含磷氮丙烯酸酯核壳粒子的制备
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摘要
以苯基膦酰二氯、丙烯酸-β-羟乙酯和二乙胺为原料,合成了含磷氮丙烯酸酯(APEEA)功能单体。以APEEA和丙烯酸丁酯(BA)为内核材料、甲基丙烯酸甲酯(MMA)为壳层材料,通过种子乳液聚合法制备了含磷氮丙烯酸酯核壳粒子[poly(APEEA-co-BA-co-MMA)]。采用激光粒度仪(LPS)、扫描电子显微镜(SEM)、透射电镜(TEM)、热重分析(TG)和微型燃烧量热仪(MCC)对所得的样品进行了表征。结果表明:poly(APEEA-co-BAco-MMA)平均粒径在0.08~0.10μm,具有明显的核壳结构,核壳的尺寸约100 nm。当poly(APEEA-co-BA-coMMA)粒子中APEEA质量分数为15%时,分解5%的初始分解温度(Td5%)可达277℃;500℃时残炭量为5.8%,是poly(BA-co-MMA)粒子的3.87倍。质量分数15%的APEEA的引入可以使粒子的热释放率峰值降幅达55%,表明APEEA具有明显的凝聚相阻燃作用,可通过催化粒子成炭改善其燃烧性质。
A functional phosphorus-nitrogen-containing monomer( APEEA) was first synthesized by using phenylphosphonic dichloride,hydroxyethyl acrylate and diethylamine as raw materials. And then,a series of novel[poly( APEEA-co-BA-co-MMA) ]particles with core-shell structure were prepared via seeded emulsion polymerization with APEEA and butyl acrylate( BA) as core monomers,methyl methacrylate( MMA) as a shell monomer. The prepared particles were characterized by laser particle size analyzer( LPS),scanning electron microscope( SEM),transmission electron microscope( TEM),thermogravimetric analysis( TG) and micro-combustion calorimetry( MCC). The results showed that the average particle diameters of poly( APEEA-co-BA-co-MMA) particles with core-shell structure were in the range of 0. 08 μm to 0. 10 μm,and the size of core shell was about 100 nm. When the mass fraction of APEEA was 15%,the temperature at 5% weight loss( Td5%) of poly( APEEA-co-BA-coMMA) reached 277 ℃,while the char yield at 500 ℃ was only 5. 8%,which was 3. 87 times that of poly( BA-co-MMA) particles. Moreover,the introduction of 15% APEEA could make the peak heat release rate of poly( APEEA-co-BA-co-MMA) be a decrease of 55% compared with that of poly( BAco-MMA). These results indicated that APEEA presented an obvious condensed-phase flame retardant effect and improved the combustion properties of particles by catalyzing the particles to form char.
A functional phosphorus-nitrogen-containing monomer( APEEA) was first synthesized by using phenylphosphonic dichloride,hydroxyethyl acrylate and diethylamine as raw materials. And then,a series of novel[poly( APEEA-co-BA-co-MMA) ]particles with core-shell structure were prepared via seeded emulsion polymerization with APEEA and butyl acrylate( BA) as core monomers,methyl methacrylate( MMA) as a shell monomer. The prepared particles were characterized by laser particle size analyzer( LPS),scanning electron microscope( SEM),transmission electron microscope( TEM),thermogravimetric analysis( TG) and micro-combustion calorimetry( MCC). The results showed that the average particle diameters of poly( APEEA-co-BA-co-MMA) particles with core-shell structure were in the range of 0. 08 μm to 0. 10 μm,and the size of core shell was about 100 nm. When the mass fraction of APEEA was 15%,the temperature at 5% weight loss( Td5%) of poly( APEEA-co-BA-coMMA) reached 277 ℃,while the char yield at 500 ℃ was only 5. 8%,which was 3. 87 times that of poly( BA-co-MMA) particles. Moreover,the introduction of 15% APEEA could make the peak heat release rate of poly( APEEA-co-BA-co-MMA) be a decrease of 55% compared with that of poly( BAco-MMA). These results indicated that APEEA presented an obvious condensed-phase flame retardant effect and improved the combustion properties of particles by catalyzing the particles to form char.
引文
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[2]Sun Shulin(孙树林),Tong Yanling(童艳玲),Zou Deyin(邹德音),et al.Toughening of PBT/PC blends with core-shell modifier[J].Polymer Materials Science and Engineering(高分子材料科学与工程),2011,27(12):52-55.
[3]Chen Ming(陈明),Liu Lang(刘浪),Zhou Chao(周超),et al.Morphology structure and property of PVC blends with MBS coreshell particles[J].Acta Materiae Compositae Sinica(复合材料学报),2010,27(1):32-36.
[4]Hong Yuerong(洪月蓉),Zhang Ling(张玲),Niu Jianhua(牛建华),et al.PBT matrix compositeswith elastomer-modified nanoSi O2particles[J].Acta Materiae Compositae Sinica(复合材料学报),2009,26(3):55-59.
[5]Yang F,Wu G B,Zhang S L,et al.Synthesis of a core-shell acrylate elastomer with UV stabilization and its application in polyoxymethylene[J].Journal of Applied Polymer Science,2011,239-242(5):2609-2615.
[6]Wu Guibo(吴桂波),Zhao Guodong(赵国栋),Wang Jun(王军),et al.Sythesis of P(MMA-BA-BPMA)and study on the light stabilization of its modification on POM[J].China Plastics Industry(塑料工业),2010,38(3):36-39.
[7]You Bin(游斌),Zhou Daojun(周道军),Zhang Shiling(张适龄),et al.Preparation of UV-stabilized core-shell elastomer[J].Journal of Sichuan university(engineering science edition)(四川大学学报:工程科学版),2012,44(3):170-173.
[8]Feng Meng(冯猛).Study on the preparation of polysiloxane-acrylate with core-shell structure and its toughening of PC/ABS blends[D].South China University of Technology(华南理工大学),2015.
[9]Price D,Cunliffe L K,Bullet K J,et al.Thermal behavior of covalently bonded phosphonate flame-retarded poly(methyl methacrylate)systems[J].Polymers for Advanced Technologies,2008,19(6):710-723.
[10]Hu W,Zhan J,Hong N,et al.Flame retardant polystyrene copolymers:preparation,thermal properties,and fire toxicities[J].Polymers for Advanced Technologies,2014,25(6):631-637.
[11]Jiang S H,Lo S M,Hu Y.Enhanced Thermal Stability and Flame retardancy of a novel transparent poly(methyl methacrylate)-based copolymer[J].Advanced Materials Research,2014,911:423-427.
[12]Liu Junhui(刘军辉),Zhang Jun(张军),Li Feng(李枫).Flame retardancy of styrene and butyl-acrylate/montmorillonite nanocomposites[J].Polymer Materials Science and Engineering(高分子材料科学与工程),2005,21(4):156-159.
[13]Tai Q,Kan Y,Chen L,et al.Morphologies and thermal properties of flame-retardant polystyrene/α-zirconium phosphate nanocomposites[J].Reactive&Functional Polymers,2010,70(6):340-345.
[14]Tai Q,Song L,Lv X,et al.Flame-retarded polystyrene with phosphorus-and nitrogen-containing oligomer:Preparation and thermal properties[J].Journal of Applied Polymer Science,2012,123(2):770-778.
[15]Jiang S,Shi Y,Qian X,et al.Synthesis of a novel phosphorus-and nitrogen-containing acrylate and its performance as an intumescent flame retardant for epoxy acrylate[J].Ind eng chem res,2013,52(49):17442-17450.
[16]Zhang Xinya(张心亚),Sun Zhijuan(孙志娟),Jiang Qingmei(江庆梅),et al.Nucleation process and nucleation mechanism of MMA/BA seeded semi-continuous emulsion polymerization[J].Acta Polymerica Sinica(高分子学报),2009,9(5):409-418.
[17]Liu Qiongyu(刘琼宇),Zeng Xingrong(曾幸荣),Li Hongqiang(李红强),et al.Synthesis and properties of phosphoruscontained acrylate emulsion[J].Chemistryand Adhesion(化学与粘合),2012,34(6):7-9.
[18]Liu Qingquan(刘清泉),Zhou Shixiang(周仕祥),Yang Zhen(杨震),et al.Preparation of oxidized polyethylene wax microemulsion with a single nonionic emulsifier[J].Paint&Coatings Industry(涂料工业),2012,42(11):43-45.
[19]Yu Jian(于建),Zhang Liangfang(张良方),Guo Zhaoxia(郭朝霞).Design of phase-containing particles with core-shell morphology and their toughening to POM resin[J].Sci-tech Innovation and Productivity(科技创新与生产力),2006,8(8):24-27.
[20]Hu Jinsheng(胡金生)et al.Emulsion Polymerization(乳液聚合)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),1987,383-399.
[21]Karthik R,Meenakshi S.Removal of hexavalent chromium ions using polyaniline/silica gel composite[J].Journal of Water Process Engineering,2014,1(1):37-45.
[22]Qian X,Song L,Hu Y,et al.Combustion and thermal degradation mechanism of a novel intumescent flame retardant for epoxy acrylate containing phosphorus and nitrogen[J].Industrial&Engineering Chemistry Research,2011,50(4):1881-1892.
[23]Yang H,Wang X,Yuan H,et al.Fire performance and mechanical properties of phenolic foams modified by phosphoruscontaining polyethers[J].Journal of Polymer Research,2012,19(3):140-149.