JP5482426B2 - Method for producing polyoxamide resin by solid phase polymerization - Google Patents
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Description
本発明は、固相重合によるポリオキサミド樹脂の製造方法に関するものである。 The present invention relates to a method for producing a polyoxamide resin by solid phase polymerization.
ポリオキサミド樹脂は、アミド結合と炭化水素が同じ比率の他のポリアミド樹脂と比較して吸水率が低いことが知られている（特許文献１）。 It is known that the polyoxamide resin has a lower water absorption rate than other polyamide resins having the same ratio of amide bond and hydrocarbon (Patent Document 1).
ポリオキサミド樹脂は、シュウ酸もしくはシュウ酸ジエステルと、脂肪族、脂環族もしくは芳香族ジアミンとの重縮合反応により得られる。しかしながら、シュウ酸は１８０℃を超えると熱分解するため、原料としてシュウ酸を用いた場合に高分子量のポリオキサミド樹脂が得られることはなく、合成例も無い。 The polyoxamide resin is obtained by a polycondensation reaction between oxalic acid or an oxalic acid diester and an aliphatic, alicyclic or aromatic diamine. However, since oxalic acid is thermally decomposed when it exceeds 180 ° C., when oxalic acid is used as a raw material, a high molecular weight polyoxamide resin is not obtained, and there is no synthesis example.
一方、シュウ酸ジアルキルのようなシュウ酸ジエステルをモノマーとして用いた場合は、種々のジアミンとの重縮合反応によるポリオキサミド樹脂が提案されている。例えば、ジアミン成分として1，１０−デカンジアミン、１，９−ノナンジアミン、１，８−オクタンジアミンを用いたポリオキサミド樹脂（いずれも特許文献２）や１，６−ヘキサンジアミンを用いたポリオキサミド樹脂（非特許文献１）など数多くのポリオキサミド樹脂が提案されている。 On the other hand, when an oxalic acid diester such as dialkyl oxalate is used as a monomer, a polyoxamide resin by a polycondensation reaction with various diamines has been proposed. For example, a polyoxamide resin using 1,10-decanediamine, 1,9-nonanediamine, or 1,8-octanediamine as a diamine component (all are Patent Document 2) or a polyoxamide resin using 1,6-hexanediamine (non- Many polyoxamide resins have been proposed, such as Patent Document 1).
ポリオキサミド樹脂は、シュウ酸ジエステルとジアミンとをトルエンなどの溶媒中で重縮合反応させる前重合工程と、溶媒を留去して得られたプレポリマーを溶融重合もしくは固相重合して高分子量のポリマーを得る後重合工程の２段階の重合工程によって製造される。 Polyoxamide resin is a high molecular weight polymer obtained by pre-polymerization reaction of oxalic acid diester and diamine in a solvent such as toluene and a prepolymer obtained by distilling off the solvent by melt polymerization or solid phase polymerization. Is produced by a two-stage polymerization process of a post-polymerization process.
固相重合の例として、シュウ酸ジエチルとテトラメチレンジアミンから得られたプレポリマーを、流動床型の反応槽を用いて２７０〜２９０℃の温度範囲で重縮合反応させた例が知られている。得られたポリオキサミド樹脂は黄色または薄茶色に着色しており、従来技術では着色を抑えることができないという問題点があった（非特許文献２）。 As an example of solid phase polymerization, an example is known in which a prepolymer obtained from diethyl oxalate and tetramethylenediamine is subjected to a polycondensation reaction in a temperature range of 270 to 290 ° C. using a fluidized bed reactor. . The obtained polyoxamide resin was colored yellow or light brown, and there was a problem that coloring could not be suppressed by the prior art (Non-patent Document 2).
本発明が解決しようとする課題は、ポリオキサミド樹脂を製造する際の後重合工程において分解や着色を抑え、固相重合により、還元粘度が１．３〜５．０のポリオキサミド樹脂を効果的に製造する方法を提供することにある。 The problem to be solved by the present invention is to effectively produce a polyoxamide resin having a reduced viscosity of 1.3 to 5.0 by solid-phase polymerization while suppressing decomposition and coloring in the post-polymerization step when producing the polyoxamide resin. It is to provide a way to do.
本発明者らは上記の課題を解決するために鋭意検討を重ねた結果、後重合工程において横型回転式反応器を用いることにより、分解や着色を抑えることができ、還元粘度が１．３〜５．０のポリオキサミド樹脂を製造できることを見出して、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors can suppress decomposition and coloring by using a horizontal rotary reactor in the post-polymerization step, and have a reduced viscosity of 1.3 to The present invention was completed by finding that a polyoxamide resin of 5.0 could be produced.
横型回転式反応器の中の反応槽にプレポリマーのパウダーを仕込むと、パウダーが薄く広がり表面積が大きくなる。さらに反応槽が回転することにより、反応槽壁面で持ち上げられたパウダーが重力により落下することで、表面更新が効果的に行われる。これにより、重縮合反応の進行に伴って生成するアルコールの留去が容易になり、より高分子量化しやすくなった。本製造方法により、より短時間の固相重合で、還元粘度が１．３〜５．０であり、着色が抑えられたポリオキサミド樹脂の製造が可能となった。 When prepolymer powder is charged into a reaction tank in a horizontal rotary reactor, the powder spreads thinly and the surface area increases. Furthermore, when the reaction vessel rotates, the powder lifted on the reaction vessel wall surface falls due to gravity, so that the surface is renewed effectively. As a result, the alcohol produced with the progress of the polycondensation reaction can be easily distilled off, and the molecular weight can be easily increased. According to this production method, it was possible to produce a polyoxamide resin having a reduced viscosity of 1.3 to 5.0 and suppressed coloring in a shorter time solid phase polymerization.
本発明者は、上記問題点を解決するために、鋭意検討した結果を以下に示す。
［１］シュウ酸ジエステルと１，５−ペンタンジアミンからポリオキサミド樹脂を得る製造法において、前記シュウ酸ジエステルと前記１，５−ペンタンジアミンを用いて前重合工程でプレポリマーを合成し、次いで、得られた前記プレポリマーのパウダーを横型回転式反応器を用いて固相重合することを特徴とするポリオキサミド樹脂の製造方法。
In order to solve the above problems, the present inventor has intensively examined the following results.
[1] In a production method for obtaining a polyoxamide resin from an oxalic acid diester and 1,5-pentanediamine, a prepolymer is synthesized in the prepolymerization step using the oxalic acid diester and the 1,5-pentanediamine, and then obtained. A method for producing a polyoxamide resin, comprising subjecting the obtained prepolymer powder to solid phase polymerization using a horizontal rotary reactor.
また以下の態様も好ましい。
［２］還元粘度が１．３〜５．０である、請求項１に記載の製造方法により製造されるポリオキサミド樹脂。
The following embodiments are also preferable.
[2] The polyoxamide resin produced by the production method according to claim 1, wherein the reduced viscosity is 1.3 to 5.0.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
（１）ポリオキサミド樹脂の構成成分
本発明で製造対象となるポリオキサミド樹脂の原料のシュウ酸としては、シュウ酸ジエステルが用いられ、これはアミノ基との反応性を有するものであれば特に制限はなく、シュウ酸ジメチル、シュウ酸ジエチル、シュウ酸ジｎ−（またはｉ−）プロピル、シュウ酸ジｎ−（またはｉ−、またはｔ−）ブチル等の脂肪族１価アルコールのシュウ酸ジエステル、シュウ酸ジシクロヘキシル等の脂環式アルコールのシュウ酸ジエステル、シュウ酸ジフェニル等の芳香族アルコールのシュウ酸ジエステル等が挙げられる。これらのうち、固相重合温度において、完全に取り除くことができるアルコールを生成するシュウ酸ジエステルが好ましく用いられる。このようなシュウ酸ジエステルの例としては、シュウ酸ジメチル、シュウ酸ジエチル、シュウ酸ジｎ−（またはｉ−）プロピル、シュウ酸ジｎ−（またはｉ−、またはｔ−）ブチルを挙げることができる。
(1) Constituents of polyoxamide resin As the raw material for the polyoxamide resin to be produced in the present invention, oxalic acid is an oxalic acid diester, which is not particularly limited as long as it has reactivity with an amino group. Oxalic acid diesters of aliphatic monohydric alcohols such as dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate, Examples include oxalic acid diesters of alicyclic alcohols such as dicyclohexyl and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate. Of these, oxalic acid diesters that produce alcohol that can be completely removed at the solid-state polymerization temperature are preferably used. Examples of such oxalic acid diesters include dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate. it can.
（２）ポリオキサミド樹脂のプレポリマーの製造法
以下、本発明の製造方法を具体的に説明する。まず撹拌器、還流管および窒素導入ラインを備えた反応容器に、原料である１，５−ペンタンジアミンとトルエン等の溶媒を仕込み、窒素気流下で５０〜１００℃に加熱し、撹拌混合する。次いで、容器内のジアミン溶液にシュウ酸ジエステルを注入し、窒素気流下ではげしく撹拌させる。混合するジアミンとシュウ酸ジエステルの比率は、ジアミン／シュウ酸ジエステル（モル比）で、０．８〜１．２、好ましくは０．９１〜１．０９、更に好ましくは０．９８〜１．０２である。原料を混合する温度は５０℃以上１９０℃未満の範囲が好ましい。１９０℃より高い温度で混合した場合は、原料中および反応系中の水分とアルコキシ基の反応、または、アミノ基とアルコキシ基の反応により分子鎖末端に生成するホルムアミド基の濃度が高くなるため、得られるポリオキサミド樹脂の数平均分子量が低くなって物性が低下するために好ましくない。ホルムアミド基の生成については後述する。最後に、トルエン等の溶媒や重縮合反応に伴って生成するアルコールを留去させ、プレポリマーのパウダーを得る。
(2) Production method of prepolymer of polyoxamide resin Hereinafter, the production method of the present invention will be described in detail. First, a solvent such as 1,5-pentanediamine and toluene as raw materials is charged into a reaction vessel equipped with a stirrer, a reflux pipe and a nitrogen introduction line, and heated to 50 to 100 ° C. under a nitrogen stream and stirred and mixed. Next, oxalic acid diester is poured into the diamine solution in the container and stirred vigorously under a nitrogen stream. The ratio of the diamine and oxalic acid diester to be mixed is diamine / oxalic acid diester (molar ratio), 0.8 to 1.2, preferably 0.91 to 1.09, more preferably 0.98 to 1.02. It is. The temperature at which the raw materials are mixed is preferably in the range of 50 ° C. or higher and lower than 190 ° C. When mixed at a temperature higher than 190 ° C., the concentration of the formamide group generated at the end of the molecular chain due to the reaction of moisture and alkoxy groups in the raw materials and reaction system, or the reaction of amino groups and alkoxy groups increases. Since the number average molecular weight of the obtained polyoxamide resin is lowered and the physical properties are lowered, it is not preferable. The formation of the formamide group will be described later. Finally, a solvent such as toluene and alcohol produced with the polycondensation reaction are distilled off to obtain a prepolymer powder.
（３）横型回転式反応器を用いた固相重合
次に、上記により得られたポリオキサミド樹脂のプレポリマーのパウダーを横型回転式反応器の反応槽に仕込み、ポリオキサミド樹脂の融点以下に昇温し、常圧窒素気流下もしくは減圧下において固相重合を行う。減圧下で固相重合を行う場合の好ましい最終到達圧力は７６０〜０．１Ｔｏｒｒである。重合温度は、得られるポリオキサミド樹脂の融点に応じて変化させることができるが、融点−１５０〜−５℃、好ましくは融点-１００〜-１０℃である。上記範囲にある場合には、ポリオキサミドの熱分解、あるいは熱による変性が起こる可能性は小さい。重縮合反応に伴い生成するアルコールは、コンデンサで冷却して凝縮させ回収する。
(3) Solid-phase polymerization using a horizontal rotary reactor Next, the prepolymer powder of the polyoxamide resin obtained as described above was charged into the reaction vessel of the horizontal rotary reactor, and the temperature was raised below the melting point of the polyoxamide resin. Solid-phase polymerization is performed under a normal pressure nitrogen stream or under reduced pressure. A preferable final ultimate pressure when solid phase polymerization is performed under reduced pressure is 760 to 0.1 Torr. The polymerization temperature can be changed according to the melting point of the polyoxamide resin to be obtained, and is a melting point of −150 to −5 ° C., preferably a melting point of −100 to −10 ° C. When it is in the above range, there is little possibility that polyoxamide is thermally decomposed or modified by heat. The alcohol produced by the polycondensation reaction is cooled by a condenser, condensed and recovered.
横型回転式反応器の反応槽としては、直径が３０ｍｍφ〜６５ｍｍφのものがよく、ボトル型、球型、円筒型等を用いることができる。反応槽は、その回転により仕込んだプレポリマーのパウダーが反応槽壁面で持ち上げられやすくするために、反応槽の外側から凹みを設けておいてもよい。このようにして反応槽の内壁面に設けられた突起により、プレポリマーのパウダーは、反応槽の回転に伴い持ち上げられ、反応槽が９０度以上回転したところで重力により落ちる。この突起の高さは０．５ｍｍ〜３ｍｍが良い。この範囲のときは反応槽を回転させた際にパウダーを流動させやすくし、効果的に表面更新ができる。回転速度は１ｒｐｍ〜２０ｒｐｍ、好ましくは５〜１５ｒｐｍ、更に好ましくは８〜１２ｒｐｍである。上記範囲にある場合には、プレポリマーのパウダーは表面更新を頻繁に行うので、短時間での高分子量化が可能になる。さらに短時間の重合により、着色や分解を抑えることも可能である。 As a reaction tank of a horizontal rotary reactor, those having a diameter of 30 mmφ to 65 mmφ are preferable, and a bottle type, a spherical type, a cylindrical type and the like can be used. The reaction vessel may be provided with a dent from the outside of the reaction vessel so that the prepolymer powder charged by the rotation can be easily lifted on the reaction vessel wall surface. Thus, the prepolymer powder is lifted by the rotation of the reaction tank by the protrusions provided on the inner wall surface of the reaction tank, and drops by gravity when the reaction tank rotates 90 degrees or more. The height of the protrusion is preferably 0.5 mm to 3 mm. In this range, the powder can be easily flowed when the reaction vessel is rotated, and the surface can be renewed effectively. The rotation speed is 1 to 20 rpm, preferably 5 to 15 rpm, and more preferably 8 to 12 rpm. When it is in the above range, the prepolymer powder frequently renews the surface, so that a high molecular weight can be achieved in a short time. Furthermore, coloring and decomposition can be suppressed by short-time polymerization.
必要に応じて重合触媒を添加することができる。重合触媒としては、リン酸、ピロリン酸、ポリリン酸などのリン化合物、ヒ素、アンチモンなど周期表Ｖ族元素の酸化物およびハロゲン化物、例えば、フッ化アンチモン、三酸化二ヒ素などが挙げられる。また触媒と耐熱剤の両方の効果をねらって、亜リン酸、次亜リン酸、及びこれらのアルカリ金属塩、アルカリ土類金属塩などの無機系リン化合物を添加することもできる。重合触媒は、プレポリマーの製造のとき反応容器にジアミンを仕込んだ後に添加し、シュウ酸ジエステルを添加する前にあらかじめ均一に混合しておくのが望ましい。添加量は、通常、仕込み原料に対して５０〜３０００ｐｐｍである。 A polymerization catalyst can be added as needed. Examples of the polymerization catalyst include phosphorous compounds such as phosphoric acid, pyrophosphoric acid, and polyphosphoric acid, and oxides and halides of Group V elements of the periodic table such as arsenic and antimony, such as antimony fluoride and diarsenic trioxide. In addition, phosphorous acid, hypophosphorous acid, and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof can be added for the effect of both the catalyst and the heat-resistant agent. It is desirable that the polymerization catalyst be added after the diamine is charged into the reaction vessel during the production of the prepolymer, and mixed in advance before adding the oxalic acid diester. The addition amount is usually 50 to 3000 ppm with respect to the charged raw materials.
（４）ポリオキサミドの性状および物性
本発明により得られるポリオキサミドの粘度に特別の制限はないが、還元粘度が１．３〜５．０の範囲内が好ましく、さらに還元粘度が１．５〜４．０の範囲内がより好ましい。還元粘度が１．３より低いと成形物が脆くなり物性が低下する。一方、還元粘度が５．０より高いと溶融粘度が高くなり、成形加工性が悪くなる。また、本発明により得られるポリオキサミド樹脂の末端基は、アミノ基、アルコキシ基、ホルムアミド基のうちのいずれかである。ホルムアミド基は下記化学式１で示される末端基で、下記化学式２に示されるように、原料中および反応系中の（１）水分とアルコキシ基の反応、または、（２）アミノ基とアルコキシ基の反応により生成する。
(4) Properties and physical properties of polyoxamide There is no particular restriction on the viscosity of the polyoxamide obtained by the present invention, but the reduced viscosity is preferably in the range of 1.3 to 5.0, and the reduced viscosity is 1.5 to 4. A range of 0 is more preferable. If the reduced viscosity is lower than 1.3, the molded product becomes brittle and the physical properties deteriorate. On the other hand, when the reduced viscosity is higher than 5.0, the melt viscosity becomes high and the molding processability is deteriorated. Moreover, the terminal group of the polyoxamide resin obtained by this invention is either an amino group, an alkoxy group, or a formamide group. The formamide group is a terminal group represented by the following chemical formula 1 and, as represented by the following chemical formula 2, (1) reaction of moisture and alkoxy group in the raw material and reaction system, or (2) amino group and alkoxy group Produced by reaction.
ホルムアミド基生成反応式
（１）水とアルコキシ基の反応
Formamide group formation reaction formula (1) Reaction of water and alkoxy group
（２）アミノ基とアルコキシ基の反応 (2) Reaction of amino group and alkoxy group
（５）ポリオキサミド樹脂に配合できる成分
本発明により得られるポリオキサミド樹脂には、本発明の効果を損なわない範囲で、他のポリオキサミドや、芳香族ポリアミド、脂肪族ポリアミド、脂環式ポリアミドなどのポリアミド樹脂類を混合することが可能である。更に、ポリアミド樹脂以外の熱可塑性ポリマー、エラストマー、フィラーや、補強繊維、各種添加剤を配合することができる。
(5) Components that can be blended in the polyoxamide resin The polyoxamide resin obtained according to the present invention includes other polyoxamides, polyamide resins such as aromatic polyamides, aliphatic polyamides, and alicyclic polyamides, as long as the effects of the present invention are not impaired. Can be mixed. Furthermore, thermoplastic polymers other than polyamide resins, elastomers, fillers, reinforcing fibers, and various additives can be blended.
さらに、本発明により得られるポリオキサミド樹脂には必要に応じて、銅化合物などの安定剤、着色剤、紫外線吸収剤、光安定化剤、酸化防止剤、帯電防止剤、難燃剤、結晶化促進剤、ガラス繊維、可塑剤、潤滑剤などを、その製造時、または製造後に添加することもできる。 Further, the polyoxamide resin obtained by the present invention may contain a stabilizer such as a copper compound, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, and a crystallization accelerator, if necessary. Glass fibers, plasticizers, lubricants, and the like can be added during or after the production.
（６）ポリオキサミド樹脂の成形加工
本発明により得られるポリオキサミド樹脂の成形方法としては、射出、押出、中空、プレス、ロール、発泡、真空・圧空、延伸などポリアミドに適用できる公知の成形加工法はすべて可能であり、これらの成形法によってフィルム、シート、成形品、繊維などに加工することができる。
(6) Polyoxamide resin molding process The polyoxamide resin molding process obtained by the present invention includes all known molding process methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / compression, and stretching. The film can be processed into a film, a sheet, a molded product, a fiber, or the like by these molding methods.
（７）ポリオキサミド成形物の用途
本発明によって得られるポリオキサミドの成形物は、従来ポリアミド成形物が用いられてきた各種成形品、シート、フィルム、パイプ、チューブ、モノフィラメント、繊維、容器等として自動車部材、コンピューター及び関連機器、光学機器部材、電気・電子機器、情報・通信機器、精密機器、土木・建築用品、医療用品、家庭用品など広範な用途に使用できる。
(7) Use of Polyoxamide Molded Product The molded product of polyoxamide obtained by the present invention includes various molded products, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded products have been conventionally used. It can be used in a wide range of applications such as computers and related equipment, optical equipment components, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods.
［評価方法］
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらにより何ら制限されるものではない。なお、実施例中の還元粘度の測定は以下の方法により行った。
[Evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measurement of the reduced viscosity in an Example was performed with the following method.
［還元粘度（ηｓｐ/ｃ）］
還元粘度は、９６％硫酸に、ポリオキサミド樹脂を濃度１．０ｇ／ｄｌになるように溶解させ、オストワルド型粘度計を用いて２５℃で測定した。還元粘度の算出は、式１に従って行った。ここで９６％硫酸の流下時間をη０、ポリオキサミド樹脂の硫酸溶液の流下時間をηｔとした。
（式１）
The reduced viscosity was measured at 25 ° C. using an Ostwald viscometer after dissolving a polyoxamide resin in 96% sulfuric acid to a concentration of 1.0 g / dl. The reduced viscosity was calculated according to Equation 1. Here, the flow time of 96% sulfuric acid was η 0 , and the flow time of the sulfuric acid solution of polyoxamide resin was η t .
(Formula 1)
［実施例１］
１，５−ペンタンジアミン３４．１５ｇ（０．３３４２モル）とトルエン４００ｍＬを、撹拌器、還流管および窒素導入ラインを備えた１Ｌセパラブルフラスコに仕込み撹拌した。このセパラブルフラスコを５０℃に昇温した後、回転数３００ｒｐｍで激しく撹拌させながらシュウ酸ジブチル６７．６０ｇ（０．３３４２モル）を３０秒間かけて仕込んだ。その後セパラブルフラスコを１３０℃に昇温させ、４時間撹拌した。なお、原料仕込みから反応終了までの全ての操作は、純度９９．９９９９％の窒素気流下（５０ｍＬ／分）で行った。反応終了後にトルエンを留去させ、１１０℃、減圧下にて２４時間乾燥させ
プレポリマーのパウダーを得た。
[Example 1]
34.15 g (0.3342 mol) of 1,5-pentanediamine and 400 mL of toluene were charged into a 1 L separable flask equipped with a stirrer, a reflux tube and a nitrogen introduction line and stirred. After raising the temperature of the separable flask to 50 ° C., 67.60 g (0.3342 mol) of dibutyl oxalate was charged over 30 seconds while vigorously stirring at 300 rpm. Thereafter, the separable flask was heated to 130 ° C. and stirred for 4 hours. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream (50 mL / min) with a purity of 99.9999%. After completion of the reaction, toluene was distilled off and dried at 110 ° C. under reduced pressure for 24 hours to obtain a prepolymer powder.
上記操作によって得られたプレポリマーのパウダーを、横型回転式反応器を用いて固相重合した。プレポリマー約５ｇを、直径約４５ｍｍφ、ボトル型、ガラス製で２ｍｍの突起を有する反応槽に仕込んだ。次に、反応槽内を圧力１３．３Ｐａにまで減圧し次いで純度９９．９９９９％の窒素ガスで復圧する操作（窒素置換）を５回繰り返した。その後、回転速度１０ｒｐｍで反応槽を回転させながら、圧力１３．３Ｐａの減圧下で室温から２８０℃まで昇温し、２、４、７および１１時間の固相重合を行った。その後ヒーターを止め、回転させながら室温まで冷却してポリオキサミド樹脂を得た。得られたものは白色または淡黄色のパウダー状であった。 The prepolymer powder obtained by the above operation was subjected to solid phase polymerization using a horizontal rotary reactor. About 5 g of the prepolymer was charged into a reaction vessel having a diameter of about 45 mmφ, a bottle type, made of glass and having a projection of 2 mm. Next, the operation of reducing the pressure in the reaction vessel to 13.3 Pa and then restoring the pressure with nitrogen gas having a purity of 99.9999% (nitrogen replacement) was repeated five times. Thereafter, while rotating the reaction vessel at a rotation speed of 10 rpm, the temperature was raised from room temperature to 280 ° C. under reduced pressure of 13.3 Pa, and solid phase polymerization was performed for 2, 4, 7 and 11 hours. Thereafter, the heater was stopped and cooled to room temperature while rotating to obtain a polyoxamide resin. The obtained product was white or pale yellow powder.
［比較例１］
実施例１と同様の方法で得られたプレポリマー約１．５ｇを、アンカー型撹拌羽根を持つ撹拌機、空冷管、窒素導入ラインを備えた直径約３５ｍｍφの縦型ガラス製反応管に仕込んだ。実施例１と同様に窒素置換した後、撹拌の回転数を３０ｒｐｍ、５０ｍＬ／分の窒素気流下で２８０℃で固相重合した他は、実施例１と同様の操作を行いポリオキサミド樹脂を得た。得られたものは白色または淡黄色のパウダー状であった。
[Comparative Example 1]
About 1.5 g of the prepolymer obtained by the same method as in Example 1 was charged into a vertical glass reaction tube having a diameter of about 35 mmφ equipped with an agitator having an anchor type stirring blade, an air cooling tube, and a nitrogen introduction line. . After purging with nitrogen in the same manner as in Example 1, the same procedure as in Example 1 was performed to obtain a polyoxamide resin except that solid phase polymerization was performed at 280 ° C. under a nitrogen stream of 30 rpm and 50 mL / min. . The obtained product was white or pale yellow powder.
実施例１及び比較例１で得られた生成物を、還元粘度を測定した。 The reduced viscosity of the products obtained in Example 1 and Comparative Example 1 was measured.
実施例１及び比較例１によって得られたポリオキサミド樹脂の還元粘度（ηsp/c）を表１に示す。 Table 1 shows the reduced viscosities (η sp / c) of the polyoxamide resins obtained in Example 1 and Comparative Example 1.
以上詳述したように、本発明の製造方法により、還元粘度が１．３〜５．０であり、かつ着色を抑えたポリオキサミド樹脂を製造することができる。 As described in detail above, a polyoxamide resin having a reduced viscosity of 1.3 to 5.0 and suppressed coloring can be produced by the production method of the present invention.
Claims (1)
器を用いて固相重合することを特徴とするポリオキサミド樹脂の製造方法。 In the production method for obtaining a polyoxamide resin from oxalic acid diester and 1,5-pentanediamine, a prepolymer was synthesized in the prepolymerization step using the oxalic acid diester and the 1,5-pentanediamine, and then obtained A method for producing a polyoxamide resin, characterized by solid-phase polymerization of a prepolymer powder using a horizontal rotary reactor.
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