CN106800657B - 共聚物与环氧树脂复合物 - Google Patents
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract
Description
【技术领域】
本发明涉及环氧树脂复合物,更特别涉及其增韧剂的结构。
【背景技术】
热固型环氧树脂广泛使用于各种领域,包含建筑、涂料、电子设备与纤维复合材料,然而其热固化反应后为高密度交联的聚合物网络,因此存在有易碎与抗冲击性不佳的问题。近几年的发展中,在复合材料、涂料及电子产品的发展上特别需要有较好热稳定性的热固型环氧树脂,一般通过提高环氧树脂交联密度的方式增加其热稳定性,此方法造成环氧树脂更为易碎与抗冲击性降低,因此环氧树脂的增韧为重要发展方向。目前环氧树脂的增韧可通过添加端羧基丁腈橡胶(CTBN)来达到改善的效果,但CTBN的添加往往造成环氧树脂的热稳定性(玻璃态转变温度)下降,因此如何改善环氧树脂的韧性同时不影响其热稳定性为重要的课题。
【发明内容】
本发明一实施例提供共聚物,具有以下结构式:
其中R为C1-6烷撑基;T为封端基,包含C1-6烷基、C3-6环烷基、或C6-12芳基;l介于0.05至0.3之间,m介于0.1至0.2之间,n介于0.5至0.8之间,l+m+n=1,x介于40至100,以及o介于10至120之间。
本本发明一实施例提供环氧树脂复合物,包括:100重量份的环氧树脂;以及1至20重量份的增韧剂,其为共聚物且具有结构式:
其中R为C1-6烷撑基;T为封端基,包含C1-6烷基、C3-6环烷基、或C6-12芳基;l介于0.05至0.3之间,m介于0.1至0.2之间,n介于0.5至0.8之间,l+m+n=1,x介于40至100,以及o介于10至120之间。
【具体实施方式】
本发明一实施方式提供共聚物,具有结构式如式1:
在式1中,R为C1-6烷撑基,而T为封端基,包含C1-6烷基、C3-6环烷基、或C6-12芳基。式1的共聚物为三嵌段(ABA)共聚物,A为封端的聚乙二醇(end capped PEG),而B为端羧基丁腈橡胶(CTBN),两者之间以酯基连接。在某些实施方式中,封端基为甲基,因此共聚物可简示为MPEG-CTBN-MPEG。在一实施方式中,l介于0.05至0.3之间,m介于0.1至0.2之间,n介于0.5至0.8之间,且l+m+n=1。上述l、m、n、与x的范围可由商品选择调整,或由合成单体的比例决定。若是自行合成,可参考专利US 3285949。在这应说明的是,CTBN中对应l、m、与n的重复单元属无规排列,即CTBN为无规共聚物。
在一实施方式中,o介于10至120之间。若o过小,则无法产生环氧树脂增韧的效果。若o过大,则使环氧树脂的玻璃态转变温度(Tg)下降。上述o的范围可由商品选择调整,或由合成单体的比例决定。若是自行合成,可参考专利US20100172996。另一方面,若将对应o的重复单元(乙二醇)置换为其他烷基醇如丙二醇,则形成的共聚物将无法与后述的环氧树脂相容以增加环氧树脂复合物的韧度。
在一实施方式中,上述聚合物的合成方式如下。应理解的是,下述合成方式仅为举例而非局限本发明。本领域技术人员自可选择其他合成路径合成 上述聚合物,而不限于下述合成方式。
首先,取CTBN与SOCl2反应,使CTBN末端的羧基转变为酰氯基。接着取一侧封端的PEG(如MPEG)与酰氯基反应,即形成三嵌段共聚物。上述反应如式2所示,且式2中的R、T、l、m、n、o、与x的定义如前述。
在一实施方式中,上述共聚物可作为环氧树脂的增韧剂。举例来说,100重量份的环氧树脂搭配1至20重量份的增韧剂,该增韧剂如上述共聚物,即可有效提升环氧树脂复合物的韧度,且不会降低环氧树脂复合物的热稳定性如Tg。若上述共聚物的比例过低,则无法有效提升环氧树脂复合物的韧度。若上述共聚物的比例过高,则会使环氧树脂整体的热稳定性下降。在环氧树脂复合物中,共聚物的CTBN链段会朝内聚集,而两侧的封端PEG(如MPEG)则朝外形成微胞。上述共聚物与环氧树脂之间不会产生化学键结(交联)。若共聚物含有其他可能与环氧树脂交联的官能基如环氧基、羧基、羟基、或胺基,则共聚物将与环氧树脂交联而降低环氧树脂复合物的韧性。在一实施方式中,环氧树脂可为双酚A型环氧树脂、双酚F型环氧树脂、酚醛清漆型环氧树脂、甲酚-酚醛清漆型环氧树脂、四官能基胺型环氧树脂,或上述的组合。在一实施方式中,上述环氧树脂复合物可进一步包括1至100重量份的添加剂 如硬化剂、促进剂、阻燃剂、抑烟剂、紫外线吸收剂、或上述的组合。上述添加剂可进一步调整环氧树脂复合物的性质。举例来说,硬化剂可为脂肪族胺、芳香族胺、杂环胺、或双氰胺,促进剂可为咪唑类、有机酸酐、硫化物、或过氧化物,阻燃剂可为有卤阻燃剂、无卤阻燃剂、无机阻燃剂、或有机无机掺混阻燃剂,抑烟剂可为三氧化钼、氢氧化镁、八钼酸胺、或硼酸锌,而紫外线吸收剂可为二苯甲酮类、水杨酸酯类、芳香族化合物、或咪唑类。上述添加剂可进一步调整环氧树脂复合物的性质。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举多个实施例,作详细说明如下:
实施例
制备例1(制备MPEG750-CTBN-MPEG750)
取30g CTBN(购自Emerald/CVC的Hypro 1300X13)与100mL无水CH2Cl2,启动磁石搅拌至完全互溶后,加入4g SOCl2,加热至55℃回流反应,可得中间产物CTBN-COCl,即末端官能基为酰氯(-COCl)的CTBN。
将上述反应结果减压蒸馏(0.5torr及60℃)以除去未反应的SOCl2及无水CH2Cl2。接着以200mL无水CH2Cl2溶解CTBN-COCl,再加入14.1g MPEG750(购自Aldrich,分子量750),加热至55℃回流反应。反应完成后以热水再沉淀除去未反应的MPEG750,可得产物MPEG750-CTBN-MPEG750(如式1,其中T为甲基)。
利用FTIR鉴定产物MPEG750-CTBN-MPEG750,可观察到在1102cm-1位置出现氧乙烯(ethylene oxide)链段的特征峰,在1736cm-1位置则可观察到羰基(carbonyl group)的特征峰,即MPEG750成功键结至CTBN。利用1H NMR鉴定产物MPEG750-CTBN-MPEG750,其在3~4ppm的位置出现氧乙烯(ethylene oxide)链段的特征峰,由积分面积比较可知MPEG750与CTBN的摩尔比约为2:1,即证明MPEG750-CTBN-MPEG750已成功制备。以GPC分析MPEG750-CTBN-MPEG750可知其数均分子量为11,094。
制备例2(制备MPEG2000-CTBN-MPEG2000)
与制备例1类似,差别在于将制备例1的MPEG750置换为MPEG2000(购自Aldrich,分子量2000)。同样以FTIR与1H NMR鉴定产物MPEG2000-CTBN-MPEG2000,可观察到类似性质,证明成功制备产物 MPEG2000-CTBN-MPEG2000(如式1,其中T为甲基)。以GPC分析MPEG2000-CTBN-MPEG2000可知其数均分子量为15,009。
制备例3(制备MPEG5000-CTBN-MPEG5000)
与制备例1类似,差别在于将制备例1的MPEG750置换为MPEG5000(购自Aldrich,分子量5000)。同样以FTIR与1H NMR鉴定产物MPEG5000-CTBN-MPEG5000,可观察到类似性质,证明成功制备产物MPEG5000-CTBN-MPEG5000(如式1,其中T为甲基)。以GPC分析MPEG5000-CTBN-MPEG5000可知其数均分子量为29,525。
比较例1
取100重量份双酚A型环氧树脂(购自Ciba的Araldite LY 556)、90重量份酸酐硬化剂(购自Huntsman的Aradur 917)、与2重量份促进剂(购自Huntsman的Accelerator DY070)置入高速均质搅拌机(High Speed Dispersed Home Mixer,由台湾伸球企业有限公司所制造,型号为HC0025)中均匀混掺,以得到基质。
接着于30℃下搅拌上述基质,再将基质灌入试片模具中硬化(硬化条件:80℃恒温4小时,接着150℃恒温8小时),即得环氧树脂复合物。
比较例2-1
于30℃下搅拌85重量份比较例1的基质,再加入约15重量份CTBN(Hypro 1300X13)作为增韧剂,再搅拌30分钟。将上述混合物灌入试片模具中硬化(硬化条件:80℃恒温4小时,接着150℃恒温8小时),即得环氧树脂复合物。
比较例2-2
与比较例2-1类似,差别在于基质用量减少至80重量份,而增韧剂CTBN的用量增加至20重量份。
实施例1-1
于30℃下搅拌95重量份比较例1的基质,再加入约5重量份制备例1的MPEG750-CTBN-MPEG750作为增韧剂,再搅拌30分钟。将上述混合物灌入试片模具中硬化(硬化条件:80℃恒温4小时,接着150℃恒温8小时),即得环氧树脂复合物的试片,且试片尺寸依ASTM测试方法而定。
实施例1-2
与实施例1-1类似,差别在于基质用量减少至90重量份,而增韧剂 MPEG750-CTBN-MPEG750的用量增加至10重量份。
实施例2
于30℃下搅拌95重量份比较例1的基质,再加入约5重量份制备例2的MPEG2000-CTBN-MPEG2000作为增韧剂,再搅拌30分钟。将上述混合物灌入试片模具中硬化(硬化条件:80℃恒温4小时,接着150℃恒温8小时),即得环氧树脂复合物的试片,且试片尺寸依ASTM测试方法而定。
实施例3
于30℃下搅拌95重量份比较例1的基质,再加入约5重量份制备例2的MPEG5000-CTBN-MPEG5000作为增韧剂,再搅拌30分钟。将上述混合物灌入试片模具中硬化(硬化条件:80℃恒温4小时,接着150℃恒温8小时),即得环氧树脂复合物的试片,且试片尺寸依ASTM测试方法而定。
分别对比较例1、比较例2-1、比较例2-2、实施例1-1、实施例1-2、实施例2和实施例3进行树脂韧性评估:(1)拉伸韧性(Tensile toughness)(ASTM D638);(2)破坏韧性(Fracture toughness)(Izod impact,ASTM D256);(3)断裂韧性K1c:单边切口悬臂梁(Single-edge notched bending)(SENB,ATDM D5045);(4)断裂韧性G1c(ASTM D2344),以及(5)耐热性测试(玻璃态转变温度,Tg),测试数值越高代表破坏韧性越佳,测试结果如表1所示。
表1
由表1可知,增韧剂的添加可有效提升环氧树脂复合物的拉伸韧性与破坏韧性,且热稳定性(Tg)可维持与纯环氧树脂相同水准(约152.2℃)。综上所述,本发明制备的增韧剂可有效提升环氧树脂的韧性,且解决传统增韧剂如CTBN降低环氧树脂热稳定性的问题。
虽然本发明已以数个实施例揭露如上,然其并非用以限定本发明,任何本领域技术人员在不脱离本发明的精神和范围内,应可作任意的更动与润饰,因此本发明的保护范围应以所附权利要求书所界定的范围为准。
Claims (7)
2.如权利要求1所述的共聚物,其中T为甲基。
4.如权利要求3所述的环氧树脂复合物,其中T为甲基。
5.如权利要求3所述的环氧树脂复合物,其中该环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、酚醛清漆型环氧树脂、甲酚-酚醛清漆型环氧树脂、四官能基胺型环氧树脂,或上述的组合。
6.如权利要求3所述的环氧树脂复合物,还包括1至100重量份的添加剂。
7.如权利要求6所述的环氧树脂复合物,其中该添加剂包括硬化剂、促进剂、阻燃剂、抑烟剂、紫外线吸收剂、或上述的组合。
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