Flame Retardancy of Polycarbonate/Short Carbon Fiber/Potassium 3‑（Phenylsulfonyl）benzenesulfonate Composites

doi:10.19894/j.issn.1000-0518.230274

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (12): 1662-1671.DOI: 10.19894/j.issn.1000-0518.230274

• Full Papers • Previous Articles Next Articles

Flame Retardancy of Polycarbonate/Short Carbon Fiber/Potassium 3‑（Phenylsulfonyl）benzenesulfonate Composites

Qian-Yu LI¹^,², Jie LIU¹(), Tao TANG¹^,²()

^1.State Key Laboratory of Polymer Physics and Chemistry，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.University of Science and Technology of China，Hefei 230026，China

Received:2023-09-11 Accepted:2023-11-18 Published:2023-12-01 Online:2024-01-03
Contact: Jie LIU,Tao TANG
About author:liujie@ciac.ac.cn
ttang@ciac.ac.cn；
Supported by:
the National Natural Science Foundation of China(51991353);Science and Technology Development Plan Project of Jilin Province(20220201127GX)

Abstract

Abstract:

Polycarbonate/short carbon fiber/potassium 3-（phenylsulfonyl）benzenesulfonate （PC/sCF/KSS） composites are prepared by melt blending. The effects of sCF and KSS on the flame retardancy of PC are studied by vertical combustion （UL-94）， limiting oxygen index （LOI） and cone calorimetry. The results show that when 2% （mass percent） sCF and 0.1% （mass percent） KSS are added， the LOI of PC/2sCF/0.1KSS composites is significantly higher than that of pure PC （27.2%）， reaching 36.2%. The grade of UL-94 is V-0. SCF and KSS show synergistic effect in reducing heat release and smoke release of PC. Compared with pure PC， the peak heat release rate （pHRR） of PC/2sCF/0.1KSS composites decreases by 59%， the peak smoke release rate （pSPR） decreases by 57%， and the peak CO release rate （pCOP） decreases by 63%， all of which are better than adding sCF or KSS alone. The flame retardant mechanism of the composites is studied， and it is found that the addition of sCF and KSS plays an excellent flame retardant effect of condensed phase in PC composites. In addition， the impact strength， tensile strength and elongation at break of PC/2sCF/0.1KSS composites change little compared with pure PC， and the mechanical properties are maintained.

Key words: Polycarbonate, Short carbon fiber, Sulfonate flame retardant, Flame retardancy

CLC Number:

O631

Qian-Yu LI, Jie LIU, Tao TANG. Flame Retardancy of Polycarbonate/Short Carbon Fiber/Potassium 3‑（Phenylsulfonyl）benzenesulfonate Composites[J]. Chinese Journal of Applied Chemistry, 2023, 40(12): 1662-1671.

Figures/Tables 11

Table 1 Formulations of PC and its composites

Samples	w（PC）/%	w（sCF）/%	w（KSS）/%
PC	100	0	0
PC/0.1KSS	99.9	0	0.1
PC/2sCF	98	2	0
PC/2sCF/0.1KSS	97.9	2	0.1

Fig.1 TG （A）， DTG （B） and DSC （C） curves of PC， PC/0.1KSS， PC/2sCF and PC/2sCF/0.1KSS composites in N2 atmosphere

Table 2 Thermal stability data of PC and PC composites in N2 atmosphere

Samples	T_1%/℃	T_5%/℃	T_max/℃	w（residue）/% at 700 ℃
PC	430	471	518	21.3
PC/0.1KSS	411	454	489	17.6
PC/2sCF	432	475	514	23.7
PC/2sCF/0.1KSS	412	453	488	20.8

Table 3 LOI and UL?94 data of PC and PC composites

Samples	LOI/%	UL?94
Samples	LOI/%	t₁/s	t₂/s	Dripping	Rating
PC	27.2	6.8±2.1	22.3±3.5	Y	V?2
PC/0.1KSS	34.6	3.3±1.3	3.1±2.1	Y	V?2
PC/2sCF	29.5	2.2±0.2	5.1±1.9	Y	V?2
PC/2sCF/0.1KSS	36.2	1.8±0.6	2.5±1.2	N	V?0

Fig.2 （A） HRR，（B） THR，（C） SPR，（D） TSP，（E） COP and （F） CO2P curves of PC and PC composites

Table 4 Cone calorimeter test data of PC and PC composites

Samples	PC	PC/0.1KSS	PC/2sCF	PC/2sCF/0.1KSS
TTI/s	126	93	127	92
pHRR/（kW·m^-2）	562	483	462	230
THR/（MJ·m^-2）	67.4	66.0	70.4	70.8
pSPR/（m²·s^-1）	0.23	0.15	0.17	0.10
TSP/m²	20.2	20.3	17.1	17.8
pCOP/（g·s^-1）	0.030	0.027	0.025	0.011
pCO₂P/（g·s^-1）	0.384	0.358	0.330	0.169
FPI	0.224	0.193	0.275	0.400
Char yield/%	19.1	10.1	18.4	19.3

Fig.3 Digital and SEM photos of carbon residue after CCT of （A） PC，（B） PC/0.1KSS，（C） PC/2sCF and （D） PC/2sCF/0.1KSS

Fig.4 Complex viscosity curves of PC， PC/0.1KSS， PC/2sCF and PC/2sCF/0.1KSS

Fig.5 （A） GC spectra of pyrolysis products of PC and PC composites measured by Py-GC/MS at 550 ℃；（B） Composition of main degradation products of PC and PC composites

Fig.6 （A） Impact strength and （B） tensile stress-strain of PC and PC composites

Fig.7 SEM photographs of quenched sections of PC and PC composites

References 20

1	ALAEE M， ARIAS P， SJODIN A， et al. An overview of commercially used brominated flame retardants， their applications， their use patterns in different countries/regions and possible modes of release［J］. Environ Int， 2003， 29（6）： 683-689.
2	高振昊，任向征，苗志伟. 磷系阻燃剂阻燃聚碳酸酯研究进展［J］. 化学通报， 2021， 84（11）： 1190-1199.
	GAO Z H， REN X Z， MIAO Z W. Research advances of phosphorus flame retardants in flame retardant polycarbonate［J］. Chemistry， 2021， 84（11）： 1190-1199.
3	高烽，韦平，李林科，等. 硅系阻燃剂阻燃PC及PC/ABS复合材料研究进展［J］. 工程塑料应用， 2013， 41（5）： 103-106.
	GAO F， WEI P， LI L K， et al. Research progress of silicone-containing flame retardant in PC and PC/ABS composites［J］. Eng Plast Appl， 2013， 41（5）： 103-106.
4	刘丹丹，郭庆时. 透明聚碳酸酯用阻燃剂的研究与应用进展［J］. 工程塑料应用， 2008， 36（9）： 82-84.
	LIU D D， GUO Q S. Progress in research and application of flame retardant for transparent polycarbonate［J］. Eng Plast Appl， 2008， 36（9）： 82-84.
5	GUO J W， WANG Y Q， FENG L J， et al. Performance of a novel sulfonate flame retardant based on adamantane for polycarbonate［J］. Polymer （Korea）， 2013， 37（4）： 437-441.
6	ZHANG X Y， ZHANG D L， ZHANG W C， et al. Flame retardant polycarbonate with ultralow loading 1，3-benzenedisulfonate［J］. Polym Degrad Stab， 2023， 214： 110389.
7	LEVCHIK S V， WEIL E D. Overview of recent developments in the flame retardancy of polycarbonates［J］. Polym Int， 2005， 54（7）： 981-998.
8	CHEN Z X， ZHAO Z Y， LU P， et al. Novel macromolecular flame retardant derived from sulfonated naphthalene monomer for simultaneous fire safety and high performance of polycarbonate［J］. Polym Degrad Stab， 2023， 214： 110388.
9	LU X D， YAO Q， CAO W H， et al. An extremely efficient silylated benzensulfonate flame retardant for polycarbonate［J］. Materials， 2020， 13（16）： 3550.
10	ZHU D Y， GUO J W， XIAN J X， et al. Novel sulfonate-containing halogen-free flame-retardants： effect of ternary and quaternary sulfonates centered on adamantane on the properties of polycarbonate composites［J］. RSC Adv， 2017， 7（62）： 39270-39278.
11	LEVCHIK S V， WEIL E D. Flame retardants in commercial use or in advanced development in polycarbonates and polycarbonate blends［J］. J Fire Sci， 2006， 24（2）： 137-151.
12	KAUSAR A， ANWAR Z， MUHAMMAD B. Overview of nonflammability characteristics of graphene and graphene oxide-based polymeric composite and essential flame retardancy techniques［J］. Polym Plast Technol Eng， 2017， 56（5）： 408-505.
13	WANG D S， WEN X， CHEN X C， et al. A novel stiffener skeleton strategy in catalytic carbonization system with enhanced carbon layer structure and improved fire retardancy［J］. Compos Sci Technol， 2018， 164： 82-91.
14	WANG X， KALALI E N， WAN J T， et al. Carbon-family materials for flame retardant polymeric materials［J］. Prog Polym Sci， 2017， 69： 22-46.
15	YU R， LIU J， GAO D， et al. Striking effect of nanosized carbon black modified by grafting sodium sulfonate on improving the flame retardancy of polycarbonate［J］. Compos Commun， 2020， 20： 100359.
16	KUMAZAWA S. Review of carbon fiber reinforced composite materials［J］. J Soc Mater Sci Jpn， 1972， 21（229）： 893.
17	GONG J， NIU R， WEN X， et al. Synergistic effect of carbon fibers and carbon nanotubes on improving thermal stability and flame retardancy of polypropylene： a combination of a physical network and chemical crosslinking［J］. RSC Adv， 2015， 5（8）： 5484-5493.
18	张旭东，蒋俊奎，马悦，等. 3-苯磺酰基苯磺酸钾与三苯基氧化膦复配阻燃聚碳酸酯的研究［J］. 中国塑料， 2018， 46（2）： 54-57， 116.
	ZHANG X D， JIANG J K， MA Y， et al. Study of potassium 3-（phenylsulfonyl） benzenesulfonate and triphenylphosphine oxide on the flame retardancy of polycarbonate［J］. China Plast， 2018， 46（2）： 54-57， 116.
19	王江波，辛忠，宋文婷. 二苯砜磺酸钾阻燃PC的热降解行为及老化寿命估算［J］. 工程塑料应用， 2009， 37（2）： 60-64.
	WANG J B， XIN Z， SONG W T. Thermal degradation behaviors and lifetime of polycarbonate flame-retardanted by potassium diphenyl sulfonate［J］. Eng Plast Appl， 2009， 37（2）： 60-64.
20	CHEN W H， LIU P J， CHENG Y B， et al. Flame retardancy mechanisms of melamine cyanurate in combination with aluminum diethylphosphinate in epoxy resin［J］. J Appl Polym Sci， 2019， 136（12）： 47223.

[1]	Jun-Jie SHI, Zhe-Hang SHI, Hong-Zhou LI. Preparation of Magnesium Aluminum-Type Hydrotalcite Compounds Intercalated with Phosphorus Flame Retardants and Their Flame Retardant Application in Thermoplastic Polyurethane [J]. Chinese Journal of Applied Chemistry, 2023, 40(9): 1288-1301.
[2]	Peng-Hui FAN, Jie LIU, Sheng-Hui LOU, Tao TANG. Research Progress on Synergists of Phosphorous Flame Retardants in Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2023, 40(5): 653-665.
[3]	Yuan LIN, Jia-Lian CHEN, Hong-Zhou LI. Flame Retardant Properties of Tannic Acid/Poly（Vinyl Alcohol） [J]. Chinese Journal of Applied Chemistry, 2023, 40(1): 69-78.
[4]	Bing-Bing LENG, Chun-Hui ZHU, Cheng-Ying SHI, Zhi-Peng WANG, Yang LIU, Hong-Yan ZHANG, Wen-Ge XU, Bai-Jun LIU. Preparation and Flame Retardancy of the Irradiation‑crosslinked PE‑based Composites Containing a Cyclophosphazene Derivative [J]. Chinese Journal of Applied Chemistry, 2022, 39(11): 1672-1679.
[5]	LU Xin-Yu, MA Bin-Ze, LUO Hao, QI Huan, LI Qiang, WU Guang-Peng. Optimization of Development Process for Carbon Dioxide-Based Poly(cyclohexene carbonate) Electron Beam Resist [J]. Chinese Journal of Applied Chemistry, 2021, 38(9): 0-0.
[6]	LU Xin-Yu, MA Bin-Ze, LUO Hao, QI Huan, LI Qiang, WU Guang-Peng. Optimization of Development Process for Carbon Dioxide-Based Poly(cyclohexene carbonate) Electron Beam Resist [J]. Chinese Journal of Applied Chemistry, 2021, 38(9): 1189-1198.
[7]	LIU Yide, CHEN Jialian, LI Hongzhou, YANG Songwei, LUO Fubin, CHEN Qinghua. Flame Retardant Properties of Synergistic Flame Retardant Polypropylene [J]. Chinese Journal of Applied Chemistry, 2019, 36(10): 1165-1171.
[8]	WANG Dongsheng,WEN Xin,LI Yunhui,TANG Tao. Silica Grafted 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and Its Effect on Flame Retardancy and Transparency of Polymethyl Methacrylate Nanocomposites [J]. Chinese Journal of Applied Chemistry, 2018, 35(12): 1427-1433.
[9]	ZHANG Lili, DING Huimin, ZHANG Jitang, XU Donghua, LI Zhifeng. Thermal Conductivity and Flame Retardancy of Carbon Nanotube Modified Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2017, 34(1): 46-53.
[10]	KUANG Miao, LIANG Xianhao, LIU Jianjun, RONG Jianhua. Synergistic Flame Retardancy of Aluminum Hypophosphite and Zinc Borate in Polyethylene [J]. Chinese Journal of Applied Chemistry, 2016, 33(10): 1147-1153.
[11]	JIN Ying, SU Zhao-Hui*. Water Diffusion in Polycarbonate Film Studied by 2D FTIR Spectroscopy [J]. Chinese Journal of Applied Chemistry, 2011, 28(01): 16-21.
[12]	Ye Xiaoguang, Huang Yuhui, Cong Guangmin. Structure and Properties of SBR/PPC Elastomer [J]. Chinese Journal of Applied Chemistry, 1998, 0(5): 74-76.
[13]	Wang Xiaomei, Yang Ping, Cai Qinghua, Bao Meng. Solid Liquid Phase Transfer Catalytic Synthesis of Alkyl Phosphoric Dialkyl Ester andTheir Flame Retardancy [J]. Chinese Journal of Applied Chemistry, 1997, 0(3): 96-98.
[14]	Huang Kelong, Pan Chunyue, Tan Yougan, Liu Jian'an. Synthesis and Flame Retardancy for Polyvinyl Chloride of Organoantimony Compounds [J]. Chinese Journal of Applied Chemistry, 1995, 0(5): 76-78.
[15]	Jiang Zhenhua, Ma Rongtang, Kou Xichun, An Lijia. Mechanical Properties of Polyethersulfone/Polycarbonate Blends [J]. Chinese Journal of Applied Chemistry, 1995, 0(2): 115-116.

Flame Retardancy of Polycarbonate/Short Carbon Fiber/Potassium 3‑（Phenylsulfonyl）benzenesulfonate Composites

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 20

Related Articles 15

Recommended Articles

Metrics

Comments