JP2001139683A - Method of continuously producing polyamide composite - Google Patents
Method of continuously producing polyamide compositeInfo
- Publication number
- JP2001139683A JP2001139683A JP32671599A JP32671599A JP2001139683A JP 2001139683 A JP2001139683 A JP 2001139683A JP 32671599 A JP32671599 A JP 32671599A JP 32671599 A JP32671599 A JP 32671599A JP 2001139683 A JP2001139683 A JP 2001139683A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- pipe
- aqueous solution
- solutions
- dicarboxylic acid
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はジカルボン酸ハライ
ドを必須成分とする有機溶液と、ジアミンと水ガラスと
を必須成分とする水溶液とを、両溶液が流通するパイプ
内に攪拌体を有し、該攪拌体によって生じる乱流によっ
て、両溶液を攪拌混合させると共に、該攪拌体をパイプ
内で往復運動させて両溶液を攪拌混合させて反応させ
る、ポリアミド複合体の連続製造方法である。The present invention relates to an organic solution containing dicarboxylic acid halide as an essential component, and an aqueous solution containing diamine and water glass as essential components. This is a continuous method for producing a polyamide composite, wherein both solutions are stirred and mixed by turbulence generated by the stirring body, and the stirring body is reciprocated in a pipe to mix and react the two solutions.
【０００２】[0002]
【従来の技術】ジカルボン酸ハライドとジアミン又はジ
カルボン酸ハライドとジオール（特に２価フェノール）
から、ポリアミド又はポリエステルを２液系の界面重合
型の反応にて得る方法は、米国特許第３００６８９９号
公報、同２７０８６１７号公報、特開昭５８−１８０５
２５号公報に開示されている。またポリアミドとガラス
との複合体を重合反応を利用して行う方法が特開平１０
−１７６１０６号公報、同１１−８０５４１号公報に記
載されている。2. Description of the Related Art Dicarboxylic acid halides and diamines or dicarboxylic acid halides and diols (particularly dihydric phenols)
Are disclosed in U.S. Pat. Nos. 3,068,899 and 2,708,617, and JP-A-58-1805.
No. 25 discloses this. Further, a method of performing a composite of polyamide and glass by utilizing a polymerization reaction is disclosed in
-176106 and 11-80541.
【０００３】しかしながら、係る製法は、２液撹拌系の
バッチ式で行う方法、若しくは、静止系で２液界面から
フィルムやフィラメントの状態で引き出す方法であり、
生産効率が極めて低い。また米国特許第２８３１８３４
号公報に記載の連続製法は、連続的に２液を供給しなが
ら撹拌を行える点で、高い生産効率が期待できるもの
の、撹拌効率に限界があり生成ポリマーの収率が極めて
低く（実施例１では10%以下）、実用上、十分ではなか
った。従って、有機溶液と水溶液との二層に含まれる反
応成分を効率よく接触、反応させるポリマーの連続反応
方法の開発が求められていた。[0003] However, such a manufacturing method is a method of performing a two-liquid stirring system in a batch system, or a method of drawing out a film or a filament from a two-liquid interface in a stationary system.
Extremely low production efficiency. U.S. Pat. No. 2,831,834
In the continuous production method described in Japanese Patent Application Laid-Open Publication No. H11-207, although high production efficiency can be expected in that stirring can be performed while continuously supplying two liquids, the stirring efficiency is limited and the yield of the produced polymer is extremely low (Example 1). 10% or less), which was not practically sufficient. Accordingly, there has been a demand for the development of a continuous reaction method for a polymer in which the reaction components contained in the two layers of the organic solution and the aqueous solution are efficiently contacted and reacted.
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、有機溶液と水溶液との二層に含まれるポリ
マー反応成分を連続的に効率よく接触、反応させ、ポリ
アミドとシリカから成るポリアミド複合体を高効率、且
つ高収率で得る連続製造方法を提供することにある。An object of the present invention is to continuously and efficiently contact and react polymer reactive components contained in two layers of an organic solution and an aqueous solution, and to form a polyamide comprising silica and silica. An object of the present invention is to provide a continuous production method for obtaining a complex with high efficiency and high yield.
【０００５】[0005]
【課題を解決するための手段】本発明者は、係る状況に
鑑み鋭意検討した結果、攪拌効率のとりわけ優れた特定
の混合装置を用いることにより、界面重合型の反応が連
続的に高収率で進行することを見出し、本発明を完成す
るに至った。Means for Solving the Problems As a result of intensive studies in view of the above situation, the present inventor has found that the use of a specific mixing apparatus with particularly excellent stirring efficiency allows the interfacial polymerization type reaction to be continuously performed at a high yield. And completed the present invention.
【０００６】即ち、本発明は、（１）ジカルボン酸ハラ
イドを必須成分とする有機溶液（Ａ）と、ジアミンと水
ガラスとを必須成分とする水溶液（Ｂ）とを、両溶液が
流通するパイプ内に攪拌体を有し、該攪拌体によって生
じる乱流によって、両溶液を攪拌混合させると共に、該
攪拌体をパイプ内で往復運動させて両溶液を攪拌混合さ
せる混合装置に連続的に流通させる、ポリアミド複合体
の連続製造方法と、That is, the present invention provides (1) a pipe through which an organic solution (A) containing dicarboxylic halide as an essential component and an aqueous solution (B) containing diamine and water glass as essential components. And a turbulent flow generated by the agitator mixes and stirs the two solutions, and continuously circulates the agitator in a pipe to reciprocate in a pipe to stir and mix the two solutions. , Continuous production method of polyamide composite,
【０００７】（２）有機溶液（Ａ）が０．１〜２モル／
Ｌのジカルボン酸ハライドを、水溶液（Ｂ）が０．１〜
２モル／Ｌのジアミンと２〜１００ｇ／Ｌの水ガラスと
を含む、（１）に記載の連続製造方法と、(2) The organic solution (A) is 0.1 to 2 mol /
The aqueous solution (B) of the dicarboxylic acid halide of L
The continuous production method according to (1), comprising 2 mol / L of a diamine and 2 to 100 g / L of water glass,
【０００８】（３）溶液が流通するパイプが多段連続的
に接続され、そのパイプ同士の接続部には溶液の流通穴
が形成された仕切板が設けられており、且つパイプ内の
攪拌体が一つの軸に取付けられ、該軸を通じて振動源に
接続されいる（１）又は（２）に記載の連続製造方法
と、(3) Pipes through which the solution circulates are connected in a multi-stage manner, and a connecting plate between the pipes is provided with a partition plate having a hole through which the solution circulates. A continuous manufacturing method according to (1) or (2), wherein the method is attached to one shaft and connected to a vibration source through the shaft;
【０００９】（４）撹拌体を５〜１５mmのストローク
長、２０〜７０Ｈｚの速度で往復運動させる（３）に記
載の連続製造方法と、(4) The continuous production method according to (3), wherein the stirring body is reciprocated at a stroke length of 5 to 15 mm at a speed of 20 to 70 Hz.
【００１０】（５）撹拌体がリボン状の螺旋羽根を有す
ることを特徴とする（１）〜（４）のいずれか一つに記
載の連続製造方法とを含むものである。(5) The continuous production method according to any one of (1) to (4), wherein the stirring body has a ribbon-shaped spiral blade.
【００１１】[0011]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明では、ジカルボン酸ハライドとジアミンからポリ
アミドを界面重合型の反応を通じて得る。本発明で用い
る、有機溶液（Ａ）はジカルボン酸ハライドと有機溶媒
を必須成分とする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, a polyamide is obtained from a dicarboxylic acid halide and a diamine through an interfacial polymerization reaction. The organic solution (A) used in the present invention contains a dicarboxylic acid halide and an organic solvent as essential components.
【００１２】ジカルボン酸ハライドとしては、界面重合
反応に用いられるものであれば特に限定されないが、例
えばアジポイルクロリド、アゼラオイルクロリド、セバ
シルクロリド等の脂肪族ジカルボン酸ハライド、イソフ
タロイルクロライド、テレフタロイルクロライド、及び
これらの芳香族環の一個以上の水素をハロゲン、ニトロ
基、アルキル基で置換し芳香族ジカルボン酸ハライドが
挙げられ、これらは単独又は二種以上の組み合わせで用
いられてよい。The dicarboxylic acid halide is not particularly limited as long as it is used for an interfacial polymerization reaction. For example, aliphatic dicarboxylic acid halides such as adipoyl chloride, azelaoil chloride and sebacyl chloride, and isophthaloyl chloride , Terephthaloyl chloride, and aromatic dicarboxylic acid halides in which one or more hydrogens of these aromatic rings are substituted with a halogen, a nitro group, or an alkyl group, and these may be used alone or in combination of two or more. Good.
【００１３】有機溶媒としては、ジカルボン酸ハライド
やジアミンと反応せず、ジカルボン酸ハライドを溶解す
るものであれば特に制限なく用いることが出来るが、ト
ルエン、キシレン、クロロホルム、シクロヘキサン、シ
クロヘクサノン、テトラヒドロフラン、メチルエチルケ
トンを代表的な例として挙げることが出来る。As the organic solvent, any solvent can be used without particular limitation as long as it does not react with the dicarboxylic acid halide or diamine and dissolves the dicarboxylic acid halide. Toluene, xylene, chloroform, cyclohexane, cyclohexanone, tetrahydrofuran And methyl ethyl ketone as typical examples.
【００１４】このうちトルエン、キシレン、クロロホル
ム、シクロヘキサンは水に溶解せず、またシクロヘキサ
ノンはわずかに水に溶解し、テトラヒドロフランは水と
良く混合するが、有機溶液（Ａ）と水溶液（Ｂ）との界
面または混合液中での重縮合反応が進行しポリアミドを
生成する。Of these, toluene, xylene, chloroform, and cyclohexane are not soluble in water, cyclohexanone is slightly soluble in water, and tetrahydrofuran is well mixed with water, but the organic solution (A) and the aqueous solution (B) are mixed well. The polycondensation reaction proceeds at the interface or in the mixed solution to produce a polyamide.
【００１５】有機溶液相（Ａ）中のアシル化したジカル
ボン酸モノマーの濃度としては、重縮合反応が十分に進
行すれば特に制限されないが、０．０１〜５モル／Ｌの
濃度範囲、好ましくは、０．１〜２モル／Ｌであり、特
に０．２〜１モル／Ｌが好ましく、−１５℃から〜５０
℃の温度範囲で混合装置に連続的に供給する。水溶液
（Ｂ）は、前記ジカルボン酸ハライドと反応するジアミ
ンを含む。The concentration of the acylated dicarboxylic acid monomer in the organic solution phase (A) is not particularly limited as long as the polycondensation reaction proceeds sufficiently, but the concentration is in the range of 0.01 to 5 mol / L, preferably , 0.1 to 2 mol / L, particularly preferably 0.2 to 1 mol / L.
It is continuously fed to the mixing device in the temperature range of ° C. The aqueous solution (B) contains a diamine that reacts with the dicarboxylic acid halide.
【００１６】ジアミンとしては、１，２−ジアミノエタ
ン、１，３−ジアミノプロパン、１，４−ジアミノブタ
ン、１，５−ジアミノペンタン、１，６−ジアミノヘキ
サン、１，９−ジアミノノナン等の脂肪族ジアミン、ｍ
−キシリレンジアミン、ｐ−キシリレンジアミン、ｍ−
フェニレンジアミン、ｐ−フェニレンジアミン、１，
５’−ジアミノナフタレン、１，８−ジアミノナフタレ
ン、２，３−ジアミノナフタレン、３，４’−ジアミノ
ジフェニルエーテル、Examples of the diamine include fats such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,9-diaminononane. Group diamine, m
-Xylylenediamine, p-xylylenediamine, m-
Phenylenediamine, p-phenylenediamine, 1,
5′-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 3,4′-diaminodiphenyl ether,
【００１７】４，４’−ジアミノジフェニルエーテル、
３，４’−ジアミノジフェニルスルホン、４，４’−ジ
アミノジフェニルスルホン、３，４’−ジアミノジフェ
ニルメタン、４，４’−ジアミノジフェニルメタン、及
びこれらの芳香族環の一個以上の水素をハロゲン、ニト
ロ基、又はアルキル基で置換した芳香族ジアミンが挙げ
られ、これれは単独又は二種以上の組み合わせで用いら
れてよい。4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and one or more hydrogens of these aromatic rings are converted to halogen, nitro group Or an aromatic diamine substituted with an alkyl group, which may be used alone or in combination of two or more.
【００１８】水溶液中（Ｂ）中のジアミンの濃度範囲
は、０．０１〜５モル／Ｌの濃度範囲、好ましくは、
０．１〜２モル／Ｌ、特に好ましくは０．２〜１モル／
Ｌであり、０℃〜５０℃で混合装置に連続的に供給す
る。The concentration range of the diamine in the aqueous solution (B) is from 0.01 to 5 mol / L, preferably
0.1 to 2 mol / L, particularly preferably 0.2 to 1 mol / L
L and is continuously fed to the mixing device at 0 ° C to 50 ° C.
【００１９】水溶液（Ｂ）には、この他に水ガラスを含
む。この場合は既に特開平１０−１７６１０６号公報に
開示した如く、ガラスが微細に分散したポリアミド複合
体が得られ、得られるガラスは、ナトリウム分の除去さ
れたシリカである場合が殆どである。The aqueous solution (B) further contains water glass. In this case, as disclosed in Japanese Patent Application Laid-Open No. H10-176106, a polyamide composite in which glass is finely dispersed is obtained, and in most cases, the obtained glass is silica from which sodium has been removed.
【００２０】水ガラスは、アルカリ金属（Ｍ）と珪素と
酸素を主な構成元素とし、一般にＭ 2Ｏ・ｎＳｉＯ2の組
成式を有するガラスであり、水に対する大きな溶解度の
ため普通のガラスと区別される。尚、わが国では上記の
水ガラスを水に溶解せしめた溶液を、水ガラスと呼称す
ることが多いが、本発明においては水分を含まないガラ
ス成分自身を水ガラスと定義する。Water glass is composed of an alkali metal (M) and silicon.
Oxygen is the main constituent element; TwoOn SiOnTwoPair of
A glass with the formula
Because it is distinguished from ordinary glass. In Japan, the above
A solution of water glass dissolved in water is called water glass.
In the present invention, the water-free glass
The water component itself is defined as water glass.
【００２１】具体的には、水ガラスとして、日本工業規
格（ＪＩＳ Ｋ１４０８−１９５０）に記載の水ガラス
１号、２号、３号、４号といった予め水に溶解せしめた
もの（Ｍ2Ｏ・ｎＳｉＯ2の組成式においてＭがナトリウ
ムであり、１．２≦ｎ≦４である）を挙げることができ
る。水ガラスを用いる場合にはその濃度（固形分基準）
を２〜１００ｇ／Ｌ、好ましくは４〜１００ｇ／Ｌとす
ることが好ましい。Specifically, water glass previously dissolved in water such as water glass No. 1, No. 2, No. 3, No. 4 described in Japanese Industrial Standards (JIS K1408-1950) (M 2 O · In the composition formula of nSiO 2 , M is sodium and 1.2 ≦ n ≦ 4). If water glass is used, its concentration (based on solid content)
Is preferably 2 to 100 g / L, more preferably 4 to 100 g / L.
【００２２】重合反応を十分に促進させる目的で、
（Ｂ）に水酸化ナトリウム等の酸受容体及び／又はラウ
リル硫酸ナトリウム等の界面活性剤、メチルトリオクチ
ルアンモニウムブロマイド等の相関移動触媒が添加され
てもよい。酸受容体は反応により放出されるプロトンを
中和し、また界面活性剤はモノマー間の接触効率を上昇
させ反応を促進する。尚、水ガラス自身も塩基性であ
り、酸受容体としての作用を有する。In order to sufficiently promote the polymerization reaction,
An acid acceptor such as sodium hydroxide and / or a surfactant such as sodium lauryl sulfate and a phase transfer catalyst such as methyltrioctylammonium bromide may be added to (B). Acid acceptors neutralize the protons released by the reaction, and surfactants increase the efficiency of contact between the monomers and promote the reaction. Incidentally, the water glass itself is also basic and has an action as an acid acceptor.
【００２３】各成分の水へ溶解は室温にて行なうことが
可能である。得られた水溶液相は均一透明であることが
好ましい。また、有機溶液相に使用する有機溶媒として
は、一般的に界面重縮合に使用されるものでよく、特に
トルエン、キシレン、クロロホルム、シクロヘキサンが
好ましい。The dissolution of each component in water can be performed at room temperature. The obtained aqueous phase is preferably uniform and transparent. Further, as the organic solvent used in the organic solution phase, those generally used for interfacial polycondensation may be used, and toluene, xylene, chloroform and cyclohexane are particularly preferable.
【００２４】これら溶液の調製法は、特に限定されるも
のではないが、例えば常温で溶媒中に上述の成分を添
加、撹拌すれば良い。この際、各成分は予め該溶媒に溶
解し溶液状態とした形で添加しても良い。水溶液相と有
機溶液相はともに均一透明であることが好ましい。The method for preparing these solutions is not particularly limited. For example, the above-mentioned components may be added to a solvent at room temperature and stirred. At this time, each component may be dissolved in the solvent in advance and added in the form of a solution. It is preferable that both the aqueous solution phase and the organic solution phase are uniformly transparent.
【００２５】本発明では、上述の有機溶液（Ａ）と水溶
液（Ｂ）を混合装置に連続的に流通させて、反応を行う
が、係る混合装置は、多段に接続される複数のパイプ及
び、そのパイプ同士の接続部に流通穴が形成された仕切
板、パイプ内に配置され、振動源に接続された撹拌体か
ら構成される。In the present invention, the organic solution (A) and the aqueous solution (B) are continuously circulated through the mixing device to carry out the reaction. The mixing device includes a plurality of pipes connected in multiple stages, A partition plate having a flow hole formed at a connection portion between the pipes, and a stirring body arranged in the pipe and connected to a vibration source.
【００２６】本発明で用いられる混合装置は、溶液が流
通するパイプ内の攪拌体によって生じる乱流により、溶
液を攪拌混合させると共に、攪拌体をパイプ内で往復運
動（振動）させて溶液を攪拌混合させることにより、２
液間の接触又は混合が極めて効率的に行え、連続重合に
より、高重合度のポリマー複合体が高収率で得られる。
攪拌体の往復運動（振動）は、流通させる溶液の重力方
向に平行、即ち、垂直方向であることが好ましい。The mixing device used in the present invention stirs and mixes the solution by turbulence generated by the stirrer in the pipe through which the solution flows, and stirs the solution by reciprocating (vibrating) the stirrer in the pipe. By mixing, 2
The contact or mixing between the liquids can be performed very efficiently, and a polymer composite having a high degree of polymerization can be obtained in a high yield by continuous polymerization.
The reciprocating motion (vibration) of the stirrer is preferably parallel to, or perpendicular to, the direction of gravity of the flowing solution.
【００２７】本発明のポリアミドとシリカとの複合体の
製造方法は、二層に分離しやすい有機溶媒と水との二層
に含まれる成分間の反応であり、且つ生成するポリマー
溶液が７０００ｃｐｓ（ｍＰａ・ｓ）以上の高粘度にな
る為、通常のスタテックミキサーでの連続反応では、混
合攪拌が不十分となり、ある程度の反応収率は得られる
が、本発明の如き、短時間での高効率、高収率なポリマ
ー複合体の生産は望めない。The method for producing a composite of polyamide and silica according to the present invention is a reaction between components contained in two layers of an organic solvent and water, which is easily separated into two layers, and the resulting polymer solution is 7000 cps ( mPa · s) or more, the mixing and stirring are insufficient in a continuous reaction with a usual static mixer, and a certain reaction yield can be obtained. Efficient, high-yield production of polymer conjugates cannot be expected.
【００２８】本発明では、パイプ内の攪拌体によって生
じる乱流により、溶液を攪拌混合させる通常のスタテッ
クミキサーに、更に攪拌体の往復運動（振動）を加えた
混合装置を用いることが好ましい。攪拌体の往復運動
（振動）は、流通させる溶液の重力方向に平行、即ち、
垂直方向であることが好ましい。In the present invention, it is preferable to use a mixing device in which a reciprocating motion (vibration) of the stirring body is further added to a usual static mixer for stirring and mixing the solution by turbulence generated by the stirring body in the pipe. The reciprocating motion (vibration) of the stirrer is parallel to the direction of gravity of the flowing solution, that is,
Preferably it is vertical.
【００２９】攪拌体の往復運動（振動）は、有機溶媒と
水とが垂直方向に二層に分離するのを妨げ、二層に含ま
れる成分が互いに他層の反応成分と反応する機会を増加
させると共に、更に反応生成物であるポリマー濃度が高
まり、溶液が７０００ｃｐｓ（ｍＰａ・ｓ）以上の高粘
性溶液になっても、効率よく反応系内を混合攪拌するこ
とができる。The reciprocating motion (vibration) of the stirrer prevents the organic solvent and water from separating vertically into two layers, and increases the chance that the components contained in the two layers react with each other with the reaction components of the other layer. At the same time, even if the concentration of the polymer as a reaction product increases and the solution becomes a high-viscosity solution of 7000 cps (mPa · s) or more, the inside of the reaction system can be efficiently mixed and stirred.
【００３０】振動源に連結されている撹拌体の形状とし
ては、リボン状の螺旋羽根が挙げられ、好ましくは軸部
とその周囲に取り付けられた螺旋羽根からなるものであ
る。リボン状の螺旋羽根が取り付けられていることによ
り、混合装置のメンテナンスが容易になる。本発明に用
いる混合装置の好適な態様は、特開平４−２３５７２９
に詳述されている、実施例でも用いた冷化工業製バイブ
ロミキサーＶＭ−ＨＳ−６６―６５−１５型の混合装置
等が挙げられる。The shape of the stirring body connected to the vibration source may be a spiral blade in a ribbon shape, and preferably includes a shaft portion and a spiral blade attached around the shaft portion. The attachment of the ribbon-shaped spiral blade facilitates maintenance of the mixing device. A preferred embodiment of the mixing apparatus used in the present invention is described in JP-A-4-235729.
And the mixing apparatus of the Vibromixer VM-HS-66-65-15 manufactured by Kyowa Kogyo Co., Ltd. which was also used in the examples.
【００３１】有機溶液（Ａ）及び水溶液（Ｂ）の流通量
としては、ジカルボン酸ハライドとジアミンのモル比が
１になる比率にて、混合装置内の滞留時間が０．３〜１
２０秒とする流量が好ましい。反応熱による加熱予防の
観点から（Ａ）及び（Ｂ）の温度は各々−１５〜５０℃
及び０〜５０℃の温度、反応や物理的撹拌による加熱を
防ぐ為に、更に好ましくは各々−１５〜５℃、０〜５℃
に調節すると良い。The flow rates of the organic solution (A) and the aqueous solution (B) are such that the molar ratio of the dicarboxylic acid halide to the diamine is 1 and the residence time in the mixing device is 0.3 to 1
A flow rate of 20 seconds is preferred. From the viewpoint of prevention of heating by reaction heat, the temperatures of (A) and (B) are each -15 to 50 ° C.
And at a temperature of 0 to 50 ° C, more preferably -15 to 5 ° C and 0 to 5 ° C, respectively, in order to prevent heating due to reaction or physical stirring.
It is better to adjust.
【００３２】有機溶液（Ａ）と水溶液（Ｂ）とを連続的
に混合装置に流通させながら、撹拌体をパイプと平行な
方向に往復運動（振動）させるが、その条件としては、
２０〜７０Ｈｚ、ストローク長は５〜１５mmであること
が好ましい。振動数が２０Ｈｚ未満、ストローク長が５
mm未満では、十分な撹拌効率が得られない。一方、振動
数が７０Ｈｚを越える、あるいはストローク長が１５mm
を越えると、安定した振動操作が行えない場合がある。While continuously flowing the organic solution (A) and the aqueous solution (B) through the mixing device, the stirrer is reciprocated (vibrated) in a direction parallel to the pipe.
Preferably, the stroke length is 20 to 70 Hz and the stroke length is 5 to 15 mm. Vibration frequency is less than 20Hz, stroke length is 5
If it is less than mm, sufficient stirring efficiency cannot be obtained. On the other hand, if the frequency exceeds 70 Hz or the stroke length is 15 mm
If it exceeds, stable vibration operation may not be performed.
【００３３】[0033]
【実施例】以下に、本発明を実施例にて、より具体的に
説明するが、実施例は、あくまで本発明の代表的態様を
例示するもので、本発明はその範囲に限定されない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the examples are merely illustrative of typical embodiments of the present invention, and the present invention is not limited to the scope thereof.
【００３４】分子量評価法は以下の通りである。１．０
ｄＬ/g以上のインヘレント粘度値は十分な重合度を意味
する。 ナイロン６６の場合：ウベローデ粘度計により得られ
る、０．１ｄＬ／ｇのｍ−クレゾール中での３０℃にお
けるインヘレント粘度によった。The molecular weight evaluation method is as follows. 1.0
An inherent viscosity value of dL / g or more means a sufficient degree of polymerization. For nylon 66: by inherent viscosity at 30 ° C. in 0.1 dL / g m-cresol, obtained with an Ubbelohde viscometer.
【００３５】（参考例１）（ポリアミドの製造） ０．２５モル／Ｌのアジポイルクロライドを含むトルエ
ン溶液（Ａ１）と、０．７０モル／Ｌの１，６−ジアミ
ノヘキサンと６．１ｇ／Ｌの水酸化ナトリウムを含む水
溶液（Ｂ１）を用意し、各々２５℃で１．３２Ｌ／分、
０．４７Ｌ／分で、図１に示す冷化工業製バイブロミキ
サーＶＭ−ＨＳ−６６―６５−１５型の混合装置に流通
させた。Reference Example 1 (Production of Polyamide) A toluene solution (A1) containing 0.25 mol / L of adipoyl chloride, 0.70 mol / L of 1,6-diaminohexane, and 6.1 g / L sodium hydroxide solution (B1) was prepared at 25 ° C. and 1.32 L / min.
At 0.47 L / min, the mixture was passed through a mixing apparatus of the Vibromixer VM-HS-66-65-15 manufactured by Kyowa Kogyo shown in FIG.
【００３６】（Ａ１）は注入口（図面中の符号５）か
ら、（Ｂ１）は注入口（符号６）から、滞留時間＝１１
秒で流通させながら、リボン状の螺旋羽根である撹拌体
（３）を、それの連結した軸部（２）の運動により、こ
の軸方向に６０Hz、８ｍｍのストローク長で振動させ
て、連続重合反応を行った。ナイロン６６が、収率＝９
５％で連続的に合成できた。ナイロン６６のインヘレン
ト粘度は１．２ｄＬ／ｇであった。(A1) from the inlet (reference numeral 5 in the drawing), (B1) from the inlet (reference numeral 6), residence time = 11.
While flowing in seconds, the stirrer (3), which is a ribbon-shaped spiral blade, is vibrated at 60 Hz and a stroke length of 8 mm in the axial direction by the movement of the connected shaft (2) to continuously polymerize. The reaction was performed. Nylon 66 yield = 9
It could be synthesized continuously at 5%. The inherent viscosity of nylon 66 was 1.2 dL / g.
【００３７】（実施例１）参考例１において、０．７０
モル／Ｌの１，６−ジアミノヘキサンと６．１ｇ／Ｌの
水酸化ナトリウムを含む水溶液（Ｂ１）を、０．７０モ
ル／Ｌの１，６−ジアミノヘキサンと１８．９ｇ／Ｌの
水ガラス（キシダ化学製、３号、固形分濃度）を含む水
溶液（Ｂ２）とした以外は全く同様にして、連続重合反
応を行い、シリカとナイロン６６の複合体（シリカ分率
＝４９．６重量％）を得た。(Example 1) In Reference Example 1, 0.70
An aqueous solution (B1) containing mol / L 1,6-diaminohexane and 6.1 g / L sodium hydroxide was mixed with 0.70 mol / L 1,6-diaminohexane and 18.9 g / L water glass. A continuous polymerization reaction was carried out in exactly the same manner except that an aqueous solution (B2) containing (Kishida Chemical, No. 3, solid content concentration) was used, and a composite of silica and nylon 66 (silica content = 49.6% by weight) ) Got.
【００３８】透過型電子顕微鏡観察から、複合体中のシ
リカ成分は、粒径が約１０ｎｍの超微粒子としてナイロ
ンマトリックスに均一に分散していることがわかった。
この場合のシリカ収率＝１００％、ナイロン収率＝８９
％であった。ナイロン成分のインヘレント粘度は１．１
ｄＬ／ｇであった。From observation with a transmission electron microscope, it was found that the silica component in the composite was uniformly dispersed in the nylon matrix as ultrafine particles having a particle size of about 10 nm.
In this case, silica yield = 100%, nylon yield = 89.
%Met. The inherent viscosity of the nylon component is 1.1
dL / g.
【００３９】[0039]
【発明の効果】本発明は、有機溶液と水溶液との二層に
含まれるポリマー反応成分を連続的に効率よく接触、反
応させることにより、ポリアミドとシリカとの複合体を
高効率、且つ高収率で得る連続製造方法を提供すること
ができる。According to the present invention, the polymer-reactive components contained in the two layers of the organic solution and the aqueous solution are continuously and efficiently contacted and reacted, so that the composite of polyamide and silica can be produced with high efficiency and high yield. It is possible to provide a continuous production method which can be obtained at a high rate.
【図１】 実施例で用いた混合装置の断面の模式図であ
る。FIG. 1 is a schematic view of a cross section of a mixing device used in Examples.
１：ケーシング ２：軸部 ３：撹拌体 ４：出口 ５：注入口 ６：注入口 ７：仕切板 1: Casing 2: Shaft 3: Stirring body 4: Outlet 5: Injection port 6: Injection port 7: Partition plate
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J001 DA01 DB01 EB04 EB08 EB09 EB36 EB37 EC04 EC05 EC06 EC07 EC08 EC09 EC45 EC46 EC47 EC48 EC56 EC66 EC67 EC70 EE18F EE22F EE23F EE24F GA11 GB11 GC03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J001 DA01 DB01 EB04 EB08 EB09 EB36 EB37 EC04 EC05 EC06 EC07 EC08 EC09 EC45 EC46 EC47 EC48 EC56 EC66 EC67 EC70 EE18F EE22F EE23F EE24F GA11 GB11 GC03
Claims (5)
有機溶液（Ａ）と、ジアミンと水ガラスとを必須成分と
する水溶液（Ｂ）とを、両溶液が流通するパイプ内に攪
拌体を有し、該攪拌体によって生じる乱流によって、両
溶液を攪拌混合させると共に、該攪拌体をパイプ内で往
復運動させて両溶液を攪拌混合させる混合装置に連続的
に流通させる、ポリアミド複合体の連続製造方法。An agitator is provided in a pipe through which both an organic solution (A) containing dicarboxylic acid halide as an essential component and an aqueous solution (B) containing diamine and water glass as essential components are passed. The turbulence generated by the agitator causes the two solutions to be agitated and mixed, and the agitator is reciprocated in a pipe to continuously flow the mixture into a mixer for agitating and mixing the two solutions. Method.
ジカルボン酸ハライドを、水溶液（Ｂ）が０．１〜２モ
ル／Ｌのジアミンと２〜１００ｇ／Ｌの水ガラスとを含
む、請求項１に記載の連続製造方法。2. An organic solution (A) containing 0.1 to 2 mol / L dicarboxylic acid halide, an aqueous solution (B) containing 0.1 to 2 mol / L diamine and 2 to 100 g / L water glass. The continuous production method according to claim 1, comprising:
続され、そのパイプ同士の接続部には溶液の流通穴が形
成された仕切板が設けられており、且つパイプ内の攪拌
体が一つの軸に取付けられ、該軸を通じて振動源に接続
されいる請求項１又は２に記載の連続製造方法。3. A pipe through which the solution circulates is connected in a multi-stage manner, and a connecting plate between the pipes is provided with a partition plate having a solution circulating hole formed therein. 3. The continuous production method according to claim 1, wherein the method is attached to one shaft and connected to a vibration source through the shafts.
０〜７０Ｈｚの速度で往復運動させる請求項３に記載の
連続製造方法。4. A stirrer having a stroke length of 5 to 15 mm, 2
The continuous manufacturing method according to claim 3, wherein the reciprocating motion is performed at a speed of 0 to 70 Hz.
とを特徴とする請求項１〜４のいずれか一つに記載の連
続製造方法。5. The continuous production method according to claim 1, wherein the stirrer has a ribbon-shaped spiral blade.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32671599A JP2001139683A (en) | 1999-11-17 | 1999-11-17 | Method of continuously producing polyamide composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32671599A JP2001139683A (en) | 1999-11-17 | 1999-11-17 | Method of continuously producing polyamide composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001139683A true JP2001139683A (en) | 2001-05-22 |
Family
ID=18190875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32671599A Pending JP2001139683A (en) | 1999-11-17 | 1999-11-17 | Method of continuously producing polyamide composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001139683A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348468A (en) * | 2001-05-24 | 2002-12-04 | Dainippon Ink & Chem Inc | Electroconductive polyamide composite and its manufacturing method |
| JP2003082097A (en) * | 2001-09-11 | 2003-03-19 | Dainippon Ink & Chem Inc | Method for producing pulp and particles comprising composite of polyamide and glass |
| JP2018177617A (en) * | 2017-04-20 | 2018-11-15 | 学校法人神奈川大学 | Method for producing silica-containing fine particle, construction method for coating on surface of substrate, and sol-gel reaction catalyst |
-
1999
- 1999-11-17 JP JP32671599A patent/JP2001139683A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348468A (en) * | 2001-05-24 | 2002-12-04 | Dainippon Ink & Chem Inc | Electroconductive polyamide composite and its manufacturing method |
| JP2003082097A (en) * | 2001-09-11 | 2003-03-19 | Dainippon Ink & Chem Inc | Method for producing pulp and particles comprising composite of polyamide and glass |
| JP2018177617A (en) * | 2017-04-20 | 2018-11-15 | 学校法人神奈川大学 | Method for producing silica-containing fine particle, construction method for coating on surface of substrate, and sol-gel reaction catalyst |
| JP6991527B2 (en) | 2017-04-20 | 2022-01-12 | 学校法人神奈川大学 | Method for producing silica-containing fine particles, method for coating the surface of a base material, and catalyst for sol-gel reaction. |
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