JPH02174759A - Phthalimide compound and production thereof - Google Patents
Phthalimide compound and production thereofInfo
- Publication number
- JPH02174759A JPH02174759A JP63328045A JP32804588A JPH02174759A JP H02174759 A JPH02174759 A JP H02174759A JP 63328045 A JP63328045 A JP 63328045A JP 32804588 A JP32804588 A JP 32804588A JP H02174759 A JPH02174759 A JP H02174759A
- Authority
- JP
- Japan
- Prior art keywords
- aminobenzoate
- formula
- phthalimide
- group
- raw material
- 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
- -1 Phthalimide compound Chemical class 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- PXHIYFMTRHEUHZ-UHFFFAOYSA-N 5-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=C2C(=O)OC(=O)C2=C1 PXHIYFMTRHEUHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 229960004050 aminobenzoic acid Drugs 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 12
- 125000005462 imide group Chemical group 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 abstract description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 3
- 239000004642 Polyimide Substances 0.000 abstract description 3
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001721 polyimide Polymers 0.000 abstract description 3
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical class CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- YMQOKTHPONOAKK-UHFFFAOYSA-N hexyl 2-aminobenzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1N YMQOKTHPONOAKK-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- WOMFWGRSYUKSSE-UHFFFAOYSA-N (1,3-dioxo-2-benzofuran-5-yl) acetate Chemical compound CC(=O)OC1=CC=C2C(=O)OC(=O)C2=C1 WOMFWGRSYUKSSE-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NQHHQZDNLNKIGR-UHFFFAOYSA-N 4-(5-hydroxy-1,3-dioxoisoindol-2-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=O)C2=CC(O)=CC=C2C1=O NQHHQZDNLNKIGR-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- TWLLPUMZVVGILS-UHFFFAOYSA-N Ethyl 2-aminobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1N TWLLPUMZVVGILS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940064734 aminobenzoate Drugs 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- IUWVALYLNVXWKX-UHFFFAOYSA-N butamben Chemical compound CCCCOC(=O)C1=CC=C(N)C=C1 IUWVALYLNVXWKX-UHFFFAOYSA-N 0.000 description 1
- 229960000400 butamben Drugs 0.000 description 1
- FOFJXIVZCGTINY-UHFFFAOYSA-N butyl 3-aminobenzoate Chemical compound CCCCOC(=O)C1=CC=CC(N)=C1 FOFJXIVZCGTINY-UHFFFAOYSA-N 0.000 description 1
- HUIYGGQINIVDNW-UHFFFAOYSA-N butyl anthranilate Chemical compound CCCCOC(=O)C1=CC=CC=C1N HUIYGGQINIVDNW-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- QTURWMMVIIBRRP-UHFFFAOYSA-N diethoxymethoxybenzene Chemical compound CCOC(OCC)OC1=CC=CC=C1 QTURWMMVIIBRRP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DSUOQKARORSQFD-UHFFFAOYSA-N hexyl 3-aminobenzoate Chemical compound CCCCCCOC(=O)C1=CC=CC(N)=C1 DSUOQKARORSQFD-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VZDNXXPBYLGWOS-UHFFFAOYSA-N methyl 3-aminobenzoate Chemical compound COC(=O)C1=CC=CC(N)=C1 VZDNXXPBYLGWOS-UHFFFAOYSA-N 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCKCYPSMCQDSHT-UHFFFAOYSA-N pentyl 2-aminobenzoate Chemical compound CCCCCOC(=O)C1=CC=CC=C1N JCKCYPSMCQDSHT-UHFFFAOYSA-N 0.000 description 1
- VKYWCHMXHQTCJQ-UHFFFAOYSA-N pentyl 4-aminobenzoate Chemical compound CCCCCOC(=O)C1=CC=C(N)C=C1 VKYWCHMXHQTCJQ-UHFFFAOYSA-N 0.000 description 1
- HAZAXSFZTQULFE-UHFFFAOYSA-N phenyl 3-aminobenzoate Chemical compound NC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1 HAZAXSFZTQULFE-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- WPRQYDFLCDTFGC-UHFFFAOYSA-N propyl 3-aminobenzoate Chemical compound CCCOC(=O)C1=CC=CC(N)=C1 WPRQYDFLCDTFGC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- NBFQYHKHPBMJJV-UHFFFAOYSA-N risocaine Chemical compound CCCOC(=O)C1=CC=C(N)C=C1 NBFQYHKHPBMJJV-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- ZMCBYSBVJIMENC-UHFFFAOYSA-N tricaine Chemical compound CCOC(=O)C1=CC=CC(N)=C1 ZMCBYSBVJIMENC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- 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、ポリイミドの原料上ツマ−になり得る新規な
フタルイミドに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel phthalimide that can be used as a raw material for polyimide.
（従来の技術）
ポリイミドは主鎖にイミド結合を有する最も耐熱性の優
れた樹脂の一つであり、航空機、輸送機械、コンピュー
ターなどのエレクトロニクス分野で幅広く利用されてい
る。ポリマー主鎖あるいは側鎖にイミド基を導入すると
、一般にポリマーの耐熱性が向上することが知られてお
り、イミド基含有ポリマーは耐熱性ポリマーとして研究
、利用されてきた。(Prior Art) Polyimide is one of the most heat-resistant resins having an imide bond in its main chain, and is widely used in the electronics field such as aircraft, transportation machinery, and computers. It is known that introducing an imide group into the main chain or side chain of a polymer generally improves the heat resistance of the polymer, and imide group-containing polymers have been studied and utilized as heat-resistant polymers.
（発明が解決しようとする課題）
しかしながら、これまでにイミド基含有ポリマーの原料
となる化合物としては、例えば次式：％式％
（式中のＲ２は炭素数２〜２０のアルキレン基またはア
リーレン基を示す）で示される化合物または４−ヒドロ
キシ−Ｎ −（ｐ−ヒドロキシフェニル）フタルイミド
のようなイミド基形成性モノマーが提案されているが、
イミド基を含有するヒドロキシカルボン酸のような種々
のポリマーの原料となり得るイミド基含有モノマーは知
られていない。(Problem to be Solved by the Invention) However, so far, as a compound serving as a raw material for an imide group-containing polymer, for example, the following formula: % formula % (R2 in the formula is an alkylene group or arylene group having 2 to 20 carbon atoms) Imide group-forming monomers such as compounds represented by
There are no known imide group-containing monomers that can be used as raw materials for various polymers such as imide group-containing hydroxycarboxylic acids.
従って本発明は、イミド基を含有するヒドロキシカルボ
ン酸を提供しようとするものである。The present invention therefore seeks to provide hydroxycarboxylic acids containing imide groups.
（課題を解決するための手段）
そこで本発明者らは、種々のイミド基含有ヒドロキシカ
ルボン酸を合成し、鋭意検討の結果、新規なフタルイミ
ドがイミド基含有ポリマーの好適な原料となることを見
出した。(Means for Solving the Problems) Therefore, the present inventors synthesized various imide group-containing hydroxycarboxylic acids, and as a result of intensive studies, discovered that a new phthalimide can be a suitable raw material for imide group-containing polymers. Ta.
本発明の新規なフタルイミドは次式：
％式％
（式中のＸは水素または炭素数１〜４のアシル基、Ｒ１
は水素または炭素数１〜ｌＯのアルキル基またＩ
はアリール基を示し、−ＣＯＲ’ はオルト、メタまた
はパラ位に位置している）で表される化合物である。The novel phthalimide of the present invention has the following formula: % formula % (wherein X is hydrogen or an acyl group having 1 to 4 carbon atoms, R1
represents hydrogen or an alkyl group having 1 to 10 carbon atoms, or I represents an aryl group, and -COR' is located at the ortho, meta or para position.
この新規なフタルイミドは、４−ヒドロキシ無水フタル
酸またはそのアシル体と、２−アミノ安息香酸、３−ア
ミノ安息香酸、４−アミノ安息香酸またはそれらのエス
テル体を縮合させることによって製造することができる
。This novel phthalimide can be produced by condensing 4-hydroxyphthalic anhydride or its acyl form with 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, or their ester forms. .
４−ヒドロキシ無水フタル酸のアシル体の具体例として
は４−アセトキシ無水フタル酸、４−プロピオニルオキ
シ無水フタル酸、４−ブチリルオキシ無水フタル酸が使
用できる。Specific examples of the acyl form of 4-hydroxyphthalic anhydride include 4-acetoxyphthalic anhydride, 4-propionyloxyphthalic anhydride, and 4-butyryloxyphthalic anhydride.
アミノ安息香酸のエステルとしては、炭素数１〜１２の
アルコールまたはフェノール化合物とのエステルが好ま
しく、更に好ましいのは炭素数１〜６の脂肪族アルコー
ルまたはフェノール化合物とのエステルである。そのエ
ステル体の具体例としては、２−アミノ安息香酸メチル
、３−アミノ安息香酸メチル、４−アミノ安息香酸メチ
ル、２アミノ安息香酸エチル、３−アミノ安息香酸エチ
ル、４−アミノ安息香酸エチル、２−アミノ安息香９プ
ロピル、３−アミノ安息香酸プロピル、４アミノ安息香
酸プロピル、２−アミノ安息香酸ブチル、３−アミノ安
息香酸ブチル、４−アミノ安息香酸ブチル、２−アミノ
安息香酸ペンチル、３−アミノ安息香酸ペンチル、４−
アミノ安息香酸ヘキシル、２−アミノ安息香酸ヘキシル
、３−アミノ安息香酸ヘキシル、４−アミノ安息香酸ペ
ンチル、４−アミノ安息香酸フェニル、２−７ミノ安息
香酸フエニル、３−アミノ安息香酸フェニル等が挙げら
れる。The ester of aminobenzoic acid is preferably an ester with an alcohol having 1 to 12 carbon atoms or a phenol compound, and more preferably an ester with an aliphatic alcohol having 1 to 6 carbon atoms or a phenol compound. Specific examples of the esters include methyl 2-aminobenzoate, methyl 3-aminobenzoate, methyl 4-aminobenzoate, ethyl 2-aminobenzoate, ethyl 3-aminobenzoate, ethyl 4-aminobenzoate, 9-propyl 2-aminobenzoate, propyl 3-aminobenzoate, propyl 4-aminobenzoate, butyl 2-aminobenzoate, butyl 3-aminobenzoate, butyl 4-aminobenzoate, pentyl 2-aminobenzoate, 3- Pentyl aminobenzoate, 4-
Examples include hexyl aminobenzoate, hexyl 2-aminobenzoate, hexyl 3-aminobenzoate, pentyl 4-aminobenzoate, phenyl 4-aminobenzoate, phenyl 2-7-aminobenzoate, phenyl 3-aminobenzoate, etc. It will be done.
式（１）の母体化合物のヒドロキシカルボン酸は、実質
的に４−ヒドロキシ無水フタル酸１モルに対して、アミ
ノ安息香酸またはそのエステル１モルを反応させること
で合成できるが、この比は０．８〜１．２（モル比）で
も良好な結果を与える。The hydroxycarboxylic acid as the parent compound of formula (1) can be synthesized by reacting 1 mole of 4-hydroxyphthalic anhydride with 1 mole of aminobenzoic acid or its ester, but this ratio is 0. Even a molar ratio of 8 to 1.2 gives good results.
反応溶媒は、０−１ｍ−１ｐ−クレゾール等のフェノー
ル系溶媒、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジ
メチルホルムアミド、Ｎ−メチル２−ピロリドン等のア
ミド系溶媒、氷酢酸などを用いることができる。溶媒の
量は全反応物重量の１〜２倍量以上が好ましい。反応温
度は１００〜２００℃が好ましい。また、縮合時に生成
する水を除去するために、ベンゼン、クロロベンゼン、
トルエン等の共沸溶媒を添加することもできるが、共沸
溶媒は存在しなくてもかまわない。As the reaction solvent, phenolic solvents such as 0-1m-1p-cresol, amide solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl 2-pyrrolidone, and glacial acetic acid can be used. can. The amount of solvent is preferably 1 to 2 times or more the weight of all reactants. The reaction temperature is preferably 100 to 200°C. In addition, in order to remove water generated during condensation, benzene, chlorobenzene,
An azeotropic solvent such as toluene can also be added, but the azeotropic solvent does not need to be present.
反応は、通常３０分〜１０時間で完結する。反応混合物
を冷却後、水あるいはメタノールなどの沈澱溶媒に投入
することにより沈澱を生じさせ、濾別することにより生
成物を単離することができる。The reaction is usually completed in 30 minutes to 10 hours. After the reaction mixture is cooled, it is poured into a precipitation solvent such as water or methanol to form a precipitate, and the product can be isolated by filtration.
更に本発明のフタルイミド化合物のうち（り式中のＸが
アシル基、Ｒ１がアルキル基の化合物は前述の方法の外
に、（１）式中のＸおよびＲが共に水素であるフタルイ
ミド化合物をアシル化およびエステル化して合成するこ
とができる。Furthermore, among the phthalimide compounds of the present invention (in which X is an acyl group and R1 is an alkyl group), in addition to the above-mentioned method, a phthalimide compound in which X and R in the formula (1) are both hydrogen, It can be synthesized by esterification and esterification.
このようにして得られた新規なフタルイミドは、単独で
重合に供することもできるし、他のヒドロキシカルボン
酸あるいはジヒドロキシ化合物とジカルボン酸の混合物
と重縮合することにより、ポリエステルイミド等の耐熱
性の高いポリマーを与える。また、モノマーの適切な選
択（例えば−０００Ｒ１がパラ位の場合など）により液
晶性を有するポリマーも形成することができる。The novel phthalimide thus obtained can be subjected to polymerization alone, or can be polycondensed with other hydroxycarboxylic acids or a mixture of dihydroxy compounds and dicarboxylic acids to form highly heat-resistant products such as polyesterimide. Give the polymer. Furthermore, by appropriately selecting monomers (for example, when -000R1 is at the para position), it is also possible to form a polymer having liquid crystallinity.
ここで、他のヒドロキシカルボン酸としては、ｐ−ヒド
ロキシ安息香酸、６−ヒドロキシ−２ナフトエ酸が挙げ
られ、ジヒドロキシ化合物としては、ヒドロキノン、４
．４′−ビフェノール、ビスフェノール−Ａ、４．４′
−ジヒドロキシジフェニルケトン、２．６−シヒドロキ
シナフタレンが挙げられ、ジカルボン酸として、テレフ
タル酸、イソフタル酸、４．４゛−ジカルボキシビフェ
ニル、２，６−ジカルボキシナフタレン等を挙げること
ができる。Here, examples of other hydroxycarboxylic acids include p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and examples of dihydroxy compounds include hydroquinone and 4-hydroxybenzoic acid.
．． 4'-biphenol, bisphenol-A, 4.4'
Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, 4.4'-dicarboxybiphenyl, and 2,6-dicarboxynaphthalene.
（実施例） 以下、実施例に基づき本発明を具体的に説明する。(Example) Hereinafter, the present invention will be specifically explained based on Examples.
実施例１
三方コック、還流冷却管、磁気攪拌子を備えた３００−
ナスフラスコに、４−ヒドロキシ無水フタル酸５２．４
ミリモル、４−アミノ安息香酸５２．４ミリモルおよび
Ｎ−メチル−２−ピロリドン１００ ｍｌを仕込み、窒
素雰囲気下１９０℃で６時間加熱攪拌した。反応混合物
を放冷汲水５００−に投入し、生成物を沈澱させた。こ
れを濾別後減圧乾燥し、Ｎ。Example 1 300- equipped with three-way cock, reflux condenser, and magnetic stirrer
In an eggplant flask, add 52.4 4-hydroxyphthalic anhydride.
52.4 mmol of 4-aminobenzoic acid and 100 ml of N-methyl-2-pyrrolidone were charged, and the mixture was heated and stirred at 190° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was poured into 500 g of cooled water to precipitate the product. This was filtered and dried under reduced pressure.
Ｎ−ジメチルホルムアミドから再結晶し、４１．３ミリ
モル（収率７９％）の４−ヒドロキシ−Ｎ −（ｐ−カ
ルボキシフェニル）フタルイミドを得た。このものは、
薄黄緑色の粉末で融点は３６１℃であった。元素分析値
は、測定値Ｃ；６３．８８、Ｈ；３．２７、Ｎｉ５．Ｏ
Ｏ１計算値Ｃ；６３．６Ｌ Ｈ；３．２０、Ｎ；４．９
５であった。この化合物の赤外線吸収スペクトルおよび
プロトンＮＭＲスペクトルを第１図および第２図に示す
。Recrystallization from N-dimethylformamide gave 41.3 mmol (yield 79%) of 4-hydroxy-N-(p-carboxyphenyl)phthalimide. This thing is
It was a pale yellow-green powder with a melting point of 361°C. The elemental analysis values are measured value C: 63.88, H: 3.27, Ni5. O
O1 calculation value C; 63.6L H; 3.20, N; 4.9
It was 5. The infrared absorption spectrum and proton NMR spectrum of this compound are shown in FIGS. 1 and 2.
実施例２〜７
４−ヒドロキシ無水フタル酸の代りに表−１の八を用い
、４−アミノ安息香酸の代わりに表−１のＢを用いた以
外は、実施例１と同様にして表１に示す生成物を得た。Examples 2 to 7 Table 1 was prepared in the same manner as in Example 1, except that 8 of Table 1 was used instead of 4-hydroxyphthalic anhydride, and B of Table 1 was used instead of 4-aminobenzoic acid. The product shown in was obtained.
結果を表−１に示す。The results are shown in Table-1.
参考例１
７．６５ミリモルのポリエチレンテレフタレート、１２
．７ミリモルのｐ−ヒドロキシ安息香酸および実施例１
で得られた４−ヒドロキシ−Ｎ −（ｐ−カルポキシフ
ヱニル）フタルイミド５．０８ミリモルとを攪拌翼、窒
素ガス導入管および蒸留装置を備えたガラス容器に仕込
み、３回窒素置換した。これに２．２−の無水酢酸を加
え、窒素雰囲気下１２０℃で３０分間加熱した。続いて
３０分の間に１５０℃まで温度を上げ、更に１時間で２
００℃まで昇温した。Reference example 1 7.65 mmol polyethylene terephthalate, 12
．． 7 mmol p-hydroxybenzoic acid and Example 1
5.08 mmol of 4-hydroxy-N-(p-carpoxyphenyl)phthalimide obtained above was charged into a glass container equipped with a stirring blade, a nitrogen gas introduction tube, and a distillation device, and the mixture was purged with nitrogen three times. 2.2-acetic anhydride was added to this, and the mixture was heated at 120° C. for 30 minutes under a nitrogen atmosphere. Next, the temperature was raised to 150℃ in 30 minutes, and then raised to 2℃ in 1 hour.
The temperature was raised to 00°C.
次に１．５時間で２９０℃まで温度を上げ、この温度で
０．５ｍｍ）Ｉｇまで減圧し、３０分で反応を終了した
。Next, the temperature was raised to 290° C. over 1.5 hours, and at this temperature the pressure was reduced to 0.5 mm) Ig, and the reaction was completed in 30 minutes.
加熱台材の偏光顕微鏡で、得られた重合体を観察すると
、４１０℃で流動を開始する液晶ポリマーであった。ま
たこのものは、フェノール／１，１゜２．２−テトラク
ロロエタン＝６０／４０重量比の混合溶媒に不溶であっ
た。When the obtained polymer was observed under a polarizing microscope using a heating base, it was found to be a liquid crystal polymer that started flowing at 410°C. Further, this product was insoluble in a mixed solvent having a weight ratio of phenol/1,1°2.2-tetrachloroethane=60/40.
（発明の効果）
本発明によれば新規なフタルイミドを容易に合成するこ
とができ、このフタルイミドは、分子内にイミド基およ
び反応性の水酸基とカルボン酸基を有しているので、耐
熱性の高いイミド基含有ポリマーの原料として、あるい
は液晶ポリマーの原料として好適なモノマーである。(Effects of the Invention) According to the present invention, a novel phthalimide can be easily synthesized, and since this phthalimide has an imide group, a reactive hydroxyl group, and a carboxylic acid group in the molecule, it has excellent heat resistance. It is a monomer suitable as a raw material for polymers containing high imide groups or as a raw material for liquid crystal polymers.
第１図は、実施例１で得られた化合物の赤外線吸収スペ
クトル図であり、
第２図は、実施例１で得られた化合物のジメチルスルホ
キシド−ｄ４中のプロトンＮＭＲスペクトル図である。
特許出願人日本合成ゴム株式会社FIG. 1 is an infrared absorption spectrum diagram of the compound obtained in Example 1, and FIG. 2 is a proton NMR spectrum diagram in dimethyl sulfoxide-d4 of the compound obtained in Example 1. Patent applicant: Japan Synthetic Rubber Co., Ltd.
Claims (2)
１は水素または炭素数１〜１０のアルキル基またはアリ
ール基を示す）で表されるフタルイミド化合物。(1) The following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (X in the formula is hydrogen or an acyl group with 1 to 4 carbon atoms, R^
1 represents hydrogen or an alkyl group or aryl group having 1 to 10 carbon atoms.
およびアミノ安息香酸またはそのエステル体を縮合させ
る請求項１記載のフタルイミド化合物の製造方法。(2) The method for producing a phthalimide compound according to claim 1, wherein 4-hydroxyphthalic anhydride or its acyl form and aminobenzoic acid or its ester form are condensed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63328045A JPH02174759A (en) | 1988-12-27 | 1988-12-27 | Phthalimide compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63328045A JPH02174759A (en) | 1988-12-27 | 1988-12-27 | Phthalimide compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02174759A true JPH02174759A (en) | 1990-07-06 |
Family
ID=18205898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63328045A Pending JPH02174759A (en) | 1988-12-27 | 1988-12-27 | Phthalimide compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02174759A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017465A (en) * | 1986-12-27 | 1991-05-21 | Konica Corporation | Light-sensitive silver halide photographic material |
| JP2011236301A (en) * | 2010-05-10 | 2011-11-24 | Okayama Univ | Method for producing polyesterimide |
-
1988
- 1988-12-27 JP JP63328045A patent/JPH02174759A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017465A (en) * | 1986-12-27 | 1991-05-21 | Konica Corporation | Light-sensitive silver halide photographic material |
| JP2011236301A (en) * | 2010-05-10 | 2011-11-24 | Okayama Univ | Method for producing polyesterimide |
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