved with the modified modified asphalt, sudden property deterioration occurs and roads can not be installed. Therefore, one of the important properties of block copolymers used as an asphalt modifier is resistance to thermal aging.

Therefore, there is a demand for an asphalt modifier having a high thermal stability and a low temperature property retention ratio, which is similar to conventional asphalt production time in the production of modified asphalt.

In order to solve the problems of the prior art as described above, the present invention relates to a heat-resistant denatured conjugated diene-based copolymer which exhibits solubility similar to that of a conventional vinyl aromatic hydrocarbon-conjugated diene block copolymer and has excellent high temperature properties and low temperature property retention when aged at high temperature for a long time And a method for producing the same.

It is another object of the present invention to provide a modified asphalt composition comprising the above heat-resistant modified conjugated diene polymer as an asphalt modifier.

In order to achieve the above object,

[Chemical Formula 1]

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, 1 and k are an integer of 0 to 2, m is an integer of 1 to 3, 1 + k + m is 3, p is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain, and b is an integer of 1 to 3. When k is 2, two R ₁ may be the same or different from each other, in the same way groups (groups) corresponding thereto when at least l and m is 2 may be the same or different from each other.) a polymer of a heat-resistant-modified represented by the conjugate to bind to Thereby providing a diene polymer.

The present invention also provides a method for producing a polymer electrolyte membrane, comprising: (a) polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in the presence of a solvent using an organometallic compound to form an active polymer having a metal terminal; And (b) adding to said active polymer a compound of formula

(2)

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, and n is an integer of 0 to 2. when n is 2, two R ₁ groups bonded to nitrogen may be the same or different from each other, and when 3-n is 2 or more in the same manner, the corresponding groups may be the same or different from each other) And a step of introducing a compound to be displayed to denature the heat-denatured modified conjugated diene-based polymer.

The present invention also relates to the above heat-resistant denatured conjugated diene polymer; And an asphalt.

According to the present invention, there is provided a heat-resistant modified conjugated diene polymer exhibiting similar solubility to a conventional vinyl aromatic hydrocarbon-conjugated diene block copolymer and having excellent high-temperature properties and low-temperature property retention at the time of aging at a high temperature, a method for producing the same, There is an effect of providing an asphalt composition and a modified asphalt.

Hereinafter, the heat-resistant modified conjugated diene polymer of the present invention, a method for producing the same, and a modified asphalt composition including the heat-resistant modified conjugated diene polymer will be described in detail.

The thermostable denatured conjugated diene polymer of the present invention is represented by the following formula

[Chemical Formula 1]

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, 1 and k are an integer of 0 to 2, m Is an integer of 1 to 3, 1 + k + m is 3, p is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain, and b is an integer of 1 to 3. When k is 2 or more, Two or more R _{1 's} may be the same or different from each other, and when l and m are 2 or more in the same manner, corresponding groups may be the same or different from each other) .

The R ₁ is, for example, an alkyl group having 1 to 12 carbon atoms or an alkylsilyl group.

The R ₂ is, for example, an alkyl group or an alkylene group having 1 to 12 carbon atoms.

R ₃ and R ₄ are, for example, alkyl groups having 1 to 12 carbon atoms.

The l may be 0 or 1, for example.

M may be 1 or 2, and may be 2 or 3, for example.

The p may have a total number of 1 to 9, 1 to 5, or 1 to 3, and when applied to asphalt within this range, a softening point and a decrease in elongation at the time of staying at a high temperature are minimized,

In formula (1), k is 1, l is 0, and m is 2, for example.

In another example, k is 1, l is 1, and m is 1 in the formula (1).

In another example, the formula 1 may be a mixture of a modified conjugated diene polymer having k of 1, l of 0 and m of 2, and a modified conjugated diene polymer of which k is 1, 1 is 1, and m is 1 have.

The vinyl aromatic hydrocarbon-conjugated diene copolymer chain may be, for example, a random or block copolymer chain.

In another example, the vinyl aromatic hydrocarbon-conjugated diene copolymer chain may be a vinyl aromatic hydrocarbon-conjugated diene block copolymer chain.

As another example, the vinyl aromatic hydrocarbon-conjugated diene copolymer chain may contain 1 to 50% by weight, 10 to 40% by weight, or 20 to 35% by weight of a vinyl aromatic monomer based on 100% by weight of the total of the conjugated diene monomer and the vinyl aromatic monomer By weight of the block copolymer chain.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and the like.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene.

For example, the heat-resistant modified conjugated diene polymer may have a weight average molecular weight of 50,000 to 500,000 g / mol, 50,000 to 350,000 g / mol, or 80,000 to 350,000 g / mol.

The modified conjugated diene polymer may have a vinyl content of 5 to 60%, 10 to 40%, or 10 to 30%, for example.

Here, the vinyl content means the content of the vinyl group-containing monomer or the content of the 1,2-added conjugated diene monomer, not 1,4-addition to 100% by weight of the conjugated diene-based monomer.

The method for producing a heat resistant modified conjugated diene polymer according to the present invention comprises the steps of (a) polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in the presence of a solvent using an organometallic compound to form an active polymer having a metal terminal ; And (b) adding to said active polymer a compound of formula

(2)

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3 and n is an integer of 0 to 2. In addition, Two R ₁ groups bonded to nitrogen may be the same as or different from each other, and in the same manner, when 3-n is 2 or more, the corresponding groups may be the same or different from each other) And a step of introducing the compound to denature it.

The n may be 0 or 1, for example.

R ₁ to R ₄ are the same as described above.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and the like.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene.

The vinyl aromatic monomer may be 1-50% by weight, 10-40% by weight or 20-35% by weight based on 100% by weight of the total of the conjugated diene monomer and the vinyl aromatic monomer.

The solvent may be at least one selected from the group consisting of hydrocarbons or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

The organic metal compound may be at least one selected from the group consisting of an organic alkali metal compound, an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound and an organic cesium compound.

As another example, the organometallic compound may be at least one selected from the group consisting of methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, Naphthyl lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium Or more.

 In another example, the organometallic compound is n-butyllithium, sec-butyllithium, or a mixture thereof.

In another example, the organometallic compound is selected from the group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide And may be used in combination with other organometallic compounds.

The organometallic compound is used in an amount of 0.01 to 10 mmol, 0.05 to 7 mmol, or 0.1 to 5 mmol based on 100 g of the total amount of the monomers.

The molar ratio of the organometallic compound to the compound represented by Formula 2 is, for example, 1: 0.1 to 1:10, or 1: 0.5 to 1: 2.

The active polymer having the metal terminal of the present invention means a polymer to which a polymer anion and a metal cation are bonded.

The heat-resistant denatured conjugated diene-based polymer of the present invention may be polymerized by further adding a polar additive in the polymerization of (a).

The polar additive may be, for example, a base, and in another example, an ether, an amine, or a mixture thereof, or a mixture of at least two polar additives selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, dipropyl ether, (Dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine Ethylenediamine, and another example is diethtrahydropropyl propane, triethylamine or tetramethylethylenediamine.

The polymerization of (a) may be anionic polymerization, for example.

As another example, the polymerization of (a) may be a living anionic polymerization in which an active terminal is obtained by a growth reaction with an anion.

The polymerization temperature of (a) is, for example, -20 to 200 占 폚, 0 占 폚 to 150 占 폚, or 10 to 120 占 폚.

The denaturation step (b) may be carried out, for example, by adding one or more, preferably two or three, compounds represented by the general formula (2).

The denaturation step (b) may be carried out at 0 to 150 ° C for 1 minute to 5 hours, for example.

The heat-resistant modified conjugated diene-based polymer of the present invention is characterized in that it is produced, for example, by the above-described method for producing a heat resistant modified conjugated diene polymer.

Modified asphalt composition

The modified asphalt composition of the present invention comprises the above heat-resistant modified conjugated diene-based polymer; And asphalt.

The weight ratio of the polymer and the asphalt can be, for example, from 0.1: 99.9 to 20: 80, or from 1:99 to 10:90.

The asphalt can be a residue obtained when refining crude oil, and is mainly composed of hydrogen and carbon, and can be made of hydrocarbon compounds having a small amount of nitrogen, sulfur, or oxygen bonded thereto.

As the asphalt, straight asphalt, cut-back asphalt, goose asphalt, blown asphalt, emulsified asphalt or sebum (PG) grade asphalt may be used.

Among them, the straight asphalt can be used as a raw material for various petroleum-based asphalt containing a large amount of bituminous material which is not decomposed as a final residue obtained by distillation of the crude oil at the atmospheric distillation column and distillation of the residual atmospheric residue. Commercialized straight asphalt includes AP-3 or AP-5 supplied by SK Energy or GS Caltex.

The modified asphalt composition may comprise an oil.

The oil may be, for example, mineral oil or an aromatic oil such as Treated Distillate aromatic extract (TDAE) oil.

The oil may be used in an amount of 0.01 to 30% by weight, 0.01 to 10% by weight or 0.1 to 10% by weight based on 100% by weight of the modified asphalt composition.

The modified asphalt of the present invention is characterized by being produced from the modified asphalt composition.

The degree of improvement of the physical property maintenance rate of the modified asphalt can be determined by, for example, whether or not the softening point is increased or decreased, whether the elongation (5 ° C) is increased or decreased, or the softening point or elongation (5 ° C) after aging in an oven heated to 180 ° C It can be evaluated that the retention of the physical properties is improved when the softening point or the decrease in elongation (5 ° C) after aging with time in the oven heated to 180 ° C based on the initial softening point or elongation (5 ° C) is small.

The softening point herein refers to the high temperature properties of the modified asphalt according to the American Society for Testing and Materials (ASTM) D36, which upon heating of water or glycerin at 5 [deg.] C per minute begins to soften the specimen It can be defined as the temperature when a ball of 9.525 mm in diameter and 3.5 g in weight located on the specimen is struck by 1 inch.

The elongation (5 캜) of the present invention represents the low-temperature properties of modified asphalt according to ASTM D113. When the specimen is pulled in both directions in a thermostatic chamber maintained at 5 캜, the elongation is increased to just before the specimen is broken Can be defined.

The modified asphalt may be, for example, modified asphalt for road pavement.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. Changes and modifications may fall within the scope of the appended claims.

[ Example ]

Example 1

≪ Preparation of Modified Styrene-Butadiene Block Copolymer >

1470 g of purified cyclohexane and 93 g of styrene were charged into a 3 L reactor purged with nitrogen, and the temperature was raised to 70 캜 while stirring. The styrene block was polymerized by adding 0.32 g of n-butyllithium to the mixed solution of cyclohexane and styrene at 70 DEG C, 207 g of butadiene was added thereto, and the polymerization was continued until the butadiene completely consumed. After the butadiene is completely consumed, 0.84 g of bis (3-methyldimethoxysilylpropyl) -N-methylamine of the following formula 3 is added. After completion of the reaction, 0.1 g of water was added to the reactor to remove the activity of the active polymer. Then, 1.74 g of an antioxidant Irganox 1076 (BASF) and 0.9 g of TNPP (Weston Chemical Co.) Solution to prepare a modified styrene-butadiene block copolymer solution having a weight average molecular weight of 109,000 g / mol.

(3)

≪ Preparation of crumb by polymer recovery from polymer solution >

In order to recover only the polymer from the polymer solution, a stripping process is generally performed. Namely, 2.5 g of Tamol (TAMOL) and 0.5 g of CaCl ₂ were added to 3 L of water and boiled. Subsequently, when the polymer solution is slowly dropped into boiling water, the solvent in the solution is evaporated, and the polymer is agglomerated in water and dispersed in water to a size of 1 to 20 mm. The polymer produced in the above process was recovered and dried in an oven at 60 ° C. for 16 hours to prepare a crumb polymer.

≪ Preparation of modified asphalt composition and modified asphalt >

AP-5 product having physical properties as shown in Table 1 below was purchased from SK Innovation Co., Ltd. as an asphalt.

Intrusion (dmm) Softening point (℃) Viscosity (cPs) 100 ℃ 120 DEG C 135 ℃ SK AP-5 60 46.4 3845 998 440

In Table 1, penetration was measured at 25 캜 according to ASTM D946, softening point was measured according to ASTM D36, and viscosity was measured according to ASTM D4402 using a Brookfield DV-II + Pro Model under the condition of spindle 27.

500 g of the AP-5 was placed in a mixing container, and 10.7 g of oil and 23.87 g of the crumb were sequentially charged at 160 ° C. and 2,000 rpm, 180 DEG C, the stirring speed is increased to 2,500 rpm, and stirred for 50 minutes. 0.535 g of sulfur was added and stirred for 10 minutes. The stirring speed was lowered to 300 rpm and the mixture was stirred for 150 minutes to prepare modified asphalt, which was sampled for measurement of physical properties of the dissolved modified asphalt.

Example 2

0.36 g of the above-mentioned n-butyllithium and 0.9 g of bis (3-methyldimethoxysilylpropyl) -N-methylamine of the above formula 3 were introduced into the above-mentioned <modified styrene-butadiene block copolymer> A modified styrene-butadiene block copolymer solution and a polymer crumb having a weight average molecular weight of 97,000 g / mol were prepared in the same manner as in Example 1, except that the modified asphalt composition and modified asphalt 23.37 g of the polymer crumb and 0.524 g of sulfur were fed into the flask except that the oil was not added and the flask was stirred for 90 minutes instead of stirring at 150 rpm while lowering the stirring speed to 300 rpm A modified asphalt composition and a modified asphalt were prepared in the same manner as in Example 1 above. The samples were sampled to measure the physical properties of the dissolved modified asphalt.

Comparative Example 1

(3-methyldimethoxysilylpropyl) -N- (3-methyldimethoxysilylpropyl) -N-methylmethoxysilylpropyl) -bis (3-methyldimethoxysilylpropyl) -N- -Methylamine in Example 1 was replaced with 0.37 g of dichloromethylsilane in place of methylamine, to thereby prepare an unmodified styrene-butadiene block copolymer solution having a weight average molecular weight of 104,000 g / mol. In the same manner as in Example 1 A polymer crumb, a modified asphalt composition and a modified asphalt were prepared in the same manner as in Example 1. The samples were sampled to measure the physical properties of the dissolved modified asphalt.

Comparative Example 2

(3-methyldimethoxysilylpropyl) -N- (3-methyldimethoxysilylpropyl) -N-methylmethoxysilylpropyl) -bis (triphenylphosphine) -bis Butadiene block copolymer solution having a weight average molecular weight of 96,000 g / mol was prepared in the same manner as in Example 2, except that 0.37 g of dichloromethylsilane instead of methylamine was added thereto. In Example 2 A polymer crumb, a modified asphalt composition and a modified asphalt were prepared in the same manner as in Example 1. The samples were sampled to measure the physical properties of the dissolved modified asphalt.

[Test Example]

The properties of the asphalt compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Tables 2 to 4 below.

Weight average molecular weight: Each sample was dissolved in tetrahydrofuran (THF) for 30 minutes and then loaded on GPC (Gel Permeation Chromatography, manufacturer: Waters) and flowed. Then, the standard of PS (Polystyrene) The molecular weight was measured in comparison with the molecular weight.

* Softening point: measured according to ASTM D36.

Viscosity (135 占 폚): Measured according to ASTM D4402 under the condition of spindle 27 using Brookfield DV-II + Pro Model.

* Shindo (5 ° C): The specimen was left in a constant temperature water bath at 5 ° C for 1 hour and measured according to ASTM D113.

      * Storage stability: 50 g of modified asphalt in an aluminum tube was prepared and allowed to stand in an oven at 163 ° C for 48 hours, then allowed to stand in a cooler at -5 ° C for 4 hours or more, and then the upper and lower softening points were measured by ASTM D36 . When the temperature difference is within 2 ℃, phase separation does not occur. The smaller the difference, the better the storage stability.

      * Properties after aging: Modified asphalt specimens were aged for 10 hours to 48 hours without exposure to air in a 180 ° C oven, followed by softening by ASTM D36 and elongation at 5 ° C by ASTM D113 method.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Softening point (° C) 70.7 83.1 80.9 81.7 Shindo (5 ℃) (cm) 30 22 33 24 Viscosity (135 ° C) (cPs) 1970 1800 2055 1870 Storage stability 0.0 0.5 0.0 0.7

Aging
lapse Example 1 Comparative Example 1 Softening point Softening point
Retention rate Shindo Shindo
Retention rate Softening point Softening point
Retention rate Shindo Shindo
Retention rate (time) (° C) (%) (cm) (%) (° C) (%) (cm) (%) 0 70.7 100 30 100 80.9 100 33 100 10 72.8 103 26 87 77.7 96 26 79 17 72.1 102 23 77 73.6 91 21 64 24 74.5 105 21 70 72.2 89 20 61

Aging
lapse Example 2 Comparative Example 2 Softening point Softening point
Retention rate Shindo Shindo
Retention rate Softening point Softening point
Retention rate Shindo Shindo
Retention rate (time) (° C) (%) (cm) (%) (° C) (%) (cm) (%) 0 83.1 100 22 100 81.7 100 24 100 24 69.7 84 13 58 71.4 87 12 51

As shown in Tables 2 to 4, Example 1 of the present invention corresponds to Comparative Example 1 as a modified asphalt containing a heat resistant modified conjugated diene polymer, and Example 2 of the present invention corresponds to Comparative Example 2.

Specifically, in Table 2, the softening point of Example 1 was about 10 ° C lower than that of Comparative Example 1 in the preparation of modified asphalt, but the results of the evaluation of properties after aging in a 180 ° C oven for 24 hours 1, the softening point of Comparative Example 1 is reduced by about 10% to about 72.2 ° C at 80.9 ° C. Even in the case of the retention rate of elongation, even in the case of the aging in the 180 ° C oven for 24 hours in the case of Example 1, the elongation retention ratio of Example 1 is high at the level of 61% in Comparative Example 1 Able to know.

Also, when comparing Example 2 and Comparative Example 2 in which oil is not included in the production of modified asphalt in Table 4, it can be seen that the elongation retention ratio of Example 2 is 7% higher than that of Comparative Example 2 similarly.

In general, modified asphalt shows a decrease in physical properties over time due to continued thermal aging immediately after the production. Therefore, the manufacturer of the modified asphalt is required to adjust the amount of the asphalt modifier in consideration of the weather change after the modified asphalt is manufactured or the long- There are many cases. However, as shown in Table 3, in the case of Example 1, it is possible to realize 70 to 100% physical properties of the initially modified asphalt even after 24 hours since the physical degradation due to the thermal aging is small, so that it is not necessary to increase the amount of the asphalt modifier . Also, as shown in Table 4, even though the modified asphalt formulation is different, the elongation retention ratio of Example 2 was higher than that of Comparative Example 1 even after 24 hours of thermal aging. The phenomenon of high resistance to thermal aging is considered to be due to the fact that the aminoalkylsilyl groups in the modified conjugated diene polymer included in Examples 1 and 2 are attacked by radicals generated by thermal aging through a mechanism similar to the amine- As well.

Claims (11)

(1)
[Chemical Formula 1]

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, 1 and k are an integer of 0 to 2, m Is an integer of 1 to 3, l + k + m satisfies 3, P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain, and b is an integer of 1 to 3. When k is 2, The two R ₁ groups to be bonded may be the same or different from each other and when l and m are 2 or more in the same manner, the corresponding groups may be the same or different from each other) Heat resistant modified conjugated diene polymer. The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene copolymer chain is a random or block copolymer chain comprising a conjugated diene monomer and a vinyl aromatic monomer. The method according to claim 1,
Wherein the heat-resistant modified conjugated diene-based polymer has a weight average molecular weight of 50,000 to 500,000 g / mol. The method according to claim 1,
Wherein the heat-resistant modified conjugated diene-based polymer has a vinyl content of 5 to 60%. The method according to claim 1,
Wherein the heat-resistant modified conjugated diene-based polymer contains 1 to 50% by weight of a vinyl aromatic monomer based on 100% by weight of the total of the conjugated diene-based monomer and the vinyl aromatic monomer. The method according to claim 1,
The heat-resistant modified conjugated diene-based polymer according to claim 1, wherein P is a styrene-butadiene block copolymer chain. (a) polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and a vinyl aromatic monomer in the presence of a solvent using an organometallic compound to form an active polymer having a metal terminal; And
(b) adding to said active polymer a compound of formula
(2)

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3 and n is an integer of 0 to 2. In addition, Two R ₁ groups bonded to nitrogen may be the same as or different from each other, and in the same manner, when 3-n is 2 or more, the corresponding groups may be the same or different from each other) And a step of introducing the compound to denature the heat-resistant denatured conjugated diene-based polymer. 8. The method of claim 7,
Wherein the organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g of the total amount of the monomers. 8. The method of claim 7,
Wherein the molar ratio of the organometallic compound to the compound represented by the formula (2) is 1: 0.1 to 1:10. A heat-resistant denatured conjugated diene-based polymer according to claim 1; And asphalt. 11. The method of claim 10,
Wherein the modified asphalt composition has a weight mixing ratio of the heat-resistant modified conjugated diene polymer to asphalt of 0.1: 99.9 to 20:80.