Synthesis and properties of ternary polysulfone copolymer containing bisphenol fluorene

doi:10.19491/j.issn.1001-9278.2022.11.004

Abstract

Abstract:

A series of ternary polysulfone copolymers with different contents of bisphenol fluorene were synthesized through polycondensation of bisphenol A， bisphenol fluorine， and 4，4⁃dichlorodiphenyl sulfone. The effects of reaction solvent， rea⁃ction time and salt forming agent on the polymerization were studied. The structure and properties of ternary polysulfone copolymers containing bisphenol fluorene were characterized using gel permeation chromatograph， Fourier⁃transform infrared spectrometer， and differential scanning calorimeter. The results indicated that the ternary copolymers with a number⁃ave⁃rage molecular weight higher than 2×10⁴ were successfully synthesized at a reaction time of 4 h using N⁃methyl pyrrolidone as a reaction solvent and potassium carbonate as a salt forming agent. The heat resistance of the copolymers increased gradually with an increase in the content of bisphenol fluorene， and the decomposition temperature of the main chain was higher than 510 ℃. The copolymers presented a glass transition temperature of 254 ℃ at a bisphenol fluorene content of 80 mol%， and their transmittance was 84 % in the visible light range. This can meet the requirements of temperature resistance for aircrafts at high Mach number. This study establishes the basis of application for highly heat⁃resistant transparent materials.

Key words: bisphenol fluorene, polysulfone, heat resistance, optical property

CLC Number:

TQ322

WANG Fang, LI Yan, GUO Xintao, DOU Peng. Synthesis and properties of ternary polysulfone copolymer containing bisphenol fluorene[J]. China Plastics, 2022, 36(11): 24-29.

Figures/Tables 13

Fig.1. Molecular structure of BHPF

样品编号	DCS含量/ mol	BPA含量/ mol	BHPF含量/ mol	BHPF摩尔分数/ %
PSFF⁃0	0.05	0.050	0	0
PSFF⁃20	0.05	0.040	0.010	20
PSFF⁃30	0.05	0.035	0.015	30
PSFF⁃50	0.05	0.025	0.025	50
PSFF⁃70	0.05	0.015	0.035	70
PSFF⁃80	0.05	0.010	0.040	80
PSFF⁃100	0.05	0	0.050	100

Tab.1. Reaction monomer ratio

Fig.2. Reaction equation

反应溶剂	M_n/kg·mol^-1	M_w/kg·mol^-1	M_w/M_n	T_g/℃
NMP	21.39	38.26	1.789	252
TMS	8.62	13.67	1.586	235

Tab.2. Effect of solvent on Mw， Mn and Tg of the polymer

Fig.3. Mn of the polymer prepared at different reaction time

Fig.4. DSC curves of polymers prepared at different reaction time

Na₂CO₃/K₂CO₃ 摩尔比	M_n/ kg·mol^-1	M_w/ kg·mol^-1	M_w/M_n	T_g/℃
1/0	3.325	4.457	1.340	147
1/5	4.920	6.647	1.351	199
1/10	8.621	13.670	1.586	239
0/1	21.390	38.260	1.789	252

Tab.3. Effect of salt forming agent on Mw， Mn and Tg of the polymer

Fig.5. FTIR spectra of ternary copolymer polysulfone containing BHPF

Fig.6. 1H⁃NMR spectra of the polymer

Fig.7. DSC curves of ternary copolymer polysulfone with different BHPF contents

Fig.8. Relationship between Tg and BHPF content

Fig.9. TG curves of ternary copolymer polysulfone with different BHPF contents

Fig.10. Light transmittance of ternary copolymer polysulfone containing BPHF

References 18

1	Sastri V R. Plastics in medical devices： Properties， requirements， and applications［M］. Amsterdam Boston： William Andrew/Elsevier， 2021： 233⁃239.
2	Jin LeeHye， Sang Hoon Han， Sang Yong Nam. Gas permeation properties of poly（sulfone⁃co⁃ethylene glycol） membranes containing bis（phenyl）fluorene moieties［J］. Journal of Membrane Science， 2015， 485： 10⁃16.
3	Serbanescu O S， Voicu S I， Thakur V K. Polysulfone functionalized membranes： Properties and challenges［J］. Materials Today Chemistry， 2020， 17： 100302.
4	Lisa Marie Schönhoff， Felicitas Mayinger， Marlis Eichberger， et al. 3D printing of dental restorations： Mechanical properties of thermoplastic polymer materials［J］. Journal of the Mechanical Behavior of Biomedical Materials， 2021， 119：104544.
5	Jha G S， Seshadri G， Mohan A， et al. Sulfur containing optical plastics and its ophthalmic lenses applications［J］. E⁃Polymers， 2008， 8（1）：1⁃27.
6	Harris J E. Engineering thermoplastics［M］. Boca Raton： CRC Press， 2020： 177⁃200.
7	高庆平，王军，李占双，等. 双酚芴的合成及应用进展研究［J］. 化工科技， 2005， 14（1）： 58⁃61.
	GAO Q P， WANG J， LI Z S， et al ．Synthesis and application of 9，9⁃bis（4⁃hydroxyphenyl）⁃fluorene［J］. Chemical Engineering， 2005， 14（1）： 58⁃61.
8	杜欣瑶，王玮，林宇，等. 含双酚芴聚碳酸酯的合成与光学性能［J］. 高等学校化学学报， 2021， 42（12）： 3 765⁃3 773.
	DU X Y， WANG W， LIN Y， et al ．Synthesis and optical properties of polycarbonates copolymerized with bisphenol fluorene moiety， Chemical Journal of Chinese Universities， 2021， 42（12）： 3 765⁃3 773.
9	章家立，瞿秉华. 芳香族聚碳酸酯的化学改性研究进展［J］. 中国塑料， 2016， 30（1）：1⁃6.
	ZHANG J L， QU B G. Research progress of chemical modification of aromatic polycarbonate［J］. China Plastics， 2016， 30（1）：1⁃6.
10	丁富传，陈清松，赖寿莲，等. 含芴可交联聚芳醚酮的合成［J］. 中国塑料， 2011， 25（5）：35⁃38.
	DING F C， CHEN Q S， LA S L，et al. Preparation of fluo⁃rene⁃containing cross⁃linkable poly（arylene ether ketone）s［J］. China Plastics， 2011， 25（5）：35⁃38.
11	陈宇宏，杜力鹏，王凯，等．4，4⁃（9⁃芴）二苯酚型聚碳酸酯的合成及其耐高温性能研究［J］．高分子学报，2016 12（9）： 1 273⁃1 280.
	CHEN Y H， DU L P， WANG K，et al ． Studies on synthesis and thermal properties of polycarbonate derived from 9，9⁃bis（4⁃hydroxyphenyl） fluorene［J］. Acta Polymerica Sinica， 2016，12（9）： 1 273⁃1 280.
12	Suresh S， Gulotty Robert J Jr， Stephen E Bales， et al. A novel polycarbonate for high temperature electro⁃optics via azo bisphenol amines accessed by Ullmann coupling［J］. Polymer， 2003， 44（18）： 5 111⁃5 117.
13	卜小蒙.聚醚砜合成工艺的再研究［D］. 淄博：山东理工大学，2013.
14	王道波，高红军，孙学科，等. 成盐剂体系对聚醚砜树脂合成与性能的影响［J］. 工程塑料应用， 2021， 49（3）， 14⁃19.
	WANG D B， GAO H J， SUN X K， et al ．Influences of salt⁃forming agent systems on synthesis and properties of poly（ether sulfone） resin［J］. Engineering Plastics Application， 2021， 49（3）， 14⁃19.
15	Hu Weibin， You Yong， Tong Lifen， et al. Preparation and physical properties of polyarylene ether nitrile and polyarylene ether sulfone random copolymers［J］.High Performance Polymers， 2019， 31（6）： 686⁃693.
16	Hu Linqing， Zhong Jiachun， Tian Yuhan， et al ． Study on properties of barium titanate/polyethersulfone dielectric composites prepared by physical dispersion method［J］. Journal of Polymer Research， 2019， 30（1）： 221⁃229.
17	MengXiang⁃Li， YuGen⁃Hua， Jian Ma. Preparation and properties of poly（aryl ether sulfone ketone） ultrafiltration membrane containing fluorene group for high temperature condensed water treatment［J］. Chinese Journal of Polymer Science， 2018， 36（8）：1⁃9.
18	Witold Brostow， Rachel Chiu， KalogerasIoannis M， et al. Prediction of glass transition temperatures： Binary blends and copolymers［J］.Materials Letters， 2008， 62（17/18）： 3 152⁃3 155.

[1]	YANG Chaoyong, GUO Jinqiang, WANG Fuyu, ZHNAG Yuxia. Research progress in preparation and modification methods of high-performance plastic films [J]. China Plastics, 2022, 36(9): 167-179.
[2]	TANG Xiaoming, CAO Ning, JIANG Yuehang, WANG Qian, WANG Zhiyan, LI Jianhua, WANG Yatao, LIAN Huiqin, WANG Xiaodong, CUI Xiuguo. Research progress in polysulfone for proton⁃exchange membrane fuel cell [J]. China Plastics, 2022, 36(8): 146-158.
[3]	SHA Jin, CHEN Xin, CHEN Dongping, MA Yulu, XIE Linsheng. EHD Induced PVA Film Patterning and Its Applications for Microstructure Fabrication on Glass Substrate Surface [J]. China Plastics, 2021, 35(6): 53-59.
[4]	Baogou WU, Piming MA, Pengwu XU, Yong ZHANG, Ruyin WANG. Research Progress in Toughening and Crystalline Modification of Poly(lactic acid) [J]. China Plastics, 2020, 34(8): 113-120.
[5]	FENG Shen, WEN Liang, SUN Zhaoyang, JI Yang. Properties and Applications of PGA/PBAT Composites [J]. China Plastics, 2020, 34(11): 36-40.
[6]	HOU Lianlong, TANTAI Jianli, JIA Shaowei. Research and Development of Thermal Insulation Plastic Pipelines [J]. China Plastics, 2019, 33(12): 94-100.
[7]	. Preparation of High Rigid and High Heat-resistant Polypropylene by Combination of Sodium Phosphate and Talc [J]. China Plastics, 2018, 32(11): 102-108.
[8]	. Comparison of Properties of Polypropylene Modified by Xylitol Nucleating Agent and Sorbitol Nucleating Agent [J]. China Plastics, 2017, 31(10): 94-98.
[9]	. Study on Properties of Phthalocyanine End-capped Polyimide Film [J]. China Plastics, 2017, 31(05): 22-25 .
[10]	. Study on BMI-modified Structural Acrylic Adhesive [J]. China Plastics, 2017, 31(02): 51-55 .
[11]	. Preparation of Polysulfone Containing Tung Oil Self-healing Microcapsules by Solvent Evaporation Method [J]. China Plastics, 2016, 30(05): 34-40 .
[12]	. Preparation of Dicyclopentadiene Microcapsules Coated with Polysulfone [J]. China Plastics, 2015, 29(09): 27-31 .
[13]	. Influence of Annealing on Crystallization and Heat Resistance Properties of Poly(lactic acid) [J]. China Plastics, 2015, 29(06): 44-48.
[14]	. Study of Oil/Heat Resistance Mechanism of Rubber-plastic Blends from SEM and XPS Analyses [J]. China Plastics, 2014, 28(11): 20-24 .
[15]	. Research of Liquid Crystal Compounds Thoughening Heat Resistance Epoxy Resin [J]. China Plastics, 2014, 28(10): 24-28 .