Silyl group-containing novel compound, modified and conjugated diene-based polymer, and method for preparing same

Patent metadata

Field	Value
Publication number	US-2018170102-A1
Application number	US-201615736005-A
Country	US
Kind code	A1
Filing date	Dec 23, 2016
Priority date	Dec 24, 2015
Publication date	Jun 21, 2018
Grant date	—

Abstract

The present invention relates to a modifier useful for modifying a polymer, a method for preparing a modified and conjugated diene-based polymer using the same, and a modified and conjugated diene-based polymer prepared thereby. In the modified and conjugated diene-based polymer, a hydroxyl group and a silyl group are combined, and the affinity thereof with a silica-based filler may be excellent. Accordingly, a rubber composition including the modified and conjugated diene-based polymer may have excellent processability, and as a result, molded articles (for example, tires) manufactured from the rubber composition may have excellent tensile strength, abrasion resistance, and viscoelasticity properties.

First claim

1 . A compound comprising a constituent unit represented by the following Formula 1:

in Formula 1,
R 1 to R 3 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl, where at least one of R 1 to R 3 is C 1-20 alkoxy,
R 4 is C 1-20 alkylene,
x, y and z represent each independently a molar ratio of each repeating unit constituting the constituent unit, where x+y+z is 1,
x is 0.1 to 0.8,
y is 0.1 to 0.8, and
z is 0.1 to 0.8.

2 . The compound of claim 1 , wherein in Formula 1,
R 1 to R 3 are each independently C 1-10 alkyl, or C 1-10 alkoxy, where at least one of R 1 to R 3 is C 1-10 alkoxy, and R 4 is C 1-10 alkylene.

3 . The compound of claim 1 , wherein the compound is a modifier for a conjugated diene-based polymer.

4 . A modified and conjugated diene-based polymer represented by the following Formula 4 or Formula 5, and comprising a functional group derived from the compound described in claim 1 :

in Formula 4,
R 5 is C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl,
R 7 is C 1-20 alkyl; or C 1-20 alkyl or alkylsilyl, which is substituted or unsubstituted with C 1-20 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-20 alkyl, where the C 1-20 alkyl or alkylsilyl comprises at least one heteroatom selected from N, O and S,
P is a conjugated diene-based polymer chain,
a and b are each independently an integer of 1 or 2, where a+b is 2 or 3,

in Formula 5,
R 10 and R 13 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl,
R 15 is C 1-20 alkyl; or C 1-20 alkyl or alkylsilyl, which is substituted or unsubstituted with C 1-20 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-20 alkyl, where the C 1-20 alkyl or alkylsilyl comprises at least one heteroatom selected from N, O and S,
R 16 is a heteroatom of N, O, or S, where in a case where R 16 is O or S, R 15 is not present,
P is a conjugated diene-based polymer chain,
c to f are each independently an integer of 0 to 3, where c+e is 1 to 5, and d+f is 1 to 3,
n and m are each independently an integer of 1 to 1000,
in Formula 4 and Formula 5, A is a substituent represented by the following Formula 6:

in Formula 6,
R 1 and R 2 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl,
R 4 is C 1-20 alkylene,
x, y and z represent each independently a molar ratio of each repeating unit constituting the constituent unit, where x+y+z is 1,
x is 0.1 to 0.8,
y is 0.1 to 0.8, and
z is 0.1 to 0.8.

5 . The modified and conjugated diene-based polymer of claim 4 , wherein in Formula 4 to Formula 6,
R 1 , R 2 , R 5 , R 10 and R 13 are each independently C 1-10 alkyl, or C 1-10 alkoxy, R 4 is C 1-10 alkylene, R 7 and R 15 are each independently C 1-10 alkyl; or C 1-10 alkyl which is substituted or unsubstituted with C 1-10 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-10 alkyl, where the C 1-10 alkyl comprises N or S, R 16 is N, and n and m are each independently an integer of 1 to 50.

6 . The modified and conjugated diene-based polymer of claim 4 , wherein the polymer comprises an aromatic vinyl-based monomer derived unit in an amount of 40 wt % or less.

7 . The modified and conjugated diene-based polymer of claim 4 , wherein the polymer has a number average molecular weight of 1,000 g/mol to 5,000,000 g/mol.

8 . The modified and conjugated diene-based polymer of claim 4 , wherein the polymer has a vinyl content of 5 wt % or more.

9 . A method for preparing the modified and conjugated diene-based polymer of claim 4 , the method comprising:
1) polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organometal compound in a hydrocarbon solvent to prepare an active polymer in which an organometal is combined with at least one terminal thereof; 2) performing a first reaction of the active polymer with a compound represented by the following Formula 2 or Formula 3; and 3) performing, after performing the first reaction, a second reaction with a compound comprising a constituent unit represented by the following Formula 1:

in Formula 2,
R 5 , R 6 and R 8 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl, where at least one of R 5 , R 6 and R 8 is C 1-20 alkoxy,
R 7 is C 1-20 alkyl; or C 1-20 alkyl or alkylsilyl, which is substituted or unsubstituted with C 1-20 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-20 alkyl, where the C 1-20 alkyl or alkylsilyl comprises at least one heteroatom selected from N, O and S,

in Formula 3, R 9 to R 14 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl, where at least one of R 9 to R 14 is C 1-20 alkoxy,
R 15 is C 1-20 alkyl; or C 1-20 alkyl or alkylsilyl, which is substituted or unsubstituted with C 1-20 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-20 alkyl, where the C 1-20 alkyl or alkylsilyl comprises at least one heteroatom selected from N, O and S,
R 16 is a heteroatom of N, O, or S, where in a case where R 16 is O or S, R 15 is not present,
n and m are each independently an integer of 1 to 1000,

in Formula 1,
R 1 to R 3 are each independently C 1-20 alkyl, C 1-20 alkoxy, or C 3-20 allyl, where at least one of R 1 to R 3 is C 1-20 alkoxy,
R 4 is C 1-20 alkylene,
x, y and z represent each independently a molar ratio of each repeating unit constituting the constituent unit, where x+y+z is 1,
x is 0.1 to 0.8,
y is 0.1 to 0.8, and
z is 0.1 to 0.8.

10 . The method for preparing the modified and conjugated diene-based polymer of claim 9 , wherein in Formula 1,
R 1 to R 3 are each independently C 1-10 alkyl, or C 1-10 alkoxy, where at least one of R 1 to R 3 is C 1-10 alkoxy, and R 4 is C 1-10 alkylene.

11 . The method for preparing the modified and conjugated diene-based polymer of claim 9 , wherein in Formula 2,
R 5 , R 6 , and R 8 are each independently C 1-10 alkyl, or C 1-10 alkoxy, where at least one of R 5 , R 6 , and R 8 is C 1-10 alkoxy, and R 7 is C 1-10 alkyl; or C 1-10 alkyl which is substituted or unsubstituted with C 1-10 alkyl or alkylsilyl which is mono-, di- or tri-substituted with C 1-10 alkyl, where the C 1-10 alkyl comprises N or S.

12 . The method for preparing the modified and conjugated diene-based polymer of claim 9 , wherein in Formula 3,
R 9 to R 14 are each independently C 1-10 alkyl, or C 1-10 alkoxy, where at least one of R 9 to R 14 is C 1-10 alkoxy, R 15 is C 1-10 alkyl; or C 1-10 alkyl which is substituted or unsubstituted with C 1-10 alkyl or alkylsil

Assignees

• Lg Chemical Ltd

Inventors

• Lee He Seung
• Kim No Ma
• Sohn Hae Sung

Classifications

• C08F36/06

  Butadiene · CPC title

• C08F236/10

  with vinyl-aromatic monomers · CPC title

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08L25/10

  with conjugated dienes · CPC title

• B60C1/00 Primary

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title