JPH02251531A - Polymerization of 6.t nylon - Google Patents

Polymerization of 6.t nylon

Info

Publication number
JPH02251531A
JPH02251531A JP7040689A JP7040689A JPH02251531A JP H02251531 A JPH02251531 A JP H02251531A JP 7040689 A JP7040689 A JP 7040689A JP 7040689 A JP7040689 A JP 7040689A JP H02251531 A JPH02251531 A JP H02251531A
Authority
JP
Japan
Prior art keywords
polymerization
hexamethylene
nylon
copper
prepolymer
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
Application number
JP7040689A
Other languages
Japanese (ja)
Inventor
Toshiaki Matsumoto
俊昭 松本
Kunio Kondo
近土 邦雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP7040689A priority Critical patent/JPH02251531A/en
Publication of JPH02251531A publication Critical patent/JPH02251531A/en
Pending legal-status Critical Current

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  • Polyamides (AREA)

Abstract

PURPOSE:To synthesize a prepolymer of a poly(hexamethylene) terephthalamide having high molecular weight and causing no gel-formation in post- polymerization process by adding a small amount of a copper compound to hexamethylene diamine and terephthalic acid. CONSTITUTION:A prepolymer of poly(hexamethylene) terephthalamide is synthesized by adding a copper compound (preferably copper acetate, copper stearate or copper halide) to hexamethylenediamine and terephthalic acid in an amount of 0.01 to 0.5wt.% (preferably 0.01 to 0.2wt.%) based on the sum of the diamine and the acid.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は6.Tナイロンの重合方法に関する。[Detailed description of the invention] [Industrial application field] The present invention is 6. This invention relates to a method for polymerizing T nylon.

更に詳しくは、ポリ(ヘキサメチレン)テレフタルアミ
ドの初期重合方法に関し、後重合でゲル生成の無い高分
子量のポリ(ヘキサメチレン)テレフタルアミドにする
ことのできるプレポリマーの製造方法に関するものであ
る。
More specifically, the present invention relates to a method for initial polymerization of poly(hexamethylene) terephthalamide, and a method for producing a prepolymer that can be made into high molecular weight poly(hexamethylene) terephthalamide without gel formation through post-polymerization.

本発明により合成されるプレポリマーを後重合して得ら
れるポリ(ヘキサメチレン)テレフタルアミド(以後、
6.Tナイロンと略す)はポリマー鎖中にベンゼン核を
有する高融点ナイロンで、融点は370°Cであり、こ
のポリマーから耐熱性、耐薬品性がすぐれ、物理的にも
種々の優れた特性を有する繊維を得ることが期待できる
Poly(hexamethylene) terephthalamide (hereinafter referred to as
6. T-nylon (abbreviated as T-nylon) is a high-melting-point nylon with a benzene nucleus in the polymer chain, and has a melting point of 370°C.This polymer has excellent heat resistance, chemical resistance, and various excellent physical properties. We can expect to obtain fiber.

〔従来の技術〕[Conventional technology]

この6.Tナイロンのポリマーは高融点で分解温度が融
点に近いため、一般に6.6ナイロンや6ナイロンのよ
うなポリアミドに用いられる溶融重合は使用できず、ヘ
キサメチレンジアミンとテレフタル酸ジクロリドとの界
面重合、あるいは、ヘキサメチレンジアミンとテレフタ
ル酸とから作られるナイロン塩の固相重合により合成さ
れる。
This 6. Since the T-nylon polymer has a high melting point and a decomposition temperature close to the melting point, melt polymerization, which is generally used for polyamides such as 6.6 nylon and 6 nylon, cannot be used. Interfacial polymerization of hexamethylene diamine and terephthalic acid dichloride, Alternatively, it is synthesized by solid state polymerization of a nylon salt made from hexamethylene diamine and terephthalic acid.

界面重合による合成は、テレフタル酸クロリドの反応性
が高く取扱いが難しい上、非常に高価なため工業的に製
造することは困難である。
Synthesis by interfacial polymerization is difficult to produce industrially because terephthalic acid chloride is highly reactive and difficult to handle, and is also very expensive.

後者の固相重合も昔から数多く研究されている。The latter, solid phase polymerization, has also been extensively studied for a long time.

例えば1.特開昭62−20527号公報では、6.7
ナイロンの塩を150℃以上融点未満の温度で減圧また
は不活性ガス下で固相重合する方法が開示されているが
、この方法は、常圧または減圧下では、6、Tナイロン
の塩が重合を開始する温度よりも分解してヘキサメチレ
ンジアミンが逃散し始める温度の方が低いため、この方
法では高重合度のポリマーを製造することはできない。
For example 1. In Japanese Patent Application Laid-Open No. 62-20527, 6.7
A method is disclosed in which a salt of nylon is solid-phase polymerized at a temperature of 150°C or higher and lower than its melting point under reduced pressure or an inert gas. Since the temperature at which hexamethylene diamine begins to decompose and escape is lower than the temperature at which it begins to decompose, it is not possible to produce a polymer with a high degree of polymerization using this method.

また、特公昭41−11634号公報やUSP3,36
5,428では、6.Tナイロン塩を260〜300°
C125〜50 kg/c−の加圧下で初期重合させた
後、常圧にもどし不活性ガス下、260〜300°Cで
固相重合する方法が開示されている。また、この初期重
合の段階で少し過剰のへキサメチレンジアミンを添加す
ることや、ホスホン酸系の重合促進を添加することも併
せて開示されている。しかし、この方法で固有粘・度2
.Odl/g以上の高重合度のポリマーを得ようとして
長時間固相重合すると、濃硫酸に溶けないゲル状物が多
量に生成するという欠点を有していた。
In addition, Japanese Patent Publication No. 41-11634 and USP 3,36
5,428, 6. T nylon salt at 260-300°
A method is disclosed in which initial polymerization is carried out under pressure of C125 to 50 kg/c-, and then the pressure is returned to normal pressure and solid phase polymerization is carried out at 260 to 300°C under an inert gas. It is also disclosed that a slight excess of hexamethylene diamine is added at this initial polymerization stage, and that a phosphonic acid-based polymerization promoter is added. However, with this method, the intrinsic viscosity
.. When solid phase polymerization is carried out for a long period of time in an attempt to obtain a polymer with a high polymerization degree of Odl/g or more, it has the disadvantage that a large amount of gel-like material that is insoluble in concentrated sulfuric acid is produced.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

本発明の目的は、原料としてテレフタル酸およびヘキサ
メチレンジアミンのごとき安価な原料を用いて、ゲル状
物のない、均一で高重合度な6゜Tナイロンのポリマー
を提供することである。
An object of the present invention is to provide a uniform 6°T nylon polymer free from gelatinous substances and having a high degree of polymerization using inexpensive raw materials such as terephthalic acid and hexamethylene diamine.

本発明者らは、ゲル状物が生成しない高重合度ポリマー
の製造方法を鋭意検討した結果、プレポリマーを作る初
期重合の段階が非常に重要であることがわかり、この初
期重合のとき、銅化合物を少量添加してプレポリマーを
作ると、後重合でゲル状物の生成や着色を抑えることが
できることを発見し本発明に達したものである。
The present inventors have conducted intensive studies on a method for producing highly polymerized polymers that do not produce gel-like substances, and have found that the initial polymerization step to form a prepolymer is extremely important. The present invention was achieved by discovering that if a prepolymer is prepared by adding a small amount of a compound, it is possible to suppress the formation of gel-like substances and coloring during post-polymerization.

(課題を解決するための手段〕 即ち、本発明は、ヘキサメチレンジアミンとテレフタル
酸とからポリ (ヘキサメチレン)テレフタルアミドの
初期重合物を合成するに際して、ヘキサメチレンジアミ
ンとテレフタル酸との総量に対して銅化合物を0.O1
〜0.5 W t%加えることを特徴とするポリ(ヘキ
サメチレン)テレフタルアミドの初期重合方法である。
(Means for Solving the Problems) That is, in the present invention, when synthesizing an initial polymer of poly(hexamethylene)terephthalamide from hexamethylene diamine and terephthalic acid, copper compound at 0.01
This is a method for initial polymerization of poly(hexamethylene) terephthalamide characterized by adding ~0.5 Wt%.

ここで、銅化合物としては、酢酸銅、ステアリン酸銅、
ハロゲン化銅等が好ましく用いられ、添加量としてはへ
キサメチレンジアミンとテレフタル酸との総量に対して
0,01〜0.5 W t%、好ましくは、0.O1〜
0.2 W t%が適当で、0.01wt%以下では効
果が無く、0.5 W t%以上ではプレポリマーの生
成反応を疎外する。本発明における初期重合は、ヘキサ
メチレンジアミンの逃散を防ぐ必要があるため、加圧系
で行なわれる。原料はへキサメチレンジアミンとテレフ
タル酸をそれぞれ供給しても良いが、取扱いが面単な6
. Tナイロン塩あるいは、6.Tナイロン塩の水溶液
の形にして供給するのが一般的である。
Here, the copper compounds include copper acetate, copper stearate,
Copper halide and the like are preferably used, and the amount added is 0.01 to 0.5 Wt%, preferably 0.01 to 0.5 Wt%, based on the total amount of hexamethylene diamine and terephthalic acid. O1~
A suitable amount is 0.2 Wt%; less than 0.01wt% has no effect, and more than 0.5wt% inhibits the prepolymer production reaction. The initial polymerization in the present invention is carried out in a pressurized system because it is necessary to prevent escape of hexamethylene diamine. Hexamethylene diamine and terephthalic acid may be supplied separately as raw materials, but 6 is easy to handle.
.. T nylon salt or 6. It is common to supply the T nylon salt in the form of an aqueous solution.

初期重合条件は特別に規定されるものではなく、初期重
合後未反応の6.7ナイロン塩が残らない様な条件であ
ればよい。例えば、加圧オートクレーブに6. Tナイ
ロン塩の50%水溶液と銅化合物を所定量仕込み、室温
から260〜280°Cの温度に1〜2時間で昇温し、
その温度に3〜5時間保持する。その時内圧も温度上昇
とともに上昇するが、内圧が25〜30kg/amに達
したら調圧弁を開いたり、閉じたりすることによりその
圧力を保持して所定時間重合させる方法が挙げられる。
The initial polymerization conditions are not particularly specified, and may be such conditions that no unreacted 6.7 nylon salt remains after the initial polymerization. For example, in a pressurized autoclave 6. A predetermined amount of a 50% aqueous solution of T nylon salt and a copper compound were charged, and the temperature was raised from room temperature to 260 to 280°C in 1 to 2 hours.
Hold at that temperature for 3-5 hours. At this time, the internal pressure also increases as the temperature rises, but when the internal pressure reaches 25 to 30 kg/am, a pressure regulating valve may be opened or closed to maintain that pressure and polymerize for a predetermined period of time.

後重合は、一般的にプレポリマーを細かく粉砕して不活
性ガス下、又は減圧下で260〜300℃の温度で所定
の重合度になるまで固相重合させる。
In the post-polymerization, the prepolymer is generally finely pulverized and subjected to solid phase polymerization under an inert gas or under reduced pressure at a temperature of 260 to 300°C until a predetermined degree of polymerization is achieved.

〔実施例〕〔Example〕

以下、実施例によって本発明を説明するが、実施例にお
けるポリマーの固有粘度は0.4g/100ccの濃度
で濃硫酸溶液にて温度25゛Cで測定した値である。
The present invention will be explained below with reference to examples. The intrinsic viscosity of the polymer in the examples is a value measured at a temperature of 25°C in a concentrated sulfuric acid solution at a concentration of 0.4 g/100 cc.

実施例1 ヘキサメチレンジアミンとテレフタル酸とから作られた
6、Tナイロン塩の50wt%水溶液50gおよび酢酸
銅0. Ol gを20(ldの加圧オートクレーブに
計り取り、十分に窒素置換を行なった後オイルバスにセ
ットして約1hrで室温から280℃まで昇温する。温
度上昇とともに内圧も徐々に上昇し、内圧が25kg/
cdに達したら、調圧弁を開いて内圧を25kg/cd
に保つ、この状態を3hr保持した後、調圧弁を締めオ
ートクレーブをオイルバスより取りだし冷却する。生成
した白色のプレポリマーを取り出し、乾燥後、粉砕して
60メツシユ以下にした。このプレポリマーの固有粘度
は0.32 dl/gであり、このプレポリマーをエバ
ポレーターを用いて窒素気流下、290°Cで8hr固
相重合したものの固有粘度は1.70dl/gであり、
40hr固相重合したものの固有粘度は2、30 di
/gであった。
Example 1 50 g of a 50 wt% aqueous solution of 6,T nylon salt made from hexamethylene diamine and terephthalic acid and 0.0 g of copper acetate. Weigh out 20 g of Ol g into a pressurized autoclave of 20 (ld), and after thoroughly purging with nitrogen, set it in an oil bath and raise the temperature from room temperature to 280 ° C. in about 1 hr. As the temperature rises, the internal pressure gradually rises, Internal pressure is 25kg/
When it reaches cd, open the pressure regulating valve and reduce the internal pressure to 25kg/cd.
After maintaining this state for 3 hours, close the pressure regulating valve and take out the autoclave from the oil bath to cool it. The produced white prepolymer was taken out, dried, and pulverized to 60 meshes or less. The intrinsic viscosity of this prepolymer is 0.32 dl/g, and the intrinsic viscosity of this prepolymer subjected to solid phase polymerization at 290°C for 8 hours in a nitrogen stream using an evaporator is 1.70 dl/g.
The intrinsic viscosity of the solid phase polymerized product for 40 hours is 2.30 di.
/g.

これらのポリマーはほとんど着色しておらず、また、濃
硫酸に不溶なゲル状物も含まれていなかった。
These polymers were hardly colored and did not contain gel-like substances that are insoluble in concentrated sulfuric acid.

比較例1 酢酸銅を添加せずに実施例1と同様にして初期重合し、
同様な処理をして固相重合すると5hr固相重合したも
のの固有粘度は1.5 f dl/gであるが、この段
階ですでに少し濃硫酸に不溶のゲル状物が生成しており
、8hr固相重合するとゲル状物がさらに増え、粘度測
定が不可能になった。また、実施例1と比較すると、プ
レポリマーの段階で多少着色しており、固相重合すると
さらに着色が進む。
Comparative Example 1 Initial polymerization was carried out in the same manner as in Example 1 without adding copper acetate,
When solid phase polymerization was carried out using the same treatment, the intrinsic viscosity of the solid phase polymerized product after 5 hours of solid phase polymerization was 1.5 f dl/g, but at this stage a small amount of gel-like material insoluble in concentrated sulfuric acid was already formed. After 8 hours of solid phase polymerization, gel-like substances further increased, making viscosity measurement impossible. Moreover, when compared with Example 1, there is some coloration at the prepolymer stage, and the coloration progresses further during solid phase polymerization.

〔発明の効果〕〔Effect of the invention〕

本発明の初期重合により合成されたプレポリマーを、固
相で後重合することによりゲル状物の無い、均一で高分
子量の6.Tナイロンのポリマーを得ることを可能にし
た。
6. By post-polymerizing the prepolymer synthesized by the initial polymerization of the present invention in a solid phase, a uniform and high molecular weight product free from gel-like substances can be obtained. This made it possible to obtain a T-nylon polymer.

特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

【特許請求の範囲】[Claims] ヘキサメチレンジアミンとテレフタル酸とからポリ(ヘ
キサメチレン)テレフタルアミドの初期重合物を合成す
るに際して、ヘキサメチレンジアミンとテレフタル酸と
の総量に対して銅化合物を0.01〜0.5Wt%加え
ることを特徴とするポリ(ヘキサメチレン)テレフタル
アミドの初期重合方法。
When synthesizing an initial polymer of poly(hexamethylene) terephthalamide from hexamethylene diamine and terephthalic acid, it is recommended to add 0.01 to 0.5 wt% of a copper compound to the total amount of hexamethylene diamine and terephthalic acid. Characteristic initial polymerization method of poly(hexamethylene) terephthalamide.
JP7040689A 1989-03-24 1989-03-24 Polymerization of 6.t nylon Pending JPH02251531A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7040689A JPH02251531A (en) 1989-03-24 1989-03-24 Polymerization of 6.t nylon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7040689A JPH02251531A (en) 1989-03-24 1989-03-24 Polymerization of 6.t nylon

Publications (1)

Publication Number Publication Date
JPH02251531A true JPH02251531A (en) 1990-10-09

Family

ID=13430556

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7040689A Pending JPH02251531A (en) 1989-03-24 1989-03-24 Polymerization of 6.t nylon

Country Status (1)

Country Link
JP (1) JPH02251531A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6391983B1 (en) 1997-02-14 2002-05-21 Sola International Holdings, Ltd. Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer
JP2008239908A (en) * 2007-03-29 2008-10-09 Mitsui Chemicals Inc Method of producing polyamide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6391983B1 (en) 1997-02-14 2002-05-21 Sola International Holdings, Ltd. Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer
JP2008239908A (en) * 2007-03-29 2008-10-09 Mitsui Chemicals Inc Method of producing polyamide

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