JPH0459826A - Aromatic polyimide moldable in melt - Google Patents
Aromatic polyimide moldable in meltInfo
- Publication number
- JPH0459826A JPH0459826A JP17123090A JP17123090A JPH0459826A JP H0459826 A JPH0459826 A JP H0459826A JP 17123090 A JP17123090 A JP 17123090A JP 17123090 A JP17123090 A JP 17123090A JP H0459826 A JPH0459826 A JP H0459826A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- aromatic diamine
- polyimide
- bis
- group
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 20
- 239000004642 Polyimide Substances 0.000 title claims description 21
- 229920001721 polyimide Polymers 0.000 title claims description 21
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 26
- 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 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- LLYZABVNDKXCTJ-UHFFFAOYSA-N 4-[2-[4-[2-[4-[2-(4-aminophenoxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]aniline Chemical compound C=1C=C(OCCOC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCCOC1=CC=C(N)C=C1 LLYZABVNDKXCTJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 aminophenoxy Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性の低下を最小限に抑えつつ、押出成形や
射出成形などの溶融成形が可能となるような芳香族ポリ
イミドに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aromatic polyimide that can be melt-molded by extrusion molding, injection molding, etc. while minimizing a decrease in heat resistance.
従来より、芳香族ジアミン成分と芳香族テトラカルボン
酸二無水物成分を縮合することによって得られる芳香族
ポリイミドは、耐熱性、電気特性、機械特性が優れてい
るため、電子部品用基材、構造材料用樹脂、耐熱性接着
剤などに適用されている。Conventionally, aromatic polyimide obtained by condensing an aromatic diamine component and an aromatic tetracarboxylic dianhydride component has excellent heat resistance, electrical properties, and mechanical properties, so it has been used as a base material for electronic components and as a structural material. It is applied to material resins, heat-resistant adhesives, etc.
しかし、従来の芳香族ポリイミドは溶剤に不溶であり、
また溶融温度が高いために成形加工性に問題があった０
例えば、４．４′−ジアミノジフェニルエーテルととロ
メリット酸二無水物との縮合で得られるポリイミド（Ｋ
ａｐｔｏｎ、Ｖｅｓｐｅｌ；米国デュポン社製品名）は
融点が５００℃以上であり、高温高圧下の圧縮焼結成形
法で成形する必要があった。そのため通常は前駆体のポ
リアミド酸や極性溶媒に溶解した溶液を用い、絶縁フェ
スやそれをフィルムにキャストした後加熱閉環させると
いう方法で使用されている。However, conventional aromatic polyimides are insoluble in solvents,
In addition, there was a problem with moldability due to the high melting temperature.
For example, polyimide (K
Apton, Vespel (product name of DuPont, USA) has a melting point of 500° C. or higher and must be molded by compression sintering at high temperature and pressure. Therefore, it is usually used by using a solution dissolved in a polyamic acid precursor or a polar solvent, casting it into an insulating face or film, and then heating and ring-closing it.
このような従来の芳香族ポリイミドの成形加工性を改善
するものとして、主鎖にエーテル酸素を導入した芳香族
ポリエーテルイミド（Ｕ ｌ ｔ ｅｍ；米国ＧＥ社製
品名）がある。この芳香族ポリエーテルイミドは溶融温
度が低く射出成形が可能となったが、成形するには樹脂
を３５０℃以上という高温に加熱する必要がある。As a material that improves the moldability of such conventional aromatic polyimides, there is an aromatic polyetherimide (Ultem; product name of GE, USA) in which ether oxygen is introduced into the main chain. Although this aromatic polyetherimide has a low melting temperature and can be injection molded, molding requires heating the resin to a high temperature of 350° C. or higher.
このように従来の芳香族ポリイミドでは耐熱性は優れて
いるものの溶融温度が依然として高すぎるために常用の
成形温度で射出成形できる樹脂がなかった。As described above, although conventional aromatic polyimides have excellent heat resistance, their melting temperatures are still too high, so there has been no resin that can be injection molded at conventional molding temperatures.
本発明の目的は、耐熱性の低下を最小限に抑えて、常用
の成形温度で射出成形などの溶融成形が可能な新規芳香
族ポリイミドを提供することにある。An object of the present invention is to provide a novel aromatic polyimide that can be melt-molded, such as by injection molding, at commonly used molding temperatures while minimizing the decrease in heat resistance.
本発明者らは上記目的を果たすために鋭意検討した結果
、屈曲値としてエチレンオキシド鎖を持つ特定の芳香族
ジアミンを含有するジアミン成分を用いて製造した芳香
族ポリイミドが比較的低い溶融温度を持ち、かつ耐熱性
も通常では問題のないレベルにあることを見出し、本発
明を完成するに至った。As a result of intensive studies to achieve the above object, the present inventors found that an aromatic polyimide produced using a diamine component containing a specific aromatic diamine having an ethylene oxide chain as a bending value has a relatively low melting temperature. The inventors also discovered that the heat resistance was at a level that would not normally cause any problems, leading to the completion of the present invention.
すなわち、本発明は一般式ＣＩ）
〔Ｉ〕
（式中、ｘ Ｉ、、、ｘ ４は水素原子、ハロゲン原子
又は炭素数１〜３のアルキル基を示し、互いに同じであ
っても異なっていてもよい、Ｒ′及びＲ２は水素原子、
メチル基、エチル基、トリフルオロメチル基又はトリク
ロロメチル基を示し、互いに同じであっても異なっても
よい、ｎは１〜３゛の整数を示す、）で表される柔軟性
に優れた芳香族ジアミンを５モル％以上含有するもので
あることを特徴とする溶融成形が可能な芳香族ポリイミ
ドを提供するものである。That is, the present invention relates to the general formula CI) [I] (where x I, , x 4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other) may be used, R' and R2 are hydrogen atoms,
A highly flexible aroma represented by a methyl group, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different, n is an integer from 1 to 3. The present invention provides a melt-moldable aromatic polyimide characterized by containing 5 mol % or more of group diamine.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
本発明の特徴である柔軟性に優れた芳香族ジアミンは上
記の一般式（Ｉ）で表される構造を有するものであり、
具体的には２．２−ビス〔４−（β−ｐ−アミノフェノ
キシエトキシ）フェニル〕プロパン、２．２−ビス〔３
，５−ジブロモ−４−（β−ｐ−アミノフェノキシエト
キシ）フェニル〕プロパン及びビスフェノールＡ−エチ
レンオキシド付加物のビスアミノフェノキシエーテル化
誘導体などが挙げられ、単独又は混合物で用いることが
できる。The aromatic diamine with excellent flexibility, which is a feature of the present invention, has a structure represented by the above general formula (I),
Specifically, 2.2-bis[4-(β-p-aminophenoxyethoxy)phenyl]propane, 2.2-bis[3
, 5-dibromo-4-(β-p-aminophenoxyethoxy)phenyl]propane and bisaminophenoxyetherified derivatives of bisphenol A-ethylene oxide adducts, and the like, which can be used alone or in mixtures.
この上記の一般式（１３で表される芳香族ジアミンと併
用される他の芳香族ジアミンは、従来公知の化合物が用
いられる０例えば、フェニレンジアミン、ジアミノジフ
ェニルメタン、４．４′ジアミノジフエニルエーテル、
４．４’−ジアミノジフェニルスルホン、２．２−ビス
（アミノフェノキシフェニル）プロパン、４．４’−ジ
（アミノフェノキシ）フェニルスルホン、４．４’ジ（
アミノフェノキシ）ジフェニルエーテル、４゜４′−ジ
（アミノフェノキシ）ベンゾフェノン、４．４′−ジ（
アミノフェノキシ）ジフェニルスルフィド及びそれらの
置換様式が異なる異性体などが用いられる。これらの中
で４，４′−ジアミノジフェニルエーテル等が特に好ま
しい。Other aromatic diamines used in combination with the aromatic diamine represented by the above general formula (13) may be conventionally known compounds such as phenylene diamine, diaminodiphenylmethane, 4.4' diaminodiphenyl ether,
4.4'-diaminodiphenylsulfone, 2.2-bis(aminophenoxyphenyl)propane, 4.4'-di(aminophenoxy)phenylsulfone, 4.4'di(
aminophenoxy)diphenyl ether, 4゜4'-di(aminophenoxy)benzophenone, 4.4'-di(
Aminophenoxy) diphenyl sulfide and isomers with different substitution patterns thereof are used. Among these, 4,4'-diaminodiphenyl ether and the like are particularly preferred.
本発明の上記の一般式（１）で表される芳香族ジアミン
の配合量は、テトラカルボン酸二無水物成分と縮合する
全芳香族ジアミン成分に対して５モル％以上であること
が、溶融温度を低下させ成形加工性を改善するために必
要である。配合量の上限は、併用する他の芳香族ジアミ
ンの柔軟性の程度によって変化する。すなわち、耐熱性
の低下を最小限に抑えるため、成形加工性の改善効果が
現れる最小量とすることが望ましい。The blending amount of the aromatic diamine represented by the above general formula (1) of the present invention is 5 mol% or more based on the total aromatic diamine component to be condensed with the tetracarboxylic dianhydride component. Necessary to lower temperature and improve moldability. The upper limit of the amount to be blended varies depending on the degree of flexibility of other aromatic diamines used together. That is, in order to minimize the deterioration of heat resistance, it is desirable to set the amount to the minimum that will produce the effect of improving moldability.
また、芳香族ジアミン成分と縮合させるテトラカルボン
酸二無水物成分の種類は何ら限定されるものでなく、従
来公知の化合物、例えば、ピロメリット酸二無水物、ビ
フェニルテトラカルボン酸二無水物、ベンゾフェノンテ
トラカルボン酸二無水物、２．２−ビス（ジカルボキシ
フェニル）メタンニ無水物、２．２−ビス（ジカルボキ
シフェニル）プロパンニ無水物、２．２−ビス（ジカル
ボキシフェニル）エーテルニ無水物などを用いることが
できる。Further, the type of the tetracarboxylic dianhydride component to be condensed with the aromatic diamine component is not limited at all, and conventionally known compounds such as pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone Tetracarboxylic dianhydride, 2.2-bis(dicarboxyphenyl)methane dianhydride, 2.2-bis(dicarboxyphenyl)propanihydride, 2.2-bis(dicarboxyphenyl)ether dianhydride, etc. Can be used.
本発明において、芳香族ジアミン成分とテトラカルボン
酸二無水物成分の縮合はまずそれらのポリアミド酸フェ
スを製造し、次いでイミド化することによって行われる
。In the present invention, the condensation of the aromatic diamine component and the tetracarboxylic dianhydride component is carried out by first producing a polyamic acid phase thereof and then imidizing it.
ポリアミド酸フェスは、脱水された極性溶媒に溶解した
芳香族ジアミン成分の溶液に、テトラカルボン酸二無水
物成分を固形若しくは同様の極性溶媒の溶液で添加し、
反応温度５０℃以下で反応させることにより製造される
。あるいは、テトラカルボン酸二無水物成分の極性溶媒
溶液に芳香族ジアミン成分の固体又は溶液を添加する方
法でもポリアミド酸を製造することができる。Polyamic acid fest is made by adding a tetracarboxylic dianhydride component as a solid or a solution of a similar polar solvent to a solution of an aromatic diamine component dissolved in a dehydrated polar solvent.
It is produced by reacting at a reaction temperature of 50°C or lower. Alternatively, the polyamic acid can also be produced by adding a solid or solution of the aromatic diamine component to a polar solvent solution of the tetracarboxylic dianhydride component.
極性溶媒としてはＮ、Ｎ−ジメチルホルムアミド、Ｎ、
Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジ
メチルスルホキシド、ヘキサメチルホスホルトリアミド
、テトラヒドロフラン、ジオキサンなどが用いられる。As a polar solvent, N,N-dimethylformamide, N,
N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphortriamide, tetrahydrofuran, dioxane, etc. are used.
ポリアミド酸のイミド化は種々の方法で行うことができ
る。一つは、ポリアミド酸フェスを金属板上にキャスト
するかあるいは水中で沈澱させて粉体状にした後、１０
０〜４００℃に加熱乾燥して脱水閉環する方法でイミド
化できる。Imidization of polyamic acid can be performed by various methods. One is to cast a polyamic acid face on a metal plate or precipitate it in water to form a powder, and then
Imidization can be carried out by heating and drying at 0 to 400°C and dehydrating and ring-closing.
また、ポリアミド酸フェスを触媒存在下で無水酢酸など
の脱水剤を用いていわゆる化学閉環を行い、イミド化す
ることができる。更に、フェスにベンゼン、トルエン、
キシレンなどを添加して共沸脱水させる熱閉環によって
イミド化することができる。これら溶液でイミド化した
場合は、析出した沈澱を濾過することによりポリイミド
の粉末を得ることができる。Further, the polyamic acid phosphate can be imidized by performing so-called chemical ring closure using a dehydrating agent such as acetic anhydride in the presence of a catalyst. Furthermore, benzene, toluene,
Imidization can be achieved by thermal ring closure by adding xylene or the like and performing azeotropic dehydration. When imidization is performed using these solutions, polyimide powder can be obtained by filtering the precipitate.
得られた粉末はそのままあるいはペレット化されて成形
材料として用いられる。その際、必要に応じてガラス繊
維、炭素繊維などの無機充填剤やその他種々の添加剤を
混合してもよい。The obtained powder is used as a molding material as it is or after being made into pellets. At that time, inorganic fillers such as glass fibers and carbon fibers and other various additives may be mixed as necessary.
本発明−では、上記の一般式［Ｉ］で表される芳香族ジ
アミンをジアミン成分の一部として用いることにより、
主鎖にエチレンオキシド鎖を持つポリイミドを得られる
ようになった。このエチレンオキシド鎖は剛直な芳香族
イミド環に対して柔軟性を持った屈曲頷として働くと考
えられ、溶融温度を下げることによって剛直なポリイミ
ドの溶融成形を可能にすることができたと思われる。In the present invention, by using the aromatic diamine represented by the above general formula [I] as a part of the diamine component,
It is now possible to obtain polyimide with an ethylene oxide chain in the main chain. This ethylene oxide chain is thought to act as a flexible bend for the rigid aromatic imide ring, and it is thought that by lowering the melting temperature, it was possible to melt mold the rigid polyimide.
特に本発明の上記一般式ＣＩ）で表される芳香族ジアミ
ンでは、テトラカルボン酸の無水酸基との縮合が芳香環
に置換しているアミノ基で起きるため、これまで公知の
芳香族ジアミンと比べて反応性にほとんど差がないと考
えられる。そこで公知の芳香臓ジアミンと併用した場合
、上記一般式（Ｉ）で表される芳香族ジアミンが持って
いたエチレンオキシド鎖はポリイミド主鎖に均一に分布
し、ソフトセグメントとの交互共重合体に似た構造が得
ることができたと思われる。In particular, in the aromatic diamine represented by the above general formula CI) of the present invention, the condensation with the anhydride group of the tetracarboxylic acid occurs at the amino group substituted on the aromatic ring, so compared to the previously known aromatic diamines. It is thought that there is almost no difference in reactivity. Therefore, when used in combination with a known aromatic diamine, the ethylene oxide chains possessed by the aromatic diamine represented by the above general formula (I) are uniformly distributed in the polyimide main chain, resembling an alternating copolymer with soft segments. It seems that we were able to obtain a similar structure.
その結果、屈曲鎖の導入による耐熱性の低下を最小に抑
えつつ、溶融温度の低下が可能になったものと考えられ
る。As a result, it is thought that it became possible to lower the melting temperature while minimizing the decrease in heat resistance due to the introduction of bent chains.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
実施例１〜４
攪拌機、温度針、窒素導入管を備えた三ロフラスコに２
，２−ビス〔３，５−ジブロモ−４−（β−ｐ−アミノ
フェノキシエトキシ）フェニル〕プロパンと第１表の配
合表に示すその他の芳香族ジアミンを投入し、Ｎ−メチ
ルピロリドンを加えて窒素雰囲気下で攪拌溶解した。Examples 1 to 4 Two flasks equipped with a stirrer, a temperature needle, and a nitrogen inlet tube
,2-bis[3,5-dibromo-4-(β-p-aminophenoxyethoxy)phenyl]propane and other aromatic diamines shown in the formulation table in Table 1 were added, and N-methylpyrrolidone was added. The mixture was stirred and dissolved under a nitrogen atmosphere.
水浴でフラスコを５℃以下に冷却し、第１表に示すテト
ラカルボン酸二無水物を先の全芳香族ジアミン成分の当
量に等しい量だけ約１時間かけて少しづつ加え、その後
５℃で２時間、常温で３時間攪拌反応させポリアミド酸
のワニスを得た。The flask was cooled to below 5°C in a water bath, and the tetracarboxylic dianhydride shown in Table 1 was added little by little in an amount equal to the equivalent of the fully aromatic diamine component above over about 1 hour. The mixture was stirred and reacted at room temperature for 3 hours to obtain a polyamic acid varnish.
次に、ワニスにトリエチルアミンと酢酸ニッケルを加え
、続いて理論量の２倍の無水酢酸をゆっくり添加し室温
で一昼夜攪拌反応させた。Next, triethylamine and nickel acetate were added to the varnish, followed by slowly adding twice the theoretical amount of acetic anhydride, and the mixture was stirred and reacted at room temperature overnight.
沈澱を濾過してワーリングミキサーで微粉砕し、十分に
水洗、乾燥した後、熱風乾燥器で１５０°Ｃで２時間及
び２５０℃で２時間加熱処理した。The precipitate was filtered and pulverized using a Waring mixer, thoroughly washed with water, dried, and then heated in a hot air dryer at 150°C for 2 hours and at 250°C for 2 hours.
得られたポリイミド粉末を用い圧縮成形で（２８０’Ｃ
２３００ｋｇ／ｃｊ）試験片を作成した。引張り強さ、
伸び、熱変形温度（１８，６ｋｇ／ｃ４）の測定結果を
第２表に示した。The obtained polyimide powder was compression molded (280'C).
2300 kg/cj) test pieces were prepared. tensile strength,
The measurement results of elongation and heat distortion temperature (18.6 kg/c4) are shown in Table 2.
なお、ポリエーテルイミド（Ｕ １ ｔ ｅｍ １０
００、ＧＥ社製品名）は上記条件では成形できなかった
。In addition, polyetherimide (U 1 t em 10
00, GE product name) could not be molded under the above conditions.
第１表 配合（モル％）
第２表 測定結果
ＢＡＥＰ ：２．２−ビス〔４−（β−ｐ−アミノフ
ェノキシエトキシ）フェニル〕プロパン
ＢＢＡＥＰ：２．２−ビス〔３，５−ジブロモ−４−（
β−ｐ−アミノフェノキシエトキシ）フェニル〕プロパ
ンＤＤＥ ：４．４’−ジアミノジフェニルエーテ
ルＰＭＤＡ ：ピロメリットーに罎ジに−ＢＴＤＡ
：ベンゾフェノンテトラカルボン酸二無水物〔発明の
効果〕
本発明により、従来高温での成形が必要であったポリイ
ミドが汎用樹脂と同程度の比較的低い温度で成形加工す
ることができるようになり、しかも成形温度に比べ高い
熱変形温度を有するポリイミドを震声することやり可能
となった。Table 1: Composition (mol%) Table 2: Measurement results BAEP: 2.2-bis[4-(β-p-aminophenoxyethoxy)phenyl]propane BBAEP: 2.2-bis[3,5-dibromo-4 −(
β-p-aminophenoxyethoxy)phenyl]propane DDE: 4,4'-diaminodiphenyl ether PMDA: Pyromerite-BTDA
:benzophenonetetracarboxylic dianhydride [Effects of the invention] According to the present invention, polyimide, which conventionally required molding at high temperatures, can now be molded at a relatively low temperature comparable to that of general-purpose resins. Moreover, it has become possible to vibrate polyimide, which has a heat distortion temperature higher than the molding temperature.
Claims (1)
水物成分を縮合することによって得られるポリイミドに
おいて、芳香族ジアミン成分が、一般式 ▲数式、化学式、表等があります▼ 〔 I 〕 （式中、Ｘ＾１〜Ｘ＾４は水素原子、ハロゲン原子又は
炭素数１〜３のアルキル基を示し、互いに同じであって
も異なっていてもよい。Ｒ＾１及びＲ＾２は水素原子、
メチル基、エチル基、トリフルオロメチル基又はトリク
ロロメチル基を示し、互いに同じであっても異なっても
よい。 ｎは１〜３の整数を示す。）で表される柔軟性に優れた
芳香族ジアミンを５モル％以上含有するものであること
を特徴とする溶融成形が可能な芳香族ポリイミド。 ２、一般式〔 I 〕で表される芳香族ジアミンが２，２
−ビス〔４−（β−ｐ−アミノフェノキシエトキシ）フ
ェニル〕プロパンである請求項１に記載の芳香族ポリイ
ミド。 ３、一般式〔 I 〕で示される芳香族ジアミンが２，２
−ビス〔３，５−ジブロモ−４−（β−ｐ−アミノフェ
ノキシエトキシ）フェニ ル〕プロパンである請求項１に記載の芳香族ポリイミド
。[Claims] 1. In the polyimide obtained by condensing an aromatic diamine component and an aromatic tetracarboxylic dianhydride component, the aromatic diamine component has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [I] (In the formula, X^1 to X^4 represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other. R^1 and R^ 2 is a hydrogen atom,
It represents a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different from each other. n represents an integer of 1 to 3. ) An aromatic polyimide that can be melt-molded and contains 5 mol% or more of an aromatic diamine having excellent flexibility. 2. The aromatic diamine represented by the general formula [I] is 2,2
The aromatic polyimide according to claim 1, which is -bis[4-(β-p-aminophenoxyethoxy)phenyl]propane. 3. The aromatic diamine represented by the general formula [I] is 2,2
The aromatic polyimide according to claim 1, which is -bis[3,5-dibromo-4-(β-p-aminophenoxyethoxy)phenyl]propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17123090A JPH0459826A (en) | 1990-06-28 | 1990-06-28 | Aromatic polyimide moldable in melt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17123090A JPH0459826A (en) | 1990-06-28 | 1990-06-28 | Aromatic polyimide moldable in melt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0459826A true JPH0459826A (en) | 1992-02-26 |
Family
ID=15919460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17123090A Pending JPH0459826A (en) | 1990-06-28 | 1990-06-28 | Aromatic polyimide moldable in melt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0459826A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164857A (en) * | 1988-12-15 | 1990-06-25 | Hitachi Chem Co Ltd | New halogenated aromatic diamine and production thereof |
-
1990
- 1990-06-28 JP JP17123090A patent/JPH0459826A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164857A (en) * | 1988-12-15 | 1990-06-25 | Hitachi Chem Co Ltd | New halogenated aromatic diamine and production thereof |
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