聚对苯二甲酸丁二醇酯扩链协同阻燃改性研究
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摘要
聚对苯二甲酸丁二醇酯(PBT)作为主要的热塑性工程塑料之一，具有良好的力学性能、尺寸稳定性、热性能和加工性能，在电子电器、汽车、机械以及光纤包覆等领域得到了广泛应用。但PBT的易燃性限制了其应用范围的扩大，传统的卤系阻燃剂由于在燃烧过程中会释放出大量的有毒和腐蚀性气体，应用受到愈来愈多的限制。而常见的无卤阻燃剂在阻燃改性的同时会导致聚合物材料其他性能严重劣化。因此，研究开发新型无卤阻燃PBT材料成为了主流。
本文首先使用硅烷偶联剂(KH570)对氢氧化镁(MH)进行表面改性，然后采用具有良好熔体流动性的聚丙烯接枝马来酸酐(PP-g-MAH)包覆改性MH，最后再与PBT共混制备了PBT/PP-g-MAH/MH复合体系。PP-g-MAH对MH的包覆处理成功解决了大添加量MH阻燃PBT树脂的加工难题，所制得的复合体系具有较好的阻燃和力学性能。如MH和PP-g-MAH添加量分别为50wt%和6wt%时，PBT/PP-g-MAH/MH复合体系达到了垂直燃烧UL943.2mm V-1阻燃级别，极限氧指数(LOI)提高到35.0%，相应的拉伸强度和Izod缺口冲击强度分别为45.0MPa和22.2J/m。通过对复合体系进行脆断面SEM分析和热失重分析(TGA)后发现，MH在复合体系中分散良好，较好地发挥了热阱和凝聚相阻燃作用。
在上述基础上，采用兼具增塑润滑阻燃作用的间苯二酚双（二苯基磷酸酯）(RDP)和膨胀型石墨(EG)分别与MH复配制备了PBT/PP-g-MAH/RDP/MH和PBT/PP-g-MAH/EG/MH阻燃体系，两复配阻燃体系的加工性能进一步改善。MH和EG复配存在协同阻燃效应，如MH和EG的添加量分别为35wt%和10wt%时，PBT/PP-g-MAH/EG/MH阻燃体系通过了UL943.2mm V-0级测试，LOI达到33.3%。但MH和RDP复配则不存在协同阻燃作用。热重红外联用(TGA-FTIR)和残炭SEM分析表明，EG加入后一方面增强了PBT/PP-g-MAH复合体系的热稳定性，降低了可燃性产物的释放速率；另一方面其与MH共同作用提高了体系的残炭率和增强了残炭层的阻隔性，最终延缓了PBT的降解和燃烧。
采用二乙基次膦酸铝盐(AlPi)阻燃改性PBT，研究了其对PBT结构与性能的影响，并探讨了PBT/AlPi体系的阻燃机理。当AlPi用量分别为11wt%、13wt%和20wt%时，可使PBT分别达到UL943.2mm、1.6mm和0.8mm V-0级阻燃性能，相应的LOI则分别提高到34.3%、35.4%和39.3%，但阻燃体系的烟雾释放量与释放速率均明显增大。AlPi主要通过受热分解释放出自由基捕捉剂（二乙基次膦酸）在气相发挥阻燃作用，同时其在凝聚相也具有促进成炭作用。AlPi加入后会导致PBT的降解加剧，阻燃体系的力学性能被劣化，材料的强度和韧性明显变差。如AlPi用量为20wt%时，阻燃体系的拉伸强度、断裂伸长率、Izod缺口冲击强度和弯曲模量分别为纯PBT的68.6%、10.9%、51.0%和104.4%。AlPi在PBT中存在异相成核作用，提高了PBT的结晶速度、结晶温度和结晶度。阻燃PBT的耐热性能也有较大的提升，如AlPi用量为11wt%时，阻燃PBT的热变形温度(HDT)达到了65.7℃，较纯PBT提高了10℃。
针对PBT/AlPi阻燃体系存在降解加剧、力学性能劣化明显以及烟雾释放量显著升高等问题，本文设计合成了一种侧基带环氧基团的多官能度聚硅氧烷(EPM)，将EPM和市售扩链剂苯乙烯-甲基丙烯酸缩水甘油酯低聚物(ADR)作为扩链剂分别与AlPi复配制备了PBT/AlPi/EPM和PBT/AlPi/ADR扩链协同阻燃体系。考察了AlPi用量为11wt%时，EPM和ADR在体系中的扩链作用及其对体系综合性能的影响，并讨论了两体系的协同阻燃和抑烟机理。EPM和ADR均能发挥明显的扩链作用，提高了PBT在加工过程中的扭矩。两复合体系混炼时的扭矩随着二者用量的升高而不断增大，体系中支化与交联程度也随之升高。两复合体系均存在显著的协同阻燃效应，尤其EPM对提高复合体系阻燃性能的帮助更大。当EPM用量为0.6wt%时，PBT/AlPi/EPM体系可达到UL941.6mm V-0阻燃级别，LOI为37.1%。同时体系的综合力学性能较优，与PBT/11AlPi相比，其拉伸强度、断裂伸长率、弯曲模量和Izod缺口冲击强度分别由47.6MPa、8.0%、2.92GPa和39.7J/m提高到54.9MPa、13.1%、3.17GPa和49.0J/m，分别提高了15.3%、63.8%、8.6%和23.4%。对于PBT/AlPi/ADR体系，当ADR用量为0.4wt%时其综合性能较优，相应的力学性能数据为49.7MPa、11.2%、3.00GPa和46.8J/m，且通过UL941.6mm V-0级测试，LOI为36.1%。两复合体系的玻璃化转变温度(Tg)均随着EPM和ADR用量的增大而单调上升。适量的EPM和ADR加入后均能促进PBT结晶，两复合体系的结晶度、结晶温度和结晶速度都得到了提高。HDT测试也表明，两复合体系的HDT均有明显的上升，其中含EPM的体系表现更优。
PBT/AlPi/EPM与PBT/AlPi/ADR协同阻燃体系的凝聚相阻燃作用明显增强，而气相阻燃效应均有所减弱，相应地烟雾释放量和释放速率都有明显下降。ADR或EPM加入后能够与PBT及AlPi在热分解过程中发生强烈的相互作用，促进体系交联成炭，并形成具有优良阻隔性的残炭层。而EPM由于具有更高的反应活性与含有机硅结构，使得PBT/AlPi/EPM阻燃体系所形成的残炭层中阻燃元素的含量更高，残炭层的耐热氧分解性更强。最终导致PBT/AlPi/EPM体系的协同阻燃效率要高于PBT/AlPi/ADR体系。
Poly(butylene terephthalate)(PBT) is a major member of engineering plastics, it hasbeen widely used for industrial applications thanks to its attractive mechanical performance,dimensional stability, thermal properties and processing advantages. Nevertheless, the highflammability of neat PBT restricts its further use in the wider scope of application. Theutilization of traditional halogenated flame retardants in PBT are restrained due to the releaseof the toxic and corrosive smoke during combustion. And the employment of commonnon-halogen flame retardant will greatly impair the other key properties of PBT. Therefore,the development of novel halogen-free flame-retarded PBT has become the mainstreamnowadays.
Owing to the difficulty in processing the blend of PBT and magnesium hydroxide (MH),the fluidity improver (maleic anhydride grafted polypropylene (PP-g-MAH)) was employedto prepare the halogen-free flame-retarded PBT/MH composites. The processability ofPBT/PP-g-MAH/MH composite was improved. With the addition of50wt%MH and6wt%PP-g-MAH, PBT/PP-g-MAH/MH composite attained UL943.2mm V-1rating and a LOI of35.0%. The tensile strength and Izod notched impact strength of the correspondingPBT/PP-g-MAH/MH composite were45.0MPa and22.2J/m, respectively. According to theTGA and SEM analysis, there existed a good dispersity of MH particle in PBT matrix. Withthe good MH particle dispersity, PBT/PP-g-MAH/MH composite showed high efficiency inflame retardancy.
In addition, PBT/PP-g-MAH composite flame retarded by the combination of MH andresorcinol bis(diphenyl phosphate)(RDP) or expandable graphite (EG) was also investigated.The combination of MH and EG exhibited an obvious synergistic flame-retardant effect inPBT/PP-g-MAH composite. With the loadings of35wt%MH and10wt%EG,PBT/PP-g-MAH/EG/MH blend obtained UL943.2mm V-0classification and a LOI of33.3%.Nevertheless, there did not exist synergism in the flame retardancy ofPBT/PP-g-MAH/RDP/MH compound. The flame-retardant mechanism ofPBT/PP-g-MAH/EG/MH composite was analyzed through the TGA-FTIR and SEM characterization. The introduction of EG improved thermal stability and barrier effect of theresidual char layer, and the protection for the polymer matrix was enhanced.
Aluminum diethylphosphinate (AlPi) was applied for flame retarding PBT. The influenceof AlPi in the overall properties of PBT was examined. With the combination of differentcontent for AlPi (11,13and20wt%), the corresponding PBT/AlPi composites passed UL94V-0rating (3.2,1.6and0.8mm) and achieved the LOI with34.3%,35.4%and39.3%,respectively. AlPi acted mainly through the flame inhibition in gas phase by the realease ofdiethylphosphinic acid, and an enhanced condensed-phase flame-retardant action was alsoobserved. Correspondingly, the smoke release was intensified significantly. The presence ofAlPi would provoke the degradation of PBT, resulting in the deterioration of mechanicalperformance. The tensile strength, elongation at break, Izod notched impact strength andflexural modulus of PBT/AlPi blend (AlPi:20wt%) were68.6%,10.9%,51.0%and104.4%of the corresponding value of neat PBT, respectively. A promotion in crystallization rate,crystallization temperature and crystallinity for PBT/AlPi was perceived, which was related tothe heterogeneous nucleation effect of AlPi. The heat resistance of PBT was enhanced withthe introduction of AlPi concluded from its rising heat distortion temperature (HDT). ForPBT/AlPi (AlPi:11wt%), the HDT value was65.7°C with an increment of10°C comparedto that of neat PBT.
With the purpose of suppressing the degradation and enhancing the mechanicalproperties for PBT/AlPi composite, an epoxy-functional polysiloxane (EPM) was synthesizedand employed as chain extender to prepare the PBT/AlPi/EPM composite. Additionally,another chain-extended PBT/AlPi composite was prepared by using a commercialpolyfunctional chain extender (ADR) for comparative study. Based on the results of torquerheometer measurement, both EPM and ADR could induce evident chain extension reactionin PBT/AlPi composite. With appropriate loadings of EPM and ADR, the modified PBT/AlPicomposites not only demonstrated significant enhanced mechanical properties, but also muchbetter integrated properties including flame retardancy, crystallization performance and heatresistance. Comparatively speaking, the effect of EPM was much better than ADR due to itshigh functionality and polysiloxane chain structure.
The synergistic flame-retarded mechanism of PBT/AlPi/EPM and PBT/AlPi/ADR system mainly related to the enhanced condensed-phase action. Small percentages of EPMand ADR could interact with PBT and AlPi intensively during the decomposition process,subsequently the formation of more stable cross-linking char residue occurred. Morephosphorus element retained in the solid phase whereas the release of phosphorus into the gasphase diminished. Logically, the smoke release was greatly suppressed. Moreover, Thecross-linking residue containing silicon showed the better thermal stability and oxidationresistance, which was accounted for the greater flame-retardant efficiency existed inPBT/AlPi/EPM composite.
本文首先使用硅烷偶联剂(KH570)对氢氧化镁(MH)进行表面改性，然后采用具有良好熔体流动性的聚丙烯接枝马来酸酐(PP-g-MAH)包覆改性MH，最后再与PBT共混制备了PBT/PP-g-MAH/MH复合体系。PP-g-MAH对MH的包覆处理成功解决了大添加量MH阻燃PBT树脂的加工难题，所制得的复合体系具有较好的阻燃和力学性能。如MH和PP-g-MAH添加量分别为50wt%和6wt%时，PBT/PP-g-MAH/MH复合体系达到了垂直燃烧UL943.2mm V-1阻燃级别，极限氧指数(LOI)提高到35.0%，相应的拉伸强度和Izod缺口冲击强度分别为45.0MPa和22.2J/m。通过对复合体系进行脆断面SEM分析和热失重分析(TGA)后发现，MH在复合体系中分散良好，较好地发挥了热阱和凝聚相阻燃作用。
在上述基础上，采用兼具增塑润滑阻燃作用的间苯二酚双（二苯基磷酸酯）(RDP)和膨胀型石墨(EG)分别与MH复配制备了PBT/PP-g-MAH/RDP/MH和PBT/PP-g-MAH/EG/MH阻燃体系，两复配阻燃体系的加工性能进一步改善。MH和EG复配存在协同阻燃效应，如MH和EG的添加量分别为35wt%和10wt%时，PBT/PP-g-MAH/EG/MH阻燃体系通过了UL943.2mm V-0级测试，LOI达到33.3%。但MH和RDP复配则不存在协同阻燃作用。热重红外联用(TGA-FTIR)和残炭SEM分析表明，EG加入后一方面增强了PBT/PP-g-MAH复合体系的热稳定性，降低了可燃性产物的释放速率；另一方面其与MH共同作用提高了体系的残炭率和增强了残炭层的阻隔性，最终延缓了PBT的降解和燃烧。
采用二乙基次膦酸铝盐(AlPi)阻燃改性PBT，研究了其对PBT结构与性能的影响，并探讨了PBT/AlPi体系的阻燃机理。当AlPi用量分别为11wt%、13wt%和20wt%时，可使PBT分别达到UL943.2mm、1.6mm和0.8mm V-0级阻燃性能，相应的LOI则分别提高到34.3%、35.4%和39.3%，但阻燃体系的烟雾释放量与释放速率均明显增大。AlPi主要通过受热分解释放出自由基捕捉剂（二乙基次膦酸）在气相发挥阻燃作用，同时其在凝聚相也具有促进成炭作用。AlPi加入后会导致PBT的降解加剧，阻燃体系的力学性能被劣化，材料的强度和韧性明显变差。如AlPi用量为20wt%时，阻燃体系的拉伸强度、断裂伸长率、Izod缺口冲击强度和弯曲模量分别为纯PBT的68.6%、10.9%、51.0%和104.4%。AlPi在PBT中存在异相成核作用，提高了PBT的结晶速度、结晶温度和结晶度。阻燃PBT的耐热性能也有较大的提升，如AlPi用量为11wt%时，阻燃PBT的热变形温度(HDT)达到了65.7℃，较纯PBT提高了10℃。
针对PBT/AlPi阻燃体系存在降解加剧、力学性能劣化明显以及烟雾释放量显著升高等问题，本文设计合成了一种侧基带环氧基团的多官能度聚硅氧烷(EPM)，将EPM和市售扩链剂苯乙烯-甲基丙烯酸缩水甘油酯低聚物(ADR)作为扩链剂分别与AlPi复配制备了PBT/AlPi/EPM和PBT/AlPi/ADR扩链协同阻燃体系。考察了AlPi用量为11wt%时，EPM和ADR在体系中的扩链作用及其对体系综合性能的影响，并讨论了两体系的协同阻燃和抑烟机理。EPM和ADR均能发挥明显的扩链作用，提高了PBT在加工过程中的扭矩。两复合体系混炼时的扭矩随着二者用量的升高而不断增大，体系中支化与交联程度也随之升高。两复合体系均存在显著的协同阻燃效应，尤其EPM对提高复合体系阻燃性能的帮助更大。当EPM用量为0.6wt%时，PBT/AlPi/EPM体系可达到UL941.6mm V-0阻燃级别，LOI为37.1%。同时体系的综合力学性能较优，与PBT/11AlPi相比，其拉伸强度、断裂伸长率、弯曲模量和Izod缺口冲击强度分别由47.6MPa、8.0%、2.92GPa和39.7J/m提高到54.9MPa、13.1%、3.17GPa和49.0J/m，分别提高了15.3%、63.8%、8.6%和23.4%。对于PBT/AlPi/ADR体系，当ADR用量为0.4wt%时其综合性能较优，相应的力学性能数据为49.7MPa、11.2%、3.00GPa和46.8J/m，且通过UL941.6mm V-0级测试，LOI为36.1%。两复合体系的玻璃化转变温度(Tg)均随着EPM和ADR用量的增大而单调上升。适量的EPM和ADR加入后均能促进PBT结晶，两复合体系的结晶度、结晶温度和结晶速度都得到了提高。HDT测试也表明，两复合体系的HDT均有明显的上升，其中含EPM的体系表现更优。
PBT/AlPi/EPM与PBT/AlPi/ADR协同阻燃体系的凝聚相阻燃作用明显增强，而气相阻燃效应均有所减弱，相应地烟雾释放量和释放速率都有明显下降。ADR或EPM加入后能够与PBT及AlPi在热分解过程中发生强烈的相互作用，促进体系交联成炭，并形成具有优良阻隔性的残炭层。而EPM由于具有更高的反应活性与含有机硅结构，使得PBT/AlPi/EPM阻燃体系所形成的残炭层中阻燃元素的含量更高，残炭层的耐热氧分解性更强。最终导致PBT/AlPi/EPM体系的协同阻燃效率要高于PBT/AlPi/ADR体系。
Poly(butylene terephthalate)(PBT) is a major member of engineering plastics, it hasbeen widely used for industrial applications thanks to its attractive mechanical performance,dimensional stability, thermal properties and processing advantages. Nevertheless, the highflammability of neat PBT restricts its further use in the wider scope of application. Theutilization of traditional halogenated flame retardants in PBT are restrained due to the releaseof the toxic and corrosive smoke during combustion. And the employment of commonnon-halogen flame retardant will greatly impair the other key properties of PBT. Therefore,the development of novel halogen-free flame-retarded PBT has become the mainstreamnowadays.
Owing to the difficulty in processing the blend of PBT and magnesium hydroxide (MH),the fluidity improver (maleic anhydride grafted polypropylene (PP-g-MAH)) was employedto prepare the halogen-free flame-retarded PBT/MH composites. The processability ofPBT/PP-g-MAH/MH composite was improved. With the addition of50wt%MH and6wt%PP-g-MAH, PBT/PP-g-MAH/MH composite attained UL943.2mm V-1rating and a LOI of35.0%. The tensile strength and Izod notched impact strength of the correspondingPBT/PP-g-MAH/MH composite were45.0MPa and22.2J/m, respectively. According to theTGA and SEM analysis, there existed a good dispersity of MH particle in PBT matrix. Withthe good MH particle dispersity, PBT/PP-g-MAH/MH composite showed high efficiency inflame retardancy.
In addition, PBT/PP-g-MAH composite flame retarded by the combination of MH andresorcinol bis(diphenyl phosphate)(RDP) or expandable graphite (EG) was also investigated.The combination of MH and EG exhibited an obvious synergistic flame-retardant effect inPBT/PP-g-MAH composite. With the loadings of35wt%MH and10wt%EG,PBT/PP-g-MAH/EG/MH blend obtained UL943.2mm V-0classification and a LOI of33.3%.Nevertheless, there did not exist synergism in the flame retardancy ofPBT/PP-g-MAH/RDP/MH compound. The flame-retardant mechanism ofPBT/PP-g-MAH/EG/MH composite was analyzed through the TGA-FTIR and SEM characterization. The introduction of EG improved thermal stability and barrier effect of theresidual char layer, and the protection for the polymer matrix was enhanced.
Aluminum diethylphosphinate (AlPi) was applied for flame retarding PBT. The influenceof AlPi in the overall properties of PBT was examined. With the combination of differentcontent for AlPi (11,13and20wt%), the corresponding PBT/AlPi composites passed UL94V-0rating (3.2,1.6and0.8mm) and achieved the LOI with34.3%,35.4%and39.3%,respectively. AlPi acted mainly through the flame inhibition in gas phase by the realease ofdiethylphosphinic acid, and an enhanced condensed-phase flame-retardant action was alsoobserved. Correspondingly, the smoke release was intensified significantly. The presence ofAlPi would provoke the degradation of PBT, resulting in the deterioration of mechanicalperformance. The tensile strength, elongation at break, Izod notched impact strength andflexural modulus of PBT/AlPi blend (AlPi:20wt%) were68.6%,10.9%,51.0%and104.4%of the corresponding value of neat PBT, respectively. A promotion in crystallization rate,crystallization temperature and crystallinity for PBT/AlPi was perceived, which was related tothe heterogeneous nucleation effect of AlPi. The heat resistance of PBT was enhanced withthe introduction of AlPi concluded from its rising heat distortion temperature (HDT). ForPBT/AlPi (AlPi:11wt%), the HDT value was65.7°C with an increment of10°C comparedto that of neat PBT.
With the purpose of suppressing the degradation and enhancing the mechanicalproperties for PBT/AlPi composite, an epoxy-functional polysiloxane (EPM) was synthesizedand employed as chain extender to prepare the PBT/AlPi/EPM composite. Additionally,another chain-extended PBT/AlPi composite was prepared by using a commercialpolyfunctional chain extender (ADR) for comparative study. Based on the results of torquerheometer measurement, both EPM and ADR could induce evident chain extension reactionin PBT/AlPi composite. With appropriate loadings of EPM and ADR, the modified PBT/AlPicomposites not only demonstrated significant enhanced mechanical properties, but also muchbetter integrated properties including flame retardancy, crystallization performance and heatresistance. Comparatively speaking, the effect of EPM was much better than ADR due to itshigh functionality and polysiloxane chain structure.
The synergistic flame-retarded mechanism of PBT/AlPi/EPM and PBT/AlPi/ADR system mainly related to the enhanced condensed-phase action. Small percentages of EPMand ADR could interact with PBT and AlPi intensively during the decomposition process,subsequently the formation of more stable cross-linking char residue occurred. Morephosphorus element retained in the solid phase whereas the release of phosphorus into the gasphase diminished. Logically, the smoke release was greatly suppressed. Moreover, Thecross-linking residue containing silicon showed the better thermal stability and oxidationresistance, which was accounted for the greater flame-retardant efficiency existed inPBT/AlPi/EPM composite.
引文
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