JPS6328928B2 - - Google Patents
Info
- Publication number
- JPS6328928B2 JPS6328928B2 JP25062785A JP25062785A JPS6328928B2 JP S6328928 B2 JPS6328928 B2 JP S6328928B2 JP 25062785 A JP25062785 A JP 25062785A JP 25062785 A JP25062785 A JP 25062785A JP S6328928 B2 JPS6328928 B2 JP S6328928B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- general formula
- formula
- represented
- 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.)
- Expired
Links
- 229920006122 polyamide resin Polymers 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004957 naphthylene group Chemical group 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000004760 aramid Substances 0.000 description 5
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 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 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- AISNAASNOWRWIR-UHFFFAOYSA-N 1-iodo-3,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(I)=CC([N+]([O-])=O)=C1 AISNAASNOWRWIR-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OHSALBVJOKUUDU-UHFFFAOYSA-N 4-iodo-1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1[N+]([O-])=O OHSALBVJOKUUDU-UHFFFAOYSA-N 0.000 description 1
- -1 Aromatic dicarboxylic acids Chemical class 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
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樹脂、特に各種有機溶媒に
可溶で、なおかつ高いガラス転移点を有する新規
なポリアミド樹脂及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyamide resin, particularly a novel polyamide resin that is soluble in various organic solvents and has a high glass transition point, and a method for producing the same.
（従来の技術）
従来、全芳香族ポリアミド樹脂は、高いガラス
転移点と高い分解点を有する材料として期待され
ていた。しかし、これまで製造された多くの芳香
族ポリアミドは、有機溶媒に不溶であり、350℃
以上のガラス転移点を有しているため、その成形
性にはなお問題があつた。また、高い熱安定性を
有しているにもかかわらず、成形性が悪く、耐熱
性と加工性とを共に具備する全芳香族ポリアミド
樹脂がないことが、この樹脂を商業的に利用しよ
うとする際には大きな問題となつていた。(Prior Art) In the past, fully aromatic polyamide resins were expected to be materials with a high glass transition point and a high decomposition point. However, many aromatic polyamides produced to date are insoluble in organic solvents and
Since it has a glass transition point above, there was still a problem with its moldability. In addition, although it has high thermal stability, it has poor moldability and there is no fully aromatic polyamide resin that has both heat resistance and processability, making it difficult to use this resin commercially. It was a big problem when doing so.
（発明が解決しようとする問題点）
したがつて、本発明は、有機溶媒に可溶で、な
おかつ高いガラス転移点を有し、同時に高い分解
点を有する、加工性に優れた新規なポリアミド樹
脂およびその製造方法を提供し、前記問題点を解
決することを目的とする。(Problems to be Solved by the Invention) Therefore, the present invention provides a novel polyamide resin that is soluble in organic solvents, has a high glass transition point, and also has a high decomposition point, and has excellent processability. It is an object of the present invention to provide a method for manufacturing the same and to solve the above-mentioned problems.
（問題点を解決するための手段）
本発明の第１の発明は、前記問題点を解決し得
る構造および特性を有する新規なポリアミド樹脂
であり、すなわち、一般式
（式中、Ｒはフエニレン基とナフチレン基から選
ばれた二価の芳香族基を示し、ｎは10−200の整
数である）
で表されるポリアミド樹脂である。(Means for Solving the Problems) The first invention of the present invention is a novel polyamide resin having a structure and characteristics capable of solving the above problems, that is, a polyamide resin having the general formula (In the formula, R represents a divalent aromatic group selected from a phenylene group and a naphthylene group, and n is an integer from 10 to 200.)
本発明の第２の発明は、５−ヨードメタフエニ
レンジアミンと、一般式
（式中、Ｒはフエニレン基とナフチレン基から選
ばれた二価の芳香族基を示す）
で表される芳香族ジカルボン酸とを亜リン酸エス
テルとピリジン誘導体の存在下に有機溶媒中で反
応させ、前記一般式で表される芳香族ポリアミ
ド樹脂を生成することを特徴とするポリアミド樹
脂の製造方法である。 The second invention of the present invention provides 5-iodomethphenylenediamine and the general formula (In the formula, R represents a divalent aromatic group selected from a phenylene group and a naphthylene group) is reacted with an aromatic dicarboxylic acid represented by the following in an organic solvent in the presence of a phosphite and a pyridine derivative. This is a method for producing a polyamide resin, characterized by producing an aromatic polyamide resin represented by the above general formula.
前記一般式で表されるポリアミド樹脂は、５
−ヨードメタフエニレンジアミンと、前記一般式
で表される芳香族ジカルボン酸から製造される
が、このジアミンは工業的に安価な入手できるメ
タジニトロベンゼンとヨウ素を原料として製造し
得る、１，３−ジニトロ−５−ヨードベンゼン
を、従来公知の各種還元法により還元することに
より得られる。 The polyamide resin represented by the above general formula is 5
-iodomethphenylene diamine and an aromatic dicarboxylic acid represented by the above general formula, but this diamine can be produced from industrially available inexpensive metadinitrobenzene and iodine as raw materials, 1,3- It is obtained by reducing dinitro-5-iodobenzene using various conventionally known reduction methods.
前記一般式で表される芳香族ジカルボン酸と
しては、イソフタル酸、テレフタル酸、１，４−
ナフタレンジカルボン酸、１，５−ナフタレンジ
カルボン酸、２，６−ナフタレンジカルボン酸な
どを例示することができる。 Aromatic dicarboxylic acids represented by the above general formula include isophthalic acid, terephthalic acid, 1,4-
Examples include naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid.
前記一般式で表されるポリアミド樹脂の製造
は、５−ヨードメタフエニレンジアミンと、前記
一般式で表される芳香族ジカルボン酸とを、芳
香族亜リン酸エステルとピリジン誘導体の存在下
に、20−200℃で30分から数日間反応させること
によつて行われるものである。この方法におい
て、一般式で表されるポリアミド樹脂の重合度
は、５−ヨードメタフエニレンジアミンと一般式
で示される芳香族ジカルボン酸の仕込量によつ
て制限され、これらの反応成分を等モル量使用す
ると高重合度のポリアミド樹脂を製造することが
できる。 The polyamide resin represented by the above general formula is produced by combining 5-iodomethphenylenediamine and an aromatic dicarboxylic acid represented by the above general formula in the presence of an aromatic phosphite and a pyridine derivative. It is carried out by reacting at 20-200°C for 30 minutes to several days. In this method, the degree of polymerization of the polyamide resin represented by the general formula is limited by the amount of 5-iodomethphenylenediamine and the aromatic dicarboxylic acid represented by the general formula, and these reaction components are mixed in equimolar amounts. When used in a large amount, a polyamide resin with a high degree of polymerization can be produced.
本発明において使用する芳香族亜リン酸エステ
ルとしては、亜リン酸トリフエニル、亜リン酸ジ
フエニル、亜リン酸トリ−ｐ−トリル、亜リン酸
トリ−ｐ−クロロフエニルなどをあげることがで
きる。 Examples of the aromatic phosphite used in the present invention include triphenyl phosphite, diphenyl phosphite, tri-p-tolyl phosphite, and tri-p-chlorophenyl phosphite.
また、本発明において使用するピリジン誘導体
としては、ピリジン、２−ピコリン、３−ピコリ
ン、４−ピコリンなどをあげることができる。 Further, examples of the pyridine derivatives used in the present invention include pyridine, 2-picoline, 3-picoline, and 4-picoline.
この方法に使用し得る有機溶媒として代表的な
ものは、Ｎ−メチル−２−ピロリドンやＮ，Ｎ−
ジメチルアセトアミドなどのアミド系溶媒であ
る。ここで重合度の大きいポリアミド樹脂を得る
ために、塩化リチウムや塩化カルシウムなどの無
機塩類や、トリエチルアミン塩酸塩、テトラブチ
ルアンモニウムクロリド、セチルトリメチルアン
モニウムクロリドなどの有機塩類をこの反応系に
添加することもできる。 Typical organic solvents that can be used in this method include N-methyl-2-pyrrolidone and N,N-
An amide solvent such as dimethylacetamide. In order to obtain a polyamide resin with a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride, and organic salts such as triethylamine hydrochloride, tetrabutylammonium chloride, and cetyltrimethylammonium chloride may be added to this reaction system. can.
前記一般式で表されるポリアミド樹脂におい
て平均重合度ｎを10−200の整数に限定した理由
は、ｎが10より小ではフイルムなどに成形した成
形品の機械特性や耐熱性等の特性が十分でなく、
ｎが200を越えると有機溶媒への溶解性が悪くな
るからである。 The reason for limiting the average degree of polymerization n to an integer between 10 and 200 in the polyamide resin represented by the above general formula is that when n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, are insufficient. Not, but
This is because when n exceeds 200, solubility in organic solvents deteriorates.
かくして製造された前記一般式で表されるポ
リアミド樹脂は、使用した前記一般式で表され
る芳香族ジカルボン酸の種類により特にその溶解
性が変化するが、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−２−ピロ
リドン、ジメチルスルホキシド、メタクレゾー
ル、オルトクロロフエノール、ピリジンなどの溶
媒のすべてに、または一部に可溶となる。前記一
般式で表されるポリアミド樹脂は、400℃付近
まで加熱しても顕著な重量変化は認められない。 The solubility of the thus produced polyamide resin represented by the above general formula changes depending on the type of aromatic dicarboxylic acid represented by the above general formula used, but it can be used in dimethylformamide, N,N
- It becomes soluble in all or part of solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, metacresol, orthochlorophenol, and pyridine. The polyamide resin represented by the above general formula shows no significant weight change even when heated to around 400°C.
以下、本発明を参考例および実施例によりさら
に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.
（実施例）
参考例 １
メタジニトロベンゼン60ｇ（0.357mol）とヨ
ウ素47ｇ（0.185mol）を25％発煙硫酸に溶解し、
徐々に150℃まで加熱した。この温度で白煙が発
生しなくなるまでかくはんした後、反応混合物を
冷却し、氷に投入した粗製物を得た。純粋な１，
３−ジニトロ−５−ヨードベンゼンは、エタノー
ルから再結晶して得た。収量72.6ｇ（収率69％）、
融点96℃（文献値99−100℃）であつた。(Example) Reference example 1 60 g (0.357 mol) of metadinitrobenzene and 47 g (0.185 mol) of iodine were dissolved in 25% fuming sulfuric acid,
The mixture was gradually heated to 150°C. After stirring at this temperature until no white smoke was generated, the reaction mixture was cooled to obtain a crude product which was poured into ice. pure 1,
3-dinitro-5-iodobenzene was obtained by recrystallization from ethanol. Yield 72.6g (yield 69%),
The melting point was 96°C (literature value 99-100°C).
参考例 ２
エタノール300mlに、１，３−ジニトロ−５−
ヨードベンゼン29.4ｇ（0.1mmol）、塩化第１ス
ズ180.5ｇ（0.8mol）を溶解し、窒素気流下、70
℃で30分間かくはんした。反応後、反応混合物を
氷水に投入し、５％重炭酸ナトリウム水溶液でPH
７−８に調整した。得られた溶液を酢酸エチルで
抽出し、硫酸ナトリウムで乾燥後、溶媒を減圧留
去した。得られた５−ヨードメタフエニレンジア
ミンは、ベンゼンから再結晶した。収量8.16ｇ
（収率35％）、融点128℃であつた。Reference example 2 Add 1,3-dinitro-5- to 300 ml of ethanol.
Dissolve 29.4 g (0.1 mmol) of iodobenzene and 180.5 g (0.8 mol) of stannous chloride, and add to
Stir at ℃ for 30 minutes. After the reaction, the reaction mixture was poured into ice water and the pH was adjusted with 5% sodium bicarbonate aqueous solution.
Adjusted to 7-8. The resulting solution was extracted with ethyl acetate, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained 5-iodomethphenylenediamine was recrystallized from benzene. Yield 8.16g
(yield 35%), and the melting point was 128°C.
実施例 １
イソフタル酸0.83ｇ（5mmol）、５−ヨードメ
タフエニレンジアミン1.17ｇ（5mmol）、亜リン
酸トリフエニル3.10ｇ（10mmol）、ピリジン2.5
ml、塩化リチウム0.50ｇおよびＮ−メチル−２−
ピロリドン10mlを、窒素雰囲気下、100℃で３時
間かくはんした。反応後、重合溶液をメタノール
中に投入してポリマーを得た。収量1.82ｇ（収率
100％）。このポリマーの固有粘度は0.59（硫酸中
0.5ｇ/dlの濃度、30℃で測定）であつた。Example 1 0.83 g (5 mmol) of isophthalic acid, 1.17 g (5 mmol) of 5-iodomethphenylenediamine, 3.10 g (10 mmol) of triphenyl phosphite, 2.5 g of pyridine
ml, 0.50 g of lithium chloride and N-methyl-2-
10 ml of pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.82g (yield
100%). The intrinsic viscosity of this polymer is 0.59 (in sulfuric acid)
The concentration was 0.5 g/dl (measured at 30°C).
熱重量測定法による100％重量減少温度、415
℃。 100% weight loss temperature by thermogravimetry, 415
℃.
熱機械測定法によるガラス転移点、278℃。 Glass transition temperature by thermomechanical measurement, 278°C.
生成したポリマーはＮ−メチル−２−ピロリド
ン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルホ
ルムアミド、ジメチルスルホキシドに室温で可溶
であり、ピリジンに一部可溶であつた。 The produced polymer was soluble in N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylformamide, and dimethyl sulfoxide at room temperature, and partially soluble in pyridine.
実施例 ２
イソフタル酸0.83ｇ（5mmol）、５−ヨードメ
タフエニレンジアミン1.17ｇ（5mmol）、亜リン
酸トリフエニル3.10ｇ（10mmol）、ピリジン2.5
ml、塩化リチウム0.50ｇおよびＮ−メチル−２−
ピロリドン10mlを、窒素雰囲気下、100℃で３時
間かくはんした。反応後、重合溶液をメタノール
中に投入してポリマーを得た。収量1.82ｇ（収率
100％）、このポリマーの固有粘度は0.73（硫酸中
0.5ｇ/dlの濃度、30℃で測定）であつた。Example 2 Isophthalic acid 0.83g (5mmol), 5-iodomethphenylenediamine 1.17g (5mmol), triphenyl phosphite 3.10g (10mmol), pyridine 2.5
ml, 0.50 g of lithium chloride and N-methyl-2-
10 ml of pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.82g (yield
100%), the intrinsic viscosity of this polymer is 0.73 (in sulfuric acid
The concentration was 0.5 g/dl (measured at 30°C).
熱重量測定法による10％重量減少温度、435℃。 10% weight loss temperature by thermogravimetry, 435°C.
熱機械測定法によるガラス転移点、318℃。 Glass transition temperature by thermomechanical measurement, 318°C.
生成したポリマーはＮ，Ｎ−ジメチルアセトア
ミドに室温で可溶、Ｎ−メチル−２−ピロリドン
に熱時可溶であつた。 The produced polymer was soluble in N,N-dimethylacetamide at room temperature and in N-methyl-2-pyrrolidone when heated.
実施例 ３
２，６−ナフタレンジカルボン酸1.08ｇ
（5mmol）、５−ヨードメタフエニレンジアミン
1.17ｇ（5mmol）、亜リン酸トリフエニル3.10ｇ
（10mmol）、ピリジン2.5ml、塩化リチウム0.50ｇ
およびＮ−メチル−２−ピロリドン10mlを、窒素
雰囲気下、100℃で３時間かくはんした。反応後、
重合溶液をメタノール中に投入してポリマーを得
た。収量2.07ｇ（収率100％）。このポリマーの固
有粘度は1.11（硫酸中0.5ｇ/dlの濃度、30℃で測
定）であつた。Example 3 2,6-naphthalene dicarboxylic acid 1.08g
(5mmol), 5-iodomethphenylenediamine
1.17g (5mmol), triphenyl phosphite 3.10g
(10 mmol), pyridine 2.5 ml, lithium chloride 0.50 g
and 10 ml of N-methyl-2-pyrrolidone were stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction,
The polymerization solution was poured into methanol to obtain a polymer. Yield: 2.07g (100% yield). The intrinsic viscosity of this polymer was 1.11 (measured at 30° C. at a concentration of 0.5 g/dl in sulfuric acid).
熱重量測定法による10％重量減少温度、445℃。 10% weight loss temperature by thermogravimetry, 445°C.
生成したポリマーはＮ，Ｎ−ジメチルアセトア
ミドに熱時可溶で、ジメチルホルムアミド、ジメ
チルスルホキシドに一部可溶であつた。 The produced polymer was soluble in N,N-dimethylacetamide when heated, and partially soluble in dimethylformamide and dimethyl sulfoxide.
（発明の効果）
本発明は前記一般式で表されるポリアミド樹
脂およびこのポリアミド樹脂の有利な製造方法を
提供する。本発明のポリアミド樹脂は、従来の芳
香族ポリアミド樹脂の多くが有機溶媒に不溶であ
り、熱的に不融であり、成形性に問題を残してい
たのに対し、各種の有機溶媒に可溶であつて、溶
液成形が可能であるとともに、加熱成形可能なエ
ンジニアリングプラスチツクとして工業的価値が
高い。(Effects of the Invention) The present invention provides a polyamide resin represented by the above general formula and an advantageous method for producing the polyamide resin. The polyamide resin of the present invention is soluble in various organic solvents, whereas most conventional aromatic polyamide resins are insoluble in organic solvents and thermally infusible, leaving problems with moldability. It is solution moldable and has high industrial value as a heat moldable engineering plastic.
Claims (1)
ばれた二価の芳香族基を示し、ｎは10−200の整
数である） で表されるポリアミド樹脂。 ２ ５−ヨードメタフエニレンジアミンと、一般
式 （式中、Ｒはフエニレン基とナフチレン基から選
ばれた二価の芳香族基を示す） で表される芳香族ジカルボン酸とを亜リン酸エス
テルとピリジン誘導体の存在下に有機溶媒中で反
応させ、一般式 （式中、Ｒはフエニレン基とナフチレン基から選
ばれた二価の芳香族基を示し、ｎは10−200の整
数である） で表される芳香族ポリアミド樹脂を生成すること
を特徴とするポリアミド樹脂の製造方法。[Claims] 1. General formula (In the formula, R represents a divalent aromatic group selected from a phenylene group and a naphthylene group, and n is an integer from 10 to 200.) A polyamide resin represented by the formula: 2 5-iodomethphenylenediamine and general formula (In the formula, R represents a divalent aromatic group selected from a phenylene group and a naphthylene group) is reacted with an aromatic dicarboxylic acid represented by the following in an organic solvent in the presence of a phosphite and a pyridine derivative. Let, general formula (In the formula, R represents a divalent aromatic group selected from a phenylene group and a naphthylene group, and n is an integer from 10 to 200.) Method for producing polyamide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25062785A JPS62112626A (en) | 1985-11-11 | 1985-11-11 | Polyamide resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25062785A JPS62112626A (en) | 1985-11-11 | 1985-11-11 | Polyamide resin and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62112626A JPS62112626A (en) | 1987-05-23 |
| JPS6328928B2 true JPS6328928B2 (en) | 1988-06-10 |
Family
ID=17210665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25062785A Granted JPS62112626A (en) | 1985-11-11 | 1985-11-11 | Polyamide resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62112626A (en) |
-
1985
- 1985-11-11 JP JP25062785A patent/JPS62112626A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62112626A (en) | 1987-05-23 |
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