JPH01294737A - Polyamic acid ester and its production - Google Patents
Polyamic acid ester and its productionInfo
- Publication number
- JPH01294737A JPH01294737A JP12516188A JP12516188A JPH01294737A JP H01294737 A JPH01294737 A JP H01294737A JP 12516188 A JP12516188 A JP 12516188A JP 12516188 A JP12516188 A JP 12516188A JP H01294737 A JPH01294737 A JP H01294737A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polyamic acid
- group
- acid ester
- general formula
- 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
- 150000002148 esters Chemical class 0.000 title claims abstract description 43
- 229920005575 poly(amic acid) Polymers 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 2-(2-methoxyethyloxy)ethyl groups Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 10
- 239000004642 Polyimide Substances 0.000 abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910006124 SOCl2 Inorganic materials 0.000 abstract 3
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UZNCDNDTKNIEII-UHFFFAOYSA-N 3-[(3-aminophenyl)-methyl-trimethylsilyloxysilyl]aniline Chemical compound C=1C=CC(N)=CC=1[Si](C)(O[Si](C)(C)C)C1=CC=CC(N)=C1 UZNCDNDTKNIEII-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- CRDNXTRZWPMCAK-UHFFFAOYSA-N 4-[4-(diethylamino)phenoxy]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1OC1=CC=C(N(CC)CC)C=C1 CRDNXTRZWPMCAK-UHFFFAOYSA-N 0.000 description 1
- QQSANSAGYFSGNN-UHFFFAOYSA-N 4-[4-(dimethylamino)phenoxy]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1OC1=CC=C(N(C)C)C=C1 QQSANSAGYFSGNN-UHFFFAOYSA-N 0.000 description 1
- OJXULZRBAPPHNY-UHFFFAOYSA-N 4-[[(4-aminophenyl)-dimethylsilyl]oxy-dimethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(N)C=C1 OJXULZRBAPPHNY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 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、ポリアミド酸エステルおよびその製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a polyamic acid ester and a method for producing the same.
［従来の技術［１
従来、ポリイミドは、通常テトラカルボン酸二無水物と
ジアミン成分をＮ、Ｎ−ジメヂルアセトアミド等の溶剤
中において反応させて、まずポリアミド酸を得、次にこ
れを加熱等により、脱水閉環させることにより得られる
。[Prior art [1] Conventionally, polyimide is usually produced by reacting a tetracarboxylic dianhydride and a diamine component in a solvent such as N,N-dimethylacetamide to obtain a polyamic acid, which is then heated, etc. It can be obtained by dehydration and ring closure.
ところが最終重合体であるポリイミド自体は一般に不融
不溶性で著しく加工性に乏しく、このため加工操作はポ
リアミド酸段階でなされるのが実状である。しかし、こ
のポリアミド酸の流動性も不十分なため、ポリイミド成
形品を製造する場合圧縮成形と焼成加工が必要で、−数
的にこれらの成形条件としては極めて厳密なコントロー
ルが要求される。However, polyimide itself, which is the final polymer, is generally infusible and insoluble and has extremely poor processability, and therefore processing operations are actually performed at the polyamic acid stage. However, since the fluidity of this polyamic acid is insufficient, compression molding and firing processing are required when producing polyimide molded articles, and numerically extremely strict control of these molding conditions is required.
この問題点に対して成形性を改善する目的でポリアミド
酸エステルがある（特開昭６２−２０７３３号）。To solve this problem, polyamic acid esters are available for the purpose of improving moldability (Japanese Patent Application Laid-open No. 20733/1983).
［発明が解決しようとする問題点コ
しかし、溶融時の粘度が高く成形性は実用上優れている
とは言えない。[Problems to be Solved by the Invention] However, the viscosity during melting is high and the moldability cannot be said to be excellent in practical terms.
［問題点を解決するための手段］
本発明は、ポリイミドの成形性を改善するために、加熱
時の流動性が優れたポリアミド酸エステルおよびその製
造法を得るべく鋭意検討した結果、本発明に到達した。[Means for Solving the Problems] The present invention was developed as a result of intensive studies aimed at obtaining a polyamic acid ester with excellent fluidity during heating and a method for producing the same in order to improve the moldability of polyimide. Reached.
すなわち、本発明は、一般式；
２−（２−メトキシエチルオギシ）エチル基の中から選
ばれた１、仙または２種以上の基、Ｒ２はトリメチレン
基、テトラメチレン基またはｐ−フェニレン基、Ｒ，、
ＳＲ，、Ｒ５およびＲ６は、メチル基またはフェニル基
、Ｒ７は、−０−０−０−または、（防、ｍは１以上、
ｎは０または１以上の整数である。］で示され、０．０
５〜０．３０ｄｌ／ｇ （ジメヂルアセトアド中３０℃
）の固有粘度を有するポリアミド酸エステルおよびその
製造法である。一般式（１）において、ｍとｎの比は通
常１０：０〜４：６であり好ましくは８：２〜５：５で
ある。ｎの割合が６を越えると熱溶融性がなくなる。ま
た、一般式（１）で示されるポリアミド酸エステルのエ
ステル化率［単位；モル％］は、通常５〜６０であり、
好ましくはＲ１がメチル基の場合４０〜６０であり、２
−メトキシエチル基の場合１０〜５０であり２−（２−
メトキシエチルオキシ）エチル基の場合５〜３０である
。エステル化率が５未満であると、ポリアミド酸エステ
ルの加熱時の流動性が損なわれ、６０を越えるとポリア
ミド酸エステルを加熱によりイミド化する時に気泡や熱
収縮によるクラックが発生する。That is, the present invention is based on the general formula; one, group or two or more groups selected from 2-(2-methoxyethyloxy)ethyl group, R2 is trimethylene group, tetramethylene group or p-phenylene group; ,R,,
SR,, R5 and R6 are methyl group or phenyl group, R7 is -0-0-0- or (protection, m is 1 or more,
n is an integer of 0 or 1 or more. ], 0.0
5-0.30 dl/g (30°C in dimedylacetoad)
) and a method for producing the same. In general formula (1), the ratio of m and n is usually 10:0 to 4:6, preferably 8:2 to 5:5. When the ratio of n exceeds 6, thermal fusibility is lost. Further, the esterification rate [unit: mol%] of the polyamic acid ester represented by the general formula (1) is usually 5 to 60,
Preferably, when R1 is a methyl group, it is 40 to 60, and 2
-methoxyethyl group is 10 to 50 and 2-(2-
In the case of methoxyethyloxy)ethyl group, it is 5 to 30. If the esterification rate is less than 5, the fluidity of the polyamic acid ester during heating will be impaired, and if it exceeds 60, bubbles or cracks will occur due to heat shrinkage when the polyamic acid ester is imidized by heating.
本発明のポリアミド酸エステルの分子量の範囲は、一定
条件下での固有粘度測定値として通常０．０５〜０．３
０ｄｌ／ｇ （ジメチルアセトアミド中３０℃）好まし
くは０．０８〜０．２５ｄｌ／ｇである。固有粘度が０
、０５ｄ １／ｇ未満であれば、加熱による脱水閉環後
のポリイミドの膜強度が劣りクラックがはいる。また、
０．３０ｄ １７ｇを越えるとポリアミド酸エステルの
加熱時の流動性が損なわれる。The molecular weight range of the polyamic acid ester of the present invention is usually 0.05 to 0.3 as measured value of intrinsic viscosity under certain conditions.
0 dl/g (in dimethylacetamide at 30°C), preferably 0.08 to 0.25 dl/g. Intrinsic viscosity is 0
, 05d less than 1/g, the strength of the polyimide film after dehydration and ring closure by heating is poor and cracks occur. Also,
If it exceeds 0.30d and 17g, the fluidity of the polyamic acid ester during heating will be impaired.
本発明において固有粘度［ηコは、
１ ｎη／η０
［７７１＝ □
（ここにηは、キャノンフェンスケ粘度計を使用してジ
メチルホルムアミド中の濃度０．５ｇ／ｄｉのものをｊ
Ｋ＋’を度３０−１−０．０１℃で測定した値であり、
η３、はキャノンフェンスケ粘度計を使用し同温度にお
ける同溶媒切測定値であり、Ｃは濃度０．５ｇ／ｄｉで
ある。）で測定することができる。In the present invention, the intrinsic viscosity [η is 1 nη/η0 [771= □ (here, η is the concentration of 0.5 g/di in dimethylformamide using a Cannon-Fenske viscometer).
K+' is the value measured at 30-1-0.01°C,
η3 is a value measured by removing the same solvent at the same temperature using a Cannon Fenske viscometer, and C is a concentration of 0.5 g/di. ) can be measured.
本発明のポリアミド酸エステルの具体例を表１〜表４に
示す。Specific examples of the polyamic acid esters of the present invention are shown in Tables 1 to 4.
第１表
第２表
第３表
第４表
本発明のポリアミド酸エステルの製造法は、−般式
％式％（２）
［式中Ｒ８は、炭素数１から４までのアルキル基、Ｘは
、０〜２の整数である。］で示されるアルコールとピロ
メリット酸二無水物を部分エステル化反応させ、チオニ
ルクロライドにより酸クロライド化させたものと一般式
［式中Ｒ７，Ｒ３，Ｒ４，Ｒｙ、Ｒｅは、一般式（１）
と同じ］で示されるジアミンまたは一般式（３）で示さ
れるジアミンと４．４°−ジアミノジフェニルエーテル
または１．４−ジアミノベンゼンからなるジアミン混合
物を反応させ、アニリンまたは、無水フタル酸で反応さ
せ、０．０５〜０．３０ｄｌ／ｇ （ジメチルアセトア
ミド中、３０℃）の固有粘度を有するポリアミド酸エス
テルを製造する方法である。Table 1 Table 2 Table 3 Table 4 The method for producing the polyamic acid ester of the present invention is as follows: - General formula % Formula % (2) [In the formula, R8 is an alkyl group having 1 to 4 carbon atoms, and X is , an integer from 0 to 2. ] The alcohol represented by the formula and pyromellitic dianhydride are partially esterified and converted into acid chloride with thionyl chloride, and the general formula [where R7, R3, R4, Ry, and Re are represented by the general formula (1)]
] or a diamine represented by general formula (3) and a diamine mixture consisting of 4.4°-diaminodiphenyl ether or 1.4-diaminobenzene, and react with aniline or phthalic anhydride, This is a method for producing a polyamic acid ester having an intrinsic viscosity of 0.05 to 0.30 dl/g (in dimethylacetamide, 30°C).
一般式（２）のＩｂは、好ましくは、メチル基であり、
一般式（２）で示されるアルコールとしては、メチルア
ルコール、２−メ１）キシエチルアルコールまたは２−
（２−メトキシエチルオキシ）エヂルアルコールなどが
ｔトげられる。Ib in general formula (2) is preferably a methyl group,
The alcohol represented by the general formula (2) is methyl alcohol, 2-methoxyethyl alcohol or 2-methoxyethyl alcohol.
(2-methoxyethyloxy)ethyl alcohol and the like are used.
一般式（３）で示されるジアミンとしては、［式中ｐｈ
はフェニル基、以下同じ］
などが挙げられる。As the diamine represented by the general formula (3), [in the formula ph
is a phenyl group, the same applies hereinafter].
次に反応方法について説明する。Next, the reaction method will be explained.
一般式（２）で示されるアルコールとピロメリット酸二
無水物を反応させるに当たり、そのモル比は通常１：ｌ
Ｏ〜Ｇ＝５である。溶媒としては、Ｎ−・メチル−２−
ピロリドン、ジメチルアセトアミド、ジメチルフォルム
アミド、テトラメチル尿素ミビリジン、トルエン、キシ
レン、ジェヂルエーテル、ジオキサン、エヂレングリコ
ールジメチルエーテル、ジエチレングリコールジメヂル
エーテルおよびこれら二種以上の混合物などが使用でき
る。When reacting the alcohol represented by general formula (2) with pyromellitic dianhydride, the molar ratio is usually 1:l.
OG=5. As a solvent, N-・methyl-2-
Pyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea mibiridine, toluene, xylene, dimethyl ether, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and mixtures of two or more of these can be used.
なお、反応を促進させるために触媒としてＮ、Ｎ−ジメ
チルアニリン、ビス（ｐ−ジメチルアミノフェニル）エ
ーテル、ビス（ｐ−ジエチルアミノフェニル）エーテル
などの第３級アミンを使用してもよい。In addition, in order to promote the reaction, a tertiary amine such as N,N-dimethylaniline, bis(p-dimethylaminophenyl) ether, bis(p-diethylaminophenyl) ether, etc. may be used as a catalyst.
反応物の濃度は重量基準で１０〜５０％であり、溶媒中
５０〜１２０℃で１〜６時間反応させる。The concentration of the reactants is 10-50% by weight, and the reaction is carried out in a solvent at 50-120°C for 1-6 hours.
次に、溶媒を減圧留去し部分エステル化物を得る。該部
分エステル化物をそのカルボン酸に対して過剰量のチオ
ニルクロライドにより窒素雰１！１１気下５０〜８０℃
で１〜３時間反応させた後、過剰量のチオニルクロライ
ドを減圧留去し酸クロライドと酸無水物の混合物を得る
。次に該混合物と一般式（３）で示されるジアミンをモ
ル比１：２〜２：１で窒素雰囲気下洛媒中、１０〜３０
℃で１〜２時間反応させる。ここで該混合物と一般式（
３）で示されるジアミンの望ましいモル比は１：２〜１
：１．１または２：１〜１．１：ｌである。反応物の濃
度は重量基準で１０〜５０％である。続いて酸クロライ
ドと酸無水物の混合物をジアミンに対して過剰に用いた
場合、残存する酸無水物基および酸クロライド基と等モ
ル量以上のアニリンを加えてまたジアミンを酸クロライ
ドと酸無水物の混合物に対して過剰に用いた場合、残存
するアミノ基と等モル量以−ヒの無水フタル酸を加えて
１〜２時間反応させ一般式（１）で示される０、０５〜
０．３０ｄｌ／ｇ（ジメチルアセトアミド中３０℃）の
固有粘度を有するポリアミド酸エステルを含有する溶液
を得る。溶媒としては、Ｎ−メチル−２−ピロリドン、
ジメチルアセトアミド、ジメチルフォルムアミドなどが
使用できる。Next, the solvent is distilled off under reduced pressure to obtain a partially esterified product. The partially esterified product was heated at 50 to 80°C under a nitrogen atmosphere of 1 to 11 hours with thionyl chloride in an excess amount relative to the carboxylic acid.
After reacting for 1 to 3 hours, excess thionyl chloride is distilled off under reduced pressure to obtain a mixture of acid chloride and acid anhydride. Next, the mixture and the diamine represented by the general formula (3) were mixed in a molar ratio of 1:2 to 2:1 in a liquid medium under a nitrogen atmosphere.
React at ℃ for 1-2 hours. Here, the mixture and the general formula (
The desirable molar ratio of the diamine shown in 3) is 1:2 to 1.
:1.1 or 2:1 to 1.1:l. The concentration of reactants is 10-50% by weight. Subsequently, when the mixture of acid chloride and acid anhydride is used in excess of the diamine, aniline is added in an amount equivalent to or more than the remaining acid anhydride groups and acid chloride groups, and the diamine is mixed with the acid chloride and acid anhydride. When used in excess with respect to the mixture, phthalic anhydride in an amount equivalent to or more than the remaining amino group is added and reacted for 1 to 2 hours to form a mixture of 0,05-
A solution containing a polyamic acid ester having an intrinsic viscosity of 0.30 dl/g (30° C. in dimethylacetamide) is obtained. As a solvent, N-methyl-2-pyrrolidone,
Dimethylacetamide, dimethylformamide, etc. can be used.
本発明のポリアミド酸エステルは、溶融可能であり１０
０〜２００℃で溶融させ押し出し成形や射出成形しその
後２００℃以上の適当な温度で焼成してポリイミドのフ
ィルムやシートにすることができる。The polyamic acid ester of the present invention is meltable and has 10
It can be made into a polyimide film or sheet by melting it at 0 to 200°C, extrusion molding or injection molding, and then baking it at an appropriate temperature of 200°C or higher.
また他の使用方法としては、繊維性の基質を１００〜２
００℃で加熱溶融させた本発明のポリアミド酸エステル
中に浸漬しプレプレグをつくり、これを単一層あるいは
多層溝造物として最終的な成形品を作り、次に２００℃
以上の適当な温度に加熱してポリイミドの複合シートを
作ることができる。この繊維状の基質としては、炭素繊
維やアラミド繊維などが使え、ポリオミド組成物に対し
て容量基準で５〜７０％を添加することができる。Another method of use is to use a fibrous substrate of 100 to 20%
Prepare a prepreg by immersing it in the polyamic acid ester of the present invention heated and melted at 00°C, make a final molded product as a single layer or multilayer grooved product, and then heat it at 200°C.
A polyimide composite sheet can be produced by heating to the above appropriate temperature. Carbon fibers, aramid fibers, and the like can be used as the fibrous substrate, and can be added in an amount of 5 to 70% by volume to the polyamide composition.
本発明のポリアミド酸エステルは、
■固有粘度が、０．０５〜０．３０ｄｌ／ｇ （ジメチ
ルアセトアミド中３０℃）であり比較的低分子である。The polyamic acid ester of the present invention has (1) an intrinsic viscosity of 0.05 to 0.30 dl/g (in dimethylacetamide at 30°C) and is a relatively low molecular weight.
■ポリマーの主鎖に屈曲性の高いシロキサンｊ１カ造を
有する。■The main chain of the polymer has a highly flexible siloxane structure.
■アミド酸部分がエステル化されているため１００〜２
００℃では、剛直性の高い°イミド溝造になりにくい。■100-2 because the amic acid part is esterified
At 00°C, highly rigid °imide groove structure is difficult to form.
■ポリマーの両末端が熱安定性の高いフェニル基を有す
る化合物でキャッピングされているため縮合などの高分
子化が起こらない。■Since both ends of the polymer are capped with a compound containing a phenyl group with high thermal stability, polymerization such as condensation does not occur.
の特徴を有するため１００〜２００℃で溶融し良好な流
動性と粘度安定性を有する。It melts at 100-200°C and has good fluidity and viscosity stability.
［実施例コ
以下に本発明の実施例を示すが、本発明はこれに限定さ
れるものではない。[Examples] Examples of the present invention are shown below, but the present invention is not limited thereto.
実施例１
（ポリアミド酸エステルＮｏ、 １の製造法）１２容の
フラスコに、ピロメリット酸二無水物２１８ｇ、ジエチ
レングリコールモノメチルエーテル２４ｇ１ジメトキシ
エタン３００ｇを入れ６０℃で３時間反応させた。次に
、水流ポンプでジメトキシエタンを減圧留去した後、チ
オニルクロライド２６０ｇを入れチッ素雰囲気下８０℃
で２時間反応させた後、過剰量のチオニルクロライドを
減圧留去し酸クロライドと酸無水物の混合物を得た。次
にこの混合物をチッ素雰囲気下１０℃以下でジメチルア
セトアミド３００ｇに溶解させ、１，３−ビス（３−ア
ミノプロピル）テトラメチルジシロキサン１５９ｇ、４
．４′−ジアミノジフェニルエーテル３２ｇ１ジメチル
アセトアミド３００ｇからなる溶液を１０℃以下で加え
、その後３０℃で１時間反応させた。次にアニリン２０
ｇを加え３０℃でさらに１時間反応させた。Example 1 (Production method of polyamic acid ester No. 1) A 12-volume flask was charged with 218 g of pyromellitic dianhydride, 24 g of diethylene glycol monomethyl ether, and 300 g of dimethoxyethane, and reacted at 60° C. for 3 hours. Next, dimethoxyethane was distilled off under reduced pressure using a water pump, and then 260 g of thionyl chloride was added and the mixture was heated to 80°C under a nitrogen atmosphere.
After reacting for 2 hours, excess thionyl chloride was distilled off under reduced pressure to obtain a mixture of acid chloride and acid anhydride. Next, this mixture was dissolved in 300 g of dimethylacetamide at 10°C or less under a nitrogen atmosphere, and 159 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 4
．． A solution consisting of 32 g of 4'-diaminodiphenyl ether and 300 g of dimethylacetamide was added at a temperature below 10 DEG C., followed by reaction at 30 DEG C. for 1 hour. Next, aniline 20
g was added thereto, and the reaction was further carried out at 30°C for 1 hour.
反応液を濾過し５２のアセトンと水の１：１の昆合液に
加えてポリマーを析出させた。これをろ別しテトラヒド
ロフラン３００ｇに溶かし、これを５２のイオン交換水
に滴下し、生じた粉末をｒＩ別し水洗、減圧屹燥を行な
って淡黄色のポリアミド酸エステルＮｏ、 １の粉末３
９０ｇを得た。The reaction solution was filtered and added to a 1:1 mixture of 52 acetone and water to precipitate the polymer. This was filtered and dissolved in 300 g of tetrahydrofuran, and this was added dropwise to ion-exchanged water of No. 52. The resulting powder was separated by rI, washed with water, and dried under reduced pressure to obtain pale yellow polyamic acid ester No. 1 powder No. 3.
90g was obtained.
図１にポリアミド酸エステルＮｏ、 １の赤外吸収スペ
クトルを示す。FIG. 1 shows the infrared absorption spectrum of polyamic acid ester No. 1.
実施例２
（ポリアミド酸エステルＮｏ、 ２の製造法）１．３−
ビス（３−アミノプロピル）テトラメチルジ・・シロキ
サン１５９ｇを９９ ｇに、４．４°−ジアミノジフェ
ニルエーテル３２ｇを７９ｇにする以外は実施例１とま
ったく同様に反応を行ないポリアミド酸エステルＮｏ、
２の淡黄色粉末３７７ｇを得た。Example 2 (Production method of polyamic acid ester No. 2) 1.3-
The reaction was carried out in exactly the same manner as in Example 1, except that 159 g of bis(3-aminopropyl)tetramethyldi...siloxane was changed to 99 g and 32 g of 4.4°-diaminodiphenyl ether was changed to 79 g. Polyamic acid ester No.
377 g of pale yellow powder of No. 2 was obtained.
実施例３
（ポリアミド酸エステルＮ００３の製造法）ジエヂレン
グリコールモノメチルエーテル２４ｇを用いる代わりに
エチレングリコールモノメチルエーテル２６ｇを用いる
以外は実施例１とまったく同様に反応を行ないポリアミ
ド酸エステルＮ００３の淡黄色粉末３９２ｇを得た。Example 3 (Production method of polyamic acid ester N003) The reaction was carried out in exactly the same manner as in Example 1 except that 26 g of ethylene glycol monomethyl ether was used instead of 24 g of diethyl glycol monomethyl ether to produce a pale yellow powder of polyamic acid ester N003. 392g was obtained.
実施例４
（ポリアミド酸エステルＮ００４の製造法）ジエヂレン
グリコールモノメチルエーテル２４ｇを用いる代わりに
メチルアルコール１９ｇを用いる以外は実施例１とまっ
たく同様に反応を行ないポリアミド酸エステルＮｏ、
４の淡黄色粉末３８４ｇを得た。Example 4 (Method for producing polyamic acid ester No. 004) The reaction was carried out in exactly the same manner as in Example 1, except that 19 g of methyl alcohol was used instead of 24 g of diethylene glycol monomethyl ether. Polyamic acid ester No.
384 g of pale yellow powder of No. 4 was obtained.
実施Ｂ；１１５
（ポリアミド酸エステルＮｏ、 ５の製造法）１．３−
ビス（３−アミノプロピル）テトラメチルジシロキサン
１５９ｇを用いる代わりに１，３−ビス（ｐ−アミノフ
ェニル）テトラメチルジシロキサン２０３ｇを用いる以
外は実施例１とまったく同様に反応を行ないポリアミド
酸エステルＮｏ、 ５の淡黄色粉末４３９ｇを得た。図
２にポリアミド酸エステルＮｏ。Implementation B; 115 (Production method of polyamic acid ester No. 5) 1.3-
Polyamic acid ester No. , 439 g of pale yellow powder of 5 was obtained. Figure 2 shows polyamic acid ester No.
５の赤外吸収スペクトルを示す。The infrared absorption spectrum of No. 5 is shown.
実施例６
（ポリアミド酸エステルＮｏ、 ６の製造法）１．３−
ビス（３−アミ、ノプロビル）テトラメチルジシロキサ
ン１５９ｇを用いる代わりに１，３−ビス（ｐ−アミノ
フェニル）テトラメチルジシロキサン１２６ｇを用い、
４．４’−ジアミノジフェニルエーテル３２ｇを７９ｇ
にする以外は実施例１とまったく同様に反応を行ないポ
リアミド酸エステルＮｏ、 ６の淡黄色粉末４０７ｇを
得た。Example 6 (Production method of polyamic acid ester No. 6) 1.3-
Instead of using 159 g of bis(3-aminophenyl)tetramethyldisiloxane, 126 g of 1,3-bis(p-aminophenyl)tetramethyldisiloxane was used,
4.79g of 32g of 4'-diaminodiphenyl ether
The reaction was carried out in exactly the same manner as in Example 1 except that 407 g of pale yellow powder of polyamic acid ester No. 6 was obtained.
実施例７
（ポリアミド酸エステルＮ００７の製造法）４．４′−
ジアミノジフェニルエーテル３２ｇを１．４−ジアミノ
ベンゼン１７ｇにする以外は実施例５とまったく同様に
反応を行ないポリアミド酸エステルＮｏ、 ７の淡黄色
粉末４２５ｇを得た。Example 7 (Production method of polyamic acid ester N007) 4.4'-
The reaction was carried out in exactly the same manner as in Example 5 except that 17 g of 1,4-diaminobenzene was used instead of 32 g of diaminodiphenyl ether to obtain 425 g of pale yellow powder of polyamic acid ester No. 7.
実施例８
（ポリアミド酸エステルＮｏ、 ８の製造法）４．４°
−ジアミノジフェニルエーテル７９ｇを１．４−。Example 8 (Production method of polyamic acid ester No. 8) 4.4°
-1.4- of 79 g of diaminodiphenyl ether.
ジアミノベン−Ｖン４３ｇにする以外は実施例５とまっ
たく同様に反応を行ないポリアミド酸エステノｋＮｏ、
６の淡黄色粉末３７０ｇを得た。The reaction was carried out in exactly the same manner as in Example 5, except that 43 g of diaminoben-V was used, and polyamic acid ester No.
370 g of pale yellow powder of No. 6 was obtained.
［発明の効果］
従来のポリイミドの成形において、その前駆体のポリア
ミド酸またはポリアミド酸エステルの流動性が不十分な
ため圧縮成形と焼成加工が必要で一般的にこれらの成形
条件は極めて厳密なコントロールが必要であった。[Effect of the invention] In conventional molding of polyimide, compression molding and firing processing are required because the fluidity of the polyamic acid or polyamic acid ester precursor is insufficient, and these molding conditions generally have to be extremely strictly controlled. was necessary.
ポリイミド前駆体としての本発明のポリアミド酸エステ
ルは、良好な流動性を示し、成形性と共に作業性が良好
である。上記効果を奏することから本発明のポリアミド
酸エステルは、航空機や自動車のパネル、４ａ’ｔ’：
＋’ｉ類のハウジング、プリント配線基板、電線や電気
ケーブルの被覆材料の０１ｆ駆体どして使用することが
できる。The polyamic acid ester of the present invention as a polyimide precursor exhibits good fluidity, and has good moldability and workability. Because it exhibits the above-mentioned effects, the polyamic acid ester of the present invention can be used for aircraft and automobile panels, 4a't':
It can be used as a 01f precursor for housings of +'i class, printed wiring boards, and coating materials for electric wires and cables.
図１はポリアミド酸エステルＮｏ、 １の赤多ト吸収ス
ペクトルを示す図。図２はポリアミド酸エステルＮｏ、
５の赤外吸収スペクトルを示す図。FIG. 1 is a diagram showing the red polygon absorption spectrum of polyamic acid ester No. 1. Figure 2 shows polyamic acid ester No.
FIG. 5 is a diagram showing an infrared absorption spectrum of No. 5.
Claims (1)
＿１は一部が水素原子であり残りは、メチル基、２−メ
トキシエチル基、２−（２−メトキシエチルオキシ）エ
チル基の中から選ばれた１種または２種以上の基、Ｒ＿
２はトリメチレン基、テトラメチレン基またはｐ−フェ
ニレン基、Ｒ＿３、Ｒ＿４、Ｒ＿５およびＲ＿６は、メ
チル基またはフェニル基、Ｒ＿７は、▲数式、化学式、
表等があります▼または、▲数式、化学式、表等があり
ます▼、ｍは１以上、ｎは０または１以上の整数である
。］で示され、０．０５〜０．３０ｄｌ／ｇ（ジメチル
アセトアミド中３０℃）の固有粘度を有するポリアミド
酸エステル。 ２、ｍとｎの比が１０：０〜４：６である請求項１記載
のポリアミド酸エステル。 ３、エステル化率が５〜６０モル％である請求項１また
は２記載のポリアミド酸エステル。 ４、一般式； Ｒ＿８（ＯＣＨ＿２ＣＨ＿２）＿ｘＯＨ（２）［式中Ｒ
＿８は、炭素数１から４までのアルキル基、Ｘは、０〜
２の整数である。］ で示されるアルコールとピロメリット酸二無水物を部分
エステル化反応させ、チオニルクロライドにより酸クロ
ライド化させたものと 一般式； ▲数式、化学式、表等があります▼（３） ［式中Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５、Ｒ＿６は、一
般式（１）と同じ。］ で示されるジアミンまたは一般式（３）で示されるジア
ミンと４，４’−ジアミノジフェニルエーテルもしくは
１，４−ジアミノベンゼンからなるジアミン混合物を反
応させ、アニリンまたは無水フタル酸と反応させ、０．
０５〜０．３０ｄｌ／ｇ（ジメチルアセトアミド中３０
℃）の固有粘度を有するポリアミド酸エステルを得るこ
とを特徴とする製造法。[Claims] 1. General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R
Part of _1 is a hydrogen atom, and the rest is one or more groups selected from methyl group, 2-methoxyethyl group, 2-(2-methoxyethyloxy)ethyl group, R_
2 is trimethylene group, tetramethylene group or p-phenylene group, R_3, R_4, R_5 and R_6 are methyl group or phenyl group, R_7 is ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, m is 1 or more, and n is an integer of 0 or 1 or more. ] and has an intrinsic viscosity of 0.05 to 0.30 dl/g (in dimethylacetamide at 30°C). 2. The polyamic acid ester according to claim 1, wherein the ratio of m and n is 10:0 to 4:6. 3. The polyamic acid ester according to claim 1 or 2, which has an esterification rate of 5 to 60 mol%. 4, General formula; R_8(OCH_2CH_2)_xOH(2) [in the formula R
_8 is an alkyl group having 1 to 4 carbon atoms, and X is 0 to 4.
It is an integer of 2. ] The alcohol and pyromellitic dianhydride are subjected to a partial esterification reaction and converted into acid chloride using thionyl chloride, and the general formula is; ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) R_3, R_4, R_5, and R_6 are the same as in general formula (1). ] A diamine represented by the formula (3) or a diamine mixture consisting of 4,4'-diaminodiphenyl ether or 1,4-diaminobenzene is reacted with aniline or phthalic anhydride, and 0.
05-0.30 dl/g (30 in dimethylacetamide
A manufacturing method characterized by obtaining a polyamic acid ester having an intrinsic viscosity of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12516188A JPH01294737A (en) | 1988-05-23 | 1988-05-23 | Polyamic acid ester and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12516188A JPH01294737A (en) | 1988-05-23 | 1988-05-23 | Polyamic acid ester and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01294737A true JPH01294737A (en) | 1989-11-28 |
Family
ID=14903387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12516188A Pending JPH01294737A (en) | 1988-05-23 | 1988-05-23 | Polyamic acid ester and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01294737A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020002325A (en) * | 2018-07-02 | 2020-01-09 | 東レ株式会社 | Resin composition |
-
1988
- 1988-05-23 JP JP12516188A patent/JPH01294737A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020002325A (en) * | 2018-07-02 | 2020-01-09 | 東レ株式会社 | Resin composition |
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