JP3328846B2 - Method for producing high molecular weight polyamide - Google Patents
Method for producing high molecular weight polyamideInfo
- Publication number
- JP3328846B2 JP3328846B2 JP29441592A JP29441592A JP3328846B2 JP 3328846 B2 JP3328846 B2 JP 3328846B2 JP 29441592 A JP29441592 A JP 29441592A JP 29441592 A JP29441592 A JP 29441592A JP 3328846 B2 JP3328846 B2 JP 3328846B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- adipic acid
- polyamide
- acid
- weight polyamide
- 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 - Lifetime
Links
Landscapes
- Polyamides (AREA)
Description
【０００１】[0001]
【産業上の利用分野】近年、ポリアミドの需要が食品分
野を中心に伸びてきている。食品の多様化、保存条件あ
るいは販売経路の多様化に伴い分子量の高い機械的性能
の向上したポリアミドフィルム、および成形性を向上さ
せるため、溶融強度、溶融粘度の高いポリアミドが求め
られている。本発明はこの様な要請に見合った高分子量
でゲル状物の少ない高分子量ポリアミドの製造法に関す
る。BACKGROUND OF THE INVENTION In recent years, the demand for polyamide has been growing mainly in the food field. Along with diversification of foods, storage conditions or diversification of sales channels, polyamide films having high molecular weight and improved mechanical performance, and polyamides having high melt strength and high melt viscosity are required to improve moldability. The present invention relates to a method for producing a high-molecular-weight polyamide having a high molecular weight and a small amount of gel, which meets such a demand.
【０００２】[0002]
【従来の技術】高分子量ポリアミドの一般的な製造方法
としては、ジカルボン酸とジアミン化合物で先ず塩を形
成させ、次いで水溶液中で加圧下に反応させ、生成する
反応水を除去しながら重合を進める方法、あるいはアジ
ピン酸を溶融後、アジピン酸溶液中にジアミン化合物を
滴下させながら生成する反応水を除去しながら行う方法
等がある。2. Description of the Related Art As a general method for producing a high-molecular-weight polyamide, a salt is first formed with a dicarboxylic acid and a diamine compound, and then a reaction is performed under pressure in an aqueous solution, and polymerization is carried out while removing generated reaction water. Or a method in which adipic acid is melted, and then the reaction is performed while dropping a reaction water generated while dropping a diamine compound into an adipic acid solution.
【０００３】[0003]
【発明が解決しようとする課題】アジピン酸の工業的な
製造方法として、シクロヘキサノール、もしくはシクロ
ヘキサノンとシクロヘキサノール混合物（ＫＡオイル）
を鉱酸を用いて酸化させる方法が一般的に行われてい
る。上記鉱酸としては硝酸が用いられることが多く、ま
れには塩酸、硝酸の混合酸およびホウ酸が用いられるこ
ともある。酸化反応で得られたアジピン酸の精製方法と
しては通常水洗法が用いられるが、この精製方法を採用
すると製品アジピン酸中に塩酸、硝酸、ホウ酸等の鉱酸
が通常４〜１０ｐｐｍ含まれる。上記濃度の鉱酸を含む
アジピン酸を用いて常法によりポリアミドを製造すると
アミド化反応が促進されるのみならず、高分子量重合物
の架橋反応が同時に促進され、その結果、ポリアミドフ
ィルムにはゲル状物質が多く、得られたポリアミドは工
業的には価値の低いものになる。本発明はゲル状物質が
少なくかつ射出成形用材料、フィルム・シート等の包装
材料、およびモノフィラメント、繊維用材料として工業
的に有用な高分子量ポリアミドの製造方法を提供するこ
とにある。As an industrial method for producing adipic acid, cyclohexanol or a mixture of cyclohexanone and cyclohexanol (KA oil) is used.
Is generally performed using a mineral acid. Nitric acid is often used as the mineral acid, and rarely, a mixed acid of hydrochloric acid, nitric acid, and boric acid may be used. As a method for purifying the adipic acid obtained by the oxidation reaction, a water washing method is usually used. When this purification method is adopted, mineral acids such as hydrochloric acid, nitric acid and boric acid are usually contained in the product adipic acid in an amount of 4 to 10 ppm. When a polyamide is produced by a conventional method using adipic acid containing the above concentration of mineral acid, not only the amidation reaction is promoted, but also the crosslinking reaction of a high molecular weight polymer is simultaneously promoted, and as a result, a gel is formed on the polyamide film. And the resulting polyamide is of low industrial value. An object of the present invention is to provide a method for producing a high-molecular-weight polyamide which is low in gel-like substance and is industrially useful as a material for injection molding, a packaging material such as a film or sheet, and a material for monofilaments and fibers.
【０００４】[0004]
【課題を解決するための手段】発明者らは、アジピン酸
を溶融後、アジピン酸溶液中へジアミン化合物を滴下
し、生成する反応水を除去しながら高分子量ポリアミド
を製造する方法に関し鋭意検討した結果、鉱酸濃度が１
ｐｐｍ以下のアジピン酸を使用することでゲル状物質の
極めて少ない高分子量ポリアミドの製造が可能なことを
発見し本発明に到達した。すなわち、本発明は、ジカル
ボン酸としてアジピン酸、ジアミンとして下記一般式
（１）に示す化合物を使用して、アジピン酸を溶融後、
アジピン酸溶液中へジアミン化合物を滴下し、生成する
反応水を除去しながら高分子量ポリアミドを製造するに
際し、鉱酸濃度が１ｐｐｍ以下のアジピン酸を使用する
ことを特徴とする高分子量ポリアミドの製造方法に関す
る発明である。 Ｈ2 Ｎ−ＣＨ2 −Ｒ−ＣＨ2 −ＮＨ2 （１） （式中、Ｒはメタフェニレン基、パラフェニレン基、
１，３−シクロヘキシル基、１，４−シクロヘキシル基
のうちのいずれかである。）Means for Solving the Problems The present inventors,Adipic acid
After melting, diamine compound is dropped into adipic acid solution
And remove the reaction water generatedHigh molecular weight polyamide
As a result of intensive studies on the method for producing
The use of adipic acid of less than ppm
The ability to produce very low molecular weight polyamides
Discovered and reached the present invention. That is, the present invention
Adipic acid as boric acid, lower as diamineGeneral formula
Using the compound shown in (1),After melting adipic acid,
Diamine compound is dropped into adipic acid solution to form
While removing the reaction waterTo produce high molecular weight polyamide
At this time, use adipic acid with a mineral acid concentration of 1 ppm or less.
A process for producing a high molecular weight polyamide characterized by the following:
Invention. HTwo N-CHTwo -R-CHTwo -NHTwo (1) (wherein, R is a metaphenylene group, a paraphenylene group,
1,3-cyclohexyl group, 1,4-cyclohexyl group
Is one of )
【０００５】本発明で使用するアジピン酸中の鉱酸濃度
を１ｐｐｍ以下にする方法として水洗法がある。上記全
鉱酸濃度を１ｐｐｍ以下としたアジピン酸を使用してゲ
ル状物質の少ないポリアミドを製造し、該ポリアミドを
使用して成形して得たフィルム・シートは商品価値の高
いものである。[0005] As a method for reducing the concentration of mineral acid in adipic acid used in the present invention to 1 ppm or less, there is a water washing method. A film / sheet obtained by producing a polyamide having a small amount of a gel-like substance using adipic acid having a total mineral acid concentration of 1 ppm or less and molding using the polyamide is of high commercial value.
【０００６】本発明の高分子量ポリアミドに用いられる
ジアミン化合物は、上記一般式（１）で示されるジアミ
ン化合物である。ジアミン化合物の具体的な例として
は、メタキシリレンジアミン、パラキシリレンジアミ
ン、１、３−ビスアミノメチルシクロヘキサン、１、４
−ビスアミノメチルシクロヘキサン、およびこれらの混
合物を用いることができる。本発明における高分子量ポ
リアミドの製造方法は、アジピン酸を溶融後、アジピン
酸溶液中へジアミン化合物を滴下し、生成する反応水を
除去しながら行う方法である。この際、得られる重合物
の着色防止のために、着色防止剤を使用することも可能
である。この様にして得られた重合物は分子量で１６０
００〜２５０００程度である。分子量を更に増加して、
より高分子量のポリアミドを製造する方法として上記溶
融重合を長時間あるいはさらに溶融されたポリマーと接
する気相部の水蒸気圧をより低くして継続する方法もあ
る。[0006] diamine compound used in the high molecular weight polyamide of the present invention is a diamine compound represented by the above following general formula (1). Specific examples of the diamine compound include meta-xylylenediamine, para-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4
-Bisaminomethylcyclohexane, and mixtures thereof can be used. High molecular weight polymer in the present invention
The method for producing lamide is a method in which adipic acid is melted, then a diamine compound is dropped into an adipic acid solution, and the reaction water generated is removed . At this time, it is also possible to use a coloring inhibitor to prevent coloring of the obtained polymer. The polymer thus obtained has a molecular weight of 160
It is about 00 to 25000. Further increase the molecular weight,
As a method for producing a polyamide having a higher molecular weight, there is a method in which the above-mentioned melt polymerization is continued for a long time or by lowering the water vapor pressure of the gas phase in contact with the molten polymer.
【０００７】また、分子量２５０００までの溶融重合に
よる第１段階、さらに、固相重合による高分子量化の第
２段階の方法が採用される。分子量２５０００程度のポ
リアミドでもフィルムへの成形は可能であるが、フィル
ムの機械的性能の向上のために、あるいは高い溶融強度
を必要とする成形法を採用する際はより高い分子量のポ
リアミドを使用するのが望ましい。鉱酸濃度が１ｐｐｍ
を越えるアジピン酸をそのまま使用し、第１段階、第２
段階を経る当該方法において得られる高分子量ポリアミ
ドは、フィルム全体にゲル状物質が存在するものであり
かつ、延伸フィルムの作製も困難である。本発明の方法
により、鉱酸濃度が１ｐｐｍ以下のアジピン酸を使用し
て得た高分子量ポリアミドは、ゲル状物質が少なく、２
軸延伸も可能となる。このように、本発明の方法を用い
ることにより工業的に有用な高分子量ポリアミドを製造
することができる。Further, a method of a first stage by melt polymerization up to a molecular weight of 25,000 and a second stage of high molecular weight by solid phase polymerization are employed. A polyamide having a molecular weight of about 25,000 can be formed into a film, but a polyamide having a higher molecular weight is used for improving the mechanical performance of the film or when adopting a molding method requiring high melt strength. It is desirable. Mineral acid concentration is 1ppm
Using adipic acid over 1st stage, 2nd stage
The high-molecular-weight polyamide obtained by the method through a step has a gel-like substance present in the entire film, and it is difficult to prepare a stretched film. According to the method of the present invention, a high-molecular-weight polyamide obtained using adipic acid having a mineral acid concentration of 1 ppm or less has a low gel-like substance
Axial stretching is also possible. As described above, an industrially useful high-molecular-weight polyamide can be produced by using the method of the present invention.
【０００８】[0008]
【実施例】以下、実施例により本発明を説明する。な
お、実施例中に示す相対粘度、ゲルの測定方法は次の通
りである。 相対粘度９６％濃硫酸を測定溶媒として
用い、１ｇ／１００ｍｌの濃度で、２５℃で測定する。
ゲル測定方法無延伸フィルムの１００×１００ｍｍ
の範囲を目視で観察し、５０μｍφ以上およびそれ未満
を判別する。更に５０μｍφ以上のゲルについて拡大投
影器を用いて画像を５倍に拡大し、５０〜１００μｍφ
未満、１００〜２００μｍφ、２００μｍφ以上につい
てランク分けを行う。The present invention will be described below with reference to examples. The methods for measuring the relative viscosity and gel shown in the examples are as follows. The measurement is performed at 25 ° C. at a concentration of 1 g / 100 ml using 96% concentrated sulfuric acid as a measuring solvent.
Gel measuring method 100 × 100mm of unstretched film
Is visually observed to determine the range of 50 μmφ or more and less than 50 μmφ. Further, for a gel of 50 μmφ or more, the image is magnified 5 times using a magnifying projector, and 50 to 100 μmφ
The ranking is performed for less than 100 μmφ, 200 μmφ or more.
【０００９】実施例１ 硝酸０．６ｐｐｍを含有するアジピン酸１０ｋｇ（６
８．４ｍｏｌ）を内容積５０リットルのステンレス製反
応缶に仕込み、１７０℃に加熱してアジピン酸を溶融す
る。溶融後、メタキシリレンジアミン９．３ｋｇ（６
８．４ｍｏｌ）を徐々に滴下し、かつ内温を２４０℃ま
で上昇させる。滴下時間は２．５時間要する。滴下終了
後、内温を２６０℃に上昇する。２５０℃に到達した時
点で缶内を減圧にする。２６０℃で２０分間反応を継続
する。反応終了後、缶内を窒素で微加圧にし、５穴を有
するダイヘッドからストランドを押出し、ペレタイザー
でペレット化する。得られたペレットを内容積１５０リ
ットルのタンブラーに仕込み、減圧下に２０５℃で２時
間固相重合を行った。上記反応で得られたポリメタキシ
リレンアジパミドの相対粘度は３．７０で分子量は４２
０００であった。これをＴダイを備えた押出機で押出
し、厚さ５０μｍのフィルムを作成した。得られたフィ
ルムのゲルを測定した。結果を表１に示す。更に、３０
０μｍ厚みのシートを作成し、２軸押出機で２０μｍの
フィルムを作成したが延伸性は良好であった。Example 1 10 kg of adipic acid containing 0.6 ppm of nitric acid (6
8.4 mol) was charged into a stainless steel reactor having an inner volume of 50 liters, and heated to 170 ° C. to melt adipic acid. After melting, 9.3 kg of metaxylylenediamine (6 kg)
8.4 mol) is gradually added dropwise, and the internal temperature is raised to 240 ° C. The dripping time requires 2.5 hours. After completion of the dropping, the internal temperature is raised to 260 ° C. When the temperature reaches 250 ° C., the pressure inside the can is reduced. The reaction is continued at 260 ° C. for 20 minutes. After the reaction is completed, the inside of the can is slightly pressurized with nitrogen, and the strand is extruded from a die head having five holes, and pelletized by a pelletizer. The obtained pellets were charged into a tumbler having an internal volume of 150 liters, and subjected to solid-state polymerization at 205 ° C. for 2 hours under reduced pressure. The relative viscosity of polymetaxylylene adipamide obtained by the above reaction was 3.70 and the molecular weight was 42.
000. This was extruded with an extruder equipped with a T-die to produce a 50 μm thick film. The gel of the resulting film was measured. Table 1 shows the results. In addition, 30
A sheet having a thickness of 0 μm was prepared, and a film having a thickness of 20 μm was prepared using a twin-screw extruder.
【００１０】比較例１硝酸２．６ｐｐｍを含有するアジピン酸を使用した以外
は実施例１ と同様にポリメタキシリレンアジパミドを製
造した。得られたもののゲル測定結果を表１に示す。Comparative Example 1 Except for using adipic acid containing 2.6 ppm of nitric acid
Produced polymethaxylylene adipamide in the same manner as in Example 1 . Table 1 shows the gel measurement results of the obtained product.
【００１１】 表１ ゲル数（個／ｍ 2 ） ゲルサイズ（μｍ） ２００以上 ２００〜１００ ５０以上９９未満 実施例１ ４０ １７０ １２００ 比較例１ １５００ １１０００ ８３０００ Table 1 Gel number (pieces / m 2 ) Gel size (μm) 200 or more 200 to 100 50 or more and less than 99 Example 1 40 170 1200 Comparative Example 1 1500 11000 83000
【００１２】[0012]
【発明の効果】本発明の方法により得られる高分子量ポ
リアミドは、ゲル状物質が少なく、特にフィルム・シー
ト用に好適である。The high-molecular-weight polyamide obtained by the method of the present invention has a low gel-like substance and is particularly suitable for films and sheets.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 正広 神奈川県平塚市東八幡５丁目６番２号 三菱瓦斯化学株式会社 プラスチックス センター内 審査官 佐藤 健史 (56)参考文献 特開 平１−104654（ＪＰ，Ａ) 特開 昭62−79225（ＪＰ，Ａ) 特開 昭49−53945（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 69/00 - 69/50 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masahiro Harada 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref. Inspector, Plastics Center, Mitsubishi Gas Chemical Co., Ltd. Takeshi Sato (56) References JP-A-1-104654 ( JP, A) JP-A-62-79225 (JP, A) JP-A-49-53945 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 69/00-69/50
Claims (2)
ンとして下記一般式（１）に示す化合物を使用して、ア
ジピン酸を溶融後、アジピン酸溶液中へジアミン化合物
を滴下し、生成する反応水を除去しながら高分子量ポリ
アミドを製造するに際し、鉱酸濃度が１ｐｐｍ以下のア
ジピン酸を使用することを特徴とする高分子量ポリアミ
ドの製造方法。 Ｈ2 Ｎ−ＣＨ2 −Ｒ−ＣＨ2 −ＮＨ2 （１） （式中、Ｒは、メタフェニレン基、パラフェニレン基、
１，３−シクロヘキシル基、１，４−シクロヘキシル基
のうちのいずれかである。）1. A adipic acid as the dicarboxylic acid, using the compounds shown below following general formula (1) as a diamine, A
After melting dipic acid, diamine compound is added to adipic acid solution
A method for producing a high-molecular-weight polyamide, the method comprising using adipic acid having a mineral acid concentration of 1 ppm or less in producing a high-molecular-weight polyamide while removing formed reaction water . H 2 N—CH 2 —R—CH 2 —NH 2 (1) (wherein R is a metaphenylene group, a paraphenylene group,
One of a 1,3-cyclohexyl group and a 1,4-cyclohexyl group. )
５０００〜５００００である請求項１に記載の高分子量
ポリアミドの製造方法。2. A high molecular weight polyamide having a number average molecular weight of 2
The method for producing a high-molecular-weight polyamide according to claim 1, wherein the molecular weight is 5,000 to 50,000.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29441592A JP3328846B2 (en) | 1992-11-02 | 1992-11-02 | Method for producing high molecular weight polyamide |
| AU50262/93A AU665276B2 (en) | 1992-11-02 | 1993-10-26 | Process for production of polyamides, polyamides produced by said process and polyamide film or sheet |
| US08/141,593 US5504185A (en) | 1992-11-02 | 1993-10-27 | Process for production of polyamides, polyamides produced by said process and polyamide film or sheet |
| KR1019930023013A KR100199122B1 (en) | 1992-11-02 | 1993-11-01 | Process for production of polyamides, polyamides produced by said process and polyamide film or sheet |
| EP93308749A EP0596702A1 (en) | 1992-11-02 | 1993-11-02 | Process for production of polyamide, polyamide produced by said process, and polyamide film or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29441592A JP3328846B2 (en) | 1992-11-02 | 1992-11-02 | Method for producing high molecular weight polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06145343A JPH06145343A (en) | 1994-05-24 |
| JP3328846B2 true JP3328846B2 (en) | 2002-09-30 |
Family
ID=17807462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29441592A Expired - Lifetime JP3328846B2 (en) | 1992-11-02 | 1992-11-02 | Method for producing high molecular weight polyamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3328846B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100270385B1 (en) * | 1997-06-03 | 2000-11-01 | 가나이 쓰도무 | Color cathode ray tube having an improved phosphor screen |
| JP4774596B2 (en) * | 2001-01-18 | 2011-09-14 | 三菱瓦斯化学株式会社 | Method for producing polyamide |
| JP5531409B2 (en) * | 2009-01-07 | 2014-06-25 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
-
1992
- 1992-11-02 JP JP29441592A patent/JP3328846B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06145343A (en) | 1994-05-24 |
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