Preparation and characterizations of polymeric ionic liquid blending system based on hyperbranched poly（p⁃chloromethylstyrene）

doi:10.19491/j.issn.1001-9278.2022.03.007

Abstract

Abstract:

Hyperbranched multi?arm?grafted copolymer h?PCMS?g?PMMA， functional block copolymer PMMA?b?PGMA， and ionic liquid block copolymer PMMA?b?PIL?［MIm?TFSI］ were prepared via living/controlled radical polymeri?zation using p?chloromethylstyryl vinyl benzyl chloride， methyl methacrylate， methacrylic acid glycidyl ester （GMA）， 1?methylimidazole， and lithium bis（trifluoromethylsulfonyl）imide as raw materials. The chemical structures of the resulting products were characterized by ¹H?NMR， FTIR and GPC. Then， the obtained products were mixed through solution blending to prepare a series of hyperbranched polymer ionic liquid blending systems. Their ionic conductivity was investigated using an AC impedance technology. The results indicated that the introduction of ionic liquid segment PIL?［MIm?TFSI］， hyperbranched structure， and PGMA segment effectively enhanced the ionic conductivity of the blend system.

Key words: hyperbranch, multi?arm?grafted copolymer, block copolymer, free radical polymerization, solution blending, ionic conductivity

CLC Number:

TQ317

CHENG Manfang, BAI Jifeng, WANG Wenqing, LEI Liangcai, LI Haiying, HAN Xiangyan, HU Yuexin. Preparation and characterizations of polymeric ionic liquid blending system based on hyperbranched poly（p⁃chloromethylstyrene）[J]. China Plastics, 2022, 36(3): 40-47.

Figures/Tables 17

共混体系编号	PIL⁃［MIm⁃TFSI］	h⁃PCMS	PGMA	PMMA
1^#	25.5	21.7	24.8	28.0
2^#	36.6	14.4	25.2	23.8
3^#	48.4	10.0	24.6	17.0
4^#	62.7	6.2	24.2	6.9
5^#	19.8	21.7	17.6	40.9
6^#	20.1	30.6	12.5	36.8
7^#	21.3	38.5	7.9	32.3
8^#	20.6	45.0	4.1	30.3
9^#	22.8	16.2	23.8	37.2
10^#	22.3	11.6	31.2	36.9
11^#	23.5	3.4	41.1	31.8

Tab.1. Content ratio of different segments in the blending system of hyperbranched polymerized ionic liquid

Fig.1. Synthetic route of h?PCMS?g?PMMA

Fig.2. Synthetic route of PMMA?b?PGMA

Fig.3. GPC traces of PMMA?CTA and PMMA?b?PGMA

聚合物	M_n/g·mol^-1	M_w/g·mol^-1	PDI
PMMA⁃CTA	11 300	16 800	1.37
PMMA⁃b⁃PGMA	25 400	38 400	1.51

Tab.2. Molecular weight and polydispersity index of PMMA?CTA and PMMA?b?PGMA

Fig.4. FTIR spectra of PMMA?CTA and PMMA?b?PGMA

Fig.5. 1H?NMR spectra of PMMA?CTA and PMMA?b?PGMA

Fig.6. Synthetic route of PMMA?b?PIL?［MIm?TFSI］

Fig.7. FTIR spectra of different samples

Fig.8. 1H?NMR spectra of different samples

Fig.9. AC impednace spectra of PIL?［MIm?TFSI］ in the blend system under different mass fractions

PGMA含量/%	PIL⁃［MIm⁃TFSI含量/%	电导率/S•cm^-1
24.8	25.5	2.10×10^-3
25.2	36.6	3.70×10^-3
24.6	48.4	6.50×10^-3
24.2	62.7	1.09×10^-2

Tab.3. Influence of the mass fraction of PIL?［MIm?TFSI］ in the blend system on the ionic conductivity of the system

Fig.10. Relationship between the conductivity of the system and the mass fraction of PIL?［MIm?TFSI］ in the blend system

Fig.11. AC impednace spectra of h?PCMS with different mass fractions in the blend system

PIL⁃［MIm⁃TFSI］含量/%	h⁃PCMS含量/%	电导率/×10^-4S•cm^-1
19.8	21.7	1.90
20.1	30.6	2.83
21.3	38.5	3.39
20.6	45.0	5.37

Tab.4. Influence of the mass fraction of h?PCMS in the blend system on the ionic conductivity of the system

Fig.12. AC impednace spectra of PGMA in the blend system under different mass fractions

PIL⁃［MIm⁃TFSI］

含量/%

PGMA

含量/%

电导率/

×10^-4S•cm^-1

Tab.5. The influence of the mass fraction of PGMA in the blend system on the ionic conductivity of the system

References 20

1	ZHANG B J， YAO L， LIU X D， et al. Facilely recyclable Cu（II） macrocomplex with thermoregulated poly（ionic li⁃quid） macroligand： serving as a highly efficient atom transfer radical polymerization catalyst［J］. Acs Sustainable Chemistry & Engineering， 2016， 4（12）： 7 066⁃7 073.
2	PORCARELLIL A， SHAPLOVA， SALSAMENDI M， et al. Single⁃ion block copoly（ionic liquid）s as electrolytes for all⁃solid state lithium batteries［J］. ACS Applied Materials Interfaces， 2016， 8（16）： 10 350⁃10 359.
3	NYKAZE J， BENJAMIN R， MEEK K， et al. Polyme⁃rized ionic liquid diblock copolymer as an ionomer and anion exchange membrane for alkaline fuel cells［J］. Chemical Engineering Science， 2016， 154： 119⁃127.
4	JONGBAEK P， MEHMET I， HEAJUNG P， et al. Polystyrene⁃block⁃poly（ionic liquid） copolymers as work function modifiers in inverted organic photovoltaic cells［J］. ACS Applied Materials Interfaces， 2018， 10（5）： 4 887.
5	DU C H， MA X M， LI J， et al. Improving the charged and antifouling properties of PVDF ultrafiltration membranes by blending with polymerized ionic liquid copolymer P（MMA⁃b⁃MEBIm⁃Br）［J］. Journal of Applied Polymer Science， 2017， 134（17）： 44 751⁃44 759.
6	ZHU X Y， ZHOU Y F， YAN D Y. Influence of branching architecture on polymer properties［J］. Journal of Polymer Science Part B Polymer Physics， 2011， 49（18）：1 277⁃1 286.
7	张鹏飞. 超支化聚合物的合成与改性及其在涂料上的应用［D］. 兰州：兰州理工大学， 2013.
8	ARISTOFANIS V， THANASIS C， VALADOULA D， et al. New pyridinium type poly（ionic liquids） as membranes for CO₂ separation［J］. Polymers， 2018， 10（8）：912⁃931.
9	MATANDABUZO M， AJIBADE P. Vinyl pyridinium polymeric ionic liquid functionalized carbon nanotube composites as adsorbent for chromium（VI） in aqueous solution［J］. Journal of Molecular Liquids， 2019， 296：111 778⁃111 788.
10	KAWAIR， YADA S， YOSHIMURA T， et al. Characterization and solution properties of quaternary⁃ammonium⁃salt⁃type amphiphilic gemini ionic liquids［J］. ACS Omega， 2019， 4（10）：14 242⁃14 250.
11	ELHAJ E， WANG H J， GU Y L， et al. Functionalized quaternary ammonium salt ionic liquids （FQAILs） as an economic and ecient catalyst for synthesis of glycerol carbonate from glycerol and dimethyl carbonate［J］. Molecular Catalysis， 2019， 468： 19⁃28.
12	CAI Y G， XU T G， NICOLASVON S， et al. Multifunctional imidazolium⁃based ionic liquid as additive for silicon/carbon lithium ion batteries［J］. Electrochimica Acta， 2020， 340：135 990⁃135 998.
13	IIJIMAG U， KITAGAWA T， KATAYAMA A， et al. CO₂ reduction promoted by imidazole supported on a phosphonium⁃type ionic⁃liquid⁃modified au electrode at a low overpotential［J］. ACS Catalysis， 2018， 8（3）：1 990⁃2 000.
14	JOHNT L， DEBBY F， RONALD S， et al. Functional polymers from novel carboxyl⁃terminated trithiocarbonates as highly efficient RAFT agents［J］. Macromolecules. 2002， 35（18）： 6 754⁃6 756.
15	WANGA L， XU H， LIU X， et al. The synthesis of a hyperbranched star polymeric ionic liquid and its application in a polymer electrolyte［J］. Polymer Chemistry， 2017，（8）：3 177⁃3 185.
16	HOU Z L， HUANG T， ZHOU C Y，et al. Polymer vesicle sensor through the self⁃assembly of hyperbranched polymeric ionic liquids for the detection of SO₂ derivatives［J］. Chinese Journal of Polymer Science， 2017， 35（5）： 602⁃610.
17	CHEN S Y， ZHANG J H， ZHOU J L， et al. Dramatic toughness enhancement of benzoxazine/epoxy thermosets with a novel hyperbranched polymeric ionic liquid［J］. Chemical Engineering Journal， 2018， 334：1 371⁃1 382.
18	金妮，李致轩，海智宝，等. ATRP/RAFT联用制备星型多臂共聚物 h⁃PCMS⁃g⁃PMMA⁃b⁃PBMA［J］. 合成化学， 2019， 27（5）： 351⁃356.
	JIN N， LI Z X， HAI Z B， et al. Preparation of star⁃shaped multi⁃arm copolymer h⁃PCMS⁃g⁃PMMA⁃b⁃PBMA by ATRP/RAFT combination［J］. Synthetic Chemi⁃stry， 2019， 27（5）： 351⁃356.
19	LAI J T， DEBBY F， RONALD S， et al. Functional polymers from novel carboxyl⁃terminated trithiocarbonates as highly efficient RAFT agents［J］. Macromolecules， 2002， 35： 6 754⁃6 756.
20	王俊豪，沈越，金妮，等. 三嵌段聚合离子液体共聚物PMMA⁃b⁃PBMA⁃b⁃PILs的合成及表征［J］. 化工新型材料， 2019， 47（3）：134⁃139.
	WANG J H， SHEN Y， JIN N， et al. Synthesis and characterization of triblock polymerized ionic liquid copolymer PMMA⁃b⁃PBMA⁃b⁃PILs［J］. New Chemical Materials， 2019， 47（3）：134⁃139.

[1]	PENG Fanchang, CHEN Xiaosui, ZHANG Aiqing, ZHOU Hongfu. Controllable Preparation of Hyperbranched Polyphosphoramide Coated Carbon Nanotubes and Its Application for Flame Retardancy [J]. China Plastics, 2021, 35(9): 55-63.
[2]	WU You, WANG Bohua, SUN Jianjian, JIN Yujuan. Study on Modification of PPC/PBS Blends with Epoxy⁃terminated Hyperbranched Polymer [J]. China Plastics, 2021, 35(4): 5-11.
[3]	DONG Bingting, ZANG Meng, YIN Kai, XIN Chunling, HE Yadong. Study on Crystallization and Foaming Properties of Hyperbranched Polyamide⁃reinforced Thermoplastic Polyurethane [J]. China Plastics, 2021, 35(11): 1-6.
[4]	LI Meilan, HE Jiao, GONG Wei, HE Xiaoni, LAI Qian, LIU Bailing. Construction and Scale Inhibition Behavior of Phosphorus⁃free Green Carboxyl⁃terminated Hyperbranched Polyester [J]. China Plastics, 2021, 35(11): 55-63.
[5]	XU Weikun, WANG Huili, DONG Yizheng, YUAN Huiqiang, FAN Ping. Research Progress in Modification of Epoxy Resins with Hyperbranched Polyesters [J]. China Plastics, 2021, 35(1): 110-123.
[6]	LI Meilan, HE Zichun, MU Kaifei, GONG Wei, LAI Qian, YANG Meng, LIU Bailing. Preparation and Scale Inhibition Performance of Carboxyl-Terminated Hyperbranched Green Scale Inhibitor [J]. China Plastics, 2020, 34(9): 38-45.
[7]	Wei ZHAI, Jianjian SUN, Bohua WANG, Chong TENG, Shiyu XIE, Fenghao HAO, Yujuan JIN. Study on Toughening Modification of PLA/PPC Blends with Hyperbranched Ethylenediamine Trazine Polymer [J]. China Plastics, 2020, 34(6): 27-33.
[8]	. Study on Modification of Poly(hydroxybutyrate-co-hydroxyvalerate) with Epoxy-terminated Hyperbranched Polyester [J]. China Plastics, 2016, 30(10): 42-49 .
[9]	. Investigation on Compatibility of TPU and SEBS with Using Infrared Spectroscopy [J]. China Plastics, 2016, 30(10): 36-41 .
[10]	. Antioxidant Properties of Hyperbranched Bridged Hindered Phenols in Polyethylene Resins [J]. China Plastics, 2016, 30(08): 43-49 .
[11]	. Surface Interaction of Selfassembly Functional Polymeric Materials [J]. China Plastics, 2016, 30(02): 11-19 .
[12]	. Effects of the Structure of PLA-b-PMMA on Morphologies and Properties of PC/PLA Blends [J]. China Plastics, 2015, 29(12): 39-45 .
[13]	. Research Progress on Tetrazolyl Polymer [J]. China Plastics, 2015, 29(11): 1-6 .
[14]	. Study on the Compatibilizing of Long Chain Branched Polypropylene to the Polypropylene Blends [J]. China Plastics, 2014, 28(05): 27-31 .
[15]	Li Ting Ting . Properties of CE/PPO/Hyperbranched Polysiloxane GraftingSiO2 Composites [J]. China Plastics, 2014, 28(01): 22-27 .