CN116478538A - 一种低介电常数的交联微孔聚酰亚胺薄膜 - Google Patents
一种低介电常数的交联微孔聚酰亚胺薄膜 Download PDFInfo
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Abstract
本发明的一种低介电常数的交联微孔聚酰亚胺薄膜,其主要由芳香族二酐和芳香族二胺反应并在交联剂作用下制备得到;所述交联微孔聚酰亚胺薄膜具有微孔结构,微孔体积在1.025*10‑3‑1.062*10‑2m3·g‑1之间,比表面积在2.038‑9.713m2·g‑1之间,介电常数在2.6‑2.9之间。本发明通过改性芳香PI材料,获得微孔低介电常数2.6-2.9(1MHz)的材料,使其能够达到5G工业应用中对于介电常数的一般标准要求。
Description
技术领域
本发明属于聚酰亚胺薄膜技术领域,涉及一种交联低介电常数微孔聚酰亚胺薄膜及其制备方法,并可期望将其作为层间介质绝缘体在5G工业中应用。
背景技术
具有亚胺和芳香族环结构的聚酰亚胺(PI)是最耐热的聚合物之一。它具有优异的热稳定性、机械强度、耐溶剂性和绝缘介质性能。聚酰亚胺在微电子工业中最重要的应用是作为层间介质绝缘体(ILD)。低介电常数可以降低电阻-电容时延、串扰和功耗,是开发处理速度更快、尺寸更小的新型高集成电路(ICs)的关键参数,低介电材料将满足日益增长的便携式和小型化通信设备的需求。随着5G时代的到来,大规模天线阵列和高集成度芯片对层间介质和封装材料的性能提出了更高的要求。虽然PI具有优异的综合性能,但未改性芳香PI材料的介电常数约为3.4(1MHz),尚难达到5G工业应用的标准要求,故此开发新型低介电常数聚酰亚胺材料已成为该领域的研究热点。
发明内容
为解决现有技术中对于具有低介电常数的聚酰亚胺材料需求的问题,提供一种交联低介电常数微孔聚酰亚胺薄膜及其制备方法。具体的,本发明采用下述技术方案实现:
本发明的一种低介电常数的交联微孔聚酰亚胺薄膜,其主要由芳香族二酐和芳香族二胺反应并在交联剂作用下制备得到;所述交联微孔聚酰亚胺薄膜具有微孔结构,微孔体积在1.025*10-3-1.062*10-2cm3·g-1之间,比表面积在2.038-9.713m2·g-1之间,介电常数在2.6-2.9之间。
本发明所述交联微孔聚酰亚胺薄膜的制备方法,包括酸酐封端的聚酰胺酸制备步骤、交联聚酰胺酸的制备步骤、交联微孔聚酰亚胺薄膜的制备步骤;具体的,所述酸酐封端的聚酰胺酸制备步骤中,采用芳香族二酐和芳香族二胺反应,所述二胺为3,4'-二氨基二苯醚,二酐为4,4'-联苯醚二酐、均苯四甲酸二酐、4,4'-(六氟异丙烯)二酞酸酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐中的一种;所述芳香族二酐和芳香族二胺的摩尔比为酸酐:氨基=1:0.9;所述交联聚酰胺酸的制备步骤中,采用交联剂为1,3,5-三(4-氨苯基)苯、三(4-氨基苯基)胺、2,4,6-三(4-氨基苯基)-1,3,5-三嗪中的一种,其摩尔量为酸酐单体摩尔量的0.02-0.06之间。
作为本发明的一种低介电常数的交联微孔聚酰亚胺薄膜制备方法,其可以采用下述步骤:
(1)酸酐封端的聚酰胺酸制备
称取二胺单体3,4'-二氨基二苯醚和二酐单体,酸酐与氨基的摩尔比为1:0.9;先将3,4'-二氨基二苯醚在溶剂中完全溶解,通入N2,分批加入二酐单体,室温下反应4-12h;
(2)交联聚酰胺酸的制备
称取交联剂溶于溶剂,再加入上述酸酐封端的聚酰胺酸中,室温反应6-12h;(3)交联微孔聚酰亚胺薄膜的制备
将制备的交联聚酰胺酸涂在基板上,真空80℃ⅹ10h除去溶剂;然后放入马弗炉阶梯升温80℃ⅹ1h,150℃ⅹ1h,200℃ⅹ1h,300℃ⅹ1h,300℃ⅹ5min亚胺化,即制得低介电常数交联微孔聚酰亚胺薄膜。
所述溶剂A为N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的至少一种。
所述交联聚酰胺酸固含量为10%-30%。
本发明的交联微孔聚酰亚胺薄膜,具有以下技术特征:
首先,本发明制备的聚酰亚胺是交联结构是自具微孔的,微孔体积在1.025*10-3-1.062*10-2cm3·g-1之间。发明人研究发现,常见的直链型PI大都不具有微孔结构,而本发明则由刚性链交联后使其自具微孔,图3是薄膜测的BET。交联结构可以有效地限制链段迁移,防止聚合物段沿外电场方向定向,从而降低聚酰亚胺的介电常数;交联结构形成的固有微孔增加材料内部空隙来降低聚酰亚胺介电常数,且交联结构形成的固有微孔很小,在降低介电常数的同时保证了薄膜的耐热性和力学性能。
其中,交联网络的引入聚酰亚胺薄膜中,刚性的骨架结构能够有效地阻止聚合物分子链塌陷和分子链之间的有效堆积,从而呈现出固有的微孔增大分子间间隙来降低薄膜介电常数。
其次,根据德拜公式:
其中,k是介电常数,N为偶极子数密度,αe为电极化,αd为畸变极化,μ为与偶极矩相关的取向极化,kb为玻尔兹曼常数,T为温度。在聚酰亚胺中极化包括αe、αd、μ,交联结构可以限制链段的迁移,产生大量束缚,从而降低偶极取向;同时,交联网络可以有效地限制聚合物链段沿外电场方向定向,进一步降低了薄膜的极化;此外,交联网络可以防止聚酰亚胺分子链紧密堆积,增大分子链间的距离,使偶极子数密度N减小,所以交联结构的引入可以有效降低薄膜的介电常数。
再次,交联网络可以提高薄膜的疏水性,由于水的介电常数较高,吸收水分子会大大提高聚酰亚胺的介电常数,疏水的交联结构可以有效的阻止水分子进入薄膜,从而降低薄膜的介电常数,增加耐介电持久性。
本发明通过改性芳香PI材料,获得微孔低介电常数2.6-2.9(1MHz)的材料,使其能够达到5G工业应用中对于介电常数的一般标准要求。
附图说明
图1:交联微孔聚酰亚胺的合成过程;
图2:实施例1-4制得的不同结构微孔薄膜的介电常数;
图3:实施例1-4制得的不同结构微孔薄膜在77K时N2的吸附和解吸等温线。
具体实施方式
下述实施例是对于本发明内容的进一步说明以作为对本发明技术内容的阐释,但本发明的实质内容并不仅限于下述实施例所述,本领域的普通技术人员可以且应当知晓任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。本发明中的介电常数的检测采用常规方法,采用阻抗分析仪测得电容,再根据公式(2)计算介电常数。
实施例1
酸酐封端的聚酰胺酸的制备:称取质量为18.0g(0.09mol)3,4'-二氨基二苯醚(ODA),283g N,N-二甲基乙酰胺加入三口烧瓶,通入N2,搅拌20min待单体彻底溶解。称取31.0(0.1mol)4,4'-联苯醚二酐(ODPA)分三次加入,每次间隔20min。室温下反应4h,得到酸酐封端的聚酰胺酸。
交联聚酰胺酸的制备:称取0.95g(0.003mol)1,3,5-三(4-氨苯基)苯加入上述酸酐封端的聚酰胺酸中,室温反应8h。
交联微孔聚酰亚胺薄膜的制备:将制备的交联聚酰胺酸涂在玻璃片上,放入真空干燥箱,真空80℃×2h,160℃×2h除去溶剂;然后放入马弗炉阶梯升温80℃×1h,150℃×1h,200℃×1h,300℃×1h,300℃×5min亚胺化,即制得交联微孔聚酰亚胺薄膜。
制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.8。
实施例2
酸酐封端的聚酰胺酸的制备:称取质量为18.0g(0.09mol)3,4'-二氨基二苯醚(ODA),283g N,N-二甲基乙酰胺加入三口烧瓶,通入N2,搅拌20min待单体彻底溶解。称取31.0(0.1mol)4,4'-联苯醚二酐(ODPA)分三次加入,每次间隔20min。室温下反应4h,得到酸酐封端的聚酰胺酸。
交联聚酰胺酸的制备:称取1.28g(0.004mol)1,3,5-三(4-氨苯基)苯加入上述酸酐封端的聚酰胺酸中,室温反应8h。
交联微孔聚酰亚胺薄膜的制备:将制备的交联聚酰胺酸涂在玻璃片上,放入真空干燥箱,真空80℃×2h,160℃×2h除去溶剂;然后放入马弗炉阶梯升温80℃×1h,150℃×1h,200℃×1h,300℃×1h,300℃×5min亚胺化,即制得交联微孔聚酰亚胺薄膜。
制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.8。
实施例3
酸酐封端的聚酰胺酸的制备:称取质量为18.0g(0.09mol)3,4'-二氨基二苯醚(ODA),283g N,N-二甲基乙酰胺加入三口烧瓶,通入N2,搅拌20min待单体彻底溶解。称取31.0(0.1mol)4,4'-联苯醚二酐(ODPA)分三次加入,每次间隔20min。室温下反应4h,得到酸酐封端的聚酰胺酸。
交联聚酰胺酸的制备:称取1.6g(0.005mol)1,3,5-三(4-氨苯基)苯加入上述酸酐封端的聚酰胺酸中,室温反应8h。
交联微孔聚酰亚胺薄膜的制备:将制备的交联聚酰胺酸涂在玻璃片上,放入真空干燥箱,真空80℃×2h,160℃×2h除去溶剂;然后放入马弗炉阶梯升温80℃×1h,150℃×1h,200℃×1h,300℃×1h,300℃×5min亚胺化,即制得交联微孔聚酰亚胺薄膜。
制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.6。
实施例4
酸酐封端的聚酰胺酸的制备:称取质量为18.0g(0.09mol)3,4'-二氨基二苯醚(ODA),235g N,N-二甲基乙酰胺加入三口烧瓶,通入N2,搅拌20min待单体彻底溶解。称取21.8g(0.1mol)均苯四甲酸酐(PMDA)分三次加入,每次间隔20min。室温下反应4h,得到酸酐封端的聚酰胺酸。
交联聚酰胺酸的制备:称取1.6g(0.005mol)1,3,5-三(4-氨苯基)苯加入上述酸酐封端的聚酰胺酸中,室温反应8h。
交联微孔聚酰亚胺薄膜的制备:将制备的交联聚酰胺酸涂在玻璃片上,放入真空干燥箱,真空80℃×2h,160℃×2h除去溶剂;然后放入马弗炉阶梯升温80℃×1h,150℃×1h,200℃×1h,300℃×1h,300℃×5min亚胺化,即制得交联微孔聚酰亚胺薄膜。
制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.7。
表1:实施例1-4制得的不同结构微孔薄膜的微孔体积、比表面积
实施例5
二酐采用4,4'-(六氟异丙烯)二酞酸酐(6FDA)替换4,4'-联苯醚二酐(ODPA),其他与实施例1相同,制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.6。
实施例6
二酐采用3,3',4,4'-联苯四羧酸二酐(BPDA)替换4,4'-联苯醚二酐(ODPA),其他与实施例1相同,制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.7。
实施例7
二酐采用3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)替换4,4'-联苯醚二酐(ODPA),其他与实施例1相同,制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.7。
实施例8
交联剂采用三(4-氨基苯基)胺替换1,3,5-三(4-氨苯基)苯,其他与实施例1相同,制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.6。
实施例9
交联剂采用2,4,6-三(4-氨基苯基)-1,3,5-三嗪替换1,3,5-三(4-氨苯基)苯,其他与实施例1相同,制得交联微孔聚酰亚胺薄膜,在1MHz下薄膜介电常数为2.7。
应当说明的是,本发明的上述所述之技术内容仅为使本领域技术人员能够获知本发明技术实质而进行的解释与阐明,故所述之技术内容并非用以限制本发明的实质保护范围。本发明的实质保护范围应以权利要求书所述之为准。本领域技术人员应当知晓,凡基于本发明的实质精神所作出的任何修改、等同替换和改进等,均应在本发明的实质保护范围之内。
Claims (8)
1.一种低介电常数的交联微孔聚酰亚胺薄膜,其主要由芳香族二酐和芳香族二胺反应并在交联剂作用下制备得到;所述交联微孔聚酰亚胺薄膜具有微孔结构,微孔体积在1.025*10-3-1.062*10-2cm3·g-1之间,比表面积在2.038-9.713m2·g-1之间,介电常数在2.6-2.9之间。
2.权利要求1所述交联微孔聚酰亚胺薄膜的制备方法,包括酸酐封端的聚酰胺酸制备步骤、交联聚酰胺酸的制备步骤、交联微孔聚酰亚胺薄膜的制备步骤。
3.如权利要求2所述的制备方法,其特征在于,所述酸酐封端的聚酰胺酸制备步骤中,采用芳香族二酐和芳香族二胺反应,所述二胺为3,4'-二氨基二苯醚,二酐为4,4'-联苯醚二酐、均苯四甲酸二酐、4,4'-(六氟异丙烯)二酞酸酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐中的一种。
4.如权利要求3所述的制备方法,其特征在于,所述芳香族二酐与芳香族二胺的摩尔比为酸酐:氨基=1:0.9。
5.如权利要求2所述的制备方法,其特征在于,所述交联聚酰胺酸的制备步骤中,采用交联剂为1,3,5-三(4-氨苯基)苯、三(4-氨基苯基)胺、2,4,6-三(4-氨基苯基)-1,3,5-三嗪中的一种,其摩尔量为酸酐单体摩尔量的0.02-0.06之间。
6.如权利要求2-5任一项所述的制备方法,其特征在于,采用下述步骤:
(1)酸酐封端的聚酰胺酸制备
称取二胺单体3,4'-二氨基二苯醚和二酐单体,酸酐与氨基的摩尔比为1:0.9;先将3,4'-二氨基二苯醚在溶剂中完全溶解,通入N2,分批加入二酐单体,室温下反应4-12h;
(2)交联聚酰胺酸的制备
称取交联剂溶于溶剂,再加入上述酸酐封端的聚酰胺酸中,室温反应6-12h;
(3)交联微孔聚酰亚胺薄膜的制备
将制备的交联聚酰胺酸涂在基板上,真空80℃ⅹ10h除去溶剂;然后放入马弗炉阶梯升温80℃ⅹ1h,150℃ⅹ1h,200℃ⅹ1h,300℃ⅹ1h,300℃ⅹ5min亚胺化,即制得低介电常数交联微孔聚酰亚胺薄膜。
7.如权利要求6所述的制备方法,其特征在于,溶剂A为N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的至少一种。
8.权利要求1所述的或者由权利要求2-7任一项所述制备方法得到的低介电常数的交联微孔聚酰亚胺薄膜作为层间介质绝缘体在5G工业中的应用。
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CN111961236A (zh) * | 2019-05-20 | 2020-11-20 | 北京化工大学 | 低介电聚酰亚胺薄膜及其制备方法与应用 |
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