高阻燃UPR/粘土纳米复合材料的制备及阻燃机理研究
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摘要
不饱和聚酯树脂(UPR)性能优良,加工简便,是目前热固性树脂中产量较大的品种之一,用途极其广泛,但普遍存在易燃等问题,使得阻燃UPR成为热门研究之一。本文充分利用廉价的矿物材料,通过添加少量粘土和使用纳米粒子来减少卤-锑阻燃剂的用量,制备了高阻燃UPR/粘土纳米复合材料,并采用XRD、TEM、SEM、FTIR、TG、DSC、氧指数、垂直燃烧实验、力学性能分析等手段对材料性能进行了表征。成功解决了聚合物材料高阻燃、高力学性能之间的矛盾,研究了纳米复合材料的微观结构、形成机理及其阻燃机理,为阻燃材料的发展提供了理论依据。
以三氯化锑为原料,采用醇盐水解法,通过控制溶液过饱和度和生长界面的反应速度,采用表面活性剂降低固液界面张力,减小成核半径,首次合成单分散纳米Sb_2O_3和纤维状纳米Sb_4O_5Cl_2,以及纳米Sb_2O_3/云母、纳米Sb_4O_5Cl_2/云母复合物,揭示了纳米粒子生长规律,实现了对于最终产品维度、尺寸和形貌的控制。结果表明:单分散纳米Sb_2O_3平均粒径约为21nm,74%的粒子小于15nm;Sb_2O_3粒子均匀生长在云母表面和层间,其驱动力主要来源于云母表面与颗粒的静电引力,层间距限制了纳米粒子的生长,避免了团聚,因此得到95%的颗粒在5nm左右。优化制备条件为:反应温度45℃,醇化时间1h,SbCl_3/无水乙醇比例5g/30ml,用PEG处理纳米Sb_2O_3。纤维状纳米Sb_4O_5Cl_2分布均匀,单根最长可达1.5μm,长径比在1∶100到1∶200之间。
首次采用酸溶法和醇盐水解法制备了纳米Sb_4O_5Cl_2柱撑蒙脱土,提出纳米Sb_4O_5Cl_2柱撑蒙脱土的形成机理。结果表明:蒙脱土经Sb_4O_5Cl_2柱撑后,001面特征峰由1.2 nm扩大到1.5 nm左右,在4.0 nm层间距处出现一衍射峰;Al-OH振动峰、AlMg-OH弯曲振动的吸收带发生移动;Sb_4O_5Cl_2纳米粒子镶嵌在蒙脱土的片层空隙内。纳米Sb_4O_5Cl_2柱撑膨润土的形成主要通过Sb~(3+)或Sb(OR)_3分子与蒙脱土层间Na~+的交换和吸附,在蒙脱土层间原位水解产生Sb_4O_5Cl_2纳米粒子,达到扩充层间距的目的,同时层间距离限制了纳米粒子的生长,使它粒径小,分散好。
采用超声波法首次实现高岭土/丙二醇(K/PD)的快速插层,并从热力学和插层驱动力的角度分析了插层反应的机理。结果表明:二甲基亚砜(DMSO)是较好的一次插层剂,插层率达91%以上,反应的优化条件为水10%、温度90℃、超声波强度8KHz和3h。UPR聚合单体中,只有PD可以二次取代K/DMSO,实现快速插层,条件为:插层反应温度为80℃,插层时间为3h。插层驱动力来自于高岭土的结构、有机插层剂、水、能量等。在相同条件下,多水、结构压力大的管状结构高岭土比普通的高岭土更易于插层;有机插层剂的性质决定了能否插层和插层效率;水可以破坏插层剂的结构,改变有机分子与高岭土片层的成键方式;超声波通过超声空化作用,提供局部超高温、超高压和“活性种”,插层效率高,所需时间短。
首次以K/PD插层前驱体作为反应单体之一,采用原位聚合法制备了UPR/高岭土纳米复合物,首次采用电子束轰击的方法动态模拟复合物晶格结构变化过程,由此推断其微观结构和插层方式,分析UPR/高岭土的形成机理。结果表明:加入5%以下高岭土对树脂性能影响不大;复合材料中高岭土片层剥离,与树脂混合均匀, X衍射呈非晶态;高岭土表面羟基特征峰发生移动,出现UPR的特征峰,与溶液混合法制备的复合材料明显不同。聚合反应释放的自由能大多以有用功的形式反抗高岭土片层间的吸引力而做功,使层间距大幅度增加,甚至剥离。
以玻璃钢为载体,将纳米级锑系阻燃剂加入到UPR/高岭土纳米复合物中,制备了高阻燃的纳米复合材料,揭示了材料的微观结构与性能的关系以及阻燃机理。结果表明:UPR固化时形成网格结构,在网格结构之间存在间隙;加入阻燃剂后,阻燃剂填充在树脂网络结构中间,但材料的均匀性和紧密度不好,材料的力学性能降低;高岭土插层之后,切面颗粒相对排列紧密,片层结构分布于网格结构间隙,均匀有序,材料的拉伸强度和弹性模量有所提高;将纳米氯氧化锑加入到UPR纳米复合材料中,材料表面致密,材料的力学性能没有降低。阻燃剂提高了树脂的分解温度,Sb_4O_5Cl_2无论是单独还是与卤素协同使用,其阻燃性能都优于超细Sb_2O_3,减少了含卤化合物的用量;纳米级的阻燃效果明显高于微米级的;粘土单独使用时,阻燃效果不明显,但可以提高树脂的热稳定性。在复合材料中,原位聚合不饱和聚酯树脂/4%高岭土插层复合物+6%Sb_4O_5Cl_2+10%氯化石蜡制备的玻璃钢制品氧指数可达35%以上;材料燃烧后表面形成一层致密、光滑、发亮的高岭土吸附层,降低了材料的燃烧性,增强了力学性能。
高聚物纳米复合材料的阻燃机理包括自由基捕获机理和物理作用。聚合物的燃烧过程实际上是高分子与氧气反应生成自由基的链传递过程,Sb_4O_5Cl_2或Sb_2O_3在卤素化合物的协同下,分解生成气相的SbCl_3,捕获气相中能维持燃烧链式反应的活泼自由基,改变了气相的反应模式,减少了反应放出热量从而使火焰淬灭。纳米复合材料的高阻燃特性还取决于其结构,高岭土以纳米尺寸均匀分散在聚合物基体中,限制了UP分子链的活动,提高了树脂的分解温度和材料的阻隔性能;材料在燃烧过程中表面形成含高岭土的坚硬炭层,有效地抑制了挥发性可燃物的转移,热量的扩散和蔓延以及外界氧的进入,使材料获得良好的阻燃性能。
Unsaturated polyester resin(UPR) is widely used in many fields and becomes one of the most application amount thermoset resins because of its excellent performance and simple process. But it’s easily flammable. So flame retardant UPR is widely studied. This dissertation studied the preparation of high flame retarsant UPR/clay nanocomposites containing little halogen- antimony additives though adding little clay and nanoparticles. The properties of nanocomposites were characterized by means of XRD, FTIR, TEM, SEM, TG, DSC, limited oxygen index (LOI), vertical burning test and mechanical analysis. The microstructure, formation and flame retardant mechanism have been studied which will provide theory basis for the development of flame retardant materials.
In the first time, the monodispersed nano-Sb_2O_3, Sb_4O_5Cl_2 nanobelts, nano-Sb_2O_3/ mica and nano-Sb_4O_5Cl_2/mica composition were prepared with SbCl3 as raw material by alcoholysis, through controling supersaturation of solution and reaction rate, decreasing solide-liquid interfacial tension using surfactants. The growth rule of nanoparticles and how to control the dimensionality, size and morphology of products were discovered. The results show that the mean particle size of monodispersed nano-Sb_2O_3 is about 21nm among them the particle size of 74% particles is less than 15nm. The nanoparticles of Sb_2O_3 have assembled uniformly between mica layers and have a narrow size distribution around 5nm, 95% particles. The drive force comes from the electrostatic attraction force.
The distance between the layers limits the growth of particles. The fibers-like structure of Sb_4O_5Cl_2 with 0.3-1.0μm in length and 10-50 nm in diameter were confirmed by TEM. The nano-Sb_4O_5Cl_2 pillared montmorillonite composites were prepared in the first time and the formation mechanism was discussed. The results show that after montmorillonite has been pillared by Sb_4O_5Cl_2, the typical value of d(001) of montmorillonite was increased from 1.2nm to 1.5nm and a diffraction peak appeared in 4nm, the characteristic absorption peak moved. Montmorillonite displayed loose, porous state like honeycomb with Sb_4O_5Cl_2 nanoparticles in it.
The kaolinite/propanediol intercalation compounds (K/PD) were prepared quickly by sonochemistry method in the first time. The intercalation mechanism was discussed from the aspect of themodynamics and intercalating force. The results show that dimethylsulfoxide (DMSO) is the better once intercalating agent and the intercalation rate get up to 91%. In UPR polymerization monomers, only K/PD can be prepared by replacing DMSO in K/DMSO composition. The intercalating drive force comes from the stucture of kaolinite, organic intercalating agent, water, energy and so on. Ultrasonic can provide high temperature, high presure and active seed in some area.
In the first time, Unsaturated polyester resin/kaolinite intercalation nanocomposites (UPR/K) were prepared by in situ polymerization using K/PD intercalation usher as one of reaction monomers. The change process of composites crystal structures were simulated in dynamic mode by using electron beam bombardment, from which the microstructures and intercalation styles were deduced, and the formation mechanism of UPR/K was analysed. The results show that 5% kaolinite can’t effect the properties of resin, the kaolinte layers exfoliated and mixed uniformly in the composites. The energy released from polymerization reaction mostly changes to work resisting attraction force from kaolinite layers, makes distance of layers inlarge in extent, even exfoliate.
The high flame retardant nanocomposites were prepared by adding nano-antimony compound into UPR/K using FRP as carrier. The relationship between microstructure and properties of materials and flame retardant mechanism were discussed. The results show that UPR formed net structure when solidifying. There were holes between nets. The flame retardant addtives filled loose in the net, which result in the mechanical properties of materials decreased. The kaolinite intercalating layers dispered uniformly and tightly in the net hole, which increased the stretching intension and flexibility module, limited the movement of UPR molecular and resultes in the improvement of decomposition temperature of resin. This special nanostructure and larger length-radius ratio also conduce diffusing path more zigzag and diffusing time longer of small moleculars in matrix, so the obstruction properties of materials have improved. After adding nano-Sb_4O_5Cl_2 into UPR/nanocomposites, the materials surface got compact. UPR sample with UPR/4% kaolinite preparing by in situ polymerization +6%Sb_4O_5Cl_2+10%CP-70 has best flame retardant properties with 35% LOI. After burning, The nano-kaolinite layers array flat on the materials surface and form hardness char shell, which inhibites effedtively the volatility combustible materials producing by polymer decomposion transfering to burning zone, the quantity of heat diffusing to no-burning zone and entering of oxygen. Polymer forms active radical, and then passes quickly through a chain reaction while burning. Sb_4O_5Cl_2 or Sb_2O_3 decomposes to produce SbCl3 under synergizing with halogen which can capture active radicals in gas, decreases the energy from reaction and finally makes fire extinguish.
以三氯化锑为原料,采用醇盐水解法,通过控制溶液过饱和度和生长界面的反应速度,采用表面活性剂降低固液界面张力,减小成核半径,首次合成单分散纳米Sb_2O_3和纤维状纳米Sb_4O_5Cl_2,以及纳米Sb_2O_3/云母、纳米Sb_4O_5Cl_2/云母复合物,揭示了纳米粒子生长规律,实现了对于最终产品维度、尺寸和形貌的控制。结果表明:单分散纳米Sb_2O_3平均粒径约为21nm,74%的粒子小于15nm;Sb_2O_3粒子均匀生长在云母表面和层间,其驱动力主要来源于云母表面与颗粒的静电引力,层间距限制了纳米粒子的生长,避免了团聚,因此得到95%的颗粒在5nm左右。优化制备条件为:反应温度45℃,醇化时间1h,SbCl_3/无水乙醇比例5g/30ml,用PEG处理纳米Sb_2O_3。纤维状纳米Sb_4O_5Cl_2分布均匀,单根最长可达1.5μm,长径比在1∶100到1∶200之间。
首次采用酸溶法和醇盐水解法制备了纳米Sb_4O_5Cl_2柱撑蒙脱土,提出纳米Sb_4O_5Cl_2柱撑蒙脱土的形成机理。结果表明:蒙脱土经Sb_4O_5Cl_2柱撑后,001面特征峰由1.2 nm扩大到1.5 nm左右,在4.0 nm层间距处出现一衍射峰;Al-OH振动峰、AlMg-OH弯曲振动的吸收带发生移动;Sb_4O_5Cl_2纳米粒子镶嵌在蒙脱土的片层空隙内。纳米Sb_4O_5Cl_2柱撑膨润土的形成主要通过Sb~(3+)或Sb(OR)_3分子与蒙脱土层间Na~+的交换和吸附,在蒙脱土层间原位水解产生Sb_4O_5Cl_2纳米粒子,达到扩充层间距的目的,同时层间距离限制了纳米粒子的生长,使它粒径小,分散好。
采用超声波法首次实现高岭土/丙二醇(K/PD)的快速插层,并从热力学和插层驱动力的角度分析了插层反应的机理。结果表明:二甲基亚砜(DMSO)是较好的一次插层剂,插层率达91%以上,反应的优化条件为水10%、温度90℃、超声波强度8KHz和3h。UPR聚合单体中,只有PD可以二次取代K/DMSO,实现快速插层,条件为:插层反应温度为80℃,插层时间为3h。插层驱动力来自于高岭土的结构、有机插层剂、水、能量等。在相同条件下,多水、结构压力大的管状结构高岭土比普通的高岭土更易于插层;有机插层剂的性质决定了能否插层和插层效率;水可以破坏插层剂的结构,改变有机分子与高岭土片层的成键方式;超声波通过超声空化作用,提供局部超高温、超高压和“活性种”,插层效率高,所需时间短。
首次以K/PD插层前驱体作为反应单体之一,采用原位聚合法制备了UPR/高岭土纳米复合物,首次采用电子束轰击的方法动态模拟复合物晶格结构变化过程,由此推断其微观结构和插层方式,分析UPR/高岭土的形成机理。结果表明:加入5%以下高岭土对树脂性能影响不大;复合材料中高岭土片层剥离,与树脂混合均匀, X衍射呈非晶态;高岭土表面羟基特征峰发生移动,出现UPR的特征峰,与溶液混合法制备的复合材料明显不同。聚合反应释放的自由能大多以有用功的形式反抗高岭土片层间的吸引力而做功,使层间距大幅度增加,甚至剥离。
以玻璃钢为载体,将纳米级锑系阻燃剂加入到UPR/高岭土纳米复合物中,制备了高阻燃的纳米复合材料,揭示了材料的微观结构与性能的关系以及阻燃机理。结果表明:UPR固化时形成网格结构,在网格结构之间存在间隙;加入阻燃剂后,阻燃剂填充在树脂网络结构中间,但材料的均匀性和紧密度不好,材料的力学性能降低;高岭土插层之后,切面颗粒相对排列紧密,片层结构分布于网格结构间隙,均匀有序,材料的拉伸强度和弹性模量有所提高;将纳米氯氧化锑加入到UPR纳米复合材料中,材料表面致密,材料的力学性能没有降低。阻燃剂提高了树脂的分解温度,Sb_4O_5Cl_2无论是单独还是与卤素协同使用,其阻燃性能都优于超细Sb_2O_3,减少了含卤化合物的用量;纳米级的阻燃效果明显高于微米级的;粘土单独使用时,阻燃效果不明显,但可以提高树脂的热稳定性。在复合材料中,原位聚合不饱和聚酯树脂/4%高岭土插层复合物+6%Sb_4O_5Cl_2+10%氯化石蜡制备的玻璃钢制品氧指数可达35%以上;材料燃烧后表面形成一层致密、光滑、发亮的高岭土吸附层,降低了材料的燃烧性,增强了力学性能。
高聚物纳米复合材料的阻燃机理包括自由基捕获机理和物理作用。聚合物的燃烧过程实际上是高分子与氧气反应生成自由基的链传递过程,Sb_4O_5Cl_2或Sb_2O_3在卤素化合物的协同下,分解生成气相的SbCl_3,捕获气相中能维持燃烧链式反应的活泼自由基,改变了气相的反应模式,减少了反应放出热量从而使火焰淬灭。纳米复合材料的高阻燃特性还取决于其结构,高岭土以纳米尺寸均匀分散在聚合物基体中,限制了UP分子链的活动,提高了树脂的分解温度和材料的阻隔性能;材料在燃烧过程中表面形成含高岭土的坚硬炭层,有效地抑制了挥发性可燃物的转移,热量的扩散和蔓延以及外界氧的进入,使材料获得良好的阻燃性能。
Unsaturated polyester resin(UPR) is widely used in many fields and becomes one of the most application amount thermoset resins because of its excellent performance and simple process. But it’s easily flammable. So flame retardant UPR is widely studied. This dissertation studied the preparation of high flame retarsant UPR/clay nanocomposites containing little halogen- antimony additives though adding little clay and nanoparticles. The properties of nanocomposites were characterized by means of XRD, FTIR, TEM, SEM, TG, DSC, limited oxygen index (LOI), vertical burning test and mechanical analysis. The microstructure, formation and flame retardant mechanism have been studied which will provide theory basis for the development of flame retardant materials.
In the first time, the monodispersed nano-Sb_2O_3, Sb_4O_5Cl_2 nanobelts, nano-Sb_2O_3/ mica and nano-Sb_4O_5Cl_2/mica composition were prepared with SbCl3 as raw material by alcoholysis, through controling supersaturation of solution and reaction rate, decreasing solide-liquid interfacial tension using surfactants. The growth rule of nanoparticles and how to control the dimensionality, size and morphology of products were discovered. The results show that the mean particle size of monodispersed nano-Sb_2O_3 is about 21nm among them the particle size of 74% particles is less than 15nm. The nanoparticles of Sb_2O_3 have assembled uniformly between mica layers and have a narrow size distribution around 5nm, 95% particles. The drive force comes from the electrostatic attraction force.
The distance between the layers limits the growth of particles. The fibers-like structure of Sb_4O_5Cl_2 with 0.3-1.0μm in length and 10-50 nm in diameter were confirmed by TEM. The nano-Sb_4O_5Cl_2 pillared montmorillonite composites were prepared in the first time and the formation mechanism was discussed. The results show that after montmorillonite has been pillared by Sb_4O_5Cl_2, the typical value of d(001) of montmorillonite was increased from 1.2nm to 1.5nm and a diffraction peak appeared in 4nm, the characteristic absorption peak moved. Montmorillonite displayed loose, porous state like honeycomb with Sb_4O_5Cl_2 nanoparticles in it.
The kaolinite/propanediol intercalation compounds (K/PD) were prepared quickly by sonochemistry method in the first time. The intercalation mechanism was discussed from the aspect of themodynamics and intercalating force. The results show that dimethylsulfoxide (DMSO) is the better once intercalating agent and the intercalation rate get up to 91%. In UPR polymerization monomers, only K/PD can be prepared by replacing DMSO in K/DMSO composition. The intercalating drive force comes from the stucture of kaolinite, organic intercalating agent, water, energy and so on. Ultrasonic can provide high temperature, high presure and active seed in some area.
In the first time, Unsaturated polyester resin/kaolinite intercalation nanocomposites (UPR/K) were prepared by in situ polymerization using K/PD intercalation usher as one of reaction monomers. The change process of composites crystal structures were simulated in dynamic mode by using electron beam bombardment, from which the microstructures and intercalation styles were deduced, and the formation mechanism of UPR/K was analysed. The results show that 5% kaolinite can’t effect the properties of resin, the kaolinte layers exfoliated and mixed uniformly in the composites. The energy released from polymerization reaction mostly changes to work resisting attraction force from kaolinite layers, makes distance of layers inlarge in extent, even exfoliate.
The high flame retardant nanocomposites were prepared by adding nano-antimony compound into UPR/K using FRP as carrier. The relationship between microstructure and properties of materials and flame retardant mechanism were discussed. The results show that UPR formed net structure when solidifying. There were holes between nets. The flame retardant addtives filled loose in the net, which result in the mechanical properties of materials decreased. The kaolinite intercalating layers dispered uniformly and tightly in the net hole, which increased the stretching intension and flexibility module, limited the movement of UPR molecular and resultes in the improvement of decomposition temperature of resin. This special nanostructure and larger length-radius ratio also conduce diffusing path more zigzag and diffusing time longer of small moleculars in matrix, so the obstruction properties of materials have improved. After adding nano-Sb_4O_5Cl_2 into UPR/nanocomposites, the materials surface got compact. UPR sample with UPR/4% kaolinite preparing by in situ polymerization +6%Sb_4O_5Cl_2+10%CP-70 has best flame retardant properties with 35% LOI. After burning, The nano-kaolinite layers array flat on the materials surface and form hardness char shell, which inhibites effedtively the volatility combustible materials producing by polymer decomposion transfering to burning zone, the quantity of heat diffusing to no-burning zone and entering of oxygen. Polymer forms active radical, and then passes quickly through a chain reaction while burning. Sb_4O_5Cl_2 or Sb_2O_3 decomposes to produce SbCl3 under synergizing with halogen which can capture active radicals in gas, decreases the energy from reaction and finally makes fire extinguish.
引文
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