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WO-2026092477-A1 - MULTI-POLARITY BINARY STRUCTURE MODIFIER, AND PREPARATION METHOD THEREFOR AND USE THEREOF

WO2026092477A1WO 2026092477 A1WO2026092477 A1WO 2026092477A1WO-2026092477-A1

Abstract

The present invention provides a multi-polarity binary structure modifier, and a preparation method therefor and a use thereof. The multi-polarity binary structure modifier contains a sulfonyl hydroxide group which can fully exert the "polarity effect" of a polyamine group and an epoxy group during anionic polymerization of conjugated diene (1,3-butadiene). In one aspect, the electron supply capability is greatly improved, and the reaction is promoted to move towards a π-allyl lithium structure, and in the other aspect, the degree of association of an initiator is improved. Under the synergistic effect of the two aspects, the 1,2-structure content can be efficiently regulated, so that a high-vinyl low-gel-content polybutadiene liquid rubber can be prepared.

Inventors

  • XU, Dianhong
  • QIU, Guanjun
  • HU, Caizhong
  • ZHAO, ZHICHAO
  • WEI, Xuling
  • LI, Fuchong
  • YANG, HAILONG
  • WANG, Wancheng
  • ZHAI, Yunfang
  • ZHOU, LEI

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260507
Application Date
20251028
Priority Date
20241029

Claims (11)

  1. A multipolar binary structure modifier, characterized in that the multipolar binary structure modifier has the structure shown in Formula 1: Wherein, R1 is a straight-chain alkyl group from C1 to C4 , and R2 is an alkyl group from C1 to C12 .
  2. A method for preparing the multipolar binary structure modifier according to claim 1, characterized in that 3,5-diamino-4-alkylbenzenesulfonic acid and tetrahydro-2-furanol are subjected to an esterification reaction to obtain the multipolar binary structure modifier. The tetrahydro-2-furanol has the structure shown in Formula 2: The 3,5-diamino-4-alkylbenzenesulfonic acid has the structure shown in Formula 3:
  3. According to the preparation method of claim 2, R1 is a C1 - C4 straight-chain alkyl group, and R2 is a C1 - C12 alkyl group; preferably R1 is n-propyl or isopropyl, and preferably R2 is methyl.
  4. According to the preparation method of claim 2 or 3, the esterification reaction specifically includes the following steps: 3,5-Diamino-4-alkylbenzenesulfonic acid, chlorosulfonic acid and sodium chloride were mixed and subjected to a first heating and stirring reaction to obtain a first heating and stirring reaction system. Tetrahydro-2-furanol and sodium hydroxide aqueous solution were added to the first heating and stirring reaction system to carry out a second heating and stirring reaction, thereby obtaining a second heating and stirring reaction system. The pH of the second heating and stirring reaction system was adjusted to 6.5–7.5, and separation was performed to obtain the multipolar binary structure regulator. The stirring speed of the first heating and stirring reaction is 100-200 rpm, the reaction temperature is 43-52℃, and the reaction time is 1.6-2.4 h; The stirring speed of the second heating and stirring reaction is 100-200 rpm, the reaction temperature is 112-130℃, and the reaction time is 2.6-3.5 h.
  5. The preparation method according to any one of claims 2-4 is characterized in that, in the esterification reaction, when the sum of the masses of 3,5-diamino-4-methylbenzenesulfonic acid and tetrahydro-2-furanpropanol is 100, the mass ratio of the two is (30-40):(60-70); and/or, In the esterification reaction, the mass ratio of 3,5-diamino-4-methylbenzenesulfonic acid, chlorosulfonic acid, and sodium chloride is 1:(1.5-4.0):(0.01-0.1).
  6. A method for preparing polybutadiene liquid rubber, characterized in that 1,3-butadiene is polymerized using the multipolar binary structure modifier and initiator described in claim 1 to obtain the polybutadiene liquid rubber; The initiator is a hydrocarbon-based monolithium compound; The polymerization reaction specifically includes the following steps: Solvent, a portion of 1,3-butadiene, and a portion of the multipolar binary structure modifier are added sequentially to the reaction vessel, followed by the addition of a portion of the initiator to initiate the polymerization reaction; during the reaction, the remaining 1,3-butadiene, multipolar binary structure modifier, and initiator are added at least twice. The portion of 1,3-butadiene does not exceed 50% of the total mass of 1,3-butadiene; The polymerization reaction temperature is -10 to -5℃.
  7. According to the preparation method of claim 6, the remaining 1,3-butadiene, multipolar binary structure modifier, and initiator are added at least twice, specifically including: When the conversion rate is 14%–17%, add the first component. When the conversion rate is 65%–70%, add the second component; When the conversion rate is 95% to 96%, a terminator is added to the reaction system to obtain the polybutadiene liquid rubber. Both the first component and the second component include 1,3-butadiene, the multipolar binary structure modifier, and the initiator.
  8. According to the preparation method of claim 7, the molar ratio of the multipolar binary structure modifier to the initiator in the first component and the second component is (1.0-7.2):1; and/or, The molar ratio of a portion of the multipolar binary structure modifier and a portion of the initiator added to the container for the first time is (1.0 to 7.2):1.
  9. The preparation method according to any one of claims 6-8 is characterized in that the amount of the initiator is equal to the ratio of the expected preparation mass of the target polybutadiene liquid rubber to the molecular weight of the target polybutadiene liquid rubber.
  10. A polybutadiene liquid rubber, characterized in that it is prepared using the method for preparing polybutadiene liquid rubber according to any one of claims 6-9.
  11. According to claim 10, the polybutadiene liquid rubber is characterized in that the number average molecular weight of the liquid rubber is 3700-4900, and the vinyl content is greater than or equal to 88.6%; and/or, The gel content of the liquid rubber is less than or equal to 2.4%.

Description

A multipolar binary structure modifier, its preparation method and application This application claims priority to Chinese Patent Application No. 202411523004.8, filed on October 29, 2024, entitled “A Multipolar Binary Structure Regulator and Its Preparation Method and Application”, the entire contents of which are incorporated herein by reference. Technical Field This application relates to the field of organic synthesis technology, and in particular to a multipolar binary structure regulator, its preparation method, and its application. Background Technology With the development of modern communication, polybutadiene liquid rubber has gradually begun to be used as an adhesive for circuit boards. Since modern communication signals are transmitted at high frequency and high speed, circuit boards generate a lot of heat during use. This requires that various materials have both heat aging resistance and excellent adhesion, while not damaging the dielectric constant and dielectric loss coefficient of the substrate. In the case of polybutadiene liquid rubber, this means that the content of polymer vinyl structure (1,2-structure) should be high to facilitate curing reaction with other resins, glass fibers, etc. to form a cross-linked structure, thereby improving the overall strength and adhesion of the circuit board. However, polybutadiene liquid rubber is a viscous, flowable polymer formed by the polymerization of 1,3-butadiene monomers, resulting in a number-average molecular weight of 500-10,000. Typically, in anionic polymerization, the polymerization of 1,3-butadiene is predominantly trans-1,4-structure polymerization (over 60%), with a low content of 1,2-structure, which cannot meet the high reactivity requirements of advanced electronic materials. To obtain polybutadiene liquid rubber with a high content of vinyl structures (1,2-structure), it is necessary to achieve controllability of the polymer microstructure within a certain range. Many factors influence the polymer microstructure, such as the type and concentration of initiators, the effects of solvents and polar additives, and temperature. Among these factors, adding polar modifiers is one of the most important methods for synthesizing polymers with different microstructures. However, the high vinyl content also brings a serious drawback to polybutadiene liquid rubber. As the 1,2 content of polybutadiene liquid rubber increases, numerous active unsaturated double bonds appear on the side chains of its main chain. These bonds readily react to form a three-dimensional network of macromolecules, resulting in gel formation. This leads to a decrease in the overall bonding strength of the circuit board, affecting its quality and lifespan. Therefore, developing high-vinyl, low-gel polybutadiene liquid rubber has broad industrial application value and prospects in the field of electronic communications. In the prior art, research on high-vinyl-structure polybutadiene liquid rubber mainly involves the addition of polarity modifiers. CN113461837A provides a method for preparing low-cis, high-vinyl-terminated hydroxyl polybutadiene rubber, which uses a mixture of tetrahydrofuran and N,N-dimethylformamide, a mixture of tetrahydrofuran and tetramethylethylenediamine, a mixture of tetrahydrofuran and 2,2-di(2-tetrahydrofuranyl)propane, or a mixture of 2,2-di(2-tetrahydrofuranyl)propane and tetrahydrofurfuryl ethyl ether as the added structure modifier to prepare the high-vinyl-structure polybutadiene liquid rubber. CN1089272A discloses a method for controlling the vinyl content in butadiene homopolymers and copolymers, using a combination of diethylene glycol dimethyl ether and tetrahydrofuran as modifiers to control the vinyl content in polybutadiene rubber. CN117327219A provides a method for preparing high-vinyl polybutadiene liquid rubber, which uses a structure modifier 2,2-bis(2-tetrahydrofuranyl) to prepare high-vinyl polybutadiene liquid rubber. While the use of small-molecule organic structure modifiers can increase the vinyl content in polybutadiene liquid rubber to some extent, these methods still have limitations. These modifiers are mainly produced through compounding, resulting in large fluctuations in vinyl structure, high dosage requirements, high cost, and limited modification effectiveness. Furthermore, they can also lead to problems such as high gelation rates. Therefore, developing a method for preparing polybutadiene liquid rubber with high vinyl content and low gel content has become a current research direction. Summary of the Invention This invention provides a multipolar binary structure modifier, which has the characteristic of being able to produce high-ethylene-content polybutadiene liquid rubber. The present invention also provides a method for preparing a multipolar binary structure modifier, which has the advantage of being relatively simple in preparation process. The present invention also provides a polybutadiene liquid rubber, wh