US 12,221,537 B2
Microspheric ionomer having cross-linked structure, preparation method therefor, applications thereof, and preparation system thereof
Wenbo Song, Beijing (CN); Hao Yuan, Beijing (CN); Zhenjie Liu, Beijing (CN); Jinliang Qiao, Beijing (CN); Shijun Zhang, Beijing (CN); Hua Yin, Beijing (CN); Huijie Hu, Beijing (CN); Qing Shao, Beijing (CN); Jie Zhang, Beijing (CN); Xiaomeng Zhang, Beijing (CN); Dezhan Li, Beijing (CN); and Fuyong Bi, Beijing (CN)
Assigned to CHINA PETROLEUM & CHEMICAL CORPORATION, Beijing (CN); and BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL CORPORATION, Beijing (CN)
Filed by CHINA PETROLEUM & CHEMICAL CORPORATION, Beijing (CN); and BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL CORPORATION, Beijing (CN)
Filed on Mar. 13, 2024, as Appl. No. 18/604,473.
Application 18/604,473 is a division of application No. 16/758,839, granted, now 11,965,089, previously published as PCT/CN2018/111825, filed on Oct. 25, 2018.
Claims priority of application No. 201711016388.4 (CN), filed on Oct. 25, 2017; and application No. 201711016466.0 (CN), filed on Oct. 25, 2017.
Prior Publication US 2024/0270958 A1, Aug. 15, 2024
Int. Cl. C08L 67/02 (2006.01); C08F 212/08 (2006.01); C08F 212/36 (2006.01); C08F 222/06 (2006.01); C08L 35/06 (2006.01)
CPC C08L 67/02 (2013.01) [C08F 212/08 (2013.01); C08F 212/36 (2013.01); C08F 222/06 (2013.01); C08L 35/06 (2013.01); C08F 2500/24 (2013.01); C08F 2810/20 (2013.01)] 22 Claims
 
1. A system for carrying out a method for preparing a microspheric ionomer having a cross-linked structure,
wherein the ionomer comprises a structure unit A represented by formula (1), a structure unit B represented by formula (2), and a cross-linking structural unit provided by a cross-linking agent,

OG Complex Work Unit Chemistry
wherein:
M1 and M2 are each independently selected from the group consisting of H, a metal cation and a linear, branched or cyclic C1-C20 saturated alkyl group, and R is H or methyl; and
at least part of the structure units A in the ionomer comprises the metal cation;
wherein said method comprises:
(1) contacting maleic anhydride, a monomer MB providing the structure unit B represented by formula (2), and the cross-linking agent, in an organic solvent, in the presence of an initiator, to react to form a product; and
(2) ring-opening the maleic anhydride unit in the product obtained in step (1);
wherein the ionomer is cross-linked maleic acid ester ionomer microsphere, and the method comprises:
(1) subjecting maleic anhydride and a monomer MB represented by formula (I) to copolymerization reaction in the presence of an initiator, the cross-linking agent, and a reaction solvent, in a copolymerization unit, to obtain a polymer mother liquid containing maleic anhydride-based copolymer microspheres,

OG Complex Work Unit Chemistry
 wherein R is H or methyl;
(2) subjecting the polymer mother liquid to a continuous first separation to obtain a separated solid-containing phase and a separation liquid-I;
(3) feeding the separated solid-containing phase into a washing unit, for performing at least one alcohol washing and a continuous second separation, to obtain a copolymer slag phase and a washing clear liquid;
(4) reacting the copolymer slag phase with an alcohol solution of a base, and continuously subjecting the obtained product to a third separation, to obtain a centrifuged slag phase containing ionomer microspheres and a separation liquid-II;
(5) sending the centrifuged slag phase to a drying unit for drying, to obtain cross-linked maleic acid ester ionomer microspheres; and
(6) introducing the separation liquid-1, separation liquid-II and washing clear liquid to a solvent recovery unit, and returning the recovered solvent and recovered alcohol obtained by recovery to steps (1) and (3), respectively;
wherein the system comprises:
a copolymerization unit, a washing unit, an ionomer-forming reaction unit, a drying unit, and a solvent recovery unit that are communicated sequentially,
wherein:
the copolymerization unit is used for a copolymerization reaction of comonomers, and for continuously subjecting the obtained polymer mother liquid containing maleic anhydride-based copolymer microspheres to a first separation, to obtain a separated solid-containing phase and a separation liquid-I;
the washing unit is used for subjecting the separated solid-containing phase to at least one alcohol washing and a continuous second separation, to obtain a copolymer slag phase and a washing clear liquid;
the ionomer-forming reaction unit is used for reacting the copolymer slag phase, and for continuously subjecting the prepared ionomer reaction liquid to a third separation, to obtain a centrifuged slag phase containing ionomer microspheres and a separation liquid-II;
the drying unit is used for drying the centrifuged slag phase to obtain the cross-linked maleic acid ester ionomer microspheres;
the solvent recovery unit is used for removing impurities from the separation liquid-I, separation liquid-II and washing clear liquid, and returning the recovered solvent and recovered alcohol obtained by separation to the copolymerization unit and the washing unit, respectively; and
this system is used to achieve continuous production of the cross-linked maleic acid ester ionomer microspheres.