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US-12624054-B2 - Organozinc compound preparation method, chain transfer agent, block copolymer, and resin composition

US12624054B2US 12624054 B2US12624054 B2US 12624054B2US-12624054-B2

Abstract

The present invention relates to a chain transfer agent including an organozinc compound, a preparation method thereof, and a method for preparing a block copolymer using the same. A chain transfer agent prepared by a preparation method including preparing a Grignard reagent containing styrene residues, and reacting the prepared Grignard reagent with alkyl zinc alkoxide, which is a zinc compound, has not catalyst poison and by-products, and contains 96 wt % or more of a target compound. A block copolymer polymerized using the chain transfer agent and a resin composition including the block copolymer have excellent mechanical properties.

Inventors

  • Seok Pil SA
  • Eun Ji Shin
  • Ki Soo Lee
  • Bun Yeoul Lee
  • Jong Chul Lee

Assignees

  • LG CHEM, LTD.

Dates

Publication Date
20260512
Application Date
20210730
Priority Date
20200731

Claims (11)

  1. 1 . A chain transfer agent including 96 mol % or more of an organozinc compound represented by Formula 1 below: wherein, in Formula 1 above, R 1 and R 3 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms or —SiR4R 5 —, and R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms.
  2. 2 . The chain transfer agent of claim 1 , wherein a content of Mg and Cl is each independently 10 ppm or less by weight.
  3. 3 . The chain transfer agent of claim 1 , wherein the organozinc compound represented by Formula 1 is included in an amount of 99 mol % or more.
  4. 4 . The chain transfer agent of claim 1 , wherein R 1 and R 3 are each independently a single bond or an alkylene group having 1 to 3 carbon atoms, R 2 is an alkylene group having 1 to 3 carbon atoms or —SiR 4 R 5 —, and R 4 and R 5 are each independently an alkyl group having 1 to 3 carbon atoms.
  5. 5 . The chain transfer agent of claim 1 , wherein the organozinc compound represented by Formula 1 is one or more selected from the group consisting of organozinc compounds represented by Formulas 1-1 to 1-4 below:
  6. 6 . A method for preparing the chain transfer agent of claim 1 , the method comprising: preparing a Grignard reagent containing styrene residues; and reacting the prepared Grignard reagent with a zinc compound to prepare an organozinc compound represented by Formula 1 below, wherein the zinc compound is alkyl zinc alkoxide: wherein, in Formula 1 above, R 1 and R 3 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms or —SiR 4 R 5 —, and R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms.
  7. 7 . The method of claim 6 , wherein the Grignard reagent containing styrene residues is represented by Formula 2 below: wherein, in Formula 2 above, R 1 and R 3 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms or —SiR 4 R 5 —, R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms, and X is a halogen group.
  8. 8 . The method of claim 7 , wherein the Grignard reagent containing styrene residues and represented by Formula 2 is prepared by the reaction between a compound represented by Formula 3 below and magnesium: wherein, in Formula 3 above, R 1 and R 3 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms or —SiR 4 R 5 —, R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms, and X is a halogen group.
  9. 9 . The method of claim 7 , wherein the Grignard reagent containing styrene residues and represented by Formula 2 is any one selected from the group consisting of compounds represented by Formula 2-1 to 2-4 below: wherein X is a halogen group.
  10. 10 . The method of claim 8 , wherein the compound represented by Formula 3 is any one selected from the group consisting of compounds represented by Formulas 3-1 to 3-4 below: wherein X is a halogen group.
  11. 11 . The method of claim 6 , wherein the zinc compound is ethyl zinc methoxide.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a national stage entry under 35 U.S.C. § 371 of International Application No. PCT/KR2021/009967 filed on Jul. 30, 2021, which claims priority from Korean Patent Application Nos. 10-2020-0096160 filed on Jul. 31, 2020, and 10-2021-0100045 filed on Jul. 29, 2021, all the disclosures of which are incorporated herein by reference. TECHNICAL FIELD The present invention relates to an organozinc compound preparation method, a chain transfer agent, a block copolymer, and a resin composition, and specifically, to a method for preparing an organozinc compound having styrene residues which may be used for coordination chain transfer polymerization (CCTP) in the preparation of a block copolymer, the method for preparing an organozinc compound synthesized as a single compound without side reactions, thereby having excellent synthesis reproducibility and polymerization reproducibility, a chain transfer agent including an organozinc compound prepared thereby, a block copolymer polymerized using the same, and a resin composition including the block copolymer. BACKGROUND ART The synthesis and application of a block copolymer is a major topic in a polymer-related field. In recent years, a lot of attention has been paid to a block copolymer based on polyolefin (PO). A representative block copolymer is PS-Block-Polybutadiene-Block-PS (SBS, wherein PS is polystyrene), which is produced at a scale of 2 million tons per year worldwide through controlled anionic polymerization, as shown in Reaction Equation 1 below. The hydrogenation of the intermediate block segment (i.e., polybutadiene block) of the SBS provides a value-added product, PS-block-poly (ethylene-co-1-butene)-block-PS (SEBS), which is commercialized at a scale of 300,000 tons per year worldwide. SBS is excellent in all of weather resistance, heat resistance, abrasion resistance, impact resistance, adhesiveness, transparency, and recyclability, and thus, there is a growing demand for SEBS. However, the hydrogenation of a polymer requires a catalytic reaction in the molten state of the polymer, and accordingly, a complex process such as a catalyst removal process is necessarily accompanied, so that SEBS is sold at a price that is at least three times higher than the price of SBS, and the high resin price poses as an obstacle to market expansion. In addition, the impossibility of heat treatment of SEBS is also an obstacle to market expansion. Commercial grade SEBS is prepared through controlled anionic polymerization, and thus, exhibits a very narrow molecular weight distribution, and accordingly, does not flow in molten state. In addition, SEBS is usually used in combination with other polymers rather than being used alone. While most bulk polymers are pelletized, and thus, are conveniently supplied, SEBS is only obtained in the form of a lumpy powder, and thus, is not conveniently supplied. Therefore, as a method to solve the above problems in the preparation of SEBS, Korean Patent Laid-Open Publication No. 1829382 (Patent Document 1) proposes a one-pot synthesis of a triblock copolymer which is similar to SEBS. Specifically, Patent Document 1 discloses that a polyolefin (PO) chain is grown through coordinative chain transfer polymerization (CCTP) from a diorganozinc compound having styrene residues, and then the polystyrene (PS) chain is grown through anionic polymerization in one-pot from a Zn—C binding site and the styrene residues. Here, Patent Document 1 discloses a method for preparing a diorganozinc compound through hydroboration of divinylbenzene, as shown in Reaction Equation 2 below. However, when a diorganozinc compound is prepared through hydroboration of divinylbenzene as in Reaction Equation 2 according to Patent Document 1, triethyl borane (Et3B) and diethyl zinc (Et2Zn) should be used in excess, but triethyl borane and diethyl zinc are highly flammable, and thus, are very dangerous. In addition, triethyl borane is continuously generated as a reaction intermediate, and if triethyl borane remains in the CCTP stage, it acts as a catalyst poison, and thus, should be continuously removed. In addition, when a diorganozinc compound is prepared through hydroboration of divinylbenzene as in Reaction Equation 2 above, there is a problem in that divinylbenzene which is used as a reactant has a low purity. Particularly, since divinylbenzene generally contains about 20 mol % of ethylvinylbenzene, when CCTP is performed using a diorganozinc compound, polystyrene cannot be grown from an ethyl group by anionic polymerization, which causes the generation of a diblock copolymer. In addition, since divinylbenzene includes two vinyl groups, when the hydroboration proceeds simultaneously in the two vinyl groups, a dimer, a trimer, and the like containing two or more zinc are inevitably generated. Therefore, in order to reduce the generation of a dimer, a trimer, and the like, divinylbenzene should be used i