高效膨胀阻燃聚丙烯材料的制备与性能研究
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摘要
聚丙烯(PP)是一种通用型热塑性树脂,因其具有优良的综合性能而被人们广泛应用在生产生活的各个方面。但是聚丙烯属于易燃材料,这极大的限制了它的进一步应用。膨胀阻燃剂(IFR)具有低烟,无毒,无腐蚀性气体,可重复使用等优点。因此,新的膨胀阻燃体系不断被开发出来,用于聚丙烯的阻燃,成为目前聚丙烯阻燃剂研究与应用的热点。
本文使用本实验室设计合成的一种三嗪系高分子成炭发泡剂(CFA),与聚磷酸铵(APP)及其他助剂复配成膨胀阻燃剂,用于聚丙烯的阻燃,研究了影响PP-IFR材料阻燃性能的各种因素:APP与CFA的比例、协效剂如分子筛、稀土氧化物等的种类与用量、抗滴落剂的用量等。发现APP/CFA在4/1时效果最佳。4A、5A和H-Beta分子筛,各种稀土氧化物,二氧化硅,二氧化钛等物质都具有较好协效能力。这些物质都能够使20%IFR添加量的阻燃聚丙烯由垂直燃烧无级别提高到V0级。氧指数提高到33～35。且最佳含量都为IFR质量的5%。抗滴落剂在0.1%添加量下就能够解决大熔流指数聚丙烯阻燃材料燃烧时的熔滴现象,使材料由较低的阻燃级别提高到垂直燃烧V0级。
利用TGA、CONE、SEM等仪器对PP-IFR的热降解行为、燃烧行为、炭层形貌等进行了全面的评价和研究,结果显示对聚丙烯进行膨胀阻燃处理能够大幅度降低材料在火灾中的危险性。协效剂的加入能够进一步降低材料的热和烟的释放速率及总量,其中对烟释放速率及释放总量的降低效果更为明显。研究还发现协效剂能够催化促进体系分解,提高PP-IFR体系最终的成炭量,并有助于形成更加稳定,致密的炭阻挡层,提高炭层强度,防止炭层破裂,从而达到更高的阻燃性能。
本文还将IFR用于阻燃不同型号的聚丙烯,对其性能进行了研究,发现IFR对多种型号聚丙烯都具有优异的阻燃效果,通常在20%阻燃剂添加量下就能够使1.6mm样条达到垂直燃烧UL-94 V0级,个别型号(K9020)在18%阻燃剂添加量条件下就能够通过V0级。不同PP阻燃材料的氧指数在20%阻燃剂添加量时都能够高于30%,在26%阻燃剂添加量时都能够高于35%。但是IFR的加入对聚丙烯的力学性能有一定的影响,尤其对共聚聚丙烯的冲击强度影响较大。
Polypropylene(PP) is a sort of commodity thermoplastic resins, It is widely used in every respect of people's life and production because it has fine general performance, but the further application is restricted for its flammability. The intumescent flame retardant (IFR) have some advantages, such as lower smoke, no toxic, no corrosive gases and so on. So the new IFR systems have been worked out continuously and used as the flame retardant in polypropylene. The research and application of IFR systems have been paid a great attention.
In this paper, a new IFR system mainly consisted of a triazine polymer which was design and synthesis in our laboratory, named as a charing-foaming agent (CFA), ammonium polyphosphate (APP) and other additive. Some important factors affecting the flame retardancy were studied, such as the ratio of APP to CFA, type and amount of the synergistic agents such as zeolites, rare earth oxides, the amount of anti-dripping agent and so on. The experimental results demonstrated that the flame retardancy was the best when the weight ratio of APP/CFA is 4/1, and 4A, 5A, H-Beta zeolites, the rare earth oxides, SiO_2, TiO_2 etc all have good synergistic effects, those substance all could enhance the LOI value to 33～35 and help the UL-94 rating test (1.6mm) from no rating to V0 rating at the IFR loading of 20wt%, and those substance all have a optimal content is 5% in IFR. The anti-dripping agent could resolve the flaming dripping phenomenon of the flame ratardant PP materials which have big Melt Flow Rate, and help the UL-94 rating test (1.6mm) from low rating to V0 rating.
TGA, CONE and SEM were used to evaluate the thermal degradation, combustion and the morphological structures of the burnt char layer of PP-IFR materials respectively. The results show that the flame retardant PP have extraordinary lower fatalness in the fire compared with pure PP resin. The synergists could efficiently reduce the heat and smoke release rate and total amount, especially for the smoke production rate and total smoke production. The research also found that the synergists could accelerate the degradation of the systems, enhance the char formation in high temperature to form stabile, compact char layer, and prevent the char layer from cracking, thereby a better flame retardancy is obtained.
In this paper, we also studied the flame retardancy and properties of different type of PP-IFR materials. It was found that the IFR are quite effective in many types of PP resins. The IFR-PP materials with 20wt% IFR could pass the UL-94 rating test (1.6mm), some of types (K9020)could pass the test at 18wt% content of IFR in PP. The LOI value of all type of PP flame retardant PP-IFR materials could be higher than 30 at 20wt% IFR loading, and 35 at 26wt% IFR. However, there have some influence on the mechanical property of the PP-IFR materials, especially for the Izod Impact Strength of polypropylene(copolymer).
本文使用本实验室设计合成的一种三嗪系高分子成炭发泡剂(CFA),与聚磷酸铵(APP)及其他助剂复配成膨胀阻燃剂,用于聚丙烯的阻燃,研究了影响PP-IFR材料阻燃性能的各种因素:APP与CFA的比例、协效剂如分子筛、稀土氧化物等的种类与用量、抗滴落剂的用量等。发现APP/CFA在4/1时效果最佳。4A、5A和H-Beta分子筛,各种稀土氧化物,二氧化硅,二氧化钛等物质都具有较好协效能力。这些物质都能够使20%IFR添加量的阻燃聚丙烯由垂直燃烧无级别提高到V0级。氧指数提高到33～35。且最佳含量都为IFR质量的5%。抗滴落剂在0.1%添加量下就能够解决大熔流指数聚丙烯阻燃材料燃烧时的熔滴现象,使材料由较低的阻燃级别提高到垂直燃烧V0级。
利用TGA、CONE、SEM等仪器对PP-IFR的热降解行为、燃烧行为、炭层形貌等进行了全面的评价和研究,结果显示对聚丙烯进行膨胀阻燃处理能够大幅度降低材料在火灾中的危险性。协效剂的加入能够进一步降低材料的热和烟的释放速率及总量,其中对烟释放速率及释放总量的降低效果更为明显。研究还发现协效剂能够催化促进体系分解,提高PP-IFR体系最终的成炭量,并有助于形成更加稳定,致密的炭阻挡层,提高炭层强度,防止炭层破裂,从而达到更高的阻燃性能。
本文还将IFR用于阻燃不同型号的聚丙烯,对其性能进行了研究,发现IFR对多种型号聚丙烯都具有优异的阻燃效果,通常在20%阻燃剂添加量下就能够使1.6mm样条达到垂直燃烧UL-94 V0级,个别型号(K9020)在18%阻燃剂添加量条件下就能够通过V0级。不同PP阻燃材料的氧指数在20%阻燃剂添加量时都能够高于30%,在26%阻燃剂添加量时都能够高于35%。但是IFR的加入对聚丙烯的力学性能有一定的影响,尤其对共聚聚丙烯的冲击强度影响较大。
Polypropylene(PP) is a sort of commodity thermoplastic resins, It is widely used in every respect of people's life and production because it has fine general performance, but the further application is restricted for its flammability. The intumescent flame retardant (IFR) have some advantages, such as lower smoke, no toxic, no corrosive gases and so on. So the new IFR systems have been worked out continuously and used as the flame retardant in polypropylene. The research and application of IFR systems have been paid a great attention.
In this paper, a new IFR system mainly consisted of a triazine polymer which was design and synthesis in our laboratory, named as a charing-foaming agent (CFA), ammonium polyphosphate (APP) and other additive. Some important factors affecting the flame retardancy were studied, such as the ratio of APP to CFA, type and amount of the synergistic agents such as zeolites, rare earth oxides, the amount of anti-dripping agent and so on. The experimental results demonstrated that the flame retardancy was the best when the weight ratio of APP/CFA is 4/1, and 4A, 5A, H-Beta zeolites, the rare earth oxides, SiO_2, TiO_2 etc all have good synergistic effects, those substance all could enhance the LOI value to 33～35 and help the UL-94 rating test (1.6mm) from no rating to V0 rating at the IFR loading of 20wt%, and those substance all have a optimal content is 5% in IFR. The anti-dripping agent could resolve the flaming dripping phenomenon of the flame ratardant PP materials which have big Melt Flow Rate, and help the UL-94 rating test (1.6mm) from low rating to V0 rating.
TGA, CONE and SEM were used to evaluate the thermal degradation, combustion and the morphological structures of the burnt char layer of PP-IFR materials respectively. The results show that the flame retardant PP have extraordinary lower fatalness in the fire compared with pure PP resin. The synergists could efficiently reduce the heat and smoke release rate and total amount, especially for the smoke production rate and total smoke production. The research also found that the synergists could accelerate the degradation of the systems, enhance the char formation in high temperature to form stabile, compact char layer, and prevent the char layer from cracking, thereby a better flame retardancy is obtained.
In this paper, we also studied the flame retardancy and properties of different type of PP-IFR materials. It was found that the IFR are quite effective in many types of PP resins. The IFR-PP materials with 20wt% IFR could pass the UL-94 rating test (1.6mm), some of types (K9020)could pass the test at 18wt% content of IFR in PP. The LOI value of all type of PP flame retardant PP-IFR materials could be higher than 30 at 20wt% IFR loading, and 35 at 26wt% IFR. However, there have some influence on the mechanical property of the PP-IFR materials, especially for the Izod Impact Strength of polypropylene(copolymer).
引文
[1]钱伯章.国内外聚丙烯生产与市场分析.中国石油和化工经济分析,2006,10:45-49
[2]邸曼,张明.1993～2002年我国电气火灾的统计分析.电气工程应用,2006,1:34-41
[3]陈云国,傅智敏,周巍.1993～2003年特大火灾发生规律、特征及原因分析.安全与环境学报,2006,1:15-21
[4]欧育湘,陈宇,王筱梅.阻燃高分子材料.北京:国防工业出版社,2001,1:12-13,34-35
[5]张军,纪奎江,夏延致.聚合物燃与阻燃技术.北京:化学工业出版社,2005,3:34
[6]李凤岭,聚烯烃的阻燃技术.化工新型材料,1999,5:14
[7]唐伟,王旭,胡燕,赵博.阻燃聚丙烯的研究.阻燃材料与技术,2007,01:10-14
[8]申欣,李伟,王凤英,房国栋,刘建军.环保型阻燃聚丙烯的研制.塑料工业,2006,09:57-59
[9]李向梅,杨荣杰,八溴醚阻燃剂在聚丙烯中析出的研究.中国塑料,2004,9:77-80
[10]陈福花,李荣勋,陈国昌,李超勤,李少香,刘光烨.十溴二苯乙烷阻燃改性聚丙烯的研究.塑料科技,2004,6:30-33
[11]Hornung A,Donner S,Balabanovich A and Seifert H.Polypropylene as a reductive agent for dehalogenation of brominated organic compounds.Journal of Cleaner Production,2005,13:525-530
[12]Zhang Sheng,Richard Horrocks A.A review of flame retardant polypropylene fibres.Progress in Polymer Science,2003,28:1517-1538
[13]Dvir H,Goldraich M,Gottlieb M,Daren S and Lopez Cuesta J.Distribution of a brominated acrylate flame retardant in polypropylene.Polymer Degradation and Stability,2001,74:465-474
[14]Dettmer F T,Wichmann H,J de Boer and Bahadir M.Isolation and identification of tetrabromobisphenol-S-bis-(2,3-dibromopropyl ether) as flame retardant in polypropylene.Chemosphere,1999,39:1523-1532
[15]赵敏,高俊刚,邓奎林,赵兴艺.改性聚丙烯新材料.北京:化学工业出版社,2002,8:586
[16]张化廷.煤矿工程塑料(PE、PP)的阻燃研究.塑料科技,2000,1:24-25
[17]Ess J W,Hornsby P R,Characterisation of distributive mixing in thermoplastics compositions.Polymer Testing,1986,6:205-218
[18]欧育湘.Exollit系列新型无卤低烟低毒阻燃剂.塑料科技,2001,1:1-3
[19]彭治汉.材料阻燃新技术新品种.北京:化学工业出版社,2004,3:164
[20]刘丽君,郭奋,陈建峰.纳米氢氧化铝阻燃剂表面改性及其在聚丙烯中的应用.中国塑料,2004,2:74-77
[21]李学锋,陈绪煌,周密.氢氧化铝阻燃剂在高分子材料中的应用.中国塑料,1999,6:80-85
[22]四季春,郑水林,路迈西.氢氧化铝的表面改性及应用研究.中国粉体技术,2005,2:15-20
[23]耿妍.纳米Al(OH)_3/Mg(OH)_2微胶囊APP阻燃PP复合材料的研究.中国优秀硕士学位论文.南京航空航天大学,2006
[24]王建祺.无卤阻燃聚合物基础与应用.北京:科学出版社,2005.6:50,51
[25]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅰ-Thermal degradation of ammonium polyphosphate-pentaerythritol mixtures.Polymer Degradation and Stability,1984,6:243-252
[26]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅱ-Mechanism of action in polypropylene ammonium polyphosphate pentaerythritol mixtures.Polymer Degradation and Stability,1984,7:25-31
[27]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅴ-Mechanism of formation of gaseous products in the thermal degradation of ammonium polyphosphate.Polymer Degradation and Stability,1985,12:203-211
[28]Camino G,Grassie N,McNeill IC.Influence of the fire retardant,ammonium polyphosphate,on the thermal degradation of poly(methyl methacrylate).Journal of Polymer Science- Polymer Chemistry,1978,16:95-106.
[29]周箭,杨辉,陈日新.分步碱液滴加法合成膨胀型阻燃剂b-MAP.化工进展,2005,6:651-655
[30]朱广军,刘桂涛,汪信,杨绪杰,陆路德.新型阻燃剂CN-329的合成及阻燃性能.南京理工大学学报(自然科学版),2002,1:76-79
[31]Pin Lv,Wang Zhengzhou.Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives,Polymer Degradation and Stability,2005,90:523-534
[32]Balabanovich A I.Thermal decomposition study of intumescent additives:Pentaerythritol phosphate and its blend with melamine phosphate,Thermochimica Acta,2005,435:188-196
[33]Liu Yuan,Wang Qi.Catalytic action of phospho-tungstic acid in the synthesis ofmelamine salts of pentaerythritol phosphate and theirsynergistic effects in flame retarded polypropylene,Polymer Degradation and Stability,2006,91:2513-2519
[34]孙春梅,龚铮.三季戊四醇亚磷酸酯阻燃剂的合成及应用研究.功能高分子学报,2005,6:260-264
[35]李斌,孙才英,张秀成.用CONE/TG研究含淀粉膨胀阻燃聚丙烯体系的阻燃和烟释放.高分子材料科学与工程,2000,9:146-149
[36]李斌,孙才英,张秀成.用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性.高等学校化学学报,1999,1:146-149
[37]李斌,张秀成,孙才英.淀粉对聚乙烯膨胀阻燃体系热降解和阻燃的影响.高分子材料科学与工程,2000,3:155-157
[38]董延茂,鲍治宇.淀粉磷酸酯蜜胺盐膨胀型阻燃剂的合成.材料科学与工艺,2005, 6:258-260
[39]Almeras X,Dabrowski F,Le Bras M,Poutch F,Bourbigot S,Marosi G and Anna P.Using polyamide-6 as charring agent in intumescent polypropylene Formulations Ⅰ.Effect of the compatibilising agent on the fire retardancy performance.Polymer Degradation and Stability,2002,77:305-313
[40]Almeras X,Dabrowski F,Le Bras M,Poutch F,Bourbigot S,Marosi G and Anna.P Using polyamide 6 as charring agent in intumescentpolypropylene formulationsⅡ.Thermal degradation.Polymer Degradation and Stability,2002,77:315-323
[41]Le Bras M,Bourbigot S,F(?)lix E,Pouille F,Siat C and Traisnel M.Characterization of a polyamide-6-based intumescent additive for thermoplastic formulations.Polymer,2000,41:5283-5296
[42]陆晓东,张军,谷慧敏,王长春.成炭性塑料对聚丙烯/膨胀阻燃体燃烧行为及阻燃性的影响.塑料,2006,1:18-22
[43]马志领,刘新玉.热塑性聚氨酯对膨胀型阻燃聚丙烯的增容作用.塑料工业,2005,11:45-47
[44]吴新明,王林江,谢襄漓,张坤.聚丙烯/尼龙-6/蒙脱石新型膨胀型纳米复合阻燃材料的研究.塑料工业,2007,5:23-26
[45]Li Bin,Xu Miaojun.Effect of a novel charring-foaming agent on flame retardancy and thermal degradation of intumescent flame polypropylene.Polymer Degradation and Stability,2006,91:1380-1386
[46]Li Yantao,Li Bin,Dai Jinfeng,Jia He,Gao Suliang.Synergistic effects of lanthanum oxide on a novel intumescent flame retardant polypropylene system.Polymer Degradation and Stability,2008,93:9-16
[47]Hu Xiao Ping,Li Wei Yi,Wang Yu Zhong.Synthesis and Characterization of a Novel Nitrogen-Containing Flame Retardant.Journal of Applied Polymer Science,2004,94:1556-1561
[48]Hu Xiao Ping,Li Ya Lan,Wang Yu Zhong.Synergistic Effect of the Charring Agent on the Thermaland Flame Retardant Properties of Polyethylene.Macromol Mater Eng,2004,289:208-212
[49]许苗军,李斌.新型成炭剂对膨胀阻燃PP体系的阻燃及热降解行为研究.中国阻燃学会年会,2005
[50]刘军,廖凯荣,卢泽俭.三嗪衍生物的分子结构及其对聚丙烯阻燃性能的关系.高分子材料科学与工程,1999,1:73-79
[51]张琳,新型纳米Sb_2O_3阻燃剂和含磷阻燃剂Melabis的制备.中国优秀硕士学位论文.南京理工大学,2003
[52]杨荣杰,王青才,李蕾.聚磷酸铵的制备与表征.北京第二届阻燃技术与阻燃材料研讨会特邀报告文集,2004,113-131
[53]Fukumura.US Patient,5599626,1997
[54]Watanabe,Makoto.US patent,5718875,1998
[55]Cipolli,Roberto.US Patent,5576391,1996
[56]Iwata,Masuo.US Patent,5700575,1997
[57]廖凯荣;卢泽俭;王坚;刘军,多聚磷酸铵的改性及其对聚丙烯的阻燃作用.高分子材料科学与工程,1998,4:87-89
[58]张泽江,梅秀娟,冯良荣,邱发礼.三聚氰胺聚磷酸盐阻燃剂的合成与表征.应用化学,2003,11:1035-1038
[59]曹堃,王开立,姚臻.聚磷酸铵的改性及其对聚丙烯阻燃特性的研究.高分子材料科学与工程,2007,4:135-139
[60]Barfurth.US Patent,6444315,2002
[61]奚强,常亮,邝生鲁.硅偶联剂对聚磷酸铵表面改性的研究.粘接,2005,6:19-20
[62]丁著明.高聚合度聚磷酸铵的改性和应用.塑料助剂,2005,6:31-34
[63]Bourbigot Serge,Le Bras Michel,Delobel Ren(?),Patrice Br(?)ant and Jean-Michel Tremillon.4A zeolite synergistic agent in new flameretardant intumescent formulations of polyethylenic polymers-study of the effect of the constituent monomers.Polymer Degradation and Stability,1996,54:275-287
[64]Bourbigot Serge,Le Bras Michel,Delobel Ren(?) and L(?)on Gengembre.XPS study of an intumescent coating:Ⅱ.Application to the ammonium polyphosphate/pentaerythritol /ethylenic terpolymer fire retardant system with and without synergistic agent.Applied Surface Science,1997,120:15-129
[65]Luciana R M,Estevao.Structure-property relationship in intumescent polymeric formulations containing waste zeolite-based material as a synergistic agent.European Polymer Journal,2004,40:1503-1513
[66]Demir H,Arkis E.Synergistic effect of natural zeolites on flame retardant additives.Polymer Degradation and Stability,2005,89:478-483
[67]Demir H,Balk6se D and(U|¨)lk(u|¨)S.Influence of surface modification of fillers and polymer on flammability and tensile behaviour of polypropylene-composites.Polymer Degradation and Stability,2006,91:1079-1085
[68]高瑜.分子筛在膨胀型阻燃剂(IFR)体系中的应用-IFR-PE的阻燃性能研究.硕士研究生学位论文.北京化工大学,2000
[69]韦平,王建祺.分子筛对聚丙烯膨胀型阻燃体系热降解行为的研究.高分子材料科学与工程,2002,5:124-127
[70]韦平,王建祺.4A分子筛对APP/PER膨胀阻燃剂协同作用的TGA/XPS.高分子材料科学与工程,2003,5:179-181
[71]王岩,曾幸荣.4A分子筛对三聚氰胺磷酸盐/季戊四醇阻燃PP性能的影响.塑料工业,2007,5:62-64
[72]杜建新,郝建薇,王建祺.SiO_2和Al_2O_3对PP/APP/PER膨胀阻燃体系的协同作用.高分子材料科学与工程,2004,1:165-167
[73]徐晓楠,张健.二氧化硅对膨胀型阻燃聚乙烯的性能影响研究.火灾科学,2004,7:168-172
[74]Marosi G,M(?)rton A,Anna P,Bertalan G,Marosf(o|¨)i B and Sz(?)p A.Ceramic precursor in flame retardant systems.Polymer Degradation and Stability,2002,77:259-265
[75]Laoutid F,Ferry L,Leroy E and Lopez Cuesta J M.Intumescent mineral fire retardant systems in ethylene-vinyl acetate copolymer:Effect of silica particles on char cohesion.Polymer Degradation and Stability,2006,91:2140-2145
[76]Lewin M,Endo M.Catalysis of intumescent flame retardance of polypropylene by metal compounds.Polymeric Materials Science and Engineering,2000,83:38-39
[77]刘军辉,张军,王明清,杨荣杰.金属化合物在PP膨胀阻燃体系中的研究.高分子材料科学与工程,2007,5:160-165
[78]雷远霞,杨其,姚鑫,李根林.金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响. 中国塑料,2006,10:83-85
[79]田春明,谢吉星,石建兵,屈红强,徐建中.氧化锌在膨胀阻燃体系中的协效作用.河北大学学报(自然科学版),2004,11:600-604
[80]黄承亚,龚克成,赵彦芝,李红.氧化锌催化膨胀型阻燃剂对PP阻燃及力学性能的影响.塑料工业,2006,12:57-59
[81]Wu Qiang and Qu Baojun.Synergistic effects of silicotungistic acid on intumescent flame-retardant polypropylene.Polymer Degradation and Stability,2001,74:255-261
[82]Liu Yuan and Wang Qi.Catalytic action of phospho-tungstic acid in the synthesis of melamine salts of pentaerythritol phosphate and their synergistic effects in flame retarded polypropylene.Polymer Degradation and Stability,2006,91:2513-2519
[83]Luciana R M,Estev(?)o,Michel Le Bras,Ren(?) Delobel and Regina S V Nascimento.Spent refinery catalyst as a synergistic agent in intumescent formulations:influence of the catalyst's particle size and constituents.Polymer Degradation and Stability,2005,88:444-455
[84]Hassan M A and Shehata A B.The effect of some polymeric metal chelates on the flammability properties of polypropylene.Polymer Degradation and Stability,2004,85:733-740
[85]许苗军.三嗪系阻燃剂的合成及阻燃高聚物性能研究.硕士学位论文.东北林业大学,2005
[2]邸曼,张明.1993～2002年我国电气火灾的统计分析.电气工程应用,2006,1:34-41
[3]陈云国,傅智敏,周巍.1993～2003年特大火灾发生规律、特征及原因分析.安全与环境学报,2006,1:15-21
[4]欧育湘,陈宇,王筱梅.阻燃高分子材料.北京:国防工业出版社,2001,1:12-13,34-35
[5]张军,纪奎江,夏延致.聚合物燃与阻燃技术.北京:化学工业出版社,2005,3:34
[6]李凤岭,聚烯烃的阻燃技术.化工新型材料,1999,5:14
[7]唐伟,王旭,胡燕,赵博.阻燃聚丙烯的研究.阻燃材料与技术,2007,01:10-14
[8]申欣,李伟,王凤英,房国栋,刘建军.环保型阻燃聚丙烯的研制.塑料工业,2006,09:57-59
[9]李向梅,杨荣杰,八溴醚阻燃剂在聚丙烯中析出的研究.中国塑料,2004,9:77-80
[10]陈福花,李荣勋,陈国昌,李超勤,李少香,刘光烨.十溴二苯乙烷阻燃改性聚丙烯的研究.塑料科技,2004,6:30-33
[11]Hornung A,Donner S,Balabanovich A and Seifert H.Polypropylene as a reductive agent for dehalogenation of brominated organic compounds.Journal of Cleaner Production,2005,13:525-530
[12]Zhang Sheng,Richard Horrocks A.A review of flame retardant polypropylene fibres.Progress in Polymer Science,2003,28:1517-1538
[13]Dvir H,Goldraich M,Gottlieb M,Daren S and Lopez Cuesta J.Distribution of a brominated acrylate flame retardant in polypropylene.Polymer Degradation and Stability,2001,74:465-474
[14]Dettmer F T,Wichmann H,J de Boer and Bahadir M.Isolation and identification of tetrabromobisphenol-S-bis-(2,3-dibromopropyl ether) as flame retardant in polypropylene.Chemosphere,1999,39:1523-1532
[15]赵敏,高俊刚,邓奎林,赵兴艺.改性聚丙烯新材料.北京:化学工业出版社,2002,8:586
[16]张化廷.煤矿工程塑料(PE、PP)的阻燃研究.塑料科技,2000,1:24-25
[17]Ess J W,Hornsby P R,Characterisation of distributive mixing in thermoplastics compositions.Polymer Testing,1986,6:205-218
[18]欧育湘.Exollit系列新型无卤低烟低毒阻燃剂.塑料科技,2001,1:1-3
[19]彭治汉.材料阻燃新技术新品种.北京:化学工业出版社,2004,3:164
[20]刘丽君,郭奋,陈建峰.纳米氢氧化铝阻燃剂表面改性及其在聚丙烯中的应用.中国塑料,2004,2:74-77
[21]李学锋,陈绪煌,周密.氢氧化铝阻燃剂在高分子材料中的应用.中国塑料,1999,6:80-85
[22]四季春,郑水林,路迈西.氢氧化铝的表面改性及应用研究.中国粉体技术,2005,2:15-20
[23]耿妍.纳米Al(OH)_3/Mg(OH)_2微胶囊APP阻燃PP复合材料的研究.中国优秀硕士学位论文.南京航空航天大学,2006
[24]王建祺.无卤阻燃聚合物基础与应用.北京:科学出版社,2005.6:50,51
[25]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅰ-Thermal degradation of ammonium polyphosphate-pentaerythritol mixtures.Polymer Degradation and Stability,1984,6:243-252
[26]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅱ-Mechanism of action in polypropylene ammonium polyphosphate pentaerythritol mixtures.Polymer Degradation and Stability,1984,7:25-31
[27]Camino G,Costa L,Trossarelli L.Study of the mechanism of intumescence in fire retardant polymers:Part Ⅴ-Mechanism of formation of gaseous products in the thermal degradation of ammonium polyphosphate.Polymer Degradation and Stability,1985,12:203-211
[28]Camino G,Grassie N,McNeill IC.Influence of the fire retardant,ammonium polyphosphate,on the thermal degradation of poly(methyl methacrylate).Journal of Polymer Science- Polymer Chemistry,1978,16:95-106.
[29]周箭,杨辉,陈日新.分步碱液滴加法合成膨胀型阻燃剂b-MAP.化工进展,2005,6:651-655
[30]朱广军,刘桂涛,汪信,杨绪杰,陆路德.新型阻燃剂CN-329的合成及阻燃性能.南京理工大学学报(自然科学版),2002,1:76-79
[31]Pin Lv,Wang Zhengzhou.Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives,Polymer Degradation and Stability,2005,90:523-534
[32]Balabanovich A I.Thermal decomposition study of intumescent additives:Pentaerythritol phosphate and its blend with melamine phosphate,Thermochimica Acta,2005,435:188-196
[33]Liu Yuan,Wang Qi.Catalytic action of phospho-tungstic acid in the synthesis ofmelamine salts of pentaerythritol phosphate and theirsynergistic effects in flame retarded polypropylene,Polymer Degradation and Stability,2006,91:2513-2519
[34]孙春梅,龚铮.三季戊四醇亚磷酸酯阻燃剂的合成及应用研究.功能高分子学报,2005,6:260-264
[35]李斌,孙才英,张秀成.用CONE/TG研究含淀粉膨胀阻燃聚丙烯体系的阻燃和烟释放.高分子材料科学与工程,2000,9:146-149
[36]李斌,孙才英,张秀成.用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性.高等学校化学学报,1999,1:146-149
[37]李斌,张秀成,孙才英.淀粉对聚乙烯膨胀阻燃体系热降解和阻燃的影响.高分子材料科学与工程,2000,3:155-157
[38]董延茂,鲍治宇.淀粉磷酸酯蜜胺盐膨胀型阻燃剂的合成.材料科学与工艺,2005, 6:258-260
[39]Almeras X,Dabrowski F,Le Bras M,Poutch F,Bourbigot S,Marosi G and Anna P.Using polyamide-6 as charring agent in intumescent polypropylene Formulations Ⅰ.Effect of the compatibilising agent on the fire retardancy performance.Polymer Degradation and Stability,2002,77:305-313
[40]Almeras X,Dabrowski F,Le Bras M,Poutch F,Bourbigot S,Marosi G and Anna.P Using polyamide 6 as charring agent in intumescentpolypropylene formulationsⅡ.Thermal degradation.Polymer Degradation and Stability,2002,77:315-323
[41]Le Bras M,Bourbigot S,F(?)lix E,Pouille F,Siat C and Traisnel M.Characterization of a polyamide-6-based intumescent additive for thermoplastic formulations.Polymer,2000,41:5283-5296
[42]陆晓东,张军,谷慧敏,王长春.成炭性塑料对聚丙烯/膨胀阻燃体燃烧行为及阻燃性的影响.塑料,2006,1:18-22
[43]马志领,刘新玉.热塑性聚氨酯对膨胀型阻燃聚丙烯的增容作用.塑料工业,2005,11:45-47
[44]吴新明,王林江,谢襄漓,张坤.聚丙烯/尼龙-6/蒙脱石新型膨胀型纳米复合阻燃材料的研究.塑料工业,2007,5:23-26
[45]Li Bin,Xu Miaojun.Effect of a novel charring-foaming agent on flame retardancy and thermal degradation of intumescent flame polypropylene.Polymer Degradation and Stability,2006,91:1380-1386
[46]Li Yantao,Li Bin,Dai Jinfeng,Jia He,Gao Suliang.Synergistic effects of lanthanum oxide on a novel intumescent flame retardant polypropylene system.Polymer Degradation and Stability,2008,93:9-16
[47]Hu Xiao Ping,Li Wei Yi,Wang Yu Zhong.Synthesis and Characterization of a Novel Nitrogen-Containing Flame Retardant.Journal of Applied Polymer Science,2004,94:1556-1561
[48]Hu Xiao Ping,Li Ya Lan,Wang Yu Zhong.Synergistic Effect of the Charring Agent on the Thermaland Flame Retardant Properties of Polyethylene.Macromol Mater Eng,2004,289:208-212
[49]许苗军,李斌.新型成炭剂对膨胀阻燃PP体系的阻燃及热降解行为研究.中国阻燃学会年会,2005
[50]刘军,廖凯荣,卢泽俭.三嗪衍生物的分子结构及其对聚丙烯阻燃性能的关系.高分子材料科学与工程,1999,1:73-79
[51]张琳,新型纳米Sb_2O_3阻燃剂和含磷阻燃剂Melabis的制备.中国优秀硕士学位论文.南京理工大学,2003
[52]杨荣杰,王青才,李蕾.聚磷酸铵的制备与表征.北京第二届阻燃技术与阻燃材料研讨会特邀报告文集,2004,113-131
[53]Fukumura.US Patient,5599626,1997
[54]Watanabe,Makoto.US patent,5718875,1998
[55]Cipolli,Roberto.US Patent,5576391,1996
[56]Iwata,Masuo.US Patent,5700575,1997
[57]廖凯荣;卢泽俭;王坚;刘军,多聚磷酸铵的改性及其对聚丙烯的阻燃作用.高分子材料科学与工程,1998,4:87-89
[58]张泽江,梅秀娟,冯良荣,邱发礼.三聚氰胺聚磷酸盐阻燃剂的合成与表征.应用化学,2003,11:1035-1038
[59]曹堃,王开立,姚臻.聚磷酸铵的改性及其对聚丙烯阻燃特性的研究.高分子材料科学与工程,2007,4:135-139
[60]Barfurth.US Patent,6444315,2002
[61]奚强,常亮,邝生鲁.硅偶联剂对聚磷酸铵表面改性的研究.粘接,2005,6:19-20
[62]丁著明.高聚合度聚磷酸铵的改性和应用.塑料助剂,2005,6:31-34
[63]Bourbigot Serge,Le Bras Michel,Delobel Ren(?),Patrice Br(?)ant and Jean-Michel Tremillon.4A zeolite synergistic agent in new flameretardant intumescent formulations of polyethylenic polymers-study of the effect of the constituent monomers.Polymer Degradation and Stability,1996,54:275-287
[64]Bourbigot Serge,Le Bras Michel,Delobel Ren(?) and L(?)on Gengembre.XPS study of an intumescent coating:Ⅱ.Application to the ammonium polyphosphate/pentaerythritol /ethylenic terpolymer fire retardant system with and without synergistic agent.Applied Surface Science,1997,120:15-129
[65]Luciana R M,Estevao.Structure-property relationship in intumescent polymeric formulations containing waste zeolite-based material as a synergistic agent.European Polymer Journal,2004,40:1503-1513
[66]Demir H,Arkis E.Synergistic effect of natural zeolites on flame retardant additives.Polymer Degradation and Stability,2005,89:478-483
[67]Demir H,Balk6se D and(U|¨)lk(u|¨)S.Influence of surface modification of fillers and polymer on flammability and tensile behaviour of polypropylene-composites.Polymer Degradation and Stability,2006,91:1079-1085
[68]高瑜.分子筛在膨胀型阻燃剂(IFR)体系中的应用-IFR-PE的阻燃性能研究.硕士研究生学位论文.北京化工大学,2000
[69]韦平,王建祺.分子筛对聚丙烯膨胀型阻燃体系热降解行为的研究.高分子材料科学与工程,2002,5:124-127
[70]韦平,王建祺.4A分子筛对APP/PER膨胀阻燃剂协同作用的TGA/XPS.高分子材料科学与工程,2003,5:179-181
[71]王岩,曾幸荣.4A分子筛对三聚氰胺磷酸盐/季戊四醇阻燃PP性能的影响.塑料工业,2007,5:62-64
[72]杜建新,郝建薇,王建祺.SiO_2和Al_2O_3对PP/APP/PER膨胀阻燃体系的协同作用.高分子材料科学与工程,2004,1:165-167
[73]徐晓楠,张健.二氧化硅对膨胀型阻燃聚乙烯的性能影响研究.火灾科学,2004,7:168-172
[74]Marosi G,M(?)rton A,Anna P,Bertalan G,Marosf(o|¨)i B and Sz(?)p A.Ceramic precursor in flame retardant systems.Polymer Degradation and Stability,2002,77:259-265
[75]Laoutid F,Ferry L,Leroy E and Lopez Cuesta J M.Intumescent mineral fire retardant systems in ethylene-vinyl acetate copolymer:Effect of silica particles on char cohesion.Polymer Degradation and Stability,2006,91:2140-2145
[76]Lewin M,Endo M.Catalysis of intumescent flame retardance of polypropylene by metal compounds.Polymeric Materials Science and Engineering,2000,83:38-39
[77]刘军辉,张军,王明清,杨荣杰.金属化合物在PP膨胀阻燃体系中的研究.高分子材料科学与工程,2007,5:160-165
[78]雷远霞,杨其,姚鑫,李根林.金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响. 中国塑料,2006,10:83-85
[79]田春明,谢吉星,石建兵,屈红强,徐建中.氧化锌在膨胀阻燃体系中的协效作用.河北大学学报(自然科学版),2004,11:600-604
[80]黄承亚,龚克成,赵彦芝,李红.氧化锌催化膨胀型阻燃剂对PP阻燃及力学性能的影响.塑料工业,2006,12:57-59
[81]Wu Qiang and Qu Baojun.Synergistic effects of silicotungistic acid on intumescent flame-retardant polypropylene.Polymer Degradation and Stability,2001,74:255-261
[82]Liu Yuan and Wang Qi.Catalytic action of phospho-tungstic acid in the synthesis of melamine salts of pentaerythritol phosphate and their synergistic effects in flame retarded polypropylene.Polymer Degradation and Stability,2006,91:2513-2519
[83]Luciana R M,Estev(?)o,Michel Le Bras,Ren(?) Delobel and Regina S V Nascimento.Spent refinery catalyst as a synergistic agent in intumescent formulations:influence of the catalyst's particle size and constituents.Polymer Degradation and Stability,2005,88:444-455
[84]Hassan M A and Shehata A B.The effect of some polymeric metal chelates on the flammability properties of polypropylene.Polymer Degradation and Stability,2004,85:733-740
[85]许苗军.三嗪系阻燃剂的合成及阻燃高聚物性能研究.硕士学位论文.东北林业大学,2005