CN105400196B - 一种改善八苯基笼型倍半硅氧烷在聚酰亚胺基材中分散性能的方法 - Google Patents
一种改善八苯基笼型倍半硅氧烷在聚酰亚胺基材中分散性能的方法 Download PDFInfo
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Abstract
一种改善八苯基笼型倍半硅氧烷(Ph‑POSS)在聚酰亚胺基材中分散性能的方法,属于笼型倍半硅氧烷(POSS)/聚酰亚胺(PI)杂化材料的制备技术领域。本发明通过对部分Ph‑POSS进行修饰,将单纯的共混体系变为一种共聚与共混相结合的体系,从而改变聚酰亚胺基材微观链结构,以达到改善Ph‑POSS在聚酰亚胺基材中的分散性的作用。该方法解决了单纯共混所出现的相分离问题。同时相比于在填料上修饰功能基团已达到良好分散性的传统共混方法,该方法简化了工艺、节约了成本、更利于工业化生产。其可以广泛应用于各种聚酰亚胺基材与Ph‑POSS的复合材料的制备。所制备的复合材料将具体有优异的耐高温性能,机械性能以及介电性能,可以应用于微电子、航空航天等领域。
Description
技术领域
本发明属于笼型倍半硅氧烷(POSS)/聚酰亚胺(PI)杂化材料的制备技术领域,具体涉及一种改善八苯基笼型倍半硅氧烷(Ph-POSS)在聚酰亚胺基材中分散性能的方法。
背景技术
笼型倍半硅氧烷(简称POSS)是一类具有纳米尺度(0.5~3nm)和明确结构的笼型分子。它是由一个无机基团与其周围连接的有机基团构成,其中最常见的为T8结构的POSS,其分子式可表示为(RSiO1.5)8,R基团为与硅氧烷核心连接的有机基团。POSS的独特结构使其广范应用于有机无机杂化材料的制备。作为一种新型纳米填料,POSS的加入可以有效地降低材料的介电常数,同时增加材料的机械性能与耐高温性能。
聚酰亚胺(PI)是一种高性能的特种工程塑料,其具有优异的耐热性、耐溶剂性以及介电性能,现已广泛应用在航空航天、微电子、分离膜等多个领域。各国普遍认定PI为21世纪最有希望的工程塑料之一。基于PI本身的优异性能,POSS的添加可以进一步增强其在介电、耐热、抗原子氧等方面的性能,所以POSS/PI杂化材料一直是各类POSS杂化材料中的一个研究重点。
国内外大量研究表明,单纯通过物理共混所得到的POSS/PI杂化材料会出现明显的团聚现象,产生宏观的相分离,导致材料性能下降。所以近些年对于POSS/PI杂化材料的研究一直集中于合成具有反应活性的POSS单体或是通过对POSS分子进行修饰使其更好的分散于PI基材中。这两种方法都可以达到预期的效果,获得性能优良的POSS/PI杂化材料,但是这两种方法普遍存在制备困难、成本高、难以量产等缺点。所以目前POSS/PI杂化材料的研究还多局限于科研,由科研向应用的转化也成为了一个研究者格外关注的问题。
基于POSS/PI杂化材料巨大的应用价值,以及现阶段由科研向实际应用转化过程中存在的问题,本发明从改变聚合物分子链结构的角度出发,开发出一种改善八苯基笼型倍半硅氧烷在聚酰亚胺基材中分散性能的新方法。该方法能够应用于制备各种PI基材的POSS/PI杂化材料,简化了制备工艺、降低了制备成本,在目前大量使用POSS/PI杂化材料的微电子与航空航天等领域有很大的应用前景。
发明内容
本发明的目的是提供一种改善八苯基笼型倍半硅氧烷(Ph-POSS)在聚酰亚胺基材中分散性能的新方法。
本发明通过对部分Ph-POSS进行修饰,将单纯的共混体系变为一种共聚与共混相结合的体系,从而改变聚酰亚胺基材微观链结构,以达到改善Ph-POSS在聚酰亚胺基材中的分散性的作用。该方法解决了单纯共混所出现的相分离问题。同时相比于在填料上修饰功能基团已达到良好分散性的传统共混方法,该方法简化了工艺、节约了成本、更利于工业化生产。其可以广泛应用于各种聚酰亚胺基材与Ph-POSS的复合材料的制备。所制备的复合材料将具体有优异的耐高温性能,机械性能以及介电性能,可以应用于微电子、航空航天等领域。
本发明所述方法其反应式如下所示:
具体步骤如下:
(1)合成基体聚酰胺酸(PAA)溶液
在氮气保护的容器中,将4,4`-二氨基二苯醚(ODA)和3,3,4,4-联苯二酐(BPDA)按摩尔比1:1.08~1.17投料,无水DMF为溶剂,含固量为10%~30%,0℃条件下,恒温搅拌8~24小时,获得PAA溶液,其合成反应式如下:
n值随ODA与BPDA的投料比变化,控制为6~15间的整数
(2)制备OAPS,其反应式如下
冰盐浴、搅拌条件下,将质量比1:5~6的Ph-POSS和氯仿混合,然后缓慢滴加与氯仿等体积的发烟硝酸;滴加完毕后,继续在冰盐浴条件下反应1~2小时,之后于室温条件下继续搅拌6~12小时;反应结束后,出料于冰水混合物中,收集有机相;反复水洗有机相,直至pH=7.0,蒸馏除掉氯仿,获得淡黄色粉末,为中间产物ONPS;
以等质量的ONPS与铁粉为原料,以乙醇为溶剂,含固量为10%~20%,用盐酸调节pH=3.0~5.0,之后在氮气保护下加热回流6~12小时;待体系降温至室温后过滤,滤液出料于水中,反复水洗析出淡黄色粉末,真空条件下烘干获得OAPS。(八氨基苯基笼形倍半硅氧烷改性的双马来酰亚胺树脂;黄福伟,周燕,沈学宁,黄发荣,杜磊;宇航材料工艺,2008年,第2期,17-20页)
(3)共混前对的填料的预处理
以OAPS、Ph-POSS为反应物,OAPS的摩尔用量为PAA摩尔量的1/7~1/8,Ph-POSS的质量用量为PAA质量的1%~5%,以无水DMF为溶剂,含固量为40~60%,在超声震荡条件下反应2~6小时使OAPS全部溶解并使Ph-POSS充分分散,获得由溶剂与填料组成的浊液;
(4)杂化材料的制备
于0℃氮气保护下,向PAA溶液中加入由溶剂与填料组成的浊液,机械搅拌2~4小时;体系粘度明显增大,且不溶的Ph-POSS分子均匀分散于体系之中;采用流延成膜的方法铺膜,于烘箱中采用程序升温,60~100℃时的升温速度为20~30℃/2小时,100~300℃时的升温速度为50~70℃/2小时,最后于300℃下保持2~4小时,获得亚胺化之后的POSS/PI杂化材料薄膜。
并对薄膜进行XRD,SEM,DSC,介电常数等测试,对POSS分子在材料中的分散性,以及材料的介电性能变化进行表征。
附图说明
图1:实施例1~3中杂化材料的断面电镜照片。
图2:实施例1~3中杂化材料的XRD谱图。
表1:POSS/PI杂化材料投料量以及介电常数、玻璃化转变温度
具体实施方式
实施例1
对填料的预处理:将POSS(0.20g)与DMF(5mL)加入烧瓶中,超声波震荡处理3小时,得到填料均匀分散的浊液。
八苯基POSS与线性聚酰亚胺基材的共混:在氮气保护的容器中,加入4,4`-二氨基二苯醚(2.00g)、3,3,4,4-联苯二酐(2.94g),加入无水DMF(30mL)作为溶剂,0℃条件下,恒温搅拌18小时,获得PAA溶液。再向PPA溶液中加入事先处理好的填料浊液,继续搅拌2小时。
采用流延成膜的方法铺膜,于烘箱中采用程序升温,使温度从60℃开始每隔2小时升高20℃,待100℃以后每隔2小时升高50℃,最后于300℃下保持2小时,获得亚胺化之后的POSS/PI杂化材料薄膜。
对薄膜进行SEM(见图1),XRD(见图2),介电常数(见表1),DSC(见表1)测试,对POSS分子在材料中的分散性,以及材料的介电性能变化进行表征。从电镜照片中可以看出八苯基POSS与线性聚酰亚胺基材的共混发生了明显的团聚现象(图中白色框内标识部分)。图2中对应的XRD谱图也呈现出由团聚POSS所产生的尖锐衍射峰。这说明POSS无法均匀分散于传统的线性聚酰亚胺中。其介电常数与Tg也和未经过共混的传统线性聚酰亚胺材料相近,证明团聚的POSS对聚合物性能的贡献几乎没有。
实施例2
OAPS的制备:冰盐浴、搅拌条件下,将质量比10.0g Ph-POSS和60mL氯仿置于圆底烧瓶中,然后缓慢滴加60mL发烟硝酸;滴加完毕后,继续在冰盐浴条件下反应2小时,之后于室温条件下继续搅拌10小时;反应结束后,出料于冰水混合物中,收集有机相;反复水洗有机相,直至pH=7.0,蒸馏除掉氯仿,获得淡黄色粉末9.7g,为中间产物ONPS,产率69.8%;
将9.7g ONPS,9.7g铁粉和80mL乙醇加入圆底烧瓶,用盐酸调节pH=3.5,之后在氮气保护下加热回流10小时;待体系降温至室温后过滤,滤液出料于水中,反复水洗析出淡黄色粉末,真空条件下烘干获得OAPS 7.8g,产率97.1%。
对填料的预处理:将OAPS(0.17g),POSS(0.20g)与DMF(5mL)加入烧瓶中,超声波震荡处理3小时,得到填料均匀分散的浊液。
八苯基POSS与线性聚酰亚胺基材的共混:在氮气保护的容器中,加入4,4`-二氨基二苯醚(1.88g)、3,3,4,4-联苯二酐(3.06g),加入无水DMF(30mL)作为溶剂,0℃条件下,恒温搅拌20小时,获得PAA溶液。再向PPA溶液中加入事先处理好的填料浊液,继续搅拌2小时。
采用流延成膜的方法铺膜,于烘箱中采用程序升温,使温度从60℃开始每隔2小时升高16℃,待100℃以后每隔2小时升高50℃,最后于300℃下保持2小时,获得亚胺化之后的POSS/PI杂化材料薄膜。并对薄膜进行SEM(见图1),XRD(见图2),介电常数(见表1),DSC(见表1)测试,对POSS分子在材料中的分散性,以及材料的介电性能变化进行表征。从电镜照片中可以看出在采用这种新方法制备的杂化材料中两种POSS均没有产生团聚现象。图2中对应的XRD谱图也呈现出非晶聚合物的特征曲线,由POSS产生的尖锐衍射峰几乎不可见。这说明这种新方法可以制备具有极好分散性的POSS/PI杂化材料。其介电常数相较于传统线性聚酰亚胺的数值(3.4)也有较大降低。
实施例3
OAPS的制备:冰盐浴、搅拌条件下,将质量比10.0g Ph-POSS和60mL氯仿置于圆底烧瓶中,然后缓慢滴加60mL发烟硝酸;滴加完毕后,继续在冰盐浴条件下反应2小时,之后于室温条件下继续搅拌10小时;反应结束后,出料于冰水混合物中,收集有机相;反复水洗有机相,直至pH=7.0,蒸馏除掉氯仿,获得淡黄色粉末9.7g,为中间产物ONPS,产率69.8%;
将9.7g ONPS,9.7g铁粉和80mL乙醇加入圆底烧瓶,用盐酸调节pH=3.5,之后在氮气保护下加热回流10小时;待体系降温至室温后过滤,滤液出料于水中,反复水洗析出淡黄色粉末,真空条件下烘干获得OAPS 7.8g,产率97.1%。
对填料的预处理:将OAPS(0.25g),POSS(0.20g)与DMF(5mL)加入烧瓶中,超声波震荡处理3小时,得到填料均匀分散的浊液。
八苯基POSS与线性聚酰亚胺基材的共混:在氮气保护的容器中,加入4,4`-二氨基二苯醚(1.81g)、3,3,4,4-联苯二酐(3.13g),加入无水DMF(30mL)作为溶剂,0℃条件下,恒温搅拌20小时,获得PAA溶液。再向PPA溶液中加入事先处理好的填料浊液,继续搅拌2小时。
采用流延成膜的方法铺膜,于烘箱中采用程序升温,使温度从60℃开始每隔2小时升高30℃,待100℃以后每隔2小时升高70℃,最后于300℃下保持4小时,获得亚胺化之后的POSS/PI杂化材料薄膜。并对薄膜进行SEM(见图1),XRD(见图2),介电常数(见表1),DSC(见表1)测试,对POSS分子在材料中的分散性,以及材料的介电性能变化进行表征。从电镜照片中可以看出在采用这种新方法制备的杂化材料中两种POSS均没有产生团聚现象。图2中对应的XRD谱图也呈现出非晶聚合物的特征曲线,由POSS产生的尖锐衍射峰几乎不可见。这说明这种新方法可以制备具有极好分散性的POSS/PI杂化材料。其介电常数相较于传统线性聚酰亚胺的数值(3.4)也有很大降低。
Claims (3)
1.一种改善八苯基笼型倍半硅氧烷Ph-POSS在聚酰亚胺基材中分散性能的方法,其步骤如下:
(1)合成基体聚酰胺酸PAA溶液
在氮气保护的容器中,将4,4`-二氨基二苯醚ODA和3,3,4,4-联苯二酐BPDA按摩尔比1:1.08~1.17投料,无水DMF为溶剂,固含量为10%~30%,0℃条件下,恒温搅拌8~24小时,获得PAA溶液;
(2)制备OAPS
冰盐浴、搅拌条件下,将质量比1:5~6的八苯基笼型倍半硅氧烷Ph-POSS和氯仿混合,然后缓慢滴加与氯仿等体积的发烟硝酸;滴加完毕后,继续在冰盐浴条件下反应1~2小时,之后于室温条件下继续搅拌6~12小时;反应结束后,出料于冰水混合物中,收集有机相;反复水洗有机相,直至pH=7.0,蒸馏除掉氯仿,获得淡黄色粉末,为中间产物ONPS;
以等质量的ONPS与铁粉为原料,以乙醇为溶剂,固含量为10%~20%,调节pH=3.0~5.0,之后在氮气保护下加热回流6~12小时;待体系降温至室温后过滤,滤液出料于水中,反复水洗析出淡黄色粉末,真空条件下烘干获得OAPS;
(3)共混前对填料的预处理
以OAPS、Ph-POSS为反应物,OAPS的摩尔用量为PAA摩尔量的1/7~1/8,Ph-POSS的质量用量为PAA质量的1%~5%,以无水DMF为溶剂,固含量为40~60%,在超声震荡条件下反应2~6小时使OAPS全部溶解并使Ph-POSS充分分散,获得由溶剂与填料组成的浊液;
(4)杂化材料的制备
于0℃氮气保护下,向PAA溶液中加入步骤(3)得到的由溶剂与填料组成的浊液,机械搅拌2~4小时;采用流延成膜的方法铺膜获得亚胺化之后的POSS/PI杂化材料薄膜。
2.如权利要求1所述的一种改善八苯基笼型倍半硅氧烷Ph-POSS在聚酰亚胺基材中分散性能的方法,其特征在于:步骤(2)是用盐酸调节pH=3.0~5.0。
3.如权利要求1所述的一种改善八苯基笼型倍半硅氧烷Ph-POSS在聚酰亚胺基材中分散性能的方法,其特征在于:步骤(4)所述的采用流延成膜的方法,是在烘箱中采用程序升温,60~100℃时的升温速度为20~30℃/2小时,100~300℃时的升温速度为50~70℃/2小时,最后于300℃下保持2~4小时,获得亚胺化之后的POSS/PI杂化材料薄膜。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6767930B1 (en) * | 2001-09-07 | 2004-07-27 | Steven A. Svejda | Polyhedral oligomeric silsesquioxane polyimide composites |
CN101372534A (zh) * | 2007-08-24 | 2009-02-25 | 东丽纤维研究所(中国)有限公司 | 一种低介电常数聚酰亚胺/低聚倍半硅氧烷纳米杂化膜及其制备方法 |
CN102731809A (zh) * | 2012-06-04 | 2012-10-17 | 西北工业大学 | 一种含有poss结构的抗原子氧聚酰亚胺杂化薄膜制备方法 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6767930B1 (en) * | 2001-09-07 | 2004-07-27 | Steven A. Svejda | Polyhedral oligomeric silsesquioxane polyimide composites |
CN101372534A (zh) * | 2007-08-24 | 2009-02-25 | 东丽纤维研究所(中国)有限公司 | 一种低介电常数聚酰亚胺/低聚倍半硅氧烷纳米杂化膜及其制备方法 |
CN102731809A (zh) * | 2012-06-04 | 2012-10-17 | 西北工业大学 | 一种含有poss结构的抗原子氧聚酰亚胺杂化薄膜制备方法 |
Non-Patent Citations (4)
Title |
---|
A novel structural polyimide material with synergistic phosphorus and POSS for atomic oxygen resistance;Guanghe Song, et al;《RSC Advances》;20150113(第5期);第11980-11988页 * |
Phosphorus-containing polyhedral oligomeric silsesquioxane/polyimides hybrid materials with low dielectric constant and low coefficients of thermal expansion;Xuesong Li, et al;《Journal of Applied Polymer Science》;20151231;第42611-1-6页 * |
Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties;Jun-chao Huang, et al;《Polymer》;ELSEVIER;20031231;第44卷;第4491-4499页 * |
新型POSS/PI杂化材料的制备及性能研究;史磊磊;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20141015(第10期);第22-27页 * |
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