Synthesis of polyborosiloxane flame retardant and its application to polycarbonate

doi:10.3969/j.issn.0438-1157.2012.10.051

CIESC Journal ›› 2012, Vol. 63 ›› Issue (10): 3365-3371.DOI: 10.3969/j.issn.0438-1157.2012.10.051

Synthesis of polyborosiloxane flame retardant and its application to polycarbonate

ZHOU Wenjun, SONG Jian, CHEN Youcai, WANG Xueqin, ZHANG Jingli

College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, Zhejiang, China

Received:2011-10-28 Revised:2012-06-18 Online:2012-10-05 Published:2012-10-05
Supported by:
supported by the Commonweal Technology Research Project of Zhejiang Province(2011C31047).

聚硼硅氧烷阻燃剂的合成工艺及其在聚碳酸酯中的应用

周文君, 宋健, 陈友财, 王雪芹, 张敬礼

杭州师范大学材料与化学化工学院, 浙江杭州 310036

通讯作者: 周文君
作者简介:周文君(1966- ),女,博士,副教授。
基金资助:
浙江省公益技术应用研究项目(2011C31047)。

Abstract

Abstract: Polyborosiloxane(PB)was synthesized through two-step reaction by using alkoxysilanes and boric acid as raw materials and synthesis optimization was studied through adjusting boric acid /silane molar ratio,condensation temperature and hydrolysis time.The effect of PB on flame retardancy and physical properties of polycarbonate(PC)was investigated.The results showed that strict control of boric acid/silane molar ratio and condensation temperature was the key to preparation of high efficiency flame retardant PB.When boric acid /silane molar ratio was 1:1,and condensation temperature was 100℃,PB had the best flame retardancy on PC.After adding 5%(mass)of PB,LOI of PC could increase from 26% to 39.4%.Addition of PB could decrease thermal degradation onset temperature of PC.However PB decreased mass loss rate of PC and increased degradation residue of PC at 800℃.PB could promote the formation of char residue which could serve as a good insulating barrier to reduce the radiant heat of flame and lower decomposition rate of PC.Addition of PB increased tensile strength and flexural strength of PC,but decreased impact strength of PC.In addition,PB had little effect on optical properties of PC,and the PC/PB composites were still transparent.

Key words: polyborosiloxane, polycarbonate, flame retardancy property, physical property

摘要： 采用二步合成法制备了聚硼硅氧烷阻燃剂(PB),通过改变硼酸/硅烷比、缩合温度、水解时间优化了PB的合成工艺。同时研究了PB对聚碳酸酯(PC)阻燃性能和物理性能的影响。结果表明:严格控制硼酸/硅烷比和缩合温度是制备高效阻燃PB的关键,当硼酸/硅烷比(摩尔比)为1:1、缩合温度为100℃时所制备的PB的阻燃性能最好,在PC中添加5%(质量分数)该PB阻燃剂,PC的极限氧指数(LOI)从26%提高到39.4%。在热降解过程中,PB使PC的起始降解温度降低,但可使PC的热降解速率降低,高温残炭量增加,从而提高了PC的阻燃性能。添加PB可以基本保持PC优良的力学性能。另外,PB可保持PC原有的透明性,PC/PB阻燃材料仍旧呈透明状态。

关键词: 聚硼硅氧烷, 聚碳酸酯, 阻燃性能, 物理性能

CLC Number:

TQ322.4

ZHOU Wenjun, SONG Jian, CHEN Youcai, WANG Xueqin, ZHANG Jingli. Synthesis of polyborosiloxane flame retardant and its application to polycarbonate[J]. CIESC Journal, 2012, 63(10): 3365-3371.

周文君, 宋健, 陈友财, 王雪芹, 张敬礼. 聚硼硅氧烷阻燃剂的合成工艺及其在聚碳酸酯中的应用[J]. 化工学报, 2012, 63(10): 3365-3371.

References 19

[1]	Hu Z,Chen L,Zhao B,Luo Y,Wang D Y,Wang Y Z.A novel efficient halogen-free flame retardant system for polycarbonate[J].Polym.Degrad.Stab.,2011, 96:320-327
[2]	Fang Yuyuan(方宇媛),Jin Hongmao(金红茂),Pan Zhiyan(潘志彦),Zou Xia(邹霞),Lin Chunmian(林春绵).Catalytic depolymerization of polycarbonate in sub-critical ethanol[J].CIESC Journal(化工学报),2009,60(2):372-377
[3]	Levchik S,Weil E.Overview of recent developments in the flame retardancy of polycarbonates[J].Polym.Int.,2005,54 (7):981-998
[4]	Bozi J,Czégény Z,Mészáros E.Thermal decomposition of flame retarded polycarbonates[J].J. Anal.Appl.Pyrolysis,2007,79(1/2):337-345
[5]	Hamdani S,Longuet C,Perrin D.Flame retardancy of silicone-based materials[J].Polym.Degrad.Stab.,2009,94 (4):465-495
[6]	Pawlowski K H,Schartel B,Fichera M A,Jger C.Flame retardancy mechanisms of bisphenol A bis(diphenyl phosphate)in combination with zinc borate in bisphenol A polycarbonate/acrylonitrile-butadiene-styrene blends[J].Thermochim.Acta,2010,498 (1/2):92-99
[7]	Iji M,Serizawa S.Silicone derivatives as new flame retardants for aromatic thermoplastics used in electronic devices[J].Polym.Adv.Technol.,1998,9:593-600
[8]	Nazare S,Kandola B,Horrocks A.Flame-retardant unsaturated polyester resin incorporating nanoclays paper presented as part of a special issue on nanocomposites and flame retardancy[J].Polym.Adv.Technol.,2006,17(4):294-303
[9]	Zhou W,Yang H.Flame retarding mechanism of polycarbonate containing methylphenyl-silicone[J].Thermochim.Acta,2007,452(1):43-48
[10]	Zhou W,Yang H,Zhou J.The thermal degradation of bisphenol:a polycarbonate containing methylphenyl-silicone additive[J].J.Anal.Appl.Pyrolysis,2007,78(2):413-418
[11]	Yajima S,Hayashi J,Okamura K.Pyrolysis of a polyborodiphenylsiloxane[J].Nature,1977,266:521-522
[12]	Pola J,Herlin N,Brus J,Bastl Z.IR laser production of nanostructured polyborocarbosiloxane powders with Si—O—B bonds[J].Solid State Sci.,2005,7:123-131
[13]	Huo Y,Fan Q,Dembsey N A,Patra P K.Improvements on flame retardant properties of PET/montmorillonite nanocomposite caused by polyborosiloxane[J].Mater.Res.Soc.Symp.Proc.,2007,1007(12):33
[14]	Devapal D,Packirisamy S,Sreejith K J,Ravindran P V,George B K.Synthesis,characterization and ceramic conversion studies of borosiloxane oligomers from phenyltrialkoxysilanes[J].J.Inorg.Organomet.Polym.,2010,20:666-674
[15]	Chrusciel J J,Janowska G,Fejdys M.Thermal properties of polymethylvinylborosiloxanes[J].J.Therm.Anal.Calorim.,2012,109:1049-1058
[16]	Lesniak E,Michalska Z M,Chojnowski J.One-step synthesis of thermoplastic phenylsilsesquioxane polymer and its copolymers with diphenylsiloxanes[J].J.Inorg.Organomet.Polym.,1998,8:1-21
[17]	Tiptipakorn S,Damrongsakkul S,Ando S,Hemvichian K,Rimdusit S.Thermal degradation behaviors of polybenzoxazine and silicon-containing polyimide blends[J].Polym.Degrad.Stab.,2007,92:1265-1278
[18]	Zhao Chunxia(赵春霞),Liu Bailing(刘白玲),Peng Gang(彭钢),Luo Rong(罗荣).Synthesis and properties of flame retardant vinyl acetate copolymer emulsion[J].Journal of Graduate University of Chinese Academy of Sciences(中国科学院研究生院学报),2011,28(5):591-596
[19]	Juhász A,Tasnádi P,Fábry L.Impact studies on the mechanical properties of polyborosiloxane[J].Physics Education,1984,19(6):302-304

Synthesis of polyborosiloxane flame retardant and its application to polycarbonate

聚硼硅氧烷阻燃剂的合成工艺及其在聚碳酸酯中的应用

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

References 19

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jialin DAI, Weidong BI, Yumei YONG, Wenqiang CHEN, Hanyang MO, Bing SUN, Chao YANG. Effect of thermophysical properties on the heat transfer characteristics of solid-liquid phase change for composite PCMs [J]. CIESC Journal, 2023, 74(5): 1914-1927.
[2]	Yating ZHANG,Wenjie XIONG,Tianxiang ZHAO,Chenfei YAO,Yucheng DING,Xiaomin ZHANG,Youting WU,Xingbang HU. High capacity absorption of SO₂ using imidazole ionic liquid mixtures [J]. CIESC Journal, 2020, 71(11): 5035-5042.
[3]	Cong ZHANG, Jinbo JIANG, Xudong PENG, Wenjing ZHAO, Jiyun LI. Comparison and correction of CO₂ properties model in critical region [J]. CIESC Journal, 2019, 70(8): 3058-3070.
[4]	CHEN Ying, WANG Jianying, LIU Chao, JIANG Haichao, LIU Yumin, HU Yongqi. Sulfur dioxide absorption by PEG-based functionalized ionic liquids [J]. CIESC Journal, 2015, 66(S1): 332-337.
[5]	JIANG Jing, WANG Xiaofeng, HOU Jianhua, LI Qian, XU Yiyang. Tensile properties of ICM polycarbonate part under low temperature [J]. CIESC Journal, 2015, 66(10): 4268-4274.
[6]	CHENG Huanong, LIU Qunshan, WANG Bingqiang, ZHENG Shiqing, FU Zhenbo. Fluid dynamics simulation and pilot test for polycarbonate liquid-liquid separator [J]. CIESC Journal, 2013, 64(6): 2109-2116.
[7]	QIN Gang1，3，FAN Lidan2，CAO Shaokui3，BU Zhanwei3，CHEN Tao1，YI Kui1. Research progress of catalysts for copolymerization of CO2 and epoxides [J]. Chemical Industry and Engineering Progree, 2013, 32(02): 327-332.
[8]	LI Dong1，2，AI Qing1，XIA Xinlin1. Double-thickness model of thermal radiation physical property measurement of semi-transparent liquid with transmission method [J]. CIESC Journal, 2012, 63(S1): 123-129.
[9]	SUN Jianzheng，ZHOU Hongyong，LI Yunqing，WANG Xiaomei，WANG Jiaxi. Reaction activity of alkyloxy group in synthesis of polycarbonate [J]. , 2011, 30(9): 2013-.
[10]	ZHANG Yu，DING Xuejia，GUO Tiantian，ZHOU Kebin，HAN Haijun，ZHANG Lijuan. Rheology study on PC/PETG blends [J]. , 2011, 30(12): 2685-.
[11]	FAN Guodong，YANG Rui. Progress in synthesis and ring-opening polymerization of aliphatic cyclic carbonate [J]. , 2010, 29(10): 1917-.
[12]	ZHAO Hemeng，TIAN Hengshui. Synthesis of polycarbonate through melt transesterification process catalyzed with organic amine [J]. , 2010, 29(1): 67-.
[13]	CHEN Jingyu, ZHANG Lei, CHEN Jinchun, CHEN Guoqiang. Biosynthesis and characterization of polyhydroxyalkanoate copolyesters in Ralstonia eutropha PHB^－4 harboring a low-substrate-specificity PHA synthase PhaC2_Ps from Pseudomonas stutzeri 1317 [J]. , 2007, 15(3): 391-396.
[14]	ZHOU Wenjun；YANG Hui；FANG Chenpeng. Thermal degradation of polycarbonate [J]. , 2007, 26(1): 23-.
[15]	QIN ,Jichen, XIE ,Xiaoli, CAO ,Xianwu, QU ,Jinping. Reactive flash simulation of the continuous melt transesterification process of polycarbonate [J]. , 2007, 15(1): 51-62.