JP2004292581A - Aromatic ester amide block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer excellent in the balance among heat resistance, hydrolysis resistance, and mechanical properties in a wide hardness range. <P>SOLUTION: An aromatic esteramide block copolymer consisting of 10-90 wt.% aromatic oligoamide ester units having a specific structure and 90-10 wt.% poly(vinyl ether) units and having a number average mol.wt. (measured by gel permeation chromatography (GPC), in terms of polystyrene) of 10,000-500,000 is synthesized. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中、Ｒ^１，Ｒ^２はそれぞれ独立して炭素原子数６〜２０の２価の芳香族基を示す。）
ポリ（ビニルエーテル）単位からなり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の数平均分子量が１００００〜５０００００であることを特徴とする芳香族エステルアミドブロック共重合体に関するものであり、以下詳細に説明する。
【００１０】
本発明の芳香族エステルアミドブロック共重合体は、一般式（１）に示す芳香族オリゴアミドエステル単位をハードセグメントとしている。式（１）中のＲ^１，Ｒ^２は芳香族エステルアミドブロック共重合体に耐熱性を付与するため、それぞれ独立して炭素原子数６〜２０の２価の芳香族基である。その具体例としては、下記のものを挙げることができる。
【００１１】
【化３】

【化４】

【化５】

【化６】

【化７】

【化８】

【化９】

【化１０】

【化１１】

【化１２】

なかでも、
【００１２】
【化１３】

が好ましい。これは、耐熱性と成形加工性のバランスに優れる芳香族エステルアミドブロック共重合体を製造することができるためである。
【００１３】
一方、ソフトセグメントはポリ（ビニルエーテル）単位からなり、ビニルエーテルの繰り返し単位を持つものであればその構造に特に制限はないが、例えばポリ（メチルビニルエーテル）、ポリ（エチルビニルエーテル）、ポリ（プロピルビニルエーテル）、ポリ（ブチルビニルエーテル）、ポリ（イソブチルビニルエーテル）、ポリ（ｔ−ブチルビニルエーテル）等のポリ（アルキルビニルエーテル）や飽和エステル基、不飽和エステル基、オキシエチレン鎖、イミド基、シロキシ基等を有するポリ（ビニルエーテル）等が挙げられる。なかでも、芳香族エステルアミドブロック共重合体に良好な低温特性を付与するために、ポリ（アルキルビニルエーテル）を用いることが好ましい。また、ポリ（ビニルエーテル）単位の分子量に特に制限はないが、数平均分子量が５００〜１００００のものが好ましい。数平均分子量が５００未満の場合、得られる芳香族エステルアミドブロック共重合体の融点が高くなるため成形加工性に劣り、数平均分子量が１００００を越えると重合時にポリマーの相分離が起こり、反応率の低下を招いて高分子量のブロック共重合体を得ることが困難となるばかりか、低温特性の低下を招く恐れがある。
【００１４】
芳香族エステルアミドブロック共重合体中のポリ（ビニルエーテル）単位の共重合成分含量に特に制限はないが、その含量は１０〜９０重量％が好ましく、さらに好ましくは１５〜８５重量％である。１０重量％未満では柔軟性やゴム弾性が不足し、９０重量％を越える場合は結晶性が低くなり、成形性が悪化する恐れがある。
【００１５】
本発明の芳香族エステルアミドブロック共重合体の分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した数平均分子量がポリスチレン換算で１００００〜５０００００であり、好ましくは３００００〜２０００００である。この分子量領域では、優れた機械特性を示し、溶融流動性もよく、成形加工性にも優れている。
【００１６】
本発明の芳香族エステルアミドブロック共重合体の製造方法は特に限定されるわけではなく、従来のブロック共重合体型熱可塑性エラストマーの一般的な合成法で製造することが可能である。例えば、前記芳香族オリゴアミドエステル単位の前駆体である芳香族オリゴアミドアルキルエステルとポリ（ビニルエーテル）グリコール、および必要に応じてジカルボン酸ジエステルとを溶融反応させて製造する方法、溶融反応によりポリ（ビニルエーテル）グリコールの末端を芳香族アミノカルボン酸化合物で置換した後、これを有機溶媒中で芳香族ジカルボン酸ジクロライドと反応させることにより製造する方法、もしくは芳香族オリゴアミドアルキルエステルとポリ（ビニルエーテル）グリコールを特定の溶媒中で反応させ、プレポリマーを得た後、溶媒を留去し、溶融反応により製造する方法、さらには末端に活性アシルラクタム基を有する芳香族オリゴアミド化合物とポリ（ビニルエーテル）グリコールとを溶融あるいは溶媒中で反応させる方法等が挙げられる。これらの方法により、耐熱性、耐加水分解性、機械特性のバランスに優れる本発明の芳香族エステルアミドブロック共重合体を得ることができる。
【００１７】
本発明の芳香族エステルアミドブロック共重合体の耐熱性、特に熱変色性の向上のため、製造時あるいは製造後に安定剤を添加してもよい。安定剤としては、リン酸、亜リン酸、次亜リン酸誘導体、フェニルホスホン酸、フェニルホスフィン酸、ジフェニルホスホン酸、ポリホスホネート、ジアルキルペンタエリスリトールジホスファイト、ジアルキルビスフェノールＡジホスファイト等のリン化合物、ヒンダードフェノール系化合物、チオエーテル系、ジチオ酸塩系、メルカプトベンズイミダゾール系、チオカルバニリド系、チオジプロピオン酸エステルなどの硫黄含有化合物、スズマレート、ジブチルスズモノオキシドなどのスズ系化合物が挙げられる。これらの添加量は特に制限されないが、通常、共重合体１００重量部に対して０．０１〜２重量部である。
【００１８】
また、本発明の芳香族エステルアミドブロック共重合体には、成形性向上の目的でカルシウム、バリウム、アルミニウム等のステアリン酸塩類、ステアリン酸エステル、シリコンオイル、ワックス類、エチレンビスステアリルアミドなどの滑剤を添加することができる。これらの添加量は特に制限されないが、通常、共重合体１００重量部に対して０．０５〜５重量部である。
【００１９】
さらに、本発明の芳香族エステルアミドブロック共重合体に、染料、有機あるいは無機顔料、無機補強剤、可塑剤、ヒンダードアミン系光安定剤、紫外線吸収剤、発泡剤、エポキシ化合物やイソシアネート化合物等の公知の添加剤を加えることができる。
【００２０】
本発明の芳香族エステルアミドブロック共重合体は、射出成形、押出成形、トランスファー成形、インフレーション成形、ブロー成形、加熱成形、圧縮成形、真空成形等、通常の熱可塑性樹脂の成形方法により成形加工でき、各種成形品、繊維、フィルム、シート、プラスチック改質剤、塗料、接着剤等の幅広い用途に展開可能である。
【００２１】
【実施例】
以下、本発明を実施例によって詳細に説明するが、これら実施例のみに限定されるものではない。
【００２２】
なお、本発明のジヒドロキシ芳香族アミド化合物の分析に用いた分析機器および方法は下記の通りである。
【００２３】
（１）分子量測定
東ソー（株）製 ＣＰ−８０００およびカラムにポリスチレンゲル２０００Ｈ８，ＧＭＨＸＬを連結したカラムを用い、流速１．０ｍｌ／分、溶離液に塩化リチウムを２０ミリモル／ｌ添加したＮ−メチル−２−ピロリドンを用いて、カラム温度４０℃で測定した。平均分子量はポリスチレン換算で算出した。
【００２４】
（２）^１Ｈ−ＮＭＲスペクトル
日本電子製 ＪＮＭ−ＧＳＸ２７０型を用い、重水素化ジメチルスルホキシド中、室温、積算回数６４回の条件で測定した。
【００２５】
（３）動的粘弾性
レオロジー製 ＤＶＥ−Ｖ４ ＦＴ−レオスペクトラーを用いて、振動数１０Ｈｚ、−１００〜３００℃の範囲で動的粘弾性の温度依存性を測定した。
【００２６】
（４）熱分解温度（Ｔｄ）
セイコー電子工業製 ＴＧ−ＤＴＡ２００を用い、昇温速度２０℃／分で測定した。
【００２７】
（５）ガラス転移温度（Ｔｇ）および融点（Ｔｍ）
セイコー電子工業製 ＤＳＣ２００を用い、昇温速度１０℃／分、−１００〜３００℃の範囲で測定した。
【００２８】
（６）硬度
高分子計器製 マイクロゴム硬度計を用い、厚さ１ｍｍのプレスシートを用いて測定した。
【００２９】
（７）機械特性（破断強度，破断伸び）
島津製作所製 オートグラフＤＣＳ−１００により、厚さ１ｍｍのＪＩＳ Ｋ６２５１ ６号形ダンベル状試験片を用いて、引張速度；１００ｍｍ／分の条件で測定した。
【００３０】
（８）耐加水分解性試験
厚さ１ｍｍのプレスシートを１００℃の熱水に７日間浸せきした後、サンプルの分子量を測定した。浸せき前の分子量との比より分子量保持率を算出し、評価した。
【００３１】
参考例１
窒素導入管、温度計および攪拌翼を備えた５００ｍｌの４つ口フラスコに、４−アミノ安息香酸エチル ８２．６ｇ（０．５モル）とＮ−メチル−２−ピロリドン（ＮＭＰ）２５０ｍｌを加え、撹拌して均一溶液を得た。別途に、窒素導入管を備えた２００ｍｌ滴下ロートに、ＮＭＰ１７０ｍｌおよびテレフタル酸ジクロライド５０．７ｇ（０．２５モル）を加え、撹拌して均一溶液とし、この溶液を先の溶液中に１時間かけて滴下した。さらに１時間反応を行った後、固形分を吸引濾過により回収し、ＮＭＰ２５０ｍｌ、次いで、アセトン１０００ｍｌで洗浄した。得られた固形物は８０℃で１２時間減圧乾燥し、１１２．８ｇ（収率：９８．０％）の芳香族オリゴアミドエチルエステルを得た。この化合物を化合物（ａ）とする。化合物（ａ）の構造式を下記に示す。
【００３２】
【化１４】

実施例１
窒素導入管、温度センサー、マグネチック攪拌翼、留出管を備えた３００ｍｌの４ツ口フラスコに、化合物（ａ）１０．０ｇ（０．０２１７モル）、ポリ（エチルビニルエーテル）グリコール［協和油化製：ＴＯＥ−２０００Ｈ，数平均分子量（Ｍｎ）＝１４８０）］３２．２ｇ（０．０２１７モル）、およびヒンダードフェノール系老化防止剤として１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン［チバガイギ製：イルガノックス１３３０］０．０４ｇを仕込んだ。１００℃で１時間、減圧乾燥を行った後、ＮＭＰ２０．８ｇとテトラブトキシチタン０．０９ｇを添加した。窒素気流下、２１０℃まで０．５時間かけて昇温し、１時間反応させた。その後、ＮＭＰを減圧留去しながら２４０℃まで昇温し、１ｍｍＨｇの減圧下で１時間溶融重合を行った。良好なゴム弾性を示す生成物を３９．４ｇ（収率：９８％）得た。生成物の数平均分子量；４９９００、重量平均分子量；８４７００、Ｔｍ；２３０℃、Ｔｇ；−２４℃、熱分解温度；３８２℃であった。また、その機械特性は、硬度；９５（ＪＩＳ−Ａ）、破断強度；７．７ＭＰａ、破断伸び；１１０％であった。また、生成物の^１Ｈ−ＮＭＲスペクトルを図１に、動的粘弾性の温度依存性を図２に示した。
【００３３】
耐加水分解性試験後の重量平均分子量は７２１００であり、分子量保持率：８５％であり、良好な耐水性を示した。
【００３４】
【発明の効果】
本発明の芳香族エステルアミドブロック共重合体は、ハードセグメントが芳香族オリゴアミドエステル単位、ソフトセグメントがポリ（ビニルエーテル）単位からなるため、幅広い硬度範囲において耐熱性、耐加水分解性、機械特性のバランスに優れる熱可塑性エラストマーである。
【図面の簡単な説明】
【図１】実施例１で得られた芳香族エステルアミドブロック共重合体の^１Ｈ−ＮＭＲスペクトル測定結果を示す図である。
【図２】実施例１で得られた芳香族エステルアミドブロック共重合体の動的粘弾性の温度依存性を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aromatic ester amide block copolymer having properties as a thermoplastic elastomer and having excellent balance of heat resistance, hydrolysis resistance, and mechanical properties.
[0002]
[Prior art]
In recent years, from the viewpoint of recyclability and energy saving, substitution of crosslinked rubber by a thermoplastic elastomer has been advanced. The thermoplastic elastomer is composed of a soft segment rich in rubber elasticity and a hard segment serving as a molecular chain constrained phase, and various thermoplastic elastomers having different types of hard segments have been developed and marketed. Above all, polyamide-based and polyester-based thermoplastic elastomers are widely used in automotive parts, electric / electronic parts, industrial parts and the like as thermoplastic elastomers having excellent heat resistance and oil resistance. The hard segment of the polyamide-based or polyester-based elastomer is composed of a polymer compound having a high melting point, such as 6-nylon, 6,6-nylon, or poly (butylene terephthalate). However, these are still insufficient in terms of heat resistance, and since they use a high molecular compound as a hard segment, only relatively high hardness can be obtained. It has been difficult to produce a plastic elastomer.
[0003]
On the other hand, a new type of thermoplastic elastomer having an aromatic oligomer having high crystallinity and a high melting point as a hard segment has been reported. For example, a thermoplastic elastomer having low hardness and excellent heat resistance using 4,4′-dihydroxy-p-quarterphenyl as a hard segment and an aliphatic polyester unit as a soft segment has been disclosed (for example, see Patent Document 1). ). However, since this polyester elastomer uses an aliphatic polyester unit for the soft segment, it has a problem that it is excellent in heat resistance but inferior in hydrolysis resistance.
[0004]
Further, a thermoplastic elastomer using a high crystalline, high melting point aromatic ester amide compound as a hard segment and using a poly (oxyalkylene glycol) unit as a soft segment has been reported. For example, melt polycondensation of an aromatic ester amide compound comprising an aromatic dicarboxylic acid compound and an aromatic diamine compound with poly (oxyalkylene glycol) (for example, see Patent Document 2), an aromatic dicarboxylic acid compound and an aromatic aminocarboxylic acid Melt polycondensation of an aromatic ester amide compound composed of an acid compound with poly (oxyalkylene glycol) (for example, see Patent Document 3) has been proposed. Although this elastomer is excellent in heat resistance, moldability, mechanical properties, and hydrolysis resistance, it has a problem that poly (oxyalkylene glycol) units are oxidized and deteriorated in long-term heat resistance such as heat aging. I have. Further, an aromatic ester amide compound and a polyorganosiloxane polyol (for example, see Patent Document 4), or an aromatic ester amide compound and a polyolefin polyol such as a terminal hydroxylated ethylene / butylene copolymer (for example, see Patent Document 5) And a method for producing the same by melt polycondensation with an elastomer. Although the elastomer obtained by these methods is expected to have excellent long-term heat resistance and hydrolysis resistance, the compatibility between the aromatic ester amide compound and the polyol is poor, so that a homogeneous copolymer must be produced. Is difficult. As described above, it is desired to develop a thermoplastic elastomer that satisfies heat resistance, hydrolysis resistance, and mechanical properties in a wide hardness range including a low hardness region.
[0005]
[Patent Document 1]
JP-A-2-276817 [Patent Document 2]
JP-A-6-207006 [Patent Document 3]
JP-A-6-207007 [Patent Document 4]
JP-A-8-134210 [Patent Document 5]
JP-A-8-253569
[Problems to be solved by the invention]
An object of the present invention is to provide a thermoplastic elastomer having excellent heat resistance, hydrolysis resistance, and mechanical properties in a wide range of hardness.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to achieve the above object, and have found that heat resistance, hydrolysis resistance, and mechanical properties using an aromatic oligoamide ester unit for the hard segment and a poly (vinyl ether) unit for the soft segment are improved. The present inventors have found an excellent homogeneous aromatic ester amide block copolymer, and have completed the present invention.
[0008]
That is, the present invention provides an aromatic oligoamide ester unit represented by the following general formula (1):
[0009]
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(In the formula, R ¹ and R ² each independently represent a divalent aromatic group having 6 to 20 carbon atoms.)
The present invention relates to an aromatic ester amide block copolymer comprising a poly (vinyl ether) unit and having a number average molecular weight in terms of polystyrene of 10,000 to 500,000 as measured by gel permeation chromatography (GPC). This will be described in detail.
[0010]
The aromatic ester amide block copolymer of the present invention has an aromatic oligoamide ester unit represented by the general formula (1) as a hard segment. R ¹ and R ² in the formula (1) are each independently a divalent aromatic group having 6 to 20 carbon atoms in order to impart heat resistance to the aromatic ester amide block copolymer. Specific examples thereof include the following.
[0011]
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Above all,
[0012]
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Is preferred. This is because an aromatic ester amide block copolymer having an excellent balance between heat resistance and moldability can be produced.
[0013]
On the other hand, the soft segment is composed of poly (vinyl ether) units, and its structure is not particularly limited as long as it has a repeating unit of vinyl ether. For example, poly (methyl vinyl ether), poly (ethyl vinyl ether), poly (propyl vinyl ether) Poly (alkyl vinyl ether) such as poly (butyl vinyl ether), poly (isobutyl vinyl ether), and poly (t-butyl vinyl ether); and poly (alkyl vinyl ether) having a saturated ester group, an unsaturated ester group, an oxyethylene chain, an imide group, a siloxy group, and the like. (Vinyl ether) and the like. Among them, it is preferable to use poly (alkyl vinyl ether) in order to impart good low-temperature properties to the aromatic ester amide block copolymer. The molecular weight of the poly (vinyl ether) unit is not particularly limited, but preferably has a number average molecular weight of 500 to 10,000. If the number average molecular weight is less than 500, the resulting aromatic ester amide block copolymer will have a high melting point, resulting in poor moldability. If the number average molecular weight exceeds 10,000, phase separation of the polymer will occur during polymerization, and the reaction rate will increase. This not only makes it difficult to obtain a high molecular weight block copolymer, but also causes a decrease in low-temperature characteristics.
[0014]
The content of the copolymer component of the poly (vinyl ether) unit in the aromatic ester amide block copolymer is not particularly limited, but the content is preferably from 10 to 90% by weight, more preferably from 15 to 85% by weight. If it is less than 10% by weight, the flexibility and rubber elasticity are insufficient, and if it exceeds 90% by weight, the crystallinity becomes low, and the moldability may be deteriorated.
[0015]
Regarding the molecular weight of the aromatic ester amide block copolymer of the present invention, the number average molecular weight measured by gel permeation chromatography (GPC) is 10,000 to 500,000 in terms of polystyrene, and preferably 30,000 to 200,000. In this molecular weight region, it exhibits excellent mechanical properties, good melt fluidity, and excellent moldability.
[0016]
The method for producing the aromatic ester amide block copolymer of the present invention is not particularly limited, and the aromatic ester amide block copolymer can be produced by a general synthesis method of a conventional block copolymer-type thermoplastic elastomer. For example, a method for producing a poly (vinyl ether) glycol, which is a precursor of the aromatic oligoamide ester unit, with poly (vinyl ether) glycol and, if necessary, a dicarboxylic acid diester by a melt reaction, and a poly ( (Vinyl ether) glycol, the terminal of which is substituted with an aromatic aminocarboxylic acid compound and then reacted with an aromatic dicarboxylic acid dichloride in an organic solvent, or an aromatic oligoamide alkyl ester and a poly (vinyl ether) glycol Is reacted in a specific solvent to obtain a prepolymer, then the solvent is distilled off, and the mixture is produced by a melt reaction. Furthermore, an aromatic oligoamide compound having an active acyl lactam group at a terminal and poly (vinyl ether) glycol Melt or in solvent The method or the like for reaction. By these methods, it is possible to obtain the aromatic ester amide block copolymer of the present invention which is excellent in balance among heat resistance, hydrolysis resistance and mechanical properties.
[0017]
In order to improve the heat resistance, particularly the thermochromic property of the aromatic ester amide block copolymer of the present invention, a stabilizer may be added during or after the production. Examples of the stabilizer include phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, phosphorus compounds such as dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, hinder Sulfur-containing compounds such as dophenol compounds, thioether compounds, dithioate compounds, mercaptobenzimidazole compounds, thiocarbanilide compounds, and thiodipropionate esters; and tin compounds such as tinmalate and dibutyltin monoxide. The amount of these additives is not particularly limited, but is usually 0.01 to 2 parts by weight based on 100 parts by weight of the copolymer.
[0018]
Further, the aromatic ester amide block copolymer of the present invention may further include a lubricant such as calcium, barium, aluminum, etc., stearic acid salts, stearic acid ester, silicone oil, waxes, ethylenebisstearylamide, etc. Can be added. The amount of these additives is not particularly limited, but is usually 0.05 to 5 parts by weight based on 100 parts by weight of the copolymer.
[0019]
Further, the aromatic ester amide block copolymer of the present invention may contain dyes, organic or inorganic pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, epoxy compounds, isocyanate compounds and the like. Additives can be added.
[0020]
The aromatic ester amide block copolymer of the present invention can be molded and processed by ordinary thermoplastic resin molding methods such as injection molding, extrusion molding, transfer molding, inflation molding, blow molding, heat molding, compression molding, and vacuum molding. It can be applied to a wide range of applications such as various molded products, fibers, films, sheets, plastic modifiers, paints, adhesives, and the like.
[0021]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[0022]
The analytical instrument and method used for analyzing the dihydroxy aromatic amide compound of the present invention are as follows.
[0023]
(1) Molecular weight measurement N-methyl with a flow rate of 1.0 ml / min and lithium chloride added to the eluent at 20 mmol / l using CP-8000 manufactured by Tosoh Corporation and a column connected to polystyrene gel 2000H8 and GMHXL. The measurement was performed at a column temperature of 40 ° C. using -2-pyrrolidone. The average molecular weight was calculated in terms of polystyrene.
[0024]
(2) ¹ H-NMR spectrum Measured in deuterated dimethyl sulfoxide at room temperature under the conditions of a cumulative number of 64 times using JNM-GSX270 manufactured by JEOL.
[0025]
(3) Dynamic viscoelasticity The temperature dependence of dynamic viscoelasticity was measured using a DVE-V4 FT-Rheospectral at a frequency of 10 Hz and a range of -100 to 300 ° C.
[0026]
(4) Thermal decomposition temperature (Td)
The measurement was performed at a heating rate of 20 ° C./min using TG-DTA200 manufactured by Seiko Instruments Inc.
[0027]
(5) Glass transition temperature (Tg) and melting point (Tm)
Using DSC200 manufactured by Seiko Denshi Kogyo, the temperature was measured at a rate of temperature increase of 10 ° C / min and in a range of -100 to 300 ° C.
[0028]
(6) Hardness Using a micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd., a hardness was measured using a press sheet having a thickness of 1 mm.
[0029]
(7) Mechanical properties (rupture strength, elongation at break)
The measurement was performed using a 1 mm-thick JIS K62516 dumbbell-shaped test piece with an autograph DCS-100 manufactured by Shimadzu Corporation at a tensile speed of 100 mm / min.
[0030]
(8) Hydrolysis resistance test A press sheet having a thickness of 1 mm was immersed in hot water at 100 ° C for 7 days, and then the molecular weight of the sample was measured. The molecular weight retention was calculated from the ratio to the molecular weight before immersion and evaluated.
[0031]
Reference Example 1
Ethyl 4-aminobenzoate (82.6 g, 0.5 mol) and N-methyl-2-pyrrolidone (NMP) 250 ml were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring blade. Stirring yielded a homogeneous solution. Separately, 170 ml of NMP and 50.7 g (0.25 mol) of terephthalic acid dichloride were added to a 200 ml dropping funnel equipped with a nitrogen inlet tube, and stirred to form a uniform solution. The solution was added to the above solution over 1 hour. It was dropped. After the reaction was further performed for 1 hour, the solid content was collected by suction filtration, and washed with 250 ml of NMP and then with 1000 ml of acetone. The obtained solid was dried under reduced pressure at 80 ° C. for 12 hours to obtain 112.8 g (yield: 98.0%) of an aromatic oligoamide ethyl ester. This compound is referred to as compound (a). The structural formula of the compound (a) is shown below.
[0032]
Embedded image

Example 1
Compound (a) 10.0 g (0.0217 mol), poly (ethyl vinyl ether) glycol [Kyowa Yuka, Ltd.] was placed in a 300 ml four-necked flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube. 32.2 g (0.0217 mol), and 1,3,5-trimethyl-2,4,6-tris as a hindered phenol-based antioxidant (manufactured by: TOE-2000H, number average molecular weight (Mn) = 1480). 0.04 g of (3,5-di-t-butyl-4-hydroxybenzyl) benzene [manufactured by Ciba-Geigy: Irganox 1330] was charged. After drying under reduced pressure at 100 ° C. for 1 hour, 20.8 g of NMP and 0.09 g of tetrabutoxytitanium were added. Under a nitrogen stream, the temperature was raised to 210 ° C. over 0.5 hours and reacted for 1 hour. Thereafter, the temperature was raised to 240 ° C. while NMP was distilled off under reduced pressure, and melt polymerization was performed for 1 hour under reduced pressure of 1 mmHg. 39.4 g (yield: 98%) of a product having good rubber elasticity was obtained. The product had a number average molecular weight of 49900, a weight average molecular weight of 84700, a Tm of 230 ° C, a Tg of -24 ° C, and a thermal decomposition temperature of 382 ° C. The mechanical properties were as follows: hardness: 95 (JIS-A), breaking strength: 7.7 MPa, breaking elongation: 110%. FIG. 1 shows the ¹ H-NMR spectrum of the product, and FIG. 2 shows the temperature dependence of dynamic viscoelasticity.
[0033]
The weight average molecular weight after the hydrolysis resistance test was 72100, and the molecular weight retention was 85%, indicating good water resistance.
[0034]
【The invention's effect】
The aromatic ester amide block copolymer of the present invention has heat resistance, hydrolysis resistance, and mechanical properties in a wide range of hardness because the hard segment is composed of an aromatic oligoamide ester unit and the soft segment is composed of a poly (vinyl ether) unit. It is a thermoplastic elastomer with excellent balance.
[Brief description of the drawings]
FIG. 1 is a view showing a ¹ H-NMR spectrum measurement result of an aromatic ester amide block copolymer obtained in Example 1.
FIG. 2 is a graph showing the temperature dependence of dynamic viscoelasticity of the aromatic ester amide block copolymer obtained in Example 1.

Claims (2)

An aromatic oligoamide ester unit represented by the following general formula (1):

(In the formula, R ¹ and R ² each independently represent a divalent aromatic group having 6 to 20 carbon atoms.)
An aromatic ester amide block copolymer comprising poly (vinyl ether) units and having a polystyrene equivalent number average molecular weight of 10,000 to 500,000 as measured by gel permeation chromatography (GPC). The aromatic ester amide block copolymer according to claim 1, wherein the content of the copolymer component of the poly (vinyl ether) unit is 10 to 90% by weight.

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