JP3684499B2

JP3684499B2 - Method for producing polymer composite and molecular composite

Info

Publication number: JP3684499B2
Application number: JP18177099A
Authority: JP
Inventors: 薫島村; 内田　　哲也
Original assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Current assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Priority date: 1999-06-28
Filing date: 1999-06-28
Publication date: 2005-08-17
Anticipated expiration: 2019-06-28
Also published as: JP2001011189A

Description

【０００１】
【発明の属する技術分野】
本発明は、剛直高分子の力学的特性および前記ポリマーの三次元網目状化によるポリマー軸方向のヤング率特性を維持し、屈曲性高分子により成形性を改善した、三次元網目状剛直高分子および前記高分子にグラフト重合した屈曲性高分子よりなる高分子複合体および該高分子複合体の製造方法に関する。なお、剛直性高分子とは、折り畳み結晶を作れない高分子であり、屈曲性高分子とは公知の屈曲性の特性を持つ高分子を指す。
【０００２】
【従来技術】
ポリパラフェニレンベンゾビスチアゾール（ＰＢＺＴ）、ポリパラフェニレンベンゾビスオキサゾール（ＰＢＯ）又はポリパラフェニレンピロメリットイミド（ＰＰＰＩ）などの剛直高分子ポリマーは分子主鎖方向に４００ＧＰａ以上の結晶ヤング率を示し、工業的にも大きく注目されている。しかしこのようなポリマーは分子主鎖に垂直な方向に弱いことが知られている。Ｄｏｗｅｌｌは、これらの剛直さに側鎖として同じくポリパラフェニレンテレフタルアミド（ＰＰＴＡ）、ＰＢＴ、ＰＢＯなどのセグメントを導入したポリマーを考え、ヤング率が約２倍に向上することを理論的に予測し、“ｓｕｐｅｒ−ｓｔｒｏｎｇｌｉｑｕｉｄ−ｃｒｙｓｔａｌｌｉｎｅｐｏｌｙｍｅｒ”と称した〔Ｆ．Ｄｏｗｅｌｌ，Ｍａｔ．Ｒｅｓ．Ｓｏｃ．Ｓｙｍｐ．Ｐｒｏｃ．，１３４，３３（１９８９）〕。すなわち剛直高分子ポリマーを３次元的にすることによって、更に強度を高めようという試みを考えている。また、特開平７−１３３３５３号公報には前記剛直高分子ポリマーの側鎖にアセチレンを用いて隣接する分子主鎖同士を共有結合で結び、更にそれに垂直な方向にも共有結合を導入した３次元網目鎖構造を持つポリマーを設計し、高分子主鎖方向のヤング率および弾性率を向上したポリマーを得ることの可能性を開示している。
【０００３】
屈曲性高分子、例えば脂肪族ポリアミド樹脂はフイルム、繊維、エンジニアリングプラスチックなど広く使用されている。これら成形物はガラス転移点が低いこと、耐熱性の不足などのために使用にあたっては、これら屈曲性高分子マトリックスに強化要素を加え複合化が行われている。しかし強化要素とマトリックス間の剥離が生じ、耐熱性、力学特性の劣化が生じ易い、そこでナイロン樹脂にポリ−ｐ−フェニレンベンゾビスチアゾールやポリ−ｐ−フェニレンテレフタルアミドのような剛直高分子を強化要素として加え、分子レベルで分散させ複合化するモレキュラーコンポジットの開発が試みられているが、成形時に相分離が生じるなど問題がある〔Polymer,28,2131(1987)参照〕。ところで、本発明者等は、前記剛直高分子ポリマーを、例えば２，５−ジアミノ−１，４−ベンゼン−ジチオール（ＤＡ）と前記ＤＡに対してテレフタル酸（ＴＰＡ）およびトリメシン酸（ＴＭＡ）の和が６７〜１００モル％であり，かつＴＰＡとＴＭＡの和にたいするＴＭＡの配合量が１３〜１００モル％の範囲でＴＰＡとＴＭＡを共縮合して網目構造物を合成した。そのものの見掛け密度は１．０ｇ／ｃｍ^３であり、多官能成分を共重合しなかったものの１．５７ｇ／ｃｍ^３に比べて小さく、内部に微細な空隙を多く含むことをすでに報告している。また、得られたポリマーは室温から４００℃まで吸熱および発熱ピークを示さなかった。すなわち、この温度範囲において融点を持たず、成形が難しいことが分かった。
【０００４】
【発明が解決しようとする課題】
従って、本発明の課題は、剛直高分子に網目状構造を導入することによりヤング率および弾性率の向上することの効果を維持しつつ、成形性のよいポリマーを得る方法および前記方法により得られるポリマーを提供することである。
【０００５】
【課題を解決するための手段】
本発明の第１は、２官能基重合成分と３官能基以上の重合成分の共重合反応において、３官能基以上の重合成分が２官能基重合成分と３官能基以上の重合成分の和に対して１３モル％〜１００モル％の範囲で共重合する過程において、ゲル化点以前で重合を停止し、屈曲性高分子を形成する単量体あるいはそのオリゴマーと反応する官能性基を有し、前記共重合モル％に対応する空隙を有する三次元網目状に発達した剛直性高分子を、屈曲性高分子を形成する単量体あるいはそのオリゴマーに溶解、膨潤あるいは分散させて重合させ、少なくとも屈曲性高分子の一部を剛直性高分子にグラフト重合させる剛直性高分子と屈曲性高分子からなる高分子複合体の製造方法であり、前記２官能性基重合成分は化学式（１）の群から選択される少なくとも１種を基本構造とした化学構造を有するか、あるいは化学式（２）の群から選択される少なくとも１種を基本とした化学構造を有するか、あるいはそれらの組み合わせからなる化学構造の単量体あるいはオリゴマーであり、３官能基以上の重合成分は化学式（３）の群から選択される少なくとも１種を基本とした化学構造を有するかあるいはそれらの組み合わせからなる化学構造の単量体あるいはオリゴマーであることを特徴とする剛直性高分子と屈曲性高分子からなる高分子複合体の製造方法である。
【０００６】
【化４】

【０００７】
（Ａｒ'）単位は、化学式（２）の群から選択される少なくとも１種であり、
【０００８】
【化５】

【０００９】
そして（Ｃ）単位は、化学式（３）の群から選択される少なくとも１種である。
【００１０】
【化６】

【００１１】
そして、本発明の第２は、２官能基重合成分と３官能基以上の重縮合成分の共重合反応において、３官能基以上の重合成分が２官能基重合成分と３官能基以上の重合成分の和に対して１３モル％〜１００モル％の範囲で共重合中ゲル化点以前で重合を停止し、屈曲性高分子を形成する単量体あるいはそのオリゴマーと反応する官能性基を有し、前記共重合モル％に対応する空隙を有する三次元網目状に発達した剛直性高分子を、屈曲性高分子を形成する単量体にあるいはそのオリゴマー溶解、膨潤あるいは分散させ、前記単量体を重合させ、少なくとも屈曲性高分子の一部を剛直性高分子にグラフト重合させた剛直性高分子と屈曲性高分子からなる高分子複合体であり、前記２官能性基重合成分は前記化学式（１）の群から選択される少なくとも１種を基本構造とした化学構造を有するか、あるいは前記化学式（２）の群から選択される少なくとも１種を基本とした化学構造を有するか、あるいはそれらの組み合わせからなる化学構造の単量体あるいはオリゴマーであり、３官能基以上の重合成分は前記化学式（３）の群から選択される少なくとも１種を基本とした化学構造を有するかあるいはそれらの組み合わせからなる化学構造の単量体あるいはオリゴマーであることを特徴とする剛直性高分子と屈曲性高分子からなる高分子複合体であり、
更に好ましくは、三次元網目状剛直性高分子は２，５−ジアミノ−１，４−ベンゼン−ジチオール（ＤＡ）に前記ＤＡに対してテレフタル酸（ＴＰＡ）およびトリメシン酸（ＴＭＡ）の和が６７〜１００モル％であり，かつＴＰＡとＴＭＡの和にたいするＴＭＡの配合量が１３〜１００モル％の範囲でＴＰＡとＴＭＡを共縮合して得られたものであり、屈曲性高分子を形成する単量体はラクタムであることを特徴とする前記剛直高分子と屈曲性高分子からなる高分子複合体である。本発明者はゲル化点以前で重合を停止して得られた三次元網目状に発達した３官能基以上の共重合成分からの屈曲性高分子を生成する単量体と反応する官能性基を有した剛直性高分子を屈曲性高分子を生成する単量体に溶解、膨潤あるいは分散させ、これを重合させ、少なくとも屈曲性高分子の一部を剛直性高分子にグラフト重合させることにより、前記課題を解決したのである。
【００１２】
【本発明の実施の態様】
本発明の高分子複合体の製造方法を、パラフェニレンベンゾビスチアゾール（ＢＺＴ）構造のみを持つ場合と、該構造を持たずベンゾビスチアゾールが三官能基を持つトリメチン酸とのみ結合した場合、およびその中間の組成からなる場合を例にして説明する。各成分の仕込量を表１に示した。重合溶媒としてポリリン酸（PPA）を用い、まず２，５−ジアミノ−１，４−ベンゼン−ジチオールジハイドロクロライド（ＤＡＢＤＴ）を加え、脱塩化水素を行った。ＤＡＢＤＴに対して１３〜６７モル％のトリメシン酸（ＴＭＡ）および８０〜０％のテレフタル酸（ＴＰＡ）を加え、１００〜１４０度まで段階的に昇温した〔Ｊ．Ｆ．Ｗｏｌｆｅｅｔａｌ．，Macromolecules,14,915(1981)、参照〕。トルクメーターで溶液粘度を測定しながら重合を行い、ゲル化による急激な粘度の上昇が始まる前に重合を停止した。得られた試料は粉末状で、粒径は数十〜数百ナノメーターであった。反応によって生じる結合を以下の式（２）に示す。式（２）において、ＤＡＢＤＴ１００モルに対しＴＰＡは０〜８０モル％、ＴＭＡは６７〜１３モル％の配合比とすることができる、すなわち８０〜０％とすることができる。
【００１３】
【化７】

【００１４】
【表１】

【００１５】
〔ゲル化点：重合官能基を複数持つ多官能性モノマーの反応で、その中に３官能性以上の分子が含まれていると、３次元網目構造を持った高分子が生成する。ゲル化点とは、この３次元化し得る反応系内に、重合途中に不溶部分（ゲル部分）が成長増加し始める点であり、反応系の粘度が急上昇する点として認められる。（岩波「理化学辞典」第５版ケ１７２（第４２３ページ）参照〕。
【００１６】
ゲル点以前で重合停止した三次元網目状に発達した剛直性高分子の化学構造の一例を以下に示す。ここでｎは０〜８の範囲である。
【００１７】
【化８】

【００１８】
前記ゲル化前で重合停止したＰＢＺＴの構造をモデル的に図解したものを図１（ａ）に示す（ここで◎はカルボキシル基である。）。これを重合性のモノマーである、例えばカプロラクタム○に溶解、膨潤、または分散した状態を（ｂ）に示す。これを重合処理したものを（ｃ）に示す（複合体１）。この過程で屈曲性高分子の一部は三次元網目状の剛直高分子にグラフト重合する。前記複合体１から剛直高分子にグラフトしていない６−ナイロンをギ酸を用いて抽出処理して６−ナイロンがＰＢＺＴにグラフトした構造のポリマー複合体（複合体２）を得る（Ｄ）。以上が本発明の、三次元網目構造を持つ剛直高分子に屈曲性高分子を生成する単量体をグラフト化した構造の複合高分子の構造及び該複合高分子の製造方法である。
【００１９】
剛直高分子を溶解、膨潤あるいは分散するモノマーとしては、ε−カプロラクタムの他に、γ−ブチロラクタム、δ−バレロラクタム、ζ−エナントラクタム、η−カプリロラクタム、ω−ラウリルラクタムなどのラクタム類、ヘキサメチレンジアミンのアジピン酸塩、ヘキサメチレンジアミン酸のセバシン酸塩等のナイロン塩等を好ましい材料として挙げることができる。
【００２０】
【実施例】
実施例１１．剛直高分子ポリパラフェニレンベンゾビスチアゾール（ＰＢＺＴ）の製造の際、三官能性のトリメシン酸をＤＡに対して３３モル％加えて重合を行った。テレフタル酸のＤＡに対する配合量は５０モル％である。ゲル化点以前に重合を停止することにより三次元網目構造を持つ剛直高分子を得た。走査型電子顕微鏡観察によるとその粒径は数十〜数百ｎｍであった。ＩＲ測定の結果、多量のＣＯＯＨを有することが確認された。２．得られた多官能性剛直高分子を１×１０^−３ｍｍＨｇに減圧し１２時間保持した後、１１０℃で融解したε−カプロラクタムを前記減圧を保持したまま滴下した。２時間程度その状態で保持した後、系内を常圧に戻した。続いてこれを２５０℃で４時間加熱することによりε−カプロラクタムを重合させた。得られた試料はＰＢＺＴからなる剛直高分子鎖が６−ナイロンからなる屈曲性高分子中に分子分散され、かつ屈曲性高分子の一部は剛直性高分子にグラフトした共重合体である。得られた試料をギ酸により洗浄し、取り除くことのできる６−ナイロンを全て取り除いた後においても剛直高分子とほぼ同量の６−ナイロンが残存した。このことから剛直高分子とナイロンとはグラフト共重合体を形成していることが分かる。
【００２１】
Ａ．前記で合成した高分子複合体の熱的性質図２は、複合体のＤＳＣ測定結果である。グラフトされたナイロン６はその運動が制限されているため、ＤＳＣ測定において融点を示さない（複合体２）。抽出処理前の複合体１では、剛直性高分子中の抽出できるナイロン６により融点が現れる（図２の複合体１）。融点温度、およびΔＨ（エンタルピー変化）はナイロン６の含有量により変化する（図３、図４）。前記で合成した高分子複合体の成形性を確認した。剛直高分子網目状微粉末と屈曲性高分子モノマー混合物の成形時の粘度はモノマー自体の粘度の１．２〜２．０倍と低い値を示した。Ｂ．成型物の力学的特性などを調べた。ゲル化前に重合を停止した剛直性高分子三次元網目状体に屈曲性モノマーをグラフト化した高分子複合体（複合体）からのロッドとナイロン６ホモポリマーからのロッドとの応力−ひずみ曲線から得られた物性値を表２に示す。弾性率、破断応力の大きな向上が見られる。
【００２２】
【表２】

【００２３】
Ｃ．図５に示す粘弾性測定の結果から、ナイロン６のガラス転移温度以上では、ナイロン６の軟化に伴う貯蔵弾性率の低下が生じるが、その減少率は本発明の複合体においては小さくなる。（図５に両矢印で示した。）
【００２４】
【発明の効果】
以上述べたように、本発明により、剛直高分子網目化構造によるヤング率および弾性率の向上の効果を維持しつつ、成形性のよいポリマーを得ることができるという優れた効果がもたらされる。
【図面の簡単な説明】
【図１】三次元網目構造を持つ多官能性剛直高分子に屈曲性高分子を生成する単量体をグラフト化した複合体の構造及び製造方法
【図２】ギ酸抽出前の複合体１及び抽出後の複合体２のＤＳＣ測定結果
【図３】ナイロン６の含有量とＤＳＣ曲線の関係
【図４】ナイロン６の含有量と融解温度（Ｔｍ）、ΔＨとの関係
【図５】ナイロン６ホモポリマーと本発明の複合体の粘弾性測定結果[0001]
BACKGROUND OF THE INVENTION
The present invention maintains a mechanical property of a rigid polymer and a Young's modulus property in the axial direction of the polymer due to the three-dimensional networking of the polymer, and a three-dimensional networked rigid polymer having improved formability by a flexible polymer. The present invention also relates to a polymer composite comprising a flexible polymer graft-polymerized to the polymer and a method for producing the polymer composite. The rigid polymer is a polymer that cannot form a fold crystal, and the flexible polymer refers to a polymer having a known flexibility property.
[0002]
[Prior art]
Rigid polymer such as polyparaphenylenebenzobisthiazole (PBZT), polyparaphenylenebenzobisoxazole (PBO) or polyparaphenylenepyromellitimide (PPPI) shows a crystal Young's modulus of 400 GPa or more in the molecular main chain direction, It is also attracting much attention industrially. However, such polymers are known to be weak in the direction perpendicular to the molecular backbone. Dowell thinks about the polymer which introduces segments such as polyparaphenylene terephthalamide (PPTA), PBT, and PBO as side chains in the rigidity, and theoretically predicts that Young's modulus will be improved by about 2 times. , "Super-strong liquid-crystalline polymer" [F. Dowell, Mat. Res. Soc. Symp. Proc. , 134, 33 (1989)]. In other words, an attempt is being made to further increase the strength by making the rigid polymer polymer three-dimensional. Japanese Patent Laid-Open No. 7-133353 discloses a three-dimensional structure in which acetylene is used for the side chain of the rigid polymer polymer to connect adjacent molecular main chains with a covalent bond and a covalent bond is also introduced in a direction perpendicular thereto. It discloses the possibility of designing a polymer having a network chain structure and obtaining a polymer having an improved Young's modulus and elastic modulus in the polymer main chain direction.
[0003]
Flexible polymers such as aliphatic polyamide resins are widely used for films, fibers, engineering plastics and the like. These molded products have a low glass transition point, lack of heat resistance, etc., and are used for compounding by adding reinforcing elements to these flexible polymer matrices. However, peeling between the reinforcing element and the matrix occurs, and heat resistance and mechanical properties are likely to deteriorate. Therefore, nylon polymers are reinforced with rigid polymers such as poly-p-phenylenebenzobisthiazole and poly-p-phenylene terephthalamide. Although attempts have been made to develop molecular composites that are dispersed and compounded at the molecular level in addition to elements, there are problems such as phase separation during molding (see Polymer, 28, 2131 (1987)). By the way, the present inventors have used the above-mentioned rigid polymer as terephthalic acid (TPA) and trimesic acid (TMA) for 2,5-diamino-1,4-benzene-dithiol (DA) and DA. A network structure was synthesized by co-condensing TPA and TMA when the sum was 67 to 100 mol% and the blending amount of TMA with respect to the sum of TPA and TMA was 13 to 100 mol%. Apparent density of itself is 1.0 g / cm ^3, but not by copolymerizing a polyfunctional component smaller than the 1.57 g / cm ^3, has already reported that contains many fine voids therein . Further, the obtained polymer showed no endothermic or exothermic peak from room temperature to 400 ° C. That is, it has been found that the molding does not have a melting point in this temperature range and is difficult to mold.
[0004]
[Problems to be solved by the invention]
Therefore, the object of the present invention is obtained by a method for obtaining a polymer having good moldability while maintaining the effect of improving Young's modulus and elastic modulus by introducing a network structure into a rigid polymer, and the above method. It is to provide a polymer.
[0005]
[Means for Solving the Problems]
In the first aspect of the present invention, in the copolymerization reaction of a bifunctional polymerization component and a polymerization component having three or more functional groups, the polymerization component having three or more functional groups is the sum of the polymerization component having two or more functional groups and the polymerization component having three or more functional groups. On the other hand, in the process of copolymerization in the range of 13 mol% to 100 mol%, the polymerization is stopped before the gel point, and it has a functional group that reacts with a monomer that forms a flexible polymer or an oligomer thereof. , A rigid polymer developed in a three-dimensional network having voids corresponding to the copolymerization mol% is polymerized by dissolving, swelling or dispersing in a monomer or oligomer thereof forming a flexible polymer, A method for producing a polymer composite comprising a rigid polymer and a flexible polymer, wherein a part of the flexible polymer is graft-polymerized to the rigid polymer, wherein the bifunctional group polymerization component is represented by the chemical formula (1) At least selected from the group A monomer having a chemical structure based on at least one kind, a chemical structure based on at least one selected from the group of the chemical formula (2), or a combination thereof. Alternatively, an oligomer, and a polymerization component having three or more functional groups is a monomer or oligomer having a chemical structure based on at least one selected from the group of chemical formula (3) or a combination thereof. It is a method for producing a polymer composite comprising a rigid polymer and a flexible polymer.
[0006]
[Formula 4]

[0007]
The (Ar ′) unit is at least one selected from the group of the chemical formula (2),
[0008]
[Chemical formula 5]

[0009]
The unit (C) is at least one selected from the group of the chemical formula (3).
[0010]
[Chemical 6]

[0011]
The second aspect of the present invention is that in the copolymerization reaction of a bifunctional polymerization component and a polycondensation component of 3 or more functional groups, a polymerization component of 3 or more functional groups is a polymerization component of 2 or more functional groups and a polymerization component of 3 or more functional groups. In the range of 13 mol% to 100 mol% with respect to the sum of the above, the polymerization is terminated before the gel point during the copolymerization, and has a functional group that reacts with the monomer or the oligomer forming the flexible polymer. A rigid polymer developed in a three-dimensional network having voids corresponding to the copolymerization mol% is dissolved in, or swelled or dispersed in, a monomer that forms a flexible polymer, or an oligomer thereof. Is a polymer composite composed of a rigid polymer and a flexible polymer obtained by graft-polymerizing at least a part of the flexible polymer to the rigid polymer, and the bifunctional group polymerization component has the chemical formula Less selected from group (1) Both either have a chemical structure of one basic structure, or either have a basic chemical structure at least one member selected from the group of the formula (2), Oh Rui chemical structure consisting of: Monomer of chemical structure which is a monomer or oligomer and has a chemical structure based on at least one selected from the group of chemical formula (3) or a combination thereof, wherein the polymerization component having three or more functional groups A polymer composite composed of a rigid polymer and a flexible polymer, characterized by being a body or an oligomer,
More preferably, in the three-dimensional network-like rigid polymer, the sum of terephthalic acid (TPA) and trimesic acid (TMA) to 67 is 2,5-diamino-1,4-benzene-dithiol (DA). It is obtained by co-condensation of TPA and TMA within a range of 13 to 100 mol% of TMA and the amount of TMA with respect to the sum of TPA and TMA. The polymer is a polymer composite comprising the rigid polymer and the flexible polymer, wherein the polymer is a lactam. The present inventor has a functional group that reacts with a monomer that forms a flexible polymer from a copolymerization component having three or more functional groups developed in a three-dimensional network obtained by stopping the polymerization before the gel point. By dissolving, swelling or dispersing a rigid polymer having a polymer in a monomer that forms a flexible polymer, polymerizing this, and graft-polymerizing at least a part of the flexible polymer to the rigid polymer The problem has been solved.
[0012]
[Embodiments of the present invention]
If the method for producing the polymer conjugates of the present invention, the case having only p-phenylene benzobisthiazole (B ZT) structure, benzobisthiazole without the structure is bonded only to the trimethine acid having a trifunctional group, A case where the composition is an intermediate composition will be described as an example. The amount of each component charged is shown in Table 1. Using polyphosphoric acid (PPA) as a polymerization solvent, first, 2,5-diamino-1,4-benzene-dithiol dihydrochloride (DABDT) was added to perform dehydrochlorination. 13-67 mol% of trimesic acid (TMA) and 80-0% of terephthalic acid (TPA) were added with respect to DABDT, and it heated up in steps to 100-140 degree | times [J. F. Wolfe et al. , Macromolecules, 14, 915 (1981), see]. Polymerization was carried out while measuring the solution viscosity with a torque meter, and the polymerization was stopped before a sudden increase in viscosity due to gelation began. The obtained sample was powdery and the particle size was several tens to several hundreds of nanometers. The bond produced by the reaction is shown in the following formula (2). In the formula (2), the TPA can be 0 to 80 mol% and the TMA can be 67 to 13 mol% with respect to 100 mol of DABDT, that is, 80 to 0%.
[0013]
[Chemical 7]

[0014]
[Table 1]

[0015]
[Geling point: When a polyfunctional monomer having a plurality of polymerized functional groups reacts with a molecule having three or more functional groups, a polymer having a three-dimensional network structure is formed. The gel point is a point where an insoluble part (gel part) starts to grow and increase during polymerization in the reaction system that can be three-dimensionalized, and is recognized as a point where the viscosity of the reaction system rapidly increases. (See Iwanami “Science and Chemistry Dictionary”, 5th edition 172 (page 423)).
[0016]
An example of the chemical structure of a rigid polymer developed in a three-dimensional network with polymerization terminated before the gel point is shown below. Here, n is in the range of 0-8.
[0017]
[Chemical 8]

[0018]
A model illustration of the structure of PBZT that has been polymerized before the gelation is shown in FIG. 1A (where ◎ is a carboxyl group). A state in which this is dissolved, swollen or dispersed in a polymerizable monomer such as caprolactam ○ is shown in (b). A polymerized product is shown in (c) (Composite 1). In this process, a part of the flexible polymer is graft-polymerized to a three-dimensional network-like rigid polymer. 6-Nylon that is not grafted to the rigid polymer is extracted from the composite 1 with formic acid to obtain a polymer composite (composite 2) having a structure in which 6-nylon is grafted to PBZT (D). The above is the structure of a composite polymer having a structure in which a monomer that generates a flexible polymer is grafted to a rigid polymer having a three-dimensional network structure and a method for producing the composite polymer.
[0019]
As monomers that dissolve, swell or disperse rigid polymers, in addition to ε-caprolactam, lactams such as γ-butyrolactam, δ-valerolactam, ζ-enantolactam, η-caprolactam, ω-lauryllactam, Preferable materials include nylon salts such as hexamethylenediamine adipate and hexamethylenediamine acid sebacate.
[0020]
【Example】
Example 11 In the production of the rigid polymer polyparaphenylene benzobisthiazole (PBZT), polymerization was carried out by adding 33 mol% of trifunctional trimesic acid to DA. The blending amount of terephthalic acid with respect to DA is 50 mol%. A rigid polymer with a three-dimensional network structure was obtained by stopping the polymerization before the gel point. According to the observation with a scanning electron microscope, the particle size was several tens to several hundreds nm. As a result of IR measurement, it was confirmed to have a large amount of COOH. 2. The obtained polyfunctional rigid polymer was depressurized to 1 × 10 ⁻³ mmHg and held for 12 hours, and then ε-caprolactam melted at 110 ° C. was added dropwise while maintaining the reduced pressure. After maintaining in that state for about 2 hours, the system was returned to normal pressure. Subsequently, ε-caprolactam was polymerized by heating it at 250 ° C. for 4 hours. In the obtained sample, a rigid polymer chain made of PBZT is molecularly dispersed in a flexible polymer made of 6-nylon, and a part of the flexible polymer is a copolymer grafted on the rigid polymer. The obtained sample was washed with formic acid to remove all the 6-nylon that can be removed, and the same amount of 6-nylon as the rigid polymer remained. This indicates that the rigid polymer and nylon form a graft copolymer.
[0021]
A. FIG. 2 shows DSC measurement results of the composite. Grafted nylon 6 does not show a melting point in the DSC measurement (complex 2) because of its limited movement. In the composite 1 before the extraction treatment, the melting point appears due to the extractable nylon 6 in the rigid polymer (complex 1 in FIG. 2). Melting | fusing point temperature and (DELTA) H (enthalpy change) change with content of nylon 6 (FIG. 3, FIG. 4). The moldability of the polymer composite synthesized above was confirmed. The viscosity during molding of the rigid polymer network fine powder and the flexible polymer monomer mixture was as low as 1.2 to 2.0 times the viscosity of the monomer itself. B. The mechanical properties of the moldings were investigated. Stress-strain curve between a rod from a polymer composite (composite) in which a flexible monomer is grafted to a rigid polymer three-dimensional network whose polymerization was stopped before gelation and a rod from a nylon 6 homopolymer The physical property values obtained from Table 2 are shown in Table 2. Great improvement in elastic modulus and breaking stress is observed.
[0022]
[Table 2]

[0023]
C. From the results of the viscoelasticity measurement shown in FIG. 5, when the temperature is higher than the glass transition temperature of nylon 6, the storage elastic modulus is lowered due to the softening of nylon 6, but the reduction rate is small in the composite of the present invention. (Indicated by double arrows in FIG. 5)
[0024]
【The invention's effect】
As described above, the present invention brings about an excellent effect that a polymer with good moldability can be obtained while maintaining the effect of improving the Young's modulus and elastic modulus by the rigid polymer network structure.
[Brief description of the drawings]
FIG. 1 shows the structure of a complex obtained by grafting a monomer that generates a flexible polymer to a polyfunctional rigid polymer having a three-dimensional network structure, and a manufacturing method thereof. FIG. Results of DSC measurement of composite 2 after extraction [FIG. 3] Relationship between nylon 6 content and DSC curve [FIG. 4] Relationship between nylon 6 content, melting temperature (Tm), ΔH [FIG. 5] Nylon 6 Measurement results of viscoelasticity of homopolymer and composite of the present invention

Claims

In the copolymerization reaction of a bifunctional polymerization component and a polymerization component having 3 or more functional groups, the polymerization component having 3 or more functional groups is from 13 mol% to 100 mol based on the sum of the bifunctional polymerization component and the polymerization component having 3 or more functional groups. In the process of copolymerization in the range of mol%, the polymerization is stopped before the gel point, and has a functional group that reacts with the monomer or oligomer forming the flexible polymer, and the copolymerization mol% A rigid polymer developed into a three-dimensional network having a corresponding void is polymerized by dissolving, swelling or dispersing in the monomer or oligomer thereof forming the flexible polymer, and at least a part of the flexible polymer is polymerized. Is a method for producing a polymer composite comprising a rigid polymer and a flexible polymer, wherein the bifunctional group polymerization component is at least one selected from the group of the chemical formula (1). Seeds are the basic structure Or a chemical structure monomer or oligomer having a chemical structure based on at least one selected from the group of the chemical formula (2), or a combination thereof. The polymerization component having a functional group or higher is a monomer or oligomer having a chemical structure based on at least one selected from the group of the chemical formula (3) or a combination thereof. A method for producing a polymer composite comprising a rigid polymer and a flexible polymer .

The (Ar ′) unit is at least one selected from the group of the chemical formula (2),

The unit (C) is at least one selected from the group of the chemical formula (3).

In the copolymerization reaction of the bifunctional polymerization component and the polycondensation component of 3 or more functional groups, the polymerization component of 3 or more functional groups is 13 mol% to the sum of the bifunctional polymerization component and the polymerization component of 3 or more functional groups. In the range of 100 mol%, the polymerization is terminated before the gel point during the copolymerization, and has a functional group that reacts with the monomer or oligomer that forms the flexible polymer, and corresponds to the copolymerization mol%. A rigid polymer developed in the form of a three-dimensional network having voids is dissolved, swelled or dispersed in a monomer that forms a flexible polymer, or an oligomer thereof, and the monomer is polymerized, so that at least the flexible polymer A polymer composite composed of a rigid polymer and a flexible polymer obtained by graft-polymerizing a part of the polymer to a rigid polymer, and the bifunctional group polymerization component is selected from the group of the chemical formula (1) At least one kind of basic structure A monomer or oligomer having a chemical structure or having a chemical structure based on at least one selected from the group of the above chemical formula (2), or a combination thereof; The polymerization component of the group or more is a monomer or oligomer having a chemical structure based on at least one selected from the group of the chemical formula (3) or a combination thereof. A polymer composite consisting of a rigid polymer and a flexible polymer.

The three-dimensional network-like rigid polymer is 2,5-diamino-1,4-benzene-dithiol (DA) and the sum of terephthalic acid (TPA) and trimesic acid (TMA) is 67 to 100 mol% with respect to the DA. A monomer that is obtained by co-condensation of TPA and TMA when the blending amount of TMA in the range of 13 mol% to 100 mol% is the sum of TPA and TMA, and forms a flexible polymer 3. A polymer composite comprising a rigid polymer and a flexible polymer according to claim 2, wherein is a lactam.