KR20240033784A - Siloxane compound, preparation method thereof and the use thereof - Google Patents

Abstract

One embodiment of the present specification provides a siloxane compound represented by the following formula (1).
[Formula 1]

In Formula 1, R ^1a and R ^1b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ^2a and R ^2b are each independently a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms. is a linear or branched alkyl group, R ^3a and R ^3b are each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, and R ^4a , R ^4b , R ^5a and R ^5b are each independently Independently hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 16 carbon atoms, m1 and m2 are each of 0 to 2 is an integer, and when m1 and m2 are each 0, the plurality of OR ^2a and OR ^2b are the same as or different from each other, and when m1 and m2 are each 2, the plurality of R ^1a and R ^1b are the same or different from each other, and x is 1 It is an integer from 5 to 5.

Description

Siloxane compound, its production method and its use {SILOXANE COMPOUND, PREPARATION METHOD THEREOF AND THE USE THEREOF}

This specification relates to siloxane compounds, methods for their preparation, and uses thereof.

In the automobile industry, demands for improved quality of automobile tires, including durability, stability, and fuel savings, are increasing day by day. Recently, due to the increased demand for electric vehicles with high torque values and heavier vehicle weights, the wear resistance of tire tread rubber has been improved and Demand for additional fuel efficiency improvements is particularly increasing.

In the case of conjugated diene polymers, which are commonly used as rubber materials for tire treads, there is a problem that processability is significantly reduced when mixing rubber for treads due to the low dispersibility of organic fillers in the polymer. To solve this problem, various types of terminals are used. Denaturants are used.

Aminoalkoxysilane compounds are representative compounds used as end-modifying agents in the production of rubber compositions for tire treads, and are used to improve compatibility with fillers by binding to the ends of conjugated diene-based polymers. Aminoalkoxysilane compounds ultimately play a role in improving the wet traction and rolling resistance of tires, but when aminoalkoxysilanes are reacted with low molecular weight anionic polymers, low Mooney viscosity occurs. Due to this, there is a problem that the wear resistance of the rubber composition for tire tread is reduced.

Therefore, a terminal modifier that can improve both compatibility with fillers and Mooney viscosity during a coupling reaction with an anionic polymer having a low molecular weight, and a high Mooney viscosity that provides excellent wear resistance and high filler dispersibility when mixing rubber. There is a need for the development of end-modified conjugated diene-based polymers with excellent processability.

The description in this specification is intended to solve the problems of the prior art described above, and one purpose of this specification is to provide a novel siloxane compound that can be used as an end-modifying agent for conjugated diene-based polymers and a method for producing the same.

Another object of the present specification is to provide a terminal-modified conjugated diene-based polymer using a siloxane compound as an end-modifying agent, and a rubber composition including the same with excellent processability and wear resistance.

According to one aspect, a siloxane compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1, R ^1a and R ^1b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ^2a and R ^2b are each independently a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms. is a linear or branched alkyl group, R ^3a and R ^3b are each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, and R ^4a , R ^4b , R ^5a and R ^5b are each independently Independently hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 16 carbon atoms, m1 and m2 are each of 0 to 2 is an integer, and when m1 and m2 are each 0, the plurality of OR ^2a and OR ^2b are the same as or different from each other, and when m1 and m2 are each 2, the plurality of R ^1a and R ^1b are the same or different from each other, and x is 1 It is an integer from 5 to 5.

In one embodiment, at least one of R ^4a , R ^4b , R ^5a and R ^5b may be an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2 or Formula 3 below.

[Formula 2]

-Si(R ^6a ) _m3 (OR ^6b ) _3-m3

In Formula 2, R ^6a is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, R ^6b is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and m3 is 0. It is an integer from 3 to 3, and when m3 is 0 or 1, the plurality of OR ^6b is the same as or different from each other, and when m3 is 2 or 3, the plurality of R ^6a are the same or different from each other.

[Formula 3]

-N(R ^7a )(R ^7b )

In Formula 3, R ^7a and R ^7b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms.

In one embodiment, at least one of R ^4a and R ^4b is an alkyl group or heteroalkyl group substituted with a substituent represented by Formula 2, and at least one of R ^5a and R ^5b is represented by Formula 2 or Formula 3. It may be an alkyl group or heteroalkyl group substituted by the indicated substituent.

According to another aspect, (a) preparing a mixture containing a chloroalkylalkoxysilane represented by the following formula (4), a primary or secondary amine, and a metal halide; (b) reacting the mixture to obtain an aminoalkoxysilane compound; and (c) subjecting the aminoalkoxysilane compound to a dehydration condensation reaction. It provides a method for producing a siloxane compound, including a step.

[Formula 4]

Cl-(R ³ )-Si(R ¹ ) _n (OR ² ) _3-n

In Formula 4, R ¹ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, R ² is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ³ is It is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, n is an integer of 0 to 2, and when n is 0 or 1, the plurality of OR ² are the same or different from each other, and n is 2 In this case, a plurality of R ¹ are the same or different from each other.

In one embodiment, the primary or secondary amine may be a compound represented by Formula 5 below.

[Formula 5]

NH(R ⁴ ) _o [(R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p ] _2-o

In Formula 5, R ⁴ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms, and R ⁵ is is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, R ⁶ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ⁷ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms. It is a linear or branched alkyl group of ~16, o is 0 or 1, and when o is 0, a plurality of (R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p are the same or different from each other, p is an integer from 0 to 2, and when p is 0 or 1, the plurality of OR ⁷ is the same as or different from each other, and when p is 2, the plurality of R ⁶ are the same or different from each other.

In one embodiment, the primary or secondary amine may be a compound represented by Formula 6 below.

[Formula 6]

NH(R ⁸ ) _q [(R ⁹ )-N(R ¹⁰ )(R ¹¹ )] _2-q

In Formula 6, R ⁸ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms, and R ⁹ is is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, R ¹⁰ and R ¹¹ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and q is 0 or 1, and when q is 0, a plurality of (R ⁹ )-N(R ¹⁰ )(R ¹¹ ) are the same or different from each other.

In one embodiment, the metal halide may be a compound represented by Formula 7 below.

[Formula 7]

MX

In Formula 7, M is an alkali metal, and X is a halogen element.

In one embodiment, the metal halide may be a compound represented by Formula 8 below.

[Formula 8]

M'X ₂

In Formula 8, M' is an alkaline earth metal, and X is a halogen element.

In one embodiment, the content of the chloroalkyl alkoxysilane contained in the mixture may be 1.1 to 10 moles per mole of the primary or secondary amine.

In one embodiment, the content of the metal halide contained in the mixture may be 0.01 to 5 moles per 1 mole of the primary or secondary amine.

In one embodiment, the mixture may further include a base.

In one embodiment, the base is triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and a combination of two or more thereof. It may be one selected from a group consisting of

In one embodiment, the reaction in step (b) may be performed at 60 to 200°C.

In one embodiment, the reaction in step (b) may be performed for 1 to 100 hours.

In one embodiment, the reaction in step (b) may be performed under a pressure of 0.1 to 10 bar.

According to another aspect, a terminal-modified conjugated diene-based polymer is provided in which the siloxane compound is bonded to the terminal of the conjugated diene-based polymer.

In one embodiment, the conjugated diene-based polymer may be a homopolymer of a conjugated diene-based monomer, or a copolymer of a conjugated diene-based monomer and an aromatic vinyl monomer.

According to another aspect, a rubber composition comprising the terminal-modified conjugated diene-based polymer is provided.

The siloxane compound according to one aspect of the present specification can improve the Mooney viscosity and filler dispersibility of conjugated diene-based polymers when used as an end-modifying agent.

The method for producing a siloxane compound according to another aspect of the present specification can produce a siloxane compound with high yield.

The terminal-modified conjugated diene-based polymer and the rubber composition containing the same according to another aspect of the present specification have excellent mechanical properties including processability, storage stability, and wear resistance, and can be used as a rubber material for a tire tread.

The effect of one aspect of the present specification is not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration described in the detailed description or claims of the present specification.

Hereinafter, one aspect of the present specification will be described with reference to the attached drawings. However, the description in this specification may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In order to clearly explain one aspect of the specification in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout the specification, when a part is said to be “connected” to another part, this includes not only cases where it is “directly connected,” but also cases where it is “indirectly connected” with another member in between. . Additionally, when a part is said to “include” a certain component, this does not mean that other components are excluded, but that other components can be added, unless specifically stated to the contrary.

When a range of numerical values is described herein, unless the specific range is stated otherwise, the value has the precision of significant figures given in accordance with the standard rules in chemistry for significant figures. For example, the number 10 includes the range 5.0 to 14.9, and the number 10.0 includes the range 9.50 to 10.49.

As used herein, the term “substitution” means that one or more hydrogen atoms bonded to a carbon atom of a compound are each independently replaced by another substituent. The substituent may include an alkyl group, heteroalkyl group, silyl group, alkoxy group, amino group, cyano group, nitro group, halogen group, hydroxy group, aryl group, heteroaryl group, and a substituent in which two or more of the above-exemplified substituents are connected. However, it is not limited to this. The substituent in which two or more substituents are connected means that the hydrogen of one substituent is replaced with another substituent. For example, the substituent in which three substituents are connected is (substituent 1)-(substituent 2)-(substituent 3). It includes not only those connected in succession, but also those where (substituent 2) and (substituent 3) are connected to (substituent 1).

The term “alkyl group” used in this specification refers to a hydrocarbon group “C _n H _2n+1 -“. For example, methyl group (Me), ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group. , n-hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, etc., but is not limited thereto.

As used herein, the term “heteroalkyl group” refers to an alkyl group in which one or more carbon atoms are replaced with a hetero atom.

The term “heteroatom” used in this specification refers to all atoms except carbon and hydrogen, and examples include, but are not limited to, oxygen, nitrogen, sulfur, phosphorus, and halogen atoms.

The term “alkylene group” used in this specification refers to a hydrocarbon group “-C _n H _2n -” having two valences. For example, methylene group (-CH ₂ -), ethylene group (-CH ₂ -CH ₂ -), propylene group (-CH ₂ CH ₂ CH ₂ -), etc. are included, but are not limited thereto.

Hereinafter, an embodiment of the present specification will be described in detail.

siloxane compounds

The siloxane compound according to one aspect of the present specification is represented by the following formula (1).

[Formula 1]

In Formula 1, R ^1a and R ^1b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ^2a and R ^2b are each independently a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms. is a linear or branched alkyl group, R ^3a and R ^3b are each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, and R ^4a , R ^4b , R ^5a and R ^5b are each independently Independently hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 16 carbon atoms, m1 and m2 are each of 0 to 2 is an integer, and when m1 and m2 are each 0, the plurality of OR ^2a and OR ^2b are the same as or different from each other, and when m1 and m2 are each 2, the plurality of R ^1a and R ^1b are the same or different from each other, and x is 1 It is an integer from 5 to 5. For example, in Formula 1, R ^1a and R ^1b are each independently a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, and R ^2a and R ^2b are each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. It is a linear or branched alkyl group, R ^3a and R ^3b are each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 4 carbon atoms, and R ^4a , R ^4b , R ^5a and R ^5b are each independently It may be hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 12 carbon atoms, but is not limited thereto.

At least one of R ^4a , R ^4b , R ^5a and R ^5b may be an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2 or Formula 3 below.

[Formula 2]

-Si(R ^6a ) _m3 (OR ^6b ) _3-m3

In Formula 2, R ^6a is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, R ^6b is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and m3 is 0. It is an integer from 3 to 3, and when m3 is 0 or 1, the plurality of OR ^6b is the same as or different from each other, and when m3 is 2 or 3, the plurality of R ^6a are the same or different from each other. For example, in Formula 2, R ^6a is a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, and R ^6b may be a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 4 carbon atoms, but is limited thereto. It doesn't work.

[Formula 3]

-N(R ^7a )(R ^7b )

In Formula 3, R ^7a and R ^7b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms. For example, in Formula 3, R ^7a and R ^7b may each independently be a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, but is not limited thereto.

At least one of R ^4a and R ^4b is an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2, and at least one of R ^5a and R ^5b is substituted by a substituent represented by Formula 2 or Formula 3 It may be an alkyl group or a heteroalkyl group. For example, R ^4a and R ^4b may be an alkyl group substituted by a substituent represented by Formula 2, and R ^5a and R ^5b may be an alkyl group substituted by a substituent represented by Formula 2 or Formula 3. , but is not limited to this.

The siloxane compound may be used as an end-modifying agent for conjugated diene-based polymers, a surface treatment agent, a resin additive, a coating additive, or an adhesive, but is not limited thereto.

Method for producing siloxane compounds

A method for producing a siloxane compound according to another aspect of the present specification includes the steps of (a) preparing a mixture containing a chloroalkylalkoxysilane represented by the following formula (4), a primary or secondary amine, and a metal halide; (b) reacting the mixture to obtain an aminoalkoxysilane compound; and (c) subjecting the aminoalkoxysilane compound to a dehydration condensation reaction.

[Formula 4]

Cl-(R ³ )-Si(R ¹ ) _n (OR ² ) _3-n

In Formula 4, R ¹ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, R ² is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ³ is It is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, n is an integer of 0 to 2, and when n is 0 or 1, the plurality of OR ² are the same or different from each other, and n is 2 In this case, a plurality of R ¹ are the same or different from each other. For example, in Formula 4, R ¹ is a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, R ² is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a substituted alkyl group having 1 to 4 carbon atoms. Alternatively, it may be an unsubstituted linear or branched alkylene group having 1 to 4 carbon atoms, but is not limited thereto.

The chloroalkylalkoxysilane may be (3-Chloropropyl)trimethoxysilane (Cl(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), but is not limited thereto.

The primary or secondary amine may be a compound represented by the following formula (5).

[Formula 5]

NH(R ⁴ ) _o [(R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p ] _2-o

In Formula 5, R ⁴ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms, and R ⁵ is is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, R ⁶ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and R ⁷ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms. It is a linear or branched alkyl group of ~16, o is 0 or 1, and when o is 0, a plurality of (R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p are the same or different from each other, p is an integer from 0 to 2, and when p is 0 or 1, the plurality of OR ⁷ is the same as or different from each other, and when p is 2, the plurality of R ⁶ are the same or different from each other. For example, in Formula 5, R ⁴ is hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 12 carbon atoms. , R ⁵ is a substituted or unsubstituted linear or branched alkylene group having 1 to 4 carbon atoms, R ⁶ is a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, and R ⁷ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. It may be a linear or branched alkyl group of 4, but is not limited thereto.

The primary or secondary amine may be a compound represented by the following formula (6).

[Formula 6]

NH(R ⁸ ) _q [(R ⁹ )-N(R ¹⁰ )(R ¹¹ )] _2-q

In Formula 6, R ⁸ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms, and R ⁹ is is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms, R ¹⁰ and R ¹¹ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, and q is 0 or 1, and when q is 0, a plurality of (R ⁹ )-N(R ¹⁰ )(R ¹¹ ) are the same or different from each other. For example, in Formula 6, R ⁸ is hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted straight-chain or branched heteroalkyl group having 1 to 12 carbon atoms. , R ⁹ is a substituted or unsubstituted linear or branched alkylene group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ may each independently be a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. However, it is not limited to this.

The primary or secondary amine is 3-(trimethoxysilyl)propylamine, H ₂ N(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ) or 3-(diethylamino)propylamine. It may be an amine (3-(Diethylamino)propylamine, H ₂ N(CH ₂ ) ₃ N(C ₂ H ₅ ) ₂ ), but is not limited thereto.

By using a metal halide as an additive along with chloroalkylalkoxysilane and primary or secondary amine in step (a), the reaction time in step (b) is reduced by 50% or more compared to the case where metal halide is not used. At the same time, the selectivity and yield of the product aminoalkoxysilane compound can be improved.

The metal halide may be a compound represented by the following formula (7).

[Formula 7]

MX

In Formula 7, M is an alkali metal, and X is a halogen element.

The alkali metal may be Li, Na, K, Rb, Cs, or Fr, and the halogen element may be F, Cl, Br, or I. For example, the metal halide may be NaBr, NaI, or KBr, but is not limited thereto.

The metal halide may be a compound represented by the following formula (8).

[Formula 8]

M'X ₂

In Formula 8, M' is an alkaline earth metal, and X is a halogen element.

The alkaline earth metal may be Be, Mg, Ca, Sr, Ba, or Ra, and the halogen element may be F, Cl, Br, or I.

The content of the chloroalkyl alkoxysilane contained in the mixture may be 1.1 to 10 moles per 1 mole of the primary or secondary amine, for example, 1.1 mol, 1.2 mol, 1.3 mol, 1.4 mol, 1.5 mol, 1.6 mol. mol, 1.7 mol, 1.8 mol, 1.9 mol, 2.0 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 mol, 2.9 mol, 3.0 mol, 3.1 mol, 3.2 mol, 3.3 mol, 3.4 mol, 3.5 mol, 3.6 mol, 3.7 mol, 3.8 mol, 3.9 mol, 4.0 mol, 4.1 mol, 4.2 mol, 4.3 mol, 4.4 mol, 4.5 mol, 4.6 mol, 4.7 mol, 4.8 mol, 4.9 mol. , 5.0 mol, 5.1 mol, 5.2 mol, 5.3 mol, 5.4 mol, 5.5 mol, 5.6 mol, 5.7 mol, 5.8 mol, 5.9 mol, 6.0 mol, 6.1 mol, 6.2 mol, 6.3 mol, 6.4 mol, 6.5 mol, 6.6 mol, 6.7 mol, 6.8 mol, 6.9 mol, 7.0 mol, 7.1 mol, 7.2 mol, 7.3 mol, 7.4 mol, 7.5 mol, 7.6 mol, 7.7 mol, 7.8 mol, 7.9 mol, 8.0 mol, 8.1 mol, 8.2 mol, 8.3 mol, 8.4 mol, 8.5 mol, 8.6 mol, 8.7 mol, 8.8 mol, 8.9 mol, 9.0 mol, 9.1 mol, 9.2 mol, 9.3 mol, 9.4 mol, 9.5 mol, 9.6 mol, 9.7 mol, 9.8 mol, 9.9 mol. , 10.0 mol, or a value between these two values. In one example, it may be 1.3 to 4 moles, but is not limited thereto. If the content of chloroalkyl alkoxysilane is outside the above range, the yield of the aminoalkoxysilane compound in step (b) may be reduced.

The content of the metal halide contained in the mixture may be 0.01 to 5 moles per mole of the primary or secondary amine, for example, 0.01 mole, 0.1 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole. , 0.6 mol, 0.7 mol, 0.8 mol, 0.9 mol, 1.0 mol, 1.1 mol, 1.2 mol, 1.3 mol, 1.4 mol, 1.5 mol, 1.6 mol, 1.7 mol, 1.8 mol, 1.9 mol, 2.0 mol, 2.1 mol, 2.2 mol. mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 mol, 2.9 mol, 3.0 mol, 3.1 mol, 3.2 mol, 3.3 mol, 3.4 mol, 3.5 mol, 3.6 mol, 3.7 mol, 3.8 mol, It may be 3.9 mol, 4.0 mol, 4.1 mol, 4.2 mol, 4.3 mol, 4.4 mol, 4.5 mol, 4.6 mol, 4.7 mol, 4.8 mol, 4.9 mol, 5.0 mol, or a value between two of these values. In one example, it may be 1 to 4 moles, but is not limited thereto. If the content of the metal halide is less than the above range, the reaction time in step (b) becomes longer and process efficiency may be reduced, and if it exceeds the above range, the process economics may be reduced.

The mixture may further include a base. That is, step (a) may be a step of preparing a mixture containing chloroalkyl alkoxysilane, primary or secondary amine, metal halide, and base.

The base is one selected from the group consisting of triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and combinations of two or more of these. However, it is not limited to this.

The content of the base may be 1 to 4 moles per 1 mole of the primary or secondary amine, but is not limited thereto.

Step (b) is a step of reacting the mixture prepared in step (a), and may be performed with stirring.

The reaction in step (b) may be performed at 60 to 200°C. For example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135 ℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, or a value between two of these values. . If the reaction temperature is below the above range, the reaction time may be prolonged or the yield of the aminoalkoxysilane compound may be reduced, and if the reaction temperature is above the above range, the yield and process safety of the aminoalkoxysilane compound may be reduced.

The reaction in step (b) may be performed for 1 to 100 hours. For example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16. Time, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, 37 hours, 38 hours, 39 hours, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 hours, 49 hours , 50 hours, 51 hours, 52 hours, 53 hours, 54 hours, 55 hours, 56 hours, 57 hours, 58 hours, 59 hours, 60 hours, 61 hours, 62 hours, 63 hours, 64 hours, 65 hours, 66 Time, 67 hours, 68 hours, 69 hours, 70 hours, 71 hours, 72 hours, 73 hours, 74 hours, 75 hours, 76 hours, 77 hours, 78 hours, 79 hours, 80 hours, 81 hours, 82 hours, 83 hours, 84 hours, 85 hours, 86 hours, 87 hours, 88 hours, 89 hours, 90 hours, 91 hours, 92 hours, 93 hours, 94 hours, 95 hours, 96 hours, 97 hours, 98 hours, 99 hours , may be carried out for 100 hours or any time between these two values.

The reaction in step (b) may be performed under a pressure of 0.1 to 10 bar. For example, 0.1bar, 0.2bar, 0.3bar, 0.4bar, 0.5bar, 0.6bar, 0.7bar, 0.8bar, 0.9bar, 1bar, 2bar, 3bar, 4bar, 5bar, 6bar, 7bar, 8bar, 9bar, 10bar. Alternatively, it may be performed under a pressure between any two of these values.

In step (b), the yield of the aminoalkoxysilane compound may be 80% or more. For example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95. It may be %, 96%, 97%, 98%, 99%, 99.5%, 99.9%, or a value between two of these values.

Step (c) is a step of synthesizing a siloxane compound by subjecting an aminoalkoxysilane compound to a dehydration condensation reaction, and may include reacting the aminoalkoxysilane compound with water, and the dehydration condensation reaction is carried out at a temperature of 70 to 90°C. It may be performed by stirring for 6 to 10 hours under low temperature, but is not limited to this.

Step (c) may further include filtering the reaction product after the dehydration condensation reaction. Solid trimer or higher condensates can be removed through filtration of the reaction product.

Step (c) may further include distilling the reaction product after the dehydration condensation reaction. Unreacted monomers can be removed through distillation of the reaction product.

The siloxane compound prepared by the above method may have a dimer structure in which two molecules of an aminoalkoxysilane compound are condensed. The siloxane compound of the dimer structure has twice as many alkoxysilane groups capable of reacting with anionic polymers as the monomer structure, forming a terminal-modified conjugated diene-based polymer with high Mooney viscosity even during coupling reaction with anionic polymers of low molecular weight. It can be manufactured.

End-modified conjugated diene polymer

The terminal-modified conjugated diene-based polymer according to another aspect of the present specification is one in which the above-described siloxane compound is bonded to the terminal of the conjugated diene-based polymer.

The terminal-modified conjugated diene-based polymer may be one in which the above-described siloxane compound is bonded to one or both ends of the conjugated diene-based polymer. Modification by binding a siloxane compound to the end of the conjugated diene polymer improves filler dispersibility, which improves processability when mixing rubber, and increases Mooney viscosity, which improves mechanical properties, including wear resistance, of the final product.

The conjugated diene-based polymer may be a homopolymer of a conjugated diene-based monomer, or a copolymer of a conjugated diene-based monomer and an aromatic vinyl monomer.

The conjugated diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, It may be one selected from the group consisting of 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and combinations of two or more of these. It is not limited.

The aromatic vinyl monomers include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-propylstyrene, and 4-methylstyrene. -Cyclohexylstyrene, 4-(p-methylphenyl)styrene, 5-tert-butyl-2-methylstyrene, tert-butoxystyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butyl Styrene, N,N-dimethylaminoethylstyrene, 1-vinyl-5-hexylnaphthalene, 1-vinylnaphthalene, divinylnaphthalene, divinylbenzene, trivinylbenzene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylamino One selected from the group consisting of ethyl ether, vinylpyridine, vinylxylene, diphenylethylene, diphenylethylene containing tertiary amines, styrene containing primary, secondary, or tertiary amines, and combinations of two or more thereof It may be, but is not limited to this.

The terminal-modified conjugated diene-based polymer may be produced by a solution polymerization method, but is not limited thereto.

The weight average molecular weight (Mw) of the conjugated diene-based polymer may be 1,000 to 200,000 g/mol. If the weight average molecular weight of the conjugated diene polymer is less than the above range, the Mooney viscosity may decrease and the wear resistance of the final product may decrease, and if it exceeds the above range, the filler dispersibility may decrease and processability when mixing rubber may be poor.

rubber composition

A rubber composition according to another aspect of the present specification includes the terminal-modified conjugated diene-based polymer described above.

The rubber composition may further include filler. The filler may be carbon black or silica, but is not limited thereto.

The rubber composition may be applied to manufacturing rubber for tire treads, but is not limited thereto. Tires made from the above rubber composition have excellent mechanical properties such as wear resistance, safety and fuel efficiency, and can be applied to heavy electric vehicles, etc.

Hereinafter, embodiments of the present specification will be described in more detail. However, the following experimental results describe only representative experimental results among the above examples, and the scope and content of the present specification cannot be interpreted as being reduced or limited by the examples. Each effect of various implementations of the present specification that are not explicitly presented below will be described in detail in the corresponding section.

Manufacturing Examples 1 to 9

(3-Chloropropyl)trimethoxysilane, Cl(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), 3-(trimethoxysilyl)propylamine, H ₂ N(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), base and metal halide were mixed according to Table 1 below. The mixture was reacted by stirring at a temperature and pressure of 133° C. and 2.1 bar, and then cooled to room temperature. After adding heptane (C ₇ H ₁₆ ) to precipitate the formed salt, the suspension was filtered and the solvent was evaporated. The product was distilled under reduced pressure to obtain N,N,N-Tris(trimethoxysilylpropyl)amine as a colorless liquid.

Comparative manufacturing example

A mixture of 196 mmol of (3-chloropropyl)trimethoxysilane, 55.6 mmol of 3-(trimethoxysilyl)propylamine and 224 mmol of N,N-diisopropylethylamine (DIEA) was added when the starting materials were completely consumed. It was heated to 133°C while stirring. After confirming that the starting material was completely consumed, it was cooled to room temperature. After adding 300 mL of pentane to precipitate the formed salt, the suspension was filtered and the solvent was evaporated. The crude product was distilled under reduced pressure to obtain N,N,N-tris(trimethoxysilylpropyl)amine as a yellow viscous liquid.

division Chloroalkylalkoxysilane content (mmol) Primary or secondary amine content (mmol) base Base content (mmol) metal halide Metal halide content (mmol) Manufacturing Example 1 162.6 50.8 TEAs 106.7 NaBr 106.7 Production example 2 163.8 51.2 TEAs 107.5 NaI 105.0 Production example 3 164.5 51.4 TEAs 107.9 KBr 106.9 Production example 4 170.2 53.2 DIEA 111.7 NaBr 112.8 Production example 5 178.6 55.8 DIEA 117.2 NaI 113.3 Production example 6 159.7 49.9 DIEA 104.8 KBr 102.8 Production example 7 173.4 54.2 TMG 113.8 NaBr 112.7 Production example 8 169.9 53.1 TMG 111.5 NaI 112.6 Production example 9 171.2 53.5 TMG 112.4 KBr 114.5 Comparative manufacturing example 196 55.6 DIEA 224 - - - TEA: Triethylamine (C ₂ H ₅ ) ₃ N)
- DIEA: N,N-Diisopropylethylamine, [(CH ₃ ) ₂ CH] ₂ NC ₂ H ₅
- TMG: 1,1,3,3-Tetramethylguanidine (CH ₃ ) ₂ NC(=NH)N(CH ₃ ) ₂ )

Experimental Example 1

In the preparation methods of Preparation Examples 1 to 9 and Comparative Preparation Examples, the reaction time and product yield were measured and are shown in Table 2 below.

division reaction time (hr) transference number (%) Manufacturing Example 1 48 96 Production example 2 24 85 Production example 3 36 93 Production example 4 43 96 Production example 5 24 87 Production example 6 36 92 Production example 7 40 97 Production example 8 20 86 Production example 9 36 92 Comparative manufacturing example 96 90

Referring to Table 2, the preparation methods of Preparation Examples 1 to 9 showed a high yield of 91.56% on average, and in particular, Preparation Examples 1, 4 and 7 using NaBr as an additive showed a yield of over 96%.

In addition, the preparation methods of Preparation Examples 1 to 9 had a reaction time of 20 to 48 hours, and the reaction was completed within one to two days, whereas the comparative preparation example without adding a metal halide had a reaction time of 96 hours, that is, 4 days. It was confirmed that it was necessary. In particular, Preparation Examples 2, 5, and 8, which used NaI as an additive, completed the reaction within 24 hours, requiring a shorter reaction time of less than 25% compared to the comparative preparation example.

Production example 10

(3-Chloropropyl)trimethoxysilane 162.6 mmol, 3-(Diethylamino)propylamine, H ₂ N(CH ₂ ) ₃ N(C ₂ H ₅ ) ₂ ) 50.8 mmol, A mixture of 106.7 mmol of TEA and 106.7 mmol of NaBr was reacted by stirring at a temperature and pressure of 133°C and 2.1 bar, and then cooled to room temperature. Heptane (C ₇ H ₁₆ ) was added to precipitate the formed salt, then the suspension was filtered and the solvent was evaporated. The product was distilled under reduced pressure to obtain N'-Diethylaminopropyl-N,N-bis(trimethoxysilylpropyl)amine as a colorless liquid.

Production example 11

Each of the aminoalkoxysilane compounds prepared in Preparation Examples 1 and 10 was stirred with distilled water of pH 6 to 8 at a temperature and pressure of 80°C and 1 bar, and subjected to a dehydration condensation reaction for 8 hours. The reaction product was filtered to remove solid condensates of trimer or higher, and unreacted monomers were removed through distillation to obtain a siloxane compound with a dimer structure represented by the following formula (9) or formula (10).

[Formula 9]

[Formula 10]

Example 1

140 g of styrene, 180 g of 1,3-butadiene, 2,200 g of cyclohexane, and 10 ml of tetrahydrofuran were added to a 5L reactor, and the internal temperature of the reactor was adjusted to 35°C while stirring. When the temperature inside the reactor reached 35°C, 2.4 mmol of n-butyllithium, a polymerization initiator, was added to proceed with an adiabatic temperature-elevated polymerization reaction. At this time, the progress of the polymerization reaction was observed through changes in the reaction temperature, and the polymerization conversion rate of the monomer was analyzed by sampling a small amount of reactants between reactions.

When the polymerization conversion rate reached 99%, 9 g of 1,3-butadiene was additionally added to replace the reaction terminal with 1,3-butadiene. Afterwards, 5 mmol of the compound represented by Chemical Formula 9 prepared in Preparation Example 11 was added as an end-modifying agent to proceed with the end-modification reaction.

When terminal modification is complete, 4 g of butylated hydroxy toluene (BHT), an antioxidant, is added to terminate the reaction, and then the polymer is stripped and roll dried to remove the remaining solvent and water. was obtained.

Example 2

A polymer was obtained in the same manner as in Example 1, except that 5 mmol of the compound represented by Formula 10 prepared in Preparation Example 11 was added as an end modifying agent.

Comparative Example 1

A polymer was obtained in the same manner as in Example 1, except that 3.5 mmol of N,N,N-tris(trimethoxysilylpropyl)amine prepared in Preparation Example 1 was added as an end modifying agent.

Comparative Example 2

The polymer was prepared in the same manner as in Example 1, except that 3.5 mmol of N'-diethylaminopropyl-N,N-bis(trimethoxysilylpropyl)amine prepared in Preparation Example 10 was added as an end modifying agent. Obtained.

Experimental Example 2: Characteristics of terminally modified copolymer

The properties of each terminal-modified copolymer prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 3 below. In Table 3 below, the terminal modification rate, styrene content, and vinyl content are mole percent values calculated using NMR analysis results, and the weight average molecular weight was measured through GPC (gel permeation chromatography).

division terminal denaturation rate
(mole%) Weight average molecular weight
(kg/mol) Mooney viscosity
(ML ₁₊₄ @100℃) Styrene content (mol%) vinyl content
in B.D.
unit (mole%) Example 1 89 695 86 10.2 39.7 Example 2 74 624 79 10.0 39.4 Comparative Example 1 65 564 75 9.9 39.5 Comparative Example 2 56 552 73 10.1 39.7

Experimental Example 3: Evaluation of physical properties of rubber composition for tire tread

Each copolymer prepared according to Examples 1 and 2 and Comparative Examples 1 and 2 was mixed with silica in a 500 cc lab mixer according to the conditions shown in Table 4 below to prepare a rubber composition for tire tread.

Composition Content (phr) Solution SBR 80 (respective copolymers prepared according to Examples 1 and 2 and Comparative Examples 1 and 2) High Cis-BR 20 (Nd-BR 40, Kumho Petrochemical Co., Ltd.) Stearic acid 2 Zinc oxide 3 Silica 80 Process oil 10 Si-69 6.4 C.Z. One DPG 1.5 Sulfur 1.5

The processability and physical properties after mixing of the compounded rubber were measured and compared, and the results are shown in Table 5 below. The method of measuring each physical property is as follows.

- Hardness: Measured using a SHORE-A hardness tester.

- Tensile strength, 300% modulus and elongation: Measured using a universal test machine (UTM) according to ASTM 3189 Method B.

- Dynamic physical properties of vulcanized rubber (Tanδ): Analyzed using Rheometic's DTMA 5 instrument at a frequency of 10 Hz and a deformation condition of 0.2.

- Mooney viscosity of the blend: The unvulcanized blend was attached before and after the rotor and mounted on a rotational viscometer (ALPHA Technolgies, MOONEY MV2000). After preheating to 100°C for an initial 1 minute, the rotor was started and the change in viscosity of the mixture was measured for 4 minutes to measure the Mooney viscosity of the mixture expressed as ML ₁₊₄ @100°C.

Properties division Example 1 Example 2 Comparative Example 1 Comparative Example 2 mechanical
Properties Hardness (Shore-A) 71 71 71 71 Tensile strength (Kgf/cm2) 180 172 165 163 300% modulus (Kgf/cm2) 169 167 156 148 Elongation rate (%) 384 372 360 358 dynamic
Properties Mixture glass transition temperature (℃) -48.0 -48.6 -48.1 -48.4 Wetting resistance (Tanδat 0℃) 0.2263 0.2195 0.2205 0.2143 Rotation resistance (Tanδat 60℃) 0.0695 0.0781 0.0713 0.0812 Processability/storage stability Formulation Mooney viscosity
(ML ₁₊₄ @100℃) 78 82 79 84 Low temperature flowability (mg/min) 0.65 0.79 0.78 0.98

Referring to Table 5, the rubber compositions mixed with the copolymers of Examples 1 and 2 had lower Mooney viscosity and low-temperature flowability than the rubber compositions mixed with the copolymers of Comparative Examples 1 and 2, respectively, and thus had lower processability and storage stability. You can see that it has improved. In particular, the rubber compositions of Examples 1 and 2 have low low-temperature flowability and can maintain their original packaging shape regardless of weight, pressure, and time when packaged to a certain standard, so they are suitable for consumers who use them to produce and manufacture other products. It can be advantageous. This low low-temperature flowability appears to occur when the side branch structure of the polymer increases.

In addition, the hardness, tensile strength, 300% modulus, and elongation of the rubber composition mixed with the copolymers of Examples 1 and 2 were confirmed to be partially improved compared to the rubber composition mixed with the copolymers of Comparative Examples 1 and 2. Comparing the tan δ values at 0°C and 60°C of the examples and comparative examples, the rubber composition containing the copolymers of Examples 1 and 2 was found to have high wetting resistance (0°C) and low rotational resistance (60°C). , it can be seen that both the safety and fuel efficiency of tires to which the rubber composition is applied can be improved.

The description of the present specification described above is for illustrative purposes, and a person skilled in the art to which an aspect of the present specification pertains can easily transform it into another specific form without changing the technical idea or essential features described in the present specification. You will be able to understand it. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as single may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present specification is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present specification.

Claims (18)

A siloxane compound represented by the formula (1):
[Formula 1]

In Formula 1,
R ^1a and R ^1b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ^2a and R ^2b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ^3a and R ^3b are each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms,
R ^4a , R ^4b , R ^5a and R ^5b are each independently hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms. It is a heteroalkyl group,
m1 and m2 are each integers from 0 to 2, and when m1 and m2 are each 0, the plurality of OR ^2a and OR ^2b are the same or different from each other, and when m1 and m2 are each 2, the plurality of R ^1a and R ^1b are are the same or different from each other,
x is an integer from 1 to 5. According to paragraph 1,
At least one of R ^4a , R ^4b , R ^5a and R ^5b is an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2 or Formula 3:
[Formula 2]
-Si(R ^6a ) _m3 (OR ^6b ) _3-m3
In Formula 2,
R ^6a is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ^6b is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
m3 is an integer from 0 to 3, and when m3 is 0 or 1, the plurality of OR ^6b is the same as or different from each other, and when m3 is 2 or 3, the plurality of R ^6a are the same or different from each other,
[Formula 3]
-N(R ^7a )(R ^7b )
In Formula 3 above,
R ^7a and R ^7b are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms. According to paragraph 2,
At least one of R ^4a and R ^4b is an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2,
At least one of R ^5a and R ^5b is an alkyl group or heteroalkyl group substituted by a substituent represented by Formula 2 or Formula 3. (a) preparing a mixture containing a chloroalkylalkoxysilane represented by the following formula (4), a primary or secondary amine, and a metal halide;
(b) reacting the mixture to obtain an aminoalkoxysilane compound; and
(c) subjecting the aminoalkoxysilane compound to a dehydration condensation reaction; a method for producing a siloxane compound, including:
[Formula 4]
Cl-(R ³ )-Si(R ¹ ) _n (OR ² ) _3-n
In Formula 4 above,
R ¹ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ² is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ³ is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms,
n is an integer from 0 to 2, and when n is 0 or 1, the plurality of OR ² is the same or different from each other, and when n is 2, the plurality of R ¹ are the same or different from each other. According to paragraph 4,
Method for producing a siloxane compound, wherein the primary or secondary amine is a compound represented by the following formula (5):
[Formula 5]
NH(R ⁴ ) _o [(R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p ] _2-o
In Formula 5 above,
R ⁴ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms,
R ⁵ is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms,
R ⁶ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
R ⁷ is a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
o is 0 or 1, and when o is 0, a plurality of (R ⁵ )-Si(R ⁶ ) _p (OR ⁷ ) _3-p are the same or different from each other,
p is an integer from 0 to 2, and when p is 0 or 1, the plurality of OR ⁷ is the same as or different from each other, and when p is 2, the plurality of R ⁶ are the same or different from each other. According to paragraph 4,
Method for producing a siloxane compound, wherein the primary or secondary amine is a compound represented by the following formula (6):
[Formula 6]
NH(R ⁸ ) _q [(R ⁹ )-N(R ¹⁰ )(R ¹¹ )] _2-q
In Formula 6 above,
R ⁸ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted linear or branched heteroalkyl group having 1 to 16 carbon atoms,
R ⁹ is a substituted or unsubstituted linear or branched alkylene group having 1 to 16 carbon atoms,
R ¹⁰ and R ¹¹ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 16 carbon atoms,
q is 0 or 1, and when q is 0, a plurality of (R ⁹ )-N(R ¹⁰ )(R ¹¹ ) are the same or different from each other. According to paragraph 4,
The metal halide is a method of producing a siloxane compound, which is a compound represented by the following formula (7):
[Formula 7]
MX
In Formula 7 above,
M is an alkali metal,
X is a halogen element. According to paragraph 4,
The metal halide is a method of producing a siloxane compound, which is a compound represented by the following formula (8):
[Formula 8]
M'X ₂
In Formula 8 above,
M' is an alkaline earth metal,
X is a halogen element. According to paragraph 4,
A method for producing a siloxane compound, wherein the content of the chloroalkylalkoxysilane contained in the mixture is 1.1 to 10 mol per 1 mol of the primary or secondary amine. According to paragraph 4,
A method for producing a siloxane compound, wherein the content of the metal halide contained in the mixture is 0.01 to 5 mol per 1 mol of the primary or secondary amine. According to paragraph 4,
The mixture further includes a base. According to clause 11,
The base is one selected from the group consisting of triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and combinations of two or more of these. , Method for producing siloxane compounds. According to paragraph 4,
A method for producing a siloxane compound, wherein the reaction in step (b) is performed at 60 to 200°C. According to paragraph 4,
A method for producing a siloxane compound, wherein the reaction in step (b) is performed for 1 to 100 hours. According to paragraph 4,
A method for producing a siloxane compound, wherein the reaction in step (b) is performed under a pressure of 0.1 to 10 bar. A terminal-modified conjugated diene-based polymer in which the siloxane compound of any one of claims 1 to 3 is bonded to the terminal of the conjugated diene-based polymer. According to clause 16,
The conjugated diene-based polymer is a terminal-modified conjugated diene-based polymer that is a homopolymer of a conjugated diene-based monomer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl monomer. A rubber composition comprising the terminal-modified conjugated diene-based polymer of claim 16.