CN110093015A - 一种囊泡型高性能环氧树脂复合材料 - Google Patents
一种囊泡型高性能环氧树脂复合材料 Download PDFInfo
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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Abstract
本发明提供了一种具有纳米囊泡结构的高强高韧环氧复合材料，它是由下述重量配比的原料制备而成的：环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～2份。所述BXLS嵌段共聚物中BX‑OH与PCL、PS的分子量之比为1：2.9：10.3。实验结果表明，本发明通过控制BXLS嵌段共聚物中BX‑OH、PCL与PS的分子量，制备出了BXLS//环氧树脂复合材料，使得BXLS嵌段共聚物在环氧树脂中形成了纳米囊泡囊泡结构，并在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加并且还具有更优异的力学强度，极大的拓宽了环氧树脂的应用领域。
Description
技术领域
本发明属于高分子复合材料领域，具体涉及一种囊泡型高性能环氧树脂复合材料。
背景技术
环氧树脂(EP)是一种优良的高强度热固性树脂，是应用非常广泛的基体材料。EP分子上带有两个或两个以上环氧基团，能与胺类、酸酐类、聚酰胺类物质交联固化，形成高度交联的空间三维网状结构，其固化物具有耐磨性好、耐热性优异、化学稳定性良好、电绝缘性优良、强度高、收缩率低、易加工成型、耐化学试剂、对基材具有良好的黏附性能和价格低廉等优点，作为电子涂装、涂料、电气材料、浇注封装材料、胶黏剂、密封胶的基体树脂，被广泛应用在航空航天、汽车、造船、建筑、铁路交通等国民经济的各个领域。但是EP固化后形成的固化物交联密度高，呈空间三维网状结构，分子链间不易滑动，内应力大，从而导致固化物硬脆、易开裂、耐冲击性和抗剥离性差，在实际应用中难以满足使用要求，使其应用受到一定限制，这些缺点都是EP固化物韧性不足造成的。
当前，对环氧树脂的增韧改性途径主要有橡胶弹性体增韧、树脂合金化增韧、热致液晶聚合物增韧、树枝形分子增韧、纳米粒子增韧以及在交联网络中引入柔性链段增韧等方法。随着纳米技术研究的不断深入，通过引入少量纳米结构单元(如纳米粒子、纳米线、纳米管、纳米片层等)而制备出的环氧树脂基纳米复合材料可大大提高树脂固化物的抗冲击性能，而其他物理性能很少受到影响，因而纳米增韧改性环氧树脂非常具有应用前景。
发明内容
本发明的目的在于提供了一种具有纳米囊泡结构的高强高韧环氧复合材料，它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～2份。
进一步地，它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～1.5份。
进一步地，它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～1份。
进一步地，它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5份。
进一步地，所述BXLS嵌段共聚物中BX-OH与PCL、PS的分子量之比为1：2.9：10.3。
进一步地，所述BX-OH为单羟基封端的聚二甲基硅氧烷。
进一步地，所述环氧树脂为双酚A型环氧树脂。
进一步地，所述双酚A型环氧树脂选自E-51、E-44。
进一步地，所述固化剂选自3,3′-二氯-4,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基砜、二氨基二苯甲烷。
进一步地，它是由下述方法制备而成：
(1)BXLS嵌段共聚物的制备：由BX-OH引发ε-己内酯开环聚合后，用原子转移自由基聚合方法合成BXLS嵌段共聚物即可；
(2)按重量配比称取环氧树脂以及BXLS嵌段共聚物，混匀后加入固化剂后再次混匀，真空除泡、固化即可。
本发明将BX-OH与PCL、PS的分子量之比为1：2.9：10.3的BXLS嵌段共聚物命名为PDMS1-PCL2.9-PS10.3，将PDMS1-PCL2.9-PS10.3与环氧树脂制备得到的复合材料命名为PDMS1-PCL2.9-PS10.3/EP体系。
实验结果表明，本发明通过控制BXLS嵌段共聚物中BX-OH、PCL与PS的分子量，制备出了BXLS//环氧树脂复合材料，使得BXLS嵌段共聚物在环氧树脂中形成了纳米囊泡结构，并在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加并且还具有更优异的力学强度，极大的拓宽了环氧树脂的应用领域。
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为力学性能测试试样尺寸图，(a)为拉伸性能测试试样，(b)为断裂韧性测试试样，S为测试跨距，P为载荷，B为试样厚度，W为试样宽度，A为裂纹深度。
图2为原料BX-OH、中间产物BC以及嵌段共聚物BXLS的GPC曲线。
图3为嵌段共聚物BXLS的1HNMR谱图。
图4为含不同嵌段共聚物添加量的环氧树脂的TEM照片。
图5为含不同嵌段共聚物添加量的环氧树脂SAXS曲线。
图6为含6.67wt％BXLS嵌段共聚物的环氧树脂固化前后的SAXS曲线。
图7为含3.45wt％BXLS嵌段共聚物环氧树脂的KIC断面照片。
图8为含不同嵌段共聚物添加量的环氧树脂的拉伸性能的表征图。
图9为含不同嵌段共聚物添加量的环氧树脂的断裂韧性的表征图。
图10为含6.67wt％BXLS嵌段共聚物的环氧树脂的流变性能表征图。
图11为含不同嵌段共聚物添加量的环氧树脂的Tan曲线。
图12为环氧树脂的固化过程复数粘度随时间变化曲线。
具体实施方式
实施例1、本发明复合材料的制备与性能检测
一、本发明复合材料的制备
1实验原料与试剂
BX-OH：端羟基聚二甲基硅氧烷，日本信越化学工业株式会社，货号X-22-107BX(结构式中的R以及R'为短烃链封端单元，例如：丁基(R-：CH3-CH2-CH2-CH2-)、乙基(-R'-：-CH2-CH2-)，然而厂商并没有给出具体的结构式)。己内酯、聚苯乙烯、二溴异丁酰溴、辛酸亚锡等均为化学纯，购于上海阿拉丁生化科技股份有限公司。EP：双酚A型环氧树脂(E51)，凤凰牌环氧树脂，型号WSR618(E51)，南通星成材料有限公司。色度：≤40Pt-Co，环氧当量：184～195g/mol，水解氯：≤0.2％，50mg/kg，挥发物：0.5％，粘度(25℃)：10000～16000mPa.s。4,4'-二氨基-3,3'-二氯二苯甲烷(MOCA)：工业级，常山贝尔化学有限公司。
2实验部分
2.1嵌段共聚物BX-b-PCL(BXL-OH)的合成(嵌段共聚物PDMS-PCL的合成是以辛酸亚锡[Sn(Oct)2]为催化剂，端羟基聚二甲基硅氧烷(BX-OH)引发己内酯(ε-CL)开环聚合得到。具体过程如下:首先，BX-OH(10g,2.56mmol)和干燥的甲苯(20ml)在250ml无水无氧瓶中共沸除水，蒸出多余的甲苯，然后将ε-CL(27g,236.91mmol)和Sn(Oct)2(添加量为1wt‰的ε-CL)加入到上述纯化后的BX中。经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下烧瓶置入120℃的恒温油浴中搅拌反应36h。待反应结束后，将粗产物溶解于适量的二氯甲烷溶液中，然后加入大量的冷冻甲醇沉淀，过滤。重复此溶解-沉淀-过滤过程三次以除去体系中可能存在的副产物和残余单体。将纯化后的产物在30℃的真空烘箱中干燥至恒重。
2.2大分子引发剂BX-b-PCL-Br(BXL-Br)的合成
在三乙胺(TEA)和催化剂4-二甲氨基吡啶(DMAP)存在的条件下，上述方法制备得到的BXL-OH与2-溴异丁基酰溴(2-BiB)在纯化干燥的二氯甲烷(DCM)中反应，合成大分子引发剂BXL-Br。具体过程如下：将溶有TEA(625μl，4.51mmol)、BXL-OH(34.4g，2.25mmol)和DMAP(826mg，6.76mmol)的DCM(200ml)溶液加入到三口圆底烧瓶中，在氩气及冰浴的状态下，搅拌混合均匀。将2-BiB(1.40ml，11.27mmol)溶于50ml的DCM中，冰浴状态下通过恒压漏斗加入到上述混合液中，加入完成后在室温继续搅拌反应24h。反应结束后将溶液旋蒸除去一半溶剂，将剩余产物逐滴滴入冷冻甲醇中沉淀，过滤。重复此溶解-沉淀-过滤过程三次，将纯化后的产物在30℃的真空烘箱中干燥至恒重。
2.3嵌段共聚物聚二甲基硅氧烷-聚己内酯-聚苯乙烯BX-b-PCL-b-PS(BXLS)的合成
BXLS嵌段共聚物是以溴化亚铜(CuBr)为催化剂，N,N,N',N”,N”-五甲基二乙烯三胺(PMDETA)为配位剂，上述产物为大分子引发剂进行原子转移自由基聚合得到。合成步骤表述如下：向250ml的无水无氧瓶中依次加入大分子引发剂(BXL-Br，12g,0.78mmol)、苯乙烯单体(35.76g,343.83mmol)、CuBr(112mg，0.78mmol)和PMDETA(165μL，0.78mmol)，搅拌均匀，经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下烧瓶置入110℃的油浴中磁力搅拌24小时。待反应结束后，将产物暴漏在空气中冷却至室温使反应停止。将产物溶于二氯甲烷并通过中性氧化铝柱子以除去催化剂。旋蒸浓缩溶液并逐滴滴入大量冷冻甲醇中沉淀，过滤。经三次溶解-沉淀-过滤过程后，将最终产物在30℃的真空烘箱中干燥至恒重。
2.4BXLS/环氧树脂复合材料的制备
将上述合成的嵌段共聚物加入到环氧预聚体(DGEBA)中，在120℃下剧烈搅拌直至形成均匀溶液，再将固化剂MOCA加入体系中，混合均匀。将所得共混溶液放入110℃真空烘箱以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2小时，然后升温至180℃固化2小时。固化反应结束后，脱模得到含嵌段共聚物的环氧热固性树脂。各样品编号及组成如表1所示。
表1.BXLS/环氧树脂复合材料的配方
二、本发明复合材料的性能检测
1测试与表征
1.1凝胶渗透色谱(GPC)
采用美国Waters公司的Waters1515型凝胶渗透色谱仪，以流速0.5μL/min的四氢呋喃为流动相，聚苯乙烯作为标准样，30℃下对原料及合成产物进行分子量测试。
1.2核磁共振氢谱(NMR)
采用德国Bruker公司的DRX-400核磁共振光谱仪，以氘代氯仿作为溶剂，在25℃获得了400MHz的核磁波谱图。
1.3透射电镜(TEM)
利用徕卡UC7低温超薄切片机在-120℃下对样品进行切片，所得式样厚度100～150nm。经过15min四氧化钌常温熏染后，在Tecnai G2F20型透射电镜上进行观察，低电子束流小于10mA，加速电压为120keV。
1.4小角X射线散射(SAXS)
采用法国Xenocs公司配备PILATUS 3R 300K检测器及热台的Xeuss 2.0SAXS/WAXS对样品进行小角X射线散射测试，X射线波长为50kV，0.6mA，曝光时间为10min。
1.5场发射扫描电镜(FESEM)
样品首先在液氮中进行脆断，在真空中对其脆断面进行喷金处理，采用美国FEI公司Nova NanoSEM 450型场发射扫描电镜对样品进行微观结构表征，加速电压为5kV。
1.6拉伸及断裂韧性测试
采用Instron 5567万能材料试验机，对样条进行拉伸及断裂韧性测试，样条尺寸如图1所示。拉伸性能测试速度为2mm/min。根据ASTM D5045标准测试试样的断裂韧性，由下式计算试样的断裂韧性，测试速率为2mm/min。
1.7流变测试
采用英国马尔文公司的旋转流变仪，在单频1Hz，150摄氏度恒温过程模拟环氧树脂的固化过程，研究嵌段共聚物分相及环氧树脂的固化行为。
1.8DAM测试
采用美国TA公司的Q800型动态机械分析测试仪，在三点弯曲模式下，以升温速率3℃/min在25-250℃范围内进行扫描，其中测试频率为15Hz。样品尺寸为20mm×10mm×4mm。
2结果与讨论
2.1嵌段共聚物的合成表征
从图2可以看出，BX-OH、BC和BXLS的分子量分别为3915(Mw/Mn＝1.06)，15268(Mw/Mn＝1.44)和55404(Mw/Mn＝1.29)。经计算得出BXLS中BX-OH、PCL与PS的分子量之比为3915：11353：40136，即所得BXLS嵌段共聚物中，BX-OH与PCL、PS的分子量之比为1：2.9：10.3。
从图3可以看出，合成的嵌段共聚物同时具有BX-OH、PCL以及PS的结构特征。
2.2微观结构表征
由图4的TEM照片可知，嵌段共聚物以纳米囊泡结构均匀分散在环氧树脂基体中，添加量为3.45wt％和6.67wt％时，囊泡直径分别为～40nm和～47nm。从图5看出由于纳米多层囊泡的较差的形态规整性及较宽的尺寸分布，SAXS只能观察到强度较弱的宽肩峰。随嵌段共聚物的增多，SAXS曲线具有相似的变化趋势，表明纳米结构形态不随嵌段共聚物的增多而变化。
2.3微观结构形成过程研究
图6为含6.67wt％BXLS嵌段共聚物的环氧树脂固化前后的SAXS曲线。结果表明，固化前，未观察到散射峰(肩)的存在，归因于纳米结构较差的形态及尺寸规整性及较少的分相结构。150℃固化50min后，在0.005～0.015之间出现宽肩，表明此时体系分相结构含量增加，尺寸及形态规整性提升。完全固化后，0.005～0.015之间的宽肩强度增加，表明体系纳米结构的尺寸及形态规整度随固化进程的发生逐渐提升。
图10为含6.67wt％BXLS嵌段共聚物的环氧树脂的流变性能表征图。结果表明，在环氧树脂凝胶点之前，体系粘性模量大于弹性模量，体系表现出典型的液体特性；未观察到明显的PS反应诱致微相分离阶段，归因于更大的PS分子量，在更低的交联度发生分相，且分相过程更温和，持续时间更长。
2.4拉伸性能测试
从图8可以看出，纯环氧树脂的拉伸强度和断裂伸长率分别为71.3MPa和4.4％。当嵌段共聚物添加量仅为1.75wt％时，拉伸强度达到最大值81.6MPa，为环氧树脂的1.15倍。材料断裂伸长率在添加量为1.75wt％时达到最大值5.86％，为环氧树脂的1.33倍；进一步增加嵌段共聚物的添加量断裂伸长率逐渐降低。当嵌段共聚物添加量为1.75wt％时，杨氏模量达到最大值2466MPa。
2.5断裂韧性测试
从图9可以看出，随嵌段共聚物添加量的增多，材料的断裂韧性与断裂伸长率具有相同的变化趋势。纯环氧树脂的断裂韧性为47N/mm3/2。当嵌段共聚物含量仅为1.75wt％时，材料断裂韧性即有明显的提升，达到最大值129.6N/mm3/2(为纯环氧树脂的2.76倍)。相比于现有技术，本发明可以在嵌段共聚物极低添加量下实现材料韧性的显著增加，具有明显的优势。
2.6动态热机械分析
含不同嵌段共聚物添加量的环氧树脂的动态热机械分析(DMA)结果如图11Tan曲线和表3结果所示。可以看出引入嵌段共聚物后，环氧复合材料的储能模量玻璃化转变温度、和交联密度均有不同程度的提升。当添加量为1.75wt％和3.45wt％时，材料的储能模量分别为3180MPa和4428MPa，为纯环氧树脂的1.38倍和1.93倍。
表3
2.7增韧机理研究
图7为含3.45wt％BXLS的环氧树脂KIC断面图，容易看出，复合体系断面出现裂纹偏转及终止，纳米囊泡引发基体产生了微裂纹。
综上，本发明通过控制BXLS嵌段共聚物中BX-OH、PCL与PS的分子量，制备出了BXLS//环氧树脂复合材料，使得BXLS嵌段共聚物在环氧树脂中形成了纳米囊泡结构，并在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加并且还具有更优异的力学强度，极大的拓宽了环氧树脂的应用领域。
Claims (9)
1.一种具有纳米囊泡结构的高强高韧环氧复合材料：它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～2份，所述BXLS嵌段共聚物中BX-OH与PCL、PS的分子量之比为1：2.8～3.0：10.2～10.4；BX-OH为端羟基聚二甲基硅氧烷。
2.根据权利要求1所述的复合材料，其特征在于：它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～1.5份。
3.根据权利要求2所述的复合材料，其特征在于：它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5～1份。
4.根据权利要求3所述的复合材料，其特征在于：它是由下述重量配比的原料制备而成的：
环氧树脂20份、固化剂8份、BXLS嵌段共聚物0.5份。
5.根据权利要求1～4任一项所述的复合材料，其特征在于：所述BXLS嵌段共聚物中BX-OH与PCL、PS的分子量之比为1：2.9：10.3。
6.根据权利要求5所述的复合材料，其特征在于：所述BX-OH为单羟基封端的聚二甲基硅氧烷。
7.根据权利要求1～4任一项所述的复合材料，其特征在于：所述环氧树脂为双酚A型环氧树脂。
8.根据权利要求7所述的复合材料，其特征在于：所述双酚A型环氧树脂选自E-51、E-44。
9.根据权利要求1～4任一项所述的复合材料，其特征在于：所述固化剂选自3,3′-二氯-4,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基砜、二氨基二苯甲烷。
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