Polymerization initiator composition, preparation method therefor, and method for preparing polymer using same

Patent metadata

Field	Value
Publication number	US-11214665-B2
Application number	US-201716468998-A
Country	US
Kind code	B2
Filing date	Dec 27, 2017
Priority date	Jan 4, 2017
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

A polymerization initiator composition includes isomers of the polymerization initiator, thereby preventing instability and inertness of the polymerization initiator and physical property degradation of the SSBR, minimizing by-products and unreacted materials, and remarkably improving a conversion ratio. In addition, when the polymerization initiator composition according to the present invention is used, there is no need to add a polar additive separately upon polymer polymerization, since the polar additive is already added at the time of preparing the polymerization initiator. Further, the polymer initiator composition has high polarity so that the hydrophobic SSBR and the hydrophilic silica can be effectively dispersed.

First claim

The invention claimed is:

1. A polymerization initiator composition comprising a compound represented by Formula 1 below:

wherein,
G 1 and G 2 include two or more of ortho, meta or para isomers based on a benzene structure of the compound represented by Formula 1, and
include the case when G 1 and G 2 are a para isomer,
wherein G 1 is a substituent group containing an alkali metal or an alkali earth metal,
G 1 is a form in which alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms is substituted for the benzene structure disclosed in Formula 1,
a polar substituent group forms a coordination bond on the basis of the alkali metal or alkali earth metal contained in G 1 , and
G 2 is represented by Formula 1-a below,

wherein,
R 4 and R 5 independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer of 0 to 2,
wherein n equals 0 represents a single bond, and
in the benzene structure of the compound represented by Formula 1, carbons to which G 1 and G 2 are not bonded are independently bonded by hydrogen or an alkyl group having 1 to 6 carbon atoms.

2. The polymerization initiator composition according to claim 1 ,
wherein the compound represented by Formula 1 has a ratio of the sum weight of the ortho and meta isomers to the weight of the para isomer in a range of 1 to 4:6 to 9.

3. The polymerization initiator composition according to claim 1 ,
wherein the polar substituent group has a structure in which one or more selected from the group consisting of tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylenedimethyl ether, ethylenedimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane, bis(2-dimethylaminoethyl) ether, (dimethylaminoethyl)ethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis(2-oxolanyl)propane, dipiperidinoethane, pyridine, quinuclidine, trimethylamine, triethylamine, tripropylamine, tetramethylethylenediamine, potassium tert-butyrate, sodium tert-butyrate, sodium amylate or and triphenylphosphine are coordination-bonded to the alkali metal or the alkali earth metal contained in G1.

4. A method for preparing a polymerization initiator composition according to claim 1 comprising:
reacting a compound represented by Formula 2 below and an organometallic compound to prepare a modified initiator; and
reacting the modified initiator and a polar additive:

wherein,
G′ 1 and G′ 2 include two or more of ortho, meta or para isomers based on a benzene structure of the compound represented by Formula 2, and
include the case where G′ 1 and G′ 2 are a para isomer,
where G′ 1 is represented by Formula 2-a below and
G′ 2 is represented by Formula 2-b below,

wherein,
R 1 , R 2 and R 3 independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms or an alkynyl group having 1 to 6 carbon atoms,
m is an integer of 0 to 20, and
wherein m equals 0 represents a single bond, and

wherein,
R 4 and R 5 independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer of 0 to 2,
wherein n equals 0 represents a single bond, and
in the benzene structure of the compound represented by Formula 2, carbons to which G′ 1 and G′ 2 are not bonded are independently bonded by hydrogen or an alkyl group having 1 to 6 carbon atoms.

5. The method for preparing a polymerization initiator composition according to claim 4 ,
wherein the compound represented by Formula 2 has a ratio of the sum weight of the ortho and meta isomers to the weight of the para isomer in a range of 1 to 4:6 to 9.

6. The method for preparing a polymerization initiator composition according to claim 4 ,
wherein the organometallic compound comprises an organic alkali metal compound or an organic alkali earth metal compound.

7. The method for preparing a polymerization initiator composition according to claim 4 ,
wherein a molar ratio of the compound represented by Formula 2 to the organometallic compound is 5:1 to 1:5.

8. The method for preparing a polymerization initiator composition according to claim 4 ,
wherein the polar additive comprises one or more selected from the group consisting of tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylenedimethyl ether, ethylenedimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane, bis(2-dimethylaminoethyl) ether, (dimethylaminoethyl)ethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis(2-oxolanyl)propane, dipiperidinoethane, pyridine, quinuclidine, trimethylamine, triethylamine, tripropylamine, tetramethylethylenediamine, potassium tert-butyrate, sodium tert-butyrate, sodium amylate and triphenylphosphine.

9. The method for preparing a polymerization initiator composition according to claim 4 ,
wherein an equivalent ratio of the polar additive to the compound represented by Formula 2 is 1:1 to 1:4.

10. A method for preparing a polymer comprising:
reacting a polymerization initiator composition comprising a compound represented by Formula 1 according to claim 1 ; a resin monomer; and a conjugated diene compound:

wherein,
G 1 and G 2 include two or more of ortho, meta or para isomers based on the benzene structure disclosed in Formula 1, and
include the case when G 1 and G 2 are a para isomer,
where G 1 is a substituent group containing an alkali metal or an alkali earth metal,
G 1 is a form in which alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms is substituted for the benzene structure of the compound represented by Formula 1,
a polar substituent group forms a coordination bond on the basis of the alkali metal or alkali earth metal contained in G 1 , and
G 2 is represented by Formula 1-a below,

wherein,
R 4 and R 5 independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer of 0 to 2,
wherein n equals 0 represents a single bond, and
in the benzene structure of the compound represented by Formula 1, carbons to which G 1 and G 2 are not bonded

Assignees

• Lg Chemical Ltd

Inventors

• Choe Jae Hoon
• Choi Jong Young
• Choe Dong Cheol
• Kim Hyun Ju
• Kim Hyeon Hui
• Lee Jung Yong
• Kim Chan Joong
• Lee Myung Han
• Han Hye Jin

Classifications

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title

• C07C211/53

  having the nitrogen atom of at least one of the amino groups further bound to a hydrocarbon radical substituted by amino groups · CPC title

• C08K5/18 Primary

  with aromatically bound amino groups · CPC title

• C08K5/16

  Nitrogen-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C08F2/44

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title