JP5320654B2 - Method for producing polyamide - Google Patents
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- JP5320654B2 JP5320654B2 JP2001285616A JP2001285616A JP5320654B2 JP 5320654 B2 JP5320654 B2 JP 5320654B2 JP 2001285616 A JP2001285616 A JP 2001285616A JP 2001285616 A JP2001285616 A JP 2001285616A JP 5320654 B2 JP5320654 B2 JP 5320654B2
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本発明はポリアミドの製造方法に関し、詳しくはポリアミド製造工程中に発生する形状不良成形品、スクラップ、余剰品等の産業廃棄物(以後回収ポリアミドと呼ぶ事がある)を溶融重合工程に戻し、原料の一部として再利用することを特徴とするポリアミドの製造方法及びそれによって得られる結晶化速度が調整されたポリアミドに関するものである。 The present invention relates to a method for producing polyamide, and in particular, returns industrial wastes (sometimes referred to as recovered polyamide) such as defectively shaped products, scraps, surplus products, etc. generated during the polyamide production process to the melt polymerization process. The present invention relates to a method for producing a polyamide characterized by being reused as a part of the product, and a polyamide having a controlled crystallization speed obtained thereby.
ポリアミドは家電製品や各種自動軍用部品、コンピューターのハウジング等の射出成形材料、繊糸、編織物等の衣料品、タイヤコード、漁網、釣り糸等の工業用またはレジャー用フィラメント材料、食品包装用のフィルムや各種容器用シ−トあるいはボトル用材料として使用しうる高強力、耐摩耗性、耐疲労性、良好な染色性、ガスバリヤー性等の化学的、機械的性質を有している。特にポリアミドＭＸＤ６のようなキシリレンジアミンと脂肪族ジカルボン酸とから得られるアミド結合繰り返し単位を含有するポリアミドはポリアミド６やポリアミド６６等に比べて高強度、高ヤング率、低吸水性であり、なおかつガスバリヤー性にも優れるため、各種工業用材料、あるいは食品包装用のフィルム、シート、ボトル用材料として特に有用である。 Polyamide is a household appliance, various automatic military parts, injection molding materials such as computer housings, clothing such as textiles and knitted fabrics, industrial and leisure filament materials such as tire cords, fishing nets and fishing lines, and films for food packaging. It has chemical and mechanical properties such as high strength, abrasion resistance, fatigue resistance, good dyeability and gas barrier properties that can be used as a sheet for various containers and a material for bottles. In particular, a polyamide containing an amide bond repeating unit obtained from xylylenediamine and an aliphatic dicarboxylic acid such as polyamide MXD6 has higher strength, higher Young's modulus and lower water absorption than polyamide 6 and polyamide 66, and Because of its excellent gas barrier properties, it is particularly useful as a material for various industrial materials or food packaging films, sheets and bottles.
ジアミンとジカルボン酸を原料とするポリアミドの製法には、ジアミンとジカルボン酸との等モル塩水溶液を加圧下で加熱する所謂加圧法と、溶融ジカルボン酸に昇温しながらジアミンを滴下する所謂常圧法が存在する。後者は例えばメタキシリレンジアミンとアジピン酸を原料とするポリアミドＭＸＤ６のようにジアミンの沸点よりもジカルボン酸及びポリアミドの融点が低い場合に有効な製造法であり、加圧法と比較して反応時間が短い、１バッチ当たりの生産量が大きい、工程及び装置が簡略化されるなどの利点を有する。 There are two methods for producing a polyamide using diamine and dicarboxylic acid as raw materials: a so-called pressure method in which an aqueous solution of an equimolar salt of diamine and dicarboxylic acid is heated under pressure, and a so-called atmospheric pressure method in which diamine is added dropwise to molten dicarboxylic acid while raising the temperature. Exists. The latter is an effective production method when the melting point of dicarboxylic acid and polyamide is lower than the boiling point of diamine, such as polyamide MXD6 using metaxylylenediamine and adipic acid as raw materials. It has advantages such as short production volume per batch and simplified process and equipment.
通常、重縮合の終了したポリアミドは、バッチ式の場合は重合槽内を不活性ガスで加圧することにより、また、連続式の場合はスクリュー等の機械的な動力によって複数の吐出口からストランドと呼ばれる糸状に押し出された後、冷却固化・切断してペレットとして製品化する。この際、槽内の加圧状態や溶融樹脂の状態の予期せぬ変化によってストランドの乱れが起こり、隣のストランドと接触した状態でペレット化されると、複数のペレットが数珠繋ぎに接着した異形ペレットができる。この異形ペレットは射出・押出成形時に供給不良や射出成形機、押出機の不調の原因となるため、一般にふるいにかけて工程外に取り除かれる。 Usually, the polyamide after polycondensation is made into strands from a plurality of discharge ports by pressurizing the inside of the polymerization tank with an inert gas in the case of a batch type, and by mechanical power such as a screw in the case of a continuous type. After being extruded into a so-called thread shape, it is cooled, solidified and cut to produce pellets. At this time, when the strands are disturbed due to unexpected changes in the pressurized state or molten resin state in the tank, and pelletized in a state of contact with the adjacent strand, a plurality of pellets bonded in a daisy chain Can do. Since this irregular shaped pellet causes a supply failure during injection / extrusion molding and malfunctions of the injection molding machine and the extruder, it is generally removed by sieving.
一方、ポリアミドは先に述べたように様々な用途に用いられるため、その用途に応じた成形に適した溶融粘度等の物性を必要とする。例えば射出成形用に用いられる材料は金型内の流動性を高めるために溶融粘度の低いポリアミドが用いられ、押出成形の場合は押出時の溶融強度が必要となるため溶融粘度の高いポリアミドが用いられる。また、ポリマーアロイやポリマーブレンド、あるいは多層シートやフィルムのように複数の樹脂を複合させて使用する場合、複合する材料同士の相性やその複合率あるいは量に応じて必要とされる溶融粘度が異なる場合がある。このため原料メーカーは通常、溶融粘度の異なる複数のグレードを用意して対応するが、市場の要求や需要量の変化によって、グレードによっては余剰品が発生する場合がある。 On the other hand, since polyamide is used for various applications as described above, it requires physical properties such as melt viscosity suitable for molding according to the application. For example, polyamides with low melt viscosity are used for materials used for injection molding, and polyamides with high melt viscosity are used for extrusion molding because melt strength is required during extrusion. It is done. Also, when a plurality of resins are used in combination such as a polymer alloy, a polymer blend, or a multilayer sheet or film, the melt viscosity required differs depending on the compatibility of the composite materials and the composite rate or amount. There is a case. For this reason, raw material manufacturers usually prepare and deal with a plurality of grades having different melt viscosities, but depending on the grade and the change in demand, there are cases where surplus products may be generated depending on the grade.
これらの工程選別品や余剰品は従来廃棄するしかなく、産業廃棄物として処理されるため、処理費用や運送費用が別途必要とされ、採算不良の原因となっていた。近年高まっている環境問題の観点からも廃棄物を出さないことが望まれ、収率アップの面からもこれらの工程選別品や余剰品の再利用が望まれている。 These process-sorted products and surplus products can only be disposed of in the past, and are processed as industrial wastes. Therefore, processing costs and transportation costs are separately required, causing poor profits. From the viewpoint of environmental problems that have been increasing in recent years, it is desired not to produce waste, and from the viewpoint of increasing the yield, it is desired to reuse these process-sorted products and surplus products.
ポリアミド樹脂の製造現場における工程選別品や余剰品のリサイクル方法としては一般的には押出機等を用いて再溶融した後、再造粒する方法が挙げられる。この方法はコスト的に有利だが、色調等の品質が低下し、再溶融する前の製品と同等に使用できない問題が生じる。 As a method for recycling process-selected products and surplus products at the production site of polyamide resin, a method of re-granulation after remelting using an extruder or the like is generally used. Although this method is advantageous in terms of cost, there is a problem that quality such as color tone is deteriorated and the product cannot be used in the same manner as the product before remelting.
次に、一般にサーマルリサイクルと呼ばれる、熱として回収する方法が挙げられる。しかし、この方法は材料として再利用できない場合の最終手段といえる。 Next, there is a method of recovering as heat, generally called thermal recycling. However, this method can be said to be a last resort when the material cannot be reused.
３番目の方法として、一般にケミカルリサイクルと呼ばれる、モノマーに分解して再利用する方法が挙げられる。この方法は最も一般的であり、多くの原料メーカーが検討している。例えば特許第３０４８６４４号公報には、ポリアミド縮合生成物からジアミン及びジカルボン酸を回収する方法が示されている。この発明はポリアミド縮合生成物に硝酸を加えて加水分解する事によりモノマーを回収する方法であるが、採用する際にはやはり専用の装置を必要し、また、硝酸という強酸を使用することによる装置の腐食問題が存在するため、設備費及び維持費が大きな負担となる。 As a third method, there is a method generally called chemical recycling, in which the monomer is decomposed and reused. This method is the most common and is being considered by many raw material manufacturers. For example, Japanese Patent No. 3048644 discloses a method for recovering diamine and dicarboxylic acid from a polyamide condensation product. This invention is a method for recovering a monomer by adding nitric acid to a polyamide condensation product and hydrolyzing it. However, when it is adopted, a dedicated device is still required, and a device using a strong acid called nitric acid is used. Therefore, the equipment cost and the maintenance cost become a big burden.
一方、特開平９−１２７１１号公報には、形状不良ペレットを水等の液状媒体のスラリーとして原料と混合しポリアミドを製造する方法が記載されている。この方法は設備的にはほとんど変更する必要が無く、コスト的に有利だが、水等の液状媒体を大量に使用するため、エネルギー的に不利である。 On the other hand, Japanese Patent Application Laid-Open No. 9-12711 describes a method for producing polyamide by mixing poorly shaped pellets with a raw material as a slurry of a liquid medium such as water. This method requires little change in equipment and is advantageous in terms of cost, but is disadvantageous in terms of energy because a large amount of liquid medium such as water is used.
以上の事から、設備新設等のコストを低く抑え、製造プロセスを変更せず、尚かつ回収ポリアミドと同等の品質を有するポリアミドを製造することが出来る回収ポリアミドリサイクル方法の開発が強く望まれてきた。 In view of the above, there has been a strong demand for the development of a recycled polyamide recycling method that can produce a polyamide having the same quality as the recovered polyamide without changing the manufacturing process while keeping the costs for new equipment installation low. .
ところで、上述のように射出成形用材料には金型内の流動性を高めるために溶融粘度の低いポリアミドが用いられるが、その一方で成形サイクルを速めるために結晶化速度の速いポリアミドが用いられる。一般的に結晶化速度を速める手段としては各種無機物や、結晶化速度が速く、ポリアミドと相溶しやすいポリマー等の添加が行われているが、各種物性低下の問題から添加許容量には限界があり、従って、この方法による結晶化速度の増加には限界が存在する。従って、更なる結晶化速度向上のためにはポリアミドそのものの結晶化速度向上が必要となり、その方法についても開発が強く望まれてきた。 By the way, as described above, a polyamide having a low melt viscosity is used for the injection molding material in order to increase the fluidity in the mold. On the other hand, a polyamide having a high crystallization speed is used to accelerate the molding cycle. . In general, as a means to increase the crystallization speed, various inorganic substances and polymers that are high in crystallization speed and easy to be compatible with polyamide are added. Therefore, there is a limit to increase the crystallization rate by this method. Therefore, in order to further improve the crystallization speed, it is necessary to improve the crystallization speed of the polyamide itself, and development of the method has been strongly desired.
本発明は設備新設等のコストを低く抑え、製造プロセスを変更せずに従来廃棄対象となっていた回収ポリアミドを廃棄することなく原料の一部として再利用して、品質を劣化させることなくポリアミドを製造する方法を提供することを目的とする。本発明の他の目的は、回収ポリアミドを含む原料から得られたポリアミドの結晶化速度を増加させる方法を提供することである。 The present invention keeps the cost of installing new equipment low, recycles the recovered polyamide, which has been the object of conventional disposal without changing the manufacturing process, as part of the raw material without discarding it, and without degrading the quality An object of the present invention is to provide a method of producing Another object of the present invention is to provide a method for increasing the crystallization rate of a polyamide obtained from a raw material containing recovered polyamide.
本発明者らは鋭意検討した結果、溶融ジカルボン酸にジアミンを添加し、溶融状態で重縮合反応を行ってポリアミドを製造する方法において、前記重縮合反応系中に回収ポリアミドのある一定量を添加し、重合反応中に回収ポリアミドを溶解させることにより前記目的が達成されることを見出した。また、回収ポリアミドの添加量を調整する事により、得られるポリアミドの結晶化速度が増加することを見出し、本発明を完成するに至った。
即ち、本発明は溶融ジカルボン酸にジアミンを添加し、溶融状態で重縮合反応を行ってポリアミドを製造する方法において、前記重縮合反応系中に回収ポリアミドを添加し、重縮合反応中に添加した回収ポリアミドを溶解させることを特徴とするポリアミドの製造方法を提供する。本発明は、さらに、前記製造方法によって得られる結晶化速度が調整されたポリアミドを提供する。As a result of intensive studies, the present inventors have added a certain amount of recovered polyamide in the polycondensation reaction system in a method of producing a polyamide by adding a diamine to a molten dicarboxylic acid and performing a polycondensation reaction in a molten state. The inventors have found that the above object can be achieved by dissolving the recovered polyamide during the polymerization reaction. Further, the inventors have found that the crystallization rate of the obtained polyamide is increased by adjusting the amount of the recovered polyamide added, and the present invention has been completed.
That is, the present invention is a method of adding a diamine to a molten dicarboxylic acid and performing a polycondensation reaction in a molten state to produce a polyamide. The recovered polyamide is added to the polycondensation reaction system and added during the polycondensation reaction. Disclosed is a method for producing a polyamide, wherein the recovered polyamide is dissolved. The present invention further provides a polyamide having an adjusted crystallization rate obtained by the production method.
本発明で使用する回収ポリアミド及び本発明の方法により製造されるポリアミドは、ジアミンとジカルボン酸から得られるポリアミドであれば特に限定されないが、本発明では、溶融ジカルボン酸に昇温しながらジアミンを添加する所謂常圧法でポリアミドを製造するため、ジアミンの沸点よりもジカルボン酸及びポリアミドの融点が低い事が望ましい。例えばキシリレンジアミンもしくはビスアミノシクロヘキサンとアジピン酸から得られるポリアミド、特にメタキシリレンジアミンもしくは１，３−ビスアミノシクロヘキサンとアジピン酸から得られるポリアミドが望ましい。 The recovered polyamide used in the present invention and the polyamide produced by the method of the present invention are not particularly limited as long as they are polyamides obtained from diamine and dicarboxylic acid, but in the present invention, diamine is added to molten dicarboxylic acid while raising the temperature. In order to produce polyamide by the so-called atmospheric pressure method, it is desirable that the melting point of dicarboxylic acid and polyamide is lower than the boiling point of diamine. For example, a polyamide obtained from xylylenediamine or bisaminocyclohexane and adipic acid, particularly a polyamide obtained from metaxylylenediamine or 1,3-bisaminocyclohexane and adipic acid is desirable.
本発明では重縮合反応系中に回収ポリアミドを添加するが、重合反応を終了する前に添加した回収ポリアミドが溶解する必要がある。重合反応中に回収ポリアミドが完全に溶解しないと、得られるポリアミドの品質が安定しない、あるいは製品取り出し時の吐出口閉塞等、製造時のトラブル要因となる可能性がある。従って、回収ポリアミドの添加時期は重合反応を終了する前に、添加した回収ポリアミドが溶解する条件であれば特に規定されないが、回収ポリアミドの溶解及び重縮合反応時間が延びて製品の熱履歴を多く受けるのを避けるため、溶融ジカルボン酸にジアミンが添加される前に溶融ジカルボン酸中に添加するのが望ましい。 In the present invention, the recovered polyamide is added to the polycondensation reaction system, but it is necessary to dissolve the added recovered polyamide before the polymerization reaction is completed. If the recovered polyamide is not completely dissolved during the polymerization reaction, the quality of the obtained polyamide may not be stable, or may cause troubles during production, such as blockage of the discharge port during product removal. Accordingly, the timing for adding the recovered polyamide is not particularly limited as long as the added recovered polyamide is dissolved before the polymerization reaction is completed. However, the recovery time of the recovered polyamide and the polycondensation reaction are extended, and the thermal history of the product is increased. In order to avoid receiving it, it is desirable to add it to the molten dicarboxylic acid before the diamine is added to the molten dicarboxylic acid.
回収ポリアミドとして添加される工程選別品、スクラップ、余剰品はそれぞれ単独でも良く、また、２種以上の混合品でも構わないが、その添加量は得られるポリアミドの３０重量％（ｗｔ％）未満である必要がある。３０ｗｔ％以上添加した場合、添加した回収ポリアミドが重合反応中に完全に溶解しないことにより、得られるポリアミドに品質不安定化や製造時のトラブル要因となる可能性がある。また、重合反応液の粘度上昇による重合反応の阻害によって必要な物性を得るための重合反応時間が通常よりも延びることや、回収ポリアミドが溶解したとしてもそれまでに時間がかかること等の理由により、得られるポリアミドが通常よりも多く熱遍歴を受けることになり、結果として製品の品質を損なう。 Process-selected products, scraps and surplus products added as recovered polyamide may be used alone or as a mixture of two or more, but the amount added is less than 30% by weight (wt%) of the resulting polyamide. There must be. When added in an amount of 30 wt% or more, the added recovered polyamide is not completely dissolved during the polymerization reaction, which may cause unstable quality in the obtained polyamide and cause troubles during production. In addition, the polymerization reaction time for obtaining the necessary physical properties by inhibiting the polymerization reaction due to the increase in the viscosity of the polymerization reaction solution is longer than usual, or even if the recovered polyamide is dissolved, it takes time until it is dissolved The resulting polyamide will experience more thermal homologies than usual, resulting in a loss of product quality.
また、回収ポリアミドの添加量についてはその目的に応じて選択することができる。得られるポリアミドの物性が回収ポリアミドの添加により変化することを望まない場合、回収ポリアミドの添加量は重縮合反応で得られるポリアミドの３ｗｔ％未満である必要がある。また、得られるポリアミドの結晶化速度を増大させたい場合、回収ポリアミドの添加量は重縮合反応で得られるポリアミドの３ｗｔ％以上３０ｗｔ％未満である必要があり、４ｗｔ％以上２０ｗｔ％以下であることが望ましい。 Further, the amount of the recovered polyamide added can be selected according to the purpose. When it is not desired that the properties of the resulting polyamide change due to the addition of the recovered polyamide, the added amount of the recovered polyamide needs to be less than 3 wt% of the polyamide obtained by the polycondensation reaction. Further, when it is desired to increase the crystallization speed of the obtained polyamide, the amount of the recovered polyamide needs to be 3 wt% or more and less than 30 wt% of the polyamide obtained by the polycondensation reaction, and is 4 wt% or more and 20 wt% or less. Is desirable.
溶融ジカルボン酸に添加された回収ポリアミドはジカルボン酸過剰系で少量の水分によって加水分解反応を受ける可能性がある。しかし、溶融ジカルボン酸中の水分濃度は１０ｗｔ％以下であるのが好ましい。水分濃度が１０ｗｔ％を越えると、本来の重縮合反応が阻害され、必要な物性を得るための重縮合反応時間が通常よりも延びる事から製品が熱履歴を通常よりも多く受ける事になり、結果として製品の品質を損なう。 The recovered polyamide added to the molten dicarboxylic acid may undergo a hydrolysis reaction with a small amount of water in an excess of dicarboxylic acid. However, the water concentration in the molten dicarboxylic acid is preferably 10 wt% or less. When the water concentration exceeds 10 wt%, the original polycondensation reaction is inhibited, and the polycondensation reaction time for obtaining the necessary physical properties is longer than usual, so the product receives more heat history than usual. As a result, the quality of the product is impaired.
添加される回収ポリアミドは反応系への溶解速度ができるだけ速いことが望ましく、従ってその形状は粒状もしくは粉体であることが望ましい。また、添加される回収ポリアミドの数平均分子量は好ましくは８０，０００以下、更に好ましくは６５，０００以下、更にその結晶化度は好ましくは５０％以下、更に好ましくは４０％以下である必要がある。数平均分子量が８０，０００を越える場合、もしくは結晶化度が５０％を越えると前述した添加量以内であっても重合反応中に回収ポリアミドが完全に溶解しない、もしくは、添加した回収ポリアミドが溶解するまでに時間がかかり、また、重合反応液の粘度が上昇するため、結果として製品の品質を損なう。更に、結晶化速度増加を目的とする場合は、分子量が１０，０００以上５０，０００以下であることが望ましい。 The recovered polyamide to be added preferably has a dissolution rate in the reaction system as fast as possible. Therefore, it is desirable that the shape of the recovered polyamide is granular or powder. The number average molecular weight of the recovered polyamide to be added is preferably 80,000 or less, more preferably 65,000 or less, and the crystallinity thereof is preferably 50% or less, more preferably 40% or less. . When the number average molecular weight exceeds 80,000, or when the degree of crystallinity exceeds 50%, the recovered polyamide does not completely dissolve during the polymerization reaction even if it is within the above-described addition amount, or the added recovered polyamide dissolves. It takes time to do so, and the viscosity of the polymerization reaction solution increases, resulting in a loss of product quality. Furthermore, when the purpose is to increase the crystallization rate, the molecular weight is desirably 10,000 or more and 50,000 or less.
本発明におけるポリアミドの製造方法には必要に応じて滑剤、着色防止剤、架橋防止剤、耐光剤、顔料、制電剤、難燃剤等の無機、有機化合物を組み合わせて使用することができる。添加する時期は特に制限されないが、回収ポリアミドと同時に添加することがより望ましい。 In the method for producing polyamide in the present invention, inorganic, organic compounds such as lubricants, anti-coloring agents, anti-crosslinking agents, light resistance agents, pigments, antistatic agents, and flame retardants can be used in combination as necessary. The timing of addition is not particularly limited, but it is more preferable to add it at the same time as the recovered polyamide.
以下、実施例に基づいて本発明を説明する。表中では回収ポリアミドとして添加したポリメタキシリレンアジパミドをＮ−ＭＸＤ６、数平均分子量をMnと表記する。尚、本発明における評価のための測定は以下の方法によった。
▲１▼ 水分率(重量％)
ペレット２ｇを、三菱化学(株)製カールフィッシャー微量水分測定装置(ＣＡ−０５型)及び気化装置(ＶＡ−０５型)を用い、融点温度で３０分の気化条件で水分量を定量し、水分率を求めた。
▲２▼ 数平均分子量
アミノ基及びカルボキシル基の定量値(末端基濃度)から次式により求めた。
数平均分子量＝２／（［ＮＨ2］＋［ＣＯ2Ｈ］）
［ＮＨ2］： アミノ基濃度(当量／ｇ)
［ＣＯ2Ｈ］： カルボキシル基濃度(当量／ｇ)
▲３▼ 結晶化速度
結晶化速度の評価方法として半結晶化時間を用いた。半結晶化時間とはある結晶性材料が融解状態から結晶化状態まで移行する場合に、結晶化が１／２進行するまでの時間を表し、半結晶化時間が短いほどその材料は結晶化速度が速いといえる。（有）コタキ製作所製結晶化速度測定器(ＭＫ−８０１型)を用い、半結晶化時間を測定した。２６０℃で３分間予熱した後、所定の温度の油浴中に浸漬し、放置時間に対する偏光補償電圧を測定し、一定となった電圧の半分の値に到達する時間を半結晶化時間とした。Hereinafter, the present invention will be described based on examples. In the table, polymetaxylylene adipamide added as recovered polyamide is expressed as N-MXD6, and the number average molecular weight is expressed as Mn. In addition, the measurement for evaluation in this invention was based on the following method.
(1) Moisture content (% by weight)
Using a Karl Fischer trace moisture measuring device (CA-05 type) and a vaporizer (VA-05 type) manufactured by Mitsubishi Chemical Corporation, the amount of moisture was quantified under a vaporization condition of 30 minutes at a melting point temperature, The rate was determined.
(2) Number average molecular weight The number average molecular weight was determined by the following formula from the quantitative values (end group concentration) of amino groups and carboxyl groups.
Number average molecular weight = 2 / ([NH 2 ] + [CO 2 H])
[NH 2 ]: Amino group concentration (equivalent / g)
[CO 2 H]: Carboxyl group concentration (equivalent / g)
(3) Crystallization speed Semi-crystallization time was used as a method for evaluating the crystallization speed. The half crystallization time is the time required for crystallization to progress by half when a crystalline material moves from the molten state to the crystallized state. The shorter the half crystallization time, the faster the material is crystallized. Can be said to be fast. The semi-crystallization time was measured using a crystallization rate measuring instrument (MK-801 type) manufactured by Kotaki Seisakusho. After preheating at 260 ° C. for 3 minutes, immersed in an oil bath at a predetermined temperature, the polarization compensation voltage with respect to the standing time was measured, and the time to reach half the constant voltage was defined as the half crystallization time. .
実施例１
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量１６，０００)を１４．５５ｇ(生成ポリマーに対して２．８ｗｔ％)添加し、２０分撹拌後、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表１に示す。Example 1
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and melting uniformly, 14.55 g of polymetaxylylene adipamide (number average molecular weight 16,000) (2.8 wt% with respect to the produced polymer) was added, and 20 minutes After stirring, 562.00 g of metaxylylenediamine was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 1 shows the properties of the obtained polyamide.
実施例２
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量４０，０００)を１４．５５ｇ(生成ポリマーに対して２．８ｗｔ％)添加し、２０分撹拌後、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表１に示す。Example 2
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and melting uniformly, 14.55 g of polymetaxylylene adipamide (number average molecular weight 40,000) (2.8 wt% with respect to the produced polymer) was added, and 20 minutes After stirring, 562.00 g of metaxylylenediamine was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 1 shows the properties of the obtained polyamide.
実施例３
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量１６，０００)を１４．７５ｇ(生成ポリマーに対して２．８ｗｔ％)添加し、２０分撹拌後、１，３−ビスアミノシクロヘキサン５７８．５１ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２４４℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５０℃で６０分反応を継続した。得られたポリアミドの性状を表３に示す。Example 3
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and uniformly melting, 14.75 g of polymetaxylylene adipamide (number average molecular weight 16,000) (2.8 wt% with respect to the produced polymer) was added, and 20 minutes. After stirring, 57.51 g of 1,3-bisaminocyclohexane was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 244 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued at an internal temperature of 250 ° C. for 60 minutes. Table 3 shows the properties of the obtained polyamide.
実施例４
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量１６，０００)を５８．２０ｇ(生成ポリマーに対して５．４ｗｔ％)添加し、２０分撹拌後、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表１に示す。Example 4
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and uniformly melting, 58.20 g of polymetaxylylene adipamide (number average molecular weight 16,000) (5.4 wt% with respect to the produced polymer) was added, and 20 minutes. After stirring, 562.00 g of metaxylylenediamine was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 1 shows the properties of the obtained polyamide.
実施例５
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量１６，０００)を５９．００ｇ(生成ポリマーに対して５．４ｗｔ％)添加し、２０分撹拌後、１，３−ビスアミノシクロヘキサン５７８．５１ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２４４℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５０℃で６０分反応を継続した。得られたポリアミドの性状を表３に示す。Example 5
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and uniformly melting, 59.00 g of polymetaxylylene adipamide (number average molecular weight 16,000) (5.4 wt% with respect to the produced polymer) was added, and 20 minutes After stirring, 57.51 g of 1,3-bisaminocyclohexane was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 244 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued at an internal temperature of 250 ° C. for 60 minutes. Table 3 shows the properties of the obtained polyamide.
実施例６
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、ポリメタキシリレンアジパミド(数平均分子量１６，０００)を１１６．６０ｇ(生成ポリマーに対して１０ｗｔ％)添加し、２０分撹拌後、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表２に示す。Example 6
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and melting uniformly, 116.60 g of polymetaxylylene adipamide (number average molecular weight 16,000) (10 wt% with respect to the produced polymer) was added and stirred for 20 minutes Then, 562.00 g of metaxylylenediamine was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 2 shows the properties of the obtained polyamide.
実施例７
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇ及びポリメタキシリレンアジパミド(数平均分子量１６，０００)２３３．３０ｇ(生成ポリマーに対して１８ｗｔ％)を入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表２に示す。Example 7
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid and polymetaxylylene adipamide (number average molecular weight 16, 000) 233.30 g (18 wt% with respect to the polymer produced), and after sufficiently purging with nitrogen, further heated to 190 ° C. under a small amount of nitrogen stream and uniformly melted, then 562.00 g of metaxylylenediamine Was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 2 shows the properties of the obtained polyamide.
参考例１
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後２０分そのまま撹拌し、メタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５８℃で６０分反応を継続した。得られたポリアミドの性状を表２に示す。Reference example 1
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. The mixture was heated to 190 ° C. under a nitrogen stream and uniformly melted, followed by stirring for 20 minutes. Then, 562.00 g of metaxylylenediamine was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued for 60 minutes at an internal temperature of 258 ° C. Table 2 shows the properties of the obtained polyamide.
参考例２
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇを入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、均一に溶融した後、２０分そのまま撹拌し、１，３−ビスアミノシクロヘキサン５７８．５１ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２４４℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了後、内温２５０℃で６０分反応を継続した。得られたポリアミドの性状を表３に示す。Reference example 2
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid weighed precisely was placed, and after sufficiently purging with nitrogen, a further small amount was added. After heating to 190 ° C. under a nitrogen stream and uniformly melting, the mixture was stirred as it was for 20 minutes, and 57.51 g of 1,3-bisaminocyclohexane was added dropwise over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 244 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. After completion of the diamine addition, the reaction was continued at an internal temperature of 250 ° C. for 60 minutes. Table 3 shows the properties of the obtained polyamide.
比較例１
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇ及びポリメタキシリレンアジパミド(数平均分子量１６，０００)４４１．００ｇ(生成ポリマーに対して３０ｗｔ％)を入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、更に３６０分攪拌を継続したが、添加したポリメタキシリレンアジパミドは溶融したアジピン酸に完全には溶解しなかった。その後、この不均一溶液にメタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下し、この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了時点でも添加したポリメタキシリレンアジパミドが完全に溶解せず、バッチ内の品質バラツキ、造粒時の吐出口閉塞等様々な不都合が想定されるため、以後の反応及び評価を中止した。Comparative Example 1
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid and polymetaxylylene adipamide (number average molecular weight 16, 000) 441.00 g (30 wt% with respect to the produced polymer), and after sufficiently purging with nitrogen, the mixture was further heated to 190 ° C. under a small amount of nitrogen stream, and further stirred for 360 minutes. Silylene adipamide did not dissolve completely in the molten adipic acid. Thereafter, 562.00 g of metaxylylenediamine was dropped into the heterogeneous solution over 120 minutes with stirring, and the reaction temperature was continuously raised to 250 ° C. during this period. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. Since the added polymetaxylylene adipamide does not completely dissolve even at the end of the diamine addition, various inconveniences such as quality variation in the batch and discharge port clogging during granulation are assumed. did.
比較例２
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇ及びポリメタキシリレンアジパミド(数平均分子量４０，０００)４４１．００ｇ(生成ポリマーに対して３０ｗｔ％)を入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、更に３６０分攪拌を継続したが、添加したポリメタキシリレンアジパミドは溶融したアジピン酸に完全には溶解しなかった。その後、この不均一溶液にメタキシリレンジアミン５６２．００ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２５０℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了時点でも添加したポリメタキシリレンアジパミドが完全に溶解せず、バッチ内の品質バラツキ、造粒時の吐出口閉塞等様々な不都合が想定されるため、以後の反応及び評価を中止した。Comparative Example 2
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid and polymetaxylylene adipamide (number average molecular weight 40, 000) 441.00 g (30 wt% with respect to the produced polymer), and after sufficiently purging with nitrogen, the mixture was further heated to 190 ° C. under a small amount of nitrogen stream, and further stirred for 360 minutes. Silylene adipamide did not dissolve completely in the molten adipic acid. Thereafter, 562.00 g of metaxylylenediamine was added dropwise to the heterogeneous solution over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 250 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. Since the added polymetaxylylene adipamide does not completely dissolve even at the end of the diamine addition, various inconveniences such as quality variation in the batch and discharge port clogging during granulation are assumed. did.
比較例３
攪拌機、分縮機、温度計、滴下ロート及び窒素ガス導入管を備えた内容積２リットルのセパラブルフラスコに、精秤したアジピン酸６００．００ｇ及びポリメタキシリレンアジパミド(数平均分子量１６，０００)４４６．００ｇ(生成ポリマーに対して３０ｗｔ％)を入れ、充分に窒素置換した後、更に少量の窒素気流下で１９０℃まで加熱し、更に３６０分攪拌を継続したが、添加したポリメタキシリレンアジパミドは溶融したアジピン酸に完全には溶解しなかった。その後、この不均一溶液に１，３−ビスアミノシクロヘキサン５７８．５１ｇを撹拌下に１２０分を要して滴下した。この間、反応温度は連続的に２４４℃まで昇温させた。ジアミンの滴下により生じる縮合水は分縮器及び全縮器を通して系外に除いた。ジアミン滴下終了時点でも添加したポリメタキシリレンアジパミドが完全には溶解せず、バッチ内の品質バラツキ、造粒時の吐出口閉塞等様々な不都合が想定されるため、以後の反応及び評価を中止した。Comparative Example 3
In a separable flask having an internal volume of 2 liters equipped with a stirrer, a partial condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 600.00 g of adipic acid and polymetaxylylene adipamide (number average molecular weight 16, 000) 446.00 g (30 wt% with respect to the produced polymer), and after sufficiently purging with nitrogen, the mixture was further heated to 190 ° C. under a small amount of nitrogen stream, and further stirred for 360 minutes. Silylene adipamide did not dissolve completely in the molten adipic acid. Thereafter, 578.51 g of 1,3-bisaminocyclohexane was added dropwise to the heterogeneous solution over 120 minutes with stirring. During this time, the reaction temperature was continuously raised to 244 ° C. Condensed water produced by the dropwise addition of diamine was removed from the system through a partial condenser and a full condenser. The added polymetaxylylene adipamide does not completely dissolve even at the end of the diamine dripping, and various inconveniences such as quality variation in the batch and discharge port clogging during granulation are assumed. Canceled.
表１
実施例番号 実施例１ 実施例２ 実施例４
アジピン酸（ｇ） 600.00 600.00 600.00
メタキシリレンジアミン（ｇ） 562.00 562.00 562.00
添加Ｎ−ＭＸＤ６ Ｍｎ 16,000 40,000 16,000
生成ポリマーに対する添加量（ｗｔ％） 2.8 2.8 5.4
ポリアミドの性状
水分率(％) 0.40 0.39 0.37
Ｍｎ 17,100 16,900 16,800
半結晶化時間
１２０℃(秒) 830 830 760
１６０℃(秒) 38 38 36 Table 1
Example No. Example 1 Example 2 Example 4
Adipic acid (g) 600.00 600.00 600.00
Metaxylylenediamine (g) 562.00 562.00 562.00
Addition N-MXD6 Mn 16,000 40,000 16,000
Amount added to the polymer produced (wt%) 2.8 2.8 5.4
Polyamide properties Moisture content (%) 0.40 0.39 0.37
Mn 17,100 16,900 16,800
Half crystallization time 120 ° C (seconds) 830 830 760
160 ° C (seconds) 38 38 36
表２
実施例番号 実施例６ 実施例７ 参考例１
アジピン酸（ｇ） 600.00 600.00 600.00
メタキシリレンジアミン（ｇ） 562.00 562.00 562.00
添加Ｎ−ＭＸＤ６ Ｍｎ 16,000 16,000 ---
生成ポリマーに対する添加量（ｗｔ％） 10 18 ---
ポリアミドの性状
水分率（％） 0.38 0.38 0.45
Ｍｎ 17,000 16,700 17,200
半結晶化時間
１２０℃（秒） 650 800 830
１６０℃（秒） 33 37 38 Table 2
Example No. Example 6 Example 7 Reference Example 1
Adipic acid (g) 600.00 600.00 600.00
Metaxylylenediamine (g) 562.00 562.00 562.00
Addition N-MXD6 Mn 16,000 16,000 ---
Amount added to the polymer (wt%) 10 18 ---
Polyamide properties Moisture content (%) 0.38 0.38 0.45
Mn 17,000 16,700 17,200
Half crystallization time 120 ° C (seconds) 650 800 830
160 ° C (seconds) 33 37 38
表３
参考例番号 実施例３ 実施例５ 参考例２
アジピン酸（ｇ） 600.00 600.00 600.00
１，３−ビスアミノシクロヘキサン（ｇ） 578.51 578.51 578.51
添加Ｎ−ＭＸＤ６ Ｍｎ 16,000 16,000 ---
生成ポリマーに対する添加量（ｗｔ％） 2.8 5.4 ---
ポリアミドの性状
水分率(％) 0.45 0.45 0.45
Ｍｎ 13,200 13,300 13,200
半結晶化時間
１６０℃(秒) 1200 1100 1200
１７０℃(秒) 700 640 700 Table 3
Reference Example Number Example 3 Example 5 Reference Example 2
Adipic acid (g) 600.00 600.00 600.00
1,3-bisaminocyclohexane (g) 578.51 578.51 578.51
Addition N-MXD6 Mn 16,000 16,000 ---
Amount added to the polymer produced (wt%) 2.8 5.4 ---
Polyamide properties Moisture content (%) 0.45 0.45 0.45
Mn 13,200 13,300 13,200
Half crystallization time 160 ° C (seconds) 1200 1100 1200
170 ° C (seconds) 700 640 700
表１から表３に示される結果から、実施例１及び実施例２の条件で得られるポリアミドの結晶化速度は、参考例１のＮ−ＭＸＤ６無添加品と同等である事、実施例３の条件で得られるポリアミドの結晶化速度は参考例２のＮ−ＭＸＤ６無添加品と同等である事、実施例４、実施例６及び実施例７の条件で得られるポリアミドの結晶化速度は参考例１のＮ−ＭＸＤ６無添加品と比較して増加が認められる事、実施例５の条件で得られるポリアミドの結晶化速度は参考例２のＮ−ＭＸＤ６無添加品と比較して増加が認められる事が分かる。また、上記したように、比較例１、比較例２及び比較例３の条件では添加したポリアミドが重縮合反応中に反応系に完全に溶解せず、正常な製品が得られない事が明らかである。 From the results shown in Table 1 to Table 3, the crystallization rate of the polyamide obtained under the conditions of Example 1 and Example 2 is equivalent to that of the N-MXD6 additive-free product of Reference Example 1, The crystallization rate of the polyamide obtained under the conditions is equivalent to the N-MXD6 additive-free product of Reference Example 2, and the crystallization rate of the polyamide obtained under the conditions of Example 4, Example 6 and Example 7 is the reference example. An increase is observed compared to the N-MXD6 additive-free product of No. 1, and the crystallization rate of the polyamide obtained under the conditions of Example 5 is increased compared to the N-MXD6 additive-free product of Reference Example 2. I understand that. Further, as described above, under the conditions of Comparative Example 1, Comparative Example 2 and Comparative Example 3, it is clear that the added polyamide is not completely dissolved in the reaction system during the polycondensation reaction, and a normal product cannot be obtained. is there.
本発明を用いることにより、ポリアミド製造工程中に発生する形状不良成形品等の産業廃棄物を回収ポリアミドとして溶融重合工程に戻し、製品の品質を損なうことなく原料の一部として再利用することが可能となる。また、回収ポリアミドの添加量を調整することにより、得られるポリアミドの結晶化速度調整が可能となる。 By using the present invention, it is possible to return industrial waste such as poorly shaped molded products generated during the polyamide manufacturing process as recovered polyamide to the melt polymerization process and reuse it as part of the raw material without impairing the quality of the product. It becomes possible. Further, the crystallization speed of the obtained polyamide can be adjusted by adjusting the added amount of the recovered polyamide.
Claims (23)
In a method for producing a polyamide by adding a diamine to a molten dicarboxylic acid and performing a polycondensation reaction in a molten state, the recovered polyamide is added to the molten dicarboxylic acid before the diamine is added to the molten dicarboxylic acid. A method for producing a polyamide, wherein the recovered polyamide added to is dissolved and the water concentration in the molten dicarboxylic acid is 10% by weight or less .
2. The method for producing a polyamide according to claim 1, wherein less than 30% by weight of recovered polyamide is added to the molten dicarboxylic acid with respect to the produced polymer.
2. The method for producing a polyamide according to claim 1, wherein the polyamide is produced without changing the physical properties of the obtained polyamide by adding less than 3% by weight of the recovered polyamide to the molten dicarboxylic acid. .
2. The method for producing a polyamide according to claim 1, wherein a recovered polyamide of 3 wt% or more and less than 30 wt% is added to the molten dicarboxylic acid to adjust the crystallization speed of the resulting polyamide. .
2. The method for producing a polyamide according to claim 1, wherein 3% by weight or more and less than 30% by weight of the recovered polyamide is added to the molten dicarboxylic acid to increase the crystallization rate of the resulting polyamide. .
The method for producing a polyamide according to claim 1, wherein the diamine is xylylenediamine.
The method for producing a polyamide according to claim 6, wherein the xylylenediamine is metaxylylenediamine.
The method for producing a polyamide according to claim 1, wherein the diamine is bisaminocyclohexane.
The method for producing a polyamide according to claim 8, wherein the bisaminocyclohexane is 1,3-bisaminocyclohexane.
The method for producing a polyamide according to claim 1, wherein the dicarboxylic acid is adipic acid.
The manufacturing method of the polyamide in any one of Claim 1 to 10 whose shape of the collection | recovery polyamide to add is a granular form or a powder form.
The method for producing a polyamide according to any one of claims 1 to 11 , wherein the recovered polyamide to be added has a number average molecular weight of 80,000 or less.
The method for producing a polyamide according to any one of claims 1 to 12 , wherein the recovered polyamide to be added has a crystallinity of 50% or less.
The diamine to a molten dicarboxylic acid is added, a process for the preparation of polyamide by performing a polycondensation reaction in a molten state, in the molten dicarboxylic acid before the diamine is added to the molten dicarboxylic acid, 3% by weight with respect to the resulting polymer More than 30% by weight of recovered polyamide is added, and the recovered polyamide added during the reaction is dissolved , and the water concentration in the molten dicarboxylic acid is adjusted to 10% by weight or less. Polyamide.
The diamine to a molten dicarboxylic acid is added, a process for the preparation of polyamide by performing a polycondensation reaction in a molten state, in the molten dicarboxylic acid before the diamine is added to the molten dicarboxylic acid, 3% by weight with respect to the resulting polymer More than 30% by weight of recovered polyamide is added, and the recovered polyamide added during the reaction is dissolved , and the water concentration in the molten dicarboxylic acid is reduced to 10% by weight or less, and the crystallization rate is increased. Polyamide.
The polyamide according to claim 14 or 15 , wherein the diamine is xylylenediamine.
The polyamide of claim 16 , wherein the xylylenediamine is metaxylylenediamine.
The polyamide according to claim 14 or 15 , wherein the diamine is bisaminocyclohexane.
The polyamide according to claim 18 , wherein the bisaminocyclohexane is 1,3-bisaminocyclohexane.
The polyamide according to any one of claims 14 to 19 , wherein the dicarboxylic acid is adipic acid.
The polyamide according to any one of claims 14 to 20 , wherein a shape of the recovered polyamide to be added is granular or powdery.
The polyamide according to any one of claims 14 to 21 , wherein the recovered polyamide to be added has a number average molecular weight of 80,000 or less.
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