CN111635525A - 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 - Google Patents
一种低介电常数疏水聚酰亚胺薄膜及其制备方法 Download PDFInfo
- Publication number
- CN111635525A CN111635525A CN202010631108.6A CN202010631108A CN111635525A CN 111635525 A CN111635525 A CN 111635525A CN 202010631108 A CN202010631108 A CN 202010631108A CN 111635525 A CN111635525 A CN 111635525A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- dielectric constant
- low dielectric
- molecular sieve
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 39
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 50
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000004985 diamines Chemical class 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 18
- ADLOLHYLFUJLHJ-UHFFFAOYSA-N aminosilyloxyperoxybenzene Chemical compound N[SiH2]OOOC1=CC=CC=C1 ADLOLHYLFUJLHJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 aminopropyl Chemical group 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 19
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 12
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- SXFKVWHNCURLRL-UHFFFAOYSA-N N[SiH](OC1=CC=CC=C1)O[SiH2]O Chemical compound N[SiH](OC1=CC=CC=C1)O[SiH2]O SXFKVWHNCURLRL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开了一种低介电常数疏水聚酰亚胺薄膜，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和改性TS‑1分子筛；其中，改性TS‑1分子筛的添加量为各原料总重的1‑2wt％。本发明还公开了上述低介电常数疏水聚酰亚胺薄膜的制备方法。本发明具有较低的介电常数，且具有疏水性能。
Description
技术领域
本发明涉及聚酰亚胺薄膜技术领域，尤其涉及一种低介电常数疏水聚酰亚胺薄膜及其制备方法。
背景技术
聚酰亚胺具有良好的耐高温性、机械性能等特点，是重要的特种高分子材料，被广泛应用于微电子和光电行业。由于目前微电子产业中高集成度的发展需求，需要聚酰亚胺具有更低的介电常数，而聚酰亚胺的介电常数约为3.0-4.0，需要提高其介电性能。
发明内容
基于背景技术存在的技术问题，本发明提出了一种低介电常数疏水聚酰亚胺薄膜及其制备方法，本发明具有较低的介电常数，且具有疏水性能。
本发明提出的一种低介电常数疏水聚酰亚胺薄膜，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和改性TS-1分子筛；其中，改性TS-1分子筛的添加量为各原料总重的1-2wt％。
优选地，二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷。
优选地，2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷的摩尔比为7-8:1。
优选地，二酐单体为4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐。
优选地，4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐的摩尔比为1:1-1.5。
优选地，改性TS-1分子筛为硅烷偶联剂改性TS-1分子筛。
优选地，硅烷偶联剂为3-氨基丙基三乙氧基硅烷。
优选地，八(氨基苯基三氧硅烷)的添加量为各原料总重的2.5-3.5wt％。
优选地，二胺单体、二酐单体的摩尔比为0.99-1:1。
上述TS-1分子筛可以从市场购得。
本发明还提出了上述低介电常数疏水聚酰亚胺薄膜的制备方法，包括如下步骤：在惰性气体氛围中，向二胺单体溶液中加入二酐单体进行反应得到共聚物溶液；然后向共聚物溶液中加入改性TS-1分子筛分散液进行反应得到胶液；将胶液脱泡后涂覆于基板表面，亚胺化，自然冷却至室温，剥离得到低介电常数疏水聚酰亚胺薄膜。
优选地，亚胺化的程序为：于150-160℃，保温30-50min，然后升温至380℃，保温10-15min。
优选地，于室温反应13-14h得到共聚物溶液。
优选地，于室温反应3-4h得到胶液。
优选地，胶液的固含量为10-15％。
优选地，二胺单体溶液和改性TS-1分子筛分散液的溶剂均为N,N-二甲基乙酰胺。
有益效果：
本发明选用2,2’-双(三氟甲基)-4,4’-二氨基联苯、氨丙基封端聚二甲基硅氧烷作为二胺单体，4,4’-联苯醚二酐、4,4'-(六氟异丙烯)二酞酸酐作为二酐单体，在聚酰亚胺中引入了氟元素，降低聚酰亚胺的介电常数并提高其疏水性能；通过嵌入二甲基聚硅氧烷链段，利用二甲基硅氧烷链段疏水以及长链分子结构，从而减小聚酰亚胺的吸水率和酰亚胺键堆砌密度，从而进一步降低介电常数；另外通过加入适量的八(氨基苯基三氧硅烷)和改性TS-1分子筛，在聚酰亚胺中引入多孔结构，从而进一步降低聚酰亚胺的介电常数；本发明通过选用合适的种类和比例的二胺、二酐单体，配合适量的八(氨基苯基三氧硅烷)和改性TS-1分子筛，并结合适宜的制备工艺最终得到具有低介电常数和疏水性的聚酰亚胺薄膜。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
一种低介电常数疏水聚酰亚胺薄膜，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和3-氨基丙基三乙氧基硅烷改性TS-1分子筛；其中，3-氨基丙基三乙氧基硅烷改性TS-1分子筛的添加量为各原料总重的1wt％；
二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷，2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷的摩尔比为8:1；
二酐单体为4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐，4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐的摩尔比为1:1；
二胺单体、二酐单体的摩尔比为1:1；
八(氨基苯基三氧硅烷)的添加量为各原料总重的2.5wt％。
上述低介电常数疏水聚酰亚胺薄膜的制备方法，包括如下步骤：在惰性气体氛围中，向二胺单体溶液中加入二酐单体，于室温反应14h得到共聚物溶液；然后向共聚物溶液中加入改性TS-1分子筛分散液，于室温反应3h得到固含量为15％的胶液；将胶液脱泡后涂覆于基板表面，于150℃，保温50min，然后升温至380℃，保温10min进行亚胺化，自然冷却至室温，剥离得到低介电常数疏水聚酰亚胺薄膜，其中，二胺单体溶液和改性TS-1分子筛分散液的溶剂均为N,N-二甲基乙酰胺。
实施例2
一种低介电常数疏水聚酰亚胺薄膜，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和3-氨基丙基三乙氧基硅烷改性TS-1分子筛；其中，3-氨基丙基三乙氧基硅烷改性TS-1分子筛的添加量为各原料总重的2wt％；
二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷，2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷的摩尔比为7:1；
二酐单体为4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐，4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐的摩尔比为1:1.5；
二胺单体、二酐单体的摩尔比为0.99:1；
八(氨基苯基三氧硅烷)的添加量为各原料总重的3.5wt％。
上述低介电常数疏水聚酰亚胺薄膜的制备方法，包括如下步骤：在惰性气体氛围中，向二胺单体溶液中加入二酐单体，于室温反应13h得到共聚物溶液；然后向共聚物溶液中加入改性TS-1分子筛分散液，于室温反应4h得到固含量为10％的胶液；将胶液脱泡后涂覆于基板表面，于160℃，保温30min，然后升温至380℃，保温15min进行亚胺化，自然冷却至室温，剥离得到低介电常数疏水聚酰亚胺薄膜，其中，二胺单体溶液和改性TS-1分子筛分散液的溶剂均为N,N-二甲基乙酰胺。
实施例3
一种低介电常数疏水聚酰亚胺薄膜，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和3-氨基丙基三乙氧基硅烷改性TS-1分子筛；其中，3-氨基丙基三乙氧基硅烷改性TS-1分子筛的添加量为各原料总重的1.5wt％；
二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷，2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷的摩尔比为7.5:1；
二酐单体为4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐，4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐的摩尔比为1:1.2；
二胺单体、二酐单体的摩尔比为0.995:1；
八(氨基苯基三氧硅烷)的添加量为各原料总重的3wt％。
上述低介电常数疏水聚酰亚胺薄膜的制备方法，包括如下步骤：在惰性气体氛围中，向二胺单体溶液中加入二酐单体，于室温反应13.5h得到共聚物溶液；然后向共聚物溶液中加入改性TS-1分子筛分散液，于室温反应3.5h得到固含量为12％的胶液；将胶液脱泡后涂覆于基板表面，于155℃，保温40min，然后升温至380℃，保温12min进行亚胺化，自然冷却至室温，剥离得到低介电常数疏水聚酰亚胺薄膜，其中，二胺单体溶液和改性TS-1分子筛分散液的溶剂均为N,N-二甲基乙酰胺。
对比例1
一种聚酰亚胺薄膜，其原料包括：2,2’-双(三氟甲基)-4,4’-二氨基联苯、4,4’-联苯醚二酐；
2,2’-双(三氟甲基)-4,4’-二氨基联苯、4,4’-联苯醚二酐的摩尔比为0.995:1。
其制备方法同实施例3。
取实施例1-3和对比例1的薄膜进行检测，其厚度相同，均为15μm，结果如下表所示：
由上表可以看出，本发明具有较低的介电常数，且具有疏水性能。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种低介电常数疏水聚酰亚胺薄膜，其特征在于，其原料包括：二胺单体、二酐单体、八(氨基苯基三氧硅烷)和改性TS-1分子筛；其中，改性TS-1分子筛的添加量为各原料总重的1-2wt％。
2.根据权利要求1所述低介电常数疏水聚酰亚胺薄膜，其特征在于，二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷；优选地，2,2’-双(三氟甲基)-4,4’-二氨基联苯和氨丙基封端聚二甲基硅氧烷的摩尔比为7-8:1。
3.根据权利要求1或2所述低介电常数疏水聚酰亚胺薄膜，其特征在于，二酐单体为4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐；优选地，4,4’-联苯醚二酐和4,4'-(六氟异丙烯)二酞酸酐的摩尔比为1:1-1.5。
4.根据权利要求1-3任一项所述低介电常数疏水聚酰亚胺薄膜，其特征在于，改性TS-1分子筛为硅烷偶联剂改性TS-1分子筛；优选地，硅烷偶联剂为3-氨基丙基三乙氧基硅烷。
5.根据权利要求1-4任一项所述低介电常数疏水聚酰亚胺薄膜，其特征在于，八(氨基苯基三氧硅烷)的添加量为各原料总重的2.5-3.5wt％；优选地，二胺单体、二酐单体的摩尔比为0.99-1:1。
6.一种如权利要求1-5任一项所述低介电常数疏水聚酰亚胺薄膜的制备方法，其特征在于，包括如下步骤：在惰性气体氛围中，向二胺单体溶液中加入二酐单体进行反应得到共聚物溶液；然后向共聚物溶液中加入改性TS-1分子筛分散液进行反应得到胶液；将胶液脱泡后涂覆于基板表面，亚胺化，自然冷却至室温，剥离得到低介电常数疏水聚酰亚胺薄膜。
7.根据权利要求6所述低介电常数疏水聚酰亚胺薄膜的制备方法，其特征在于，亚胺化的程序为：于150-160℃，保温30-50min，然后升温至380℃，保温10-15min。
8.根据权利要求6或7所述低介电常数疏水聚酰亚胺薄膜的制备方法，其特征在于，于室温反应13-14h得到共聚物溶液。
9.根据权利要求6-8任一项所述低介电常数疏水聚酰亚胺薄膜的制备方法，其特征在于，于室温反应3-4h得到胶液。
10.根据权利要求6-9任一项所述低介电常数疏水聚酰亚胺薄膜的制备方法，其特征在于，胶液的固含量为10-15％；优选地，二胺单体溶液和改性TS-1分子筛分散液的溶剂均为N,N-二甲基乙酰胺。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010631108.6A CN111635525A (zh) | 2020-07-03 | 2020-07-03 | 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010631108.6A CN111635525A (zh) | 2020-07-03 | 2020-07-03 | 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111635525A true CN111635525A (zh) | 2020-09-08 |
Family
ID=72327129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010631108.6A Pending CN111635525A (zh) | 2020-07-03 | 2020-07-03 | 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111635525A (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480407A (zh) * | 2020-11-30 | 2021-03-12 | 浙江中科玖源新材料有限公司 | 一种低介电、低损耗聚酰亚胺薄膜及其制备方法 |
| CN113354816A (zh) * | 2021-05-28 | 2021-09-07 | 无锡高拓新材料股份有限公司 | 一种合成聚酰胺酸溶液的方法及其制备的薄膜 |
| US11879039B1 (en) | 2022-08-17 | 2024-01-23 | Harbin Engineering University | Preparation method for thermoplastic multi-hybrid polyimide films |
| CN117801274A (zh) * | 2023-12-22 | 2024-04-02 | 哈尔滨理工大学 | 一种交联型聚酰亚胺绝缘介质薄膜及其制备方法和应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101560299A (zh) * | 2008-04-15 | 2009-10-21 | 东丽纤维研究所（中国）有限公司 | 低介电常数聚酰亚胺/介孔分子筛杂化材料及其制备方法 |
| WO2014098235A1 (ja) * | 2012-12-21 | 2014-06-26 | 旭化成イーマテリアルズ株式会社 | ポリイミド前駆体及びそれを含有する樹脂組成物 |
| CN111019175A (zh) * | 2018-10-08 | 2020-04-17 | 三星电子株式会社 | 层叠膜、以及包括其的显示设备 |
| CN111040450A (zh) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | 低介电含氟聚酰亚胺复合薄膜及其制备方法 |
| CN111253601A (zh) * | 2020-03-25 | 2020-06-09 | 太湖方舟新材料科技有限公司 | 一种高温尺寸稳定导热聚酰亚胺薄膜及其制备方法 |
-
2020
- 2020-07-03 CN CN202010631108.6A patent/CN111635525A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101560299A (zh) * | 2008-04-15 | 2009-10-21 | 东丽纤维研究所（中国）有限公司 | 低介电常数聚酰亚胺/介孔分子筛杂化材料及其制备方法 |
| WO2014098235A1 (ja) * | 2012-12-21 | 2014-06-26 | 旭化成イーマテリアルズ株式会社 | ポリイミド前駆体及びそれを含有する樹脂組成物 |
| CN111019175A (zh) * | 2018-10-08 | 2020-04-17 | 三星电子株式会社 | 层叠膜、以及包括其的显示设备 |
| CN111040450A (zh) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | 低介电含氟聚酰亚胺复合薄膜及其制备方法 |
| CN111253601A (zh) * | 2020-03-25 | 2020-06-09 | 太湖方舟新材料科技有限公司 | 一种高温尺寸稳定导热聚酰亚胺薄膜及其制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 安德里阿诺夫: "《耐热硅有机绝缘材料》", 31 March 1960, 机械工业出版社 * |
| 徐竹: "《复合材料成型工艺及应用》", 31 March 2017, 国防工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480407A (zh) * | 2020-11-30 | 2021-03-12 | 浙江中科玖源新材料有限公司 | 一种低介电、低损耗聚酰亚胺薄膜及其制备方法 |
| CN112480407B (zh) * | 2020-11-30 | 2023-07-04 | 浙江中科玖源新材料有限公司 | 一种低介电、低损耗聚酰亚胺薄膜及其制备方法 |
| CN113354816A (zh) * | 2021-05-28 | 2021-09-07 | 无锡高拓新材料股份有限公司 | 一种合成聚酰胺酸溶液的方法及其制备的薄膜 |
| US11879039B1 (en) | 2022-08-17 | 2024-01-23 | Harbin Engineering University | Preparation method for thermoplastic multi-hybrid polyimide films |
| CN117801274A (zh) * | 2023-12-22 | 2024-04-02 | 哈尔滨理工大学 | 一种交联型聚酰亚胺绝缘介质薄膜及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111635525A (zh) | 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 | |
| CN107189436B (zh) | 一种聚酰亚胺纳米泡沫及其制备方法 | |
| CN111808306B (zh) | 一种低热膨胀系数的聚酰亚胺薄膜及其制备方法 | |
| CA1334362C (en) | Process for lowering the dielectric constant of polyimides using diamic acid additives | |
| CN111253601B (zh) | 一种高温尺寸稳定导热聚酰亚胺薄膜及其制备方法 | |
| CN111748113A (zh) | 一种耐热低介电常数聚酰亚胺薄膜及其制备方法 | |
| CN113201136B (zh) | 一种聚酰亚胺树脂的制备方法及其薄膜 | |
| CN114891209B (zh) | 一种低介电常数的有机硅改性聚酰亚胺薄膜及其制备方法 | |
| CN108373542B (zh) | 一种含笼形倍半硅氧烷/聚酰亚胺纳米杂化膜及其制备方法 | |
| CN105037769A (zh) | 低热膨胀系数聚酰亚胺薄膜的制备方法 | |
| CN114196049A (zh) | 一种强疏水聚酰亚胺薄膜的制备方法 | |
| EP0349010A1 (en) | Polyimide copolymers | |
| CN112210101A (zh) | 一种低介电常数聚酰亚胺薄膜及其制备方法 | |
| CN114316591B (zh) | 一种尺寸稳定低介电聚酰亚胺薄膜及其制备方法、应用 | |
| WO2007078715A1 (en) | Thermally stable composite matrial | |
| CN111704798B (zh) | 一种耐高温聚酰亚胺薄膜及其制备方法 | |
| CN111647270A (zh) | 一种绝缘聚酰亚胺薄膜及其制备方法 | |
| CN112480405B (zh) | 本征型低介质损耗因数聚酰亚胺薄膜及其制备方法 | |
| CN114479074B (zh) | 一种耐高温透明聚酰亚胺薄膜及其制备方法、应用 | |
| CN115044204B (zh) | 一种低介电全有机交联聚酰亚胺薄膜的制备方法 | |
| CN114230791B (zh) | 本征型低介电含氟聚酰亚胺薄膜及其制备方法 | |
| JP2006131706A (ja) | ポリイミド系低誘電材料および高効率分離膜 | |
| CN111978539B (zh) | 一种oled柔性基板用聚酰亚胺薄膜及其制备方法 | |
| CN113493608A (zh) | 一种水氧阻隔聚酰亚胺薄膜 | |
| CN113512214A (zh) | 一种阻隔性好的透明聚酰亚胺薄膜及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200908 |