JPH02251531A - Polymerization of 6.t nylon - Google Patents
Polymerization of 6.t nylonInfo
- 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
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 32
- 229920001778 nylon Polymers 0.000 title description 18
- 239000004677 Nylon Substances 0.000 title description 15
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 poly(hexamethylene) terephthalamide Polymers 0.000 claims abstract description 11
- 239000005749 Copper compound Substances 0.000 claims abstract description 6
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 4
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
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.
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.
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.
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.
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)
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.
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)
| 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 |
-
1989
- 1989-03-24 JP JP7040689A patent/JPH02251531A/en active Pending
Cited By (2)
| 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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