JP6813147B2 - Dynamic covalent compound and its recombination method - Google Patents
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- 238000005215 recombination Methods 0.000 title claims description 7
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Landscapes
- Hydrogenated Pyridines (AREA)
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Description
本発明は、動的共有結合化合物及びその組換え方法に関する。本発明によれば、熱により可逆的な性質を示す動的共有結合化合物を得ることができる。 The present invention relates to dynamic covalent compounds and methods of recombination thereof. According to the present invention, it is possible to obtain a dynamic covalent bond compound which exhibits reversible properties by heat.
近年、材料開発において、強度、耐久性等の物理的性質の制御に加えて、周辺の環境に応じて構造ならびに性質が変化する外部刺激応答性の機能を発現させることが精力的に行われている。 In recent years, in material development, in addition to controlling physical properties such as strength and durability, it has been energetically performed to express an external stimulus-responsive function whose structure and properties change according to the surrounding environment. There is.
従来から、モノマーを共有結合で連結することによりポリマーが合成されている。このようなポリマーは強度が強く、そして安定性に優れている。しかしながら、ポリマーの一次構造を変化させることは困難であり、重合後に前記の刺激応答性等の機能を発現させることは容易ではなかった。 Conventionally, polymers have been synthesized by covalently linking monomers. Such polymers have high strength and excellent stability. However, it is difficult to change the primary structure of the polymer, and it is not easy to express the above-mentioned functions such as stimulus responsiveness after polymerization.
最近、熱、光、又は触媒などの外部刺激により、可逆的に開裂する特殊な共有結合（動的共有結合）を骨格中に有する動的共有結合ポリマーが報告されてきている。このような動的共有結合ポリマーは、重合後であっても分子構造を再編成することが可能であり、安定性と加工性とを両立した機能性材料として注目を集めている（非特許文献１）。 Recently, dynamic covalent polymers having a special covalent bond (dynamic covalent bond) in the skeleton that is reversibly cleaved by an external stimulus such as heat, light, or a catalyst have been reported. Such a dynamic covalent bond polymer can reorganize its molecular structure even after polymerization, and is attracting attention as a functional material having both stability and processability (Non-Patent Documents). 1).
例えば、動的共有結合の一つであるジスルフィド結合は、光に応答する代表的な動的共有結合として知られている（非特許文献２）。具体的には、近紫外光から可視光領域の光により可逆的に開裂可能であるため、直接触れられない環境でも光線により遠隔操作が可能である。 For example, a disulfide bond, which is one of the dynamic covalent bonds, is known as a typical dynamic covalent bond that responds to light (Non-Patent Document 2). Specifically, since it can be reversibly cleaved by light in the visible light region from near-ultraviolet light, remote control is possible by light rays even in an environment where it cannot be directly touched.
一方、ジスルフィド結合は、２００℃程度の高い温度で開裂することが知られているが、その温度において空気中では非常に不安定である。そのため、ジスルフィド結合をポリマーに導入して、熱的刺激応答性ポリマーとして用いることができなかった。
従って、本発明の目的は、温度応答性の動的共有結合ポリマーを提供することである。
On the other hand, the disulfide bond is known to cleave at a high temperature of about 200 ° C., but it is very unstable in air at that temperature. Therefore, it was not possible to introduce a disulfide bond into the polymer and use it as a thermal stimulus responsive polymer.
Therefore, it is an object of the present invention to provide a temperature responsive dynamic covalently bonded polymer.
本発明者は、温度応答性の動的共有結合ポリマーについて、鋭意研究した結果、驚くべきことに、ジアミノポリスルフィド骨格を有する構造が、１００℃程度の比較的低温の熱によって、動的共有結合として振る舞うことを見出した。そして、前記ジアミノポリスルフィド骨格をポリマーに導入することにより、温度応答性の動的共有結合ポリマーを提供できることを見出した。
本発明は、こうした知見に基づくものである。
従って、本発明は、
［１］下記式（１）：
［２］前記Ｒ１及びＲ２が窒素原子と一緒になってシクロヘテロアルキル基又は含窒素複素芳香環基を形成しない場合、窒素原子に結合するＲ１及びＲ２の原子は炭素原子であり、前記炭素原子が、炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、シアノ基、ニトロ基、及びアミノ基からなる群から選択される１又は２の置換基によって置換されている、［１］に記載の動的共有結合化合物の組換え方法、
［３］前記ｎが０である、［１］又は［２］に記載の動的共有結合化合物の組換え方法、
［４］前記繰り返し単位によって構成されるポリマーが、ポリウレタン、ポリエステル、ポリアミド、ポリラクトン、ポリスチレン、ポリアクリル酸、ポリメタクリル酸、ポリアルキレンオキシド、ポリシロキサン、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリオレフィン、ポリイソブチレン、ポリアミドイミド、ポリイミド、ポリフェノール、ポリウレア、ポリウレタンウレア、ポリグルコシド、ポリブタジエン、エポキシ樹脂、ポリアセチレン、及びポリビニルからなる群から選択されるポリマーである、［１］〜［３］のいずれかに記載の動的共有結合化合物の組換え方法、
［５］前記加熱温度が６０〜２００℃である、［１］〜［４］のいずれかに記載の動的共有結合化合物の組換え方法、
［６］［１］〜［５］のいずれかに記載の動的共有結合化合物の組換え方法により、成形体を結合させる方法であって、前記動的共有結合化合物を含む２つ以上の成形体を接触させる工程、前記動的共有結合化合物の硫黄−硫黄結合間を加熱により開裂することにより開裂動的共有結合化合物を得る開裂工程、及び前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを結合させる工程を含む成形体の結合方法、
［７］下記式（１）：
［８］前記（Ｂ）の動的共有結合化合物であって、窒素原子に結合するＲ１及びＲ２の原子が炭素原子であり、前記炭素原子が、炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、シアノ基、ニトロ基、及びアミノ基からなる群から選択される１又は２の置換基によって置換されている、［７］に記載の動的共有結合化合物、
［９］前記繰り返し単位によって構成されるポリマーが、ポリウレタン、ポリエステル、ポリアミド、ポリラクトン、ポリスチレン、ポリアクリル酸、ポリメタクリル酸、ポリアルキレンオキシド、ポリシロキサン、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリオレフィン、ポリイソブチレン、ポリアミドイミド、ポリイミド、ポリフェノール、ポリウレア、ポリウレタンウレア、ポリグルコシド、ポリブタジエン、エポキシ樹脂、ポリアセチレン、及びポリビニルからなる群から選択されるポリマーである、［７］又は［８］に記載の動的共有結合化合物、及び
［１０］［７］〜［９］のいずれかに記載の動的共有結合化合物を含む成形体、
に関する。
なお、ビス（２，２，６，６−テトラメチルピペリジン−１−イル）ジスルフィド（以下、ＢｉＴＥＭＰＳと称することがある）構造を有する化合物は、有機溶媒中で１００℃程度の加熱によって、ラジカル種が発生することが知られている（非特許文献３〜５）。しかしながら、発明者らの知る限りにおいて、これらの化合物が結合交換等の動的な性質を示すことは、報告されておらず、驚くべきことである。
As a result of diligent research on a temperature-responsive dynamic covalent bond polymer, the present inventor surprisingly, a structure having a diaminopolysulfide skeleton is formed as a dynamic covalent bond by heat at a relatively low temperature of about 100 ° C. I found it to behave. Then, they have found that by introducing the diaminopolysulfide skeleton into a polymer, a temperature-responsive dynamic covalent bond polymer can be provided.
The present invention is based on these findings.
Therefore, the present invention
[1] The following equation (1):
[2] When the R 1 and R 2 do not form a cycloheteroalkyl group or a nitrogen-containing heteroaromatic ring group together with the nitrogen atom, the atoms of R 1 and R 2 bonded to the nitrogen atom are carbon atoms. 1 or 2 in which the carbon atom is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a halogen element, a hydroxyl group, a cyano group, a nitro group, and an amino group. The method for recombining a dynamic covalent compound according to [1], which is substituted with a substituent.
[3] The method for recombining a dynamic covalent compound according to [1] or [2], wherein n is 0.
[4] The polymer composed of the repeating units is polyurethane, polyester, polyamide, polylactone, polystyrene, polyacrylic acid, polymethacrylic acid, polyalkylene oxide, polysiloxane, polydimethylsiloxane, polycarbonate, polylactide, polyolefin, polyisobutylene. The polymer according to any one of [1] to [3], which is a polymer selected from the group consisting of polyamideimide, polyimide, polyphenol, polyurea, polyurethane urea, polyglucoside, polybutadiene, epoxy resin, polyacetylene, and polyvinyl. Recombinant method of covalent compound,
[5] The method for recombining a dynamic covalent compound according to any one of [1] to [4], wherein the heating temperature is 60 to 200 ° C.
[6] A method of binding a compact by the method for recombining a dynamic covalent compound according to any one of [1] to [5], wherein two or more moldings containing the dynamic covalent compound are formed. A step of bringing the bodies into contact, a cleavage step of obtaining a cleavage dynamic covalent bond by cleaving the sulfur-sulfur bond of the dynamic covalent bond by heating, and a cleaving step of cooling the cleaving dynamic covalent compound. A method for binding a molded product, which comprises a step of binding the sulfur radicals of two cleavage dynamic covalent compounds.
[7] The following equation (1):
[8] In the dynamic covalent bond compound of (B), the atoms of R 1 and R 2 bonded to the nitrogen atom are carbon atoms, and the carbon atoms are alkyl groups having 1 to 20 carbon atoms and carbon. The dynamic according to [7], wherein the dynamic is substituted with 1 or 2 substituents selected from the group consisting of a heteroalkyl group of numbers 1 to 20, a halogen element, a hydroxyl group, a cyano group, a nitro group, and an amino group. Covalent compound,
[9] The polymer composed of the repeating units is polyurethane, polyester, polyamide, polylactone, polystyrene, polyacrylic acid, polymethacrylic acid, polyalkylene oxide, polysiloxane, polydimethylsiloxane, polycarbonate, polylactide, polyolefin, polyisobutylene. The dynamic covalent bond according to [7] or [8], which is a polymer selected from the group consisting of polyamideimide, polyimide, polyphenol, polyurea, polyurethane urea, polyglucoside, polybutadiene, epoxy resin, polyacetylene, and polyvinyl. A polymer containing the compound and the dynamic covalent compound according to any one of [10] [7] to [9].
Regarding.
A compound having a bis (2,2,6,6-tetramethylpiperidine-1-yl) disulfide (hereinafter, may be referred to as BiTEMPS) structure is a radical species by heating at about 100 ° C. in an organic solvent. Is known to occur (Non-Patent Documents 3 to 5). However, to the best of our knowledge, it has not been reported that these compounds exhibit dynamic properties such as bond exchange, which is surprising.
本発明の動的共有結合化合物によれば、１００℃程度の熱により安定なラジカル構造の発現を可能とし、可逆的な性質を示す新規の動的共有結合ポリマーを提供することができる。本発明の動的共有結合化合物は、ジアミノポリスルフィド骨格の任意の硫黄−硫黄結合が選択的に切断されるため、主鎖部分のＣ−Ｃ結合を分解や切断することがない。また、架橋ポリマーの熱可塑化に伴う再成形を可能とし、冷却することで元の性質に復元可能な架橋ポリマー材料を提供することができる。また、外部刺激によりポリマーの形成を制御することが可能であり、可逆的に制御できる外部刺激応答性材料を提供することができる。更に、材料が損傷を受けた場合に、その形状及び機械的強度が元の状態に戻る自己修復機能を有する材料に応用することができる。特に、本発明の組換え方法によれば、大気中において、動的共有結合化合物の交換反応を容易に実施することができる。 According to the dynamic covalent bond compound of the present invention, it is possible to provide a novel dynamic covalent bond polymer which enables the expression of a stable radical structure by heat of about 100 ° C. and exhibits reversible properties. Since the dynamic covalent bond compound of the present invention selectively cleaves any sulfur-sulfur bond in the diaminopolysulfide skeleton, it does not decompose or cleave the CC bond in the main chain portion. In addition, it is possible to provide a crosslinked polymer material that can be remolded with thermoplasticization of the crosslinked polymer and can be restored to its original properties by cooling. In addition, it is possible to control the formation of the polymer by an external stimulus, and it is possible to provide an external stimulus responsive material that can be reversibly controlled. Furthermore, it can be applied to a material having a self-healing function that restores its shape and mechanical strength to its original state when the material is damaged. In particular, according to the recombinant method of the present invention, the exchange reaction of the dynamic covalent bond compound can be easily carried out in the atmosphere.
〔１〕動的共有結合化合物の組換え方法
本発明の動的共有結合化合物の組換え方法は、下記式（１）：
《動的共有結合化合物》
本発明の組換え方法において用いる動的共有結合化合物は、下記式（２）：
The dynamic covalent compound used in the recombinant method of the present invention has the following formula (2):
（非環状動的共有化合物）
本発明で用いる動的共有結合化合物は、Ｒ１及びＲ２が環状基を形成しない動的共有結合化合物（以下、非環状動的共有化合物と称することがある）でもよい。
すなわち、Ｒ１及びＲ２は、それぞれ独立して、分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基でもよい。炭化水素基の炭素数は、本発明の効果が得られる限りにおいて特に限定されるものではないが、下限は好ましくは８以上であり、より好ましくは１４以上であり、更に好ましくは２０以上であり、更に好ましくは２６以上である。炭素数の上限は、特に限定されないが、好ましくは５００以下である。炭化水素基としては、例えば、脂肪族炭化水素基（例えば、アルキル基、アルキニル基、又はアルケニル基）、脂環式炭化水素基、又は芳香族炭化水素基を挙げることができる。
炭化水素基の分子鎖中に含まれてもよいヘテロ原子としては、窒素原子、酸素原子、ケイ素原子、フッ素原子、硫黄原子、リン原子、アルミニウム原子、又はセレン原子を挙げることができる。
更に、炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位を含んでもよい。すなわち、本発明に用いる動的共有結合化合物は、高分子化合物でもよい。ヘテロ原子を含む繰り返し単位を含むポリマーとしては、ポリウレタン、ポリエステル、ポリアミド、ポリラクトン、ポリアクリル酸、ポリメタクリル酸、ポリアルキレンオキシド、ポリシロキサン、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリアミドイミド、ポリイミド、ポリフェノール、ポリウレア、ポリウレタンウレア、ポリグルコシド、エポキシ樹脂、及びポリビニルを挙げることができる。また、ヘテロ原子を含まない繰り返し単位を含むポリマーとしては、ポリスチレン、ポリオレフィン、ポリイソブチレン、ポリブタジエン、及びポリアセチレンを挙げることができる。
(Acyclic dynamic covalent compound)
The dynamic covalent compound used in the present invention may be a dynamic covalent compound in which R 1 and R 2 do not form a cyclic group (hereinafter, may be referred to as a non-cyclic dynamic covalent compound).
That is, R 1 and R 2 may each independently be a hydrocarbon group having 1 to 500 carbon atoms which may contain a hetero atom in the molecular chain. The number of carbon atoms of the hydrocarbon group is not particularly limited as long as the effect of the present invention can be obtained, but the lower limit is preferably 8 or more, more preferably 14 or more, and further preferably 20 or more. , More preferably 26 or more. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 500 or less. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (for example, an alkyl group, an alkynyl group, or an alkenyl group), an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
Examples of the hetero atom that may be contained in the molecular chain of the hydrocarbon group include a nitrogen atom, an oxygen atom, a silicon atom, a fluorine atom, a sulfur atom, a phosphorus atom, an aluminum atom, and a selenium atom.
Further, the hydrocarbon group may contain a repeating unit containing a hetero atom or a repeating unit containing no hetero atom. That is, the dynamic covalent bond compound used in the present invention may be a polymer compound. Polymers containing repeating units containing heteroatoms include polyurethane, polyester, polyamide, polylactone, polyacrylic acid, polymethacrylic acid, polyalkylene oxide, polysiloxane, polydimethylsiloxane, polycarbonate, polylactide, polyamideimide, polyimide, polyphenol, Examples include polyurea, polyurethane urea, polyglucoside, epoxy resin, and polyvinyl. Examples of the polymer containing a repeating unit containing no heteroatom include polystyrene, polyolefin, polyisobutylene, polybutadiene, and polyacetylene.
前記Ｒ１及びＲ２のジアミノポリスルフィド基本骨格の窒素原子に結合する原子は、限定されるものではないが、炭素原子が好ましい。また、Ｒ１及びＲ２の炭素原子に結合している水素原子は、置換されていることが好ましい。置換基としては、炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、シアノ基、ニトロ基、及びアミノ基からなる群から選択される１又は２の置換基を挙げることができ、好ましくは炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、又はシアノ基である。水素原子が、前記の基に置換されていることにより、窒素原子及び２つの炭素原子からなる立体構造が固定され、硫黄−硫黄結合の開裂及び結合の温度応答性が最適に規定される。しかしながら、置換基の構造が大きすぎる場合、ジアミノポリスルフィド骨格の開裂後の結合工程の硫黄ラジカル同士の結合において、ラジカル同士の接近が困難となり、再結合の障害となることがある。 The atom bonded to the nitrogen atom of the diaminopolysulfide basic skeleton of R 1 and R 2 is not limited, but a carbon atom is preferable. Further, it is preferable that the hydrogen atom bonded to the carbon atom of R 1 and R 2 is substituted. As the substituent, a substituent of 1 or 2 selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a halogen element, a hydroxyl group, a cyano group, a nitro group, and an amino group. A group can be mentioned, preferably an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a halogen element, a hydroxyl group, or a cyano group. By substituting the hydrogen atom with the above group, the three-dimensional structure consisting of the nitrogen atom and the two carbon atoms is fixed, and the cleavage of the sulfur-sulfur bond and the temperature response of the bond are optimally defined. However, if the structure of the substituent is too large, it becomes difficult for the sulfur radicals to approach each other in the bonding step after cleavage of the diaminopolysulfide skeleton, which may hinder the recombination.
（環状動的共有結合化合物）
本発明で用いる動的共有結合化合物は、Ｒ１及びＲ２が環状基を形成する動的共有結合化合物（以下、環状動的共有結合化合物と称することがある）でもよい。
すなわち、Ｒ１とＲ２は、窒素原子と一緒になって炭素数２〜８のシクロヘテロアルキル基を形成してもよい。具体的なシクロヘテロアルキル基としては、アジリジン環などの含窒素３員環、アゼチジン環などの含窒素４員環、ピロリジン環、ピラゾリジン環、オキサゾリジン環、若しくはチアゾリジン環などの含窒素５員環、又はピペリジン環、ピペラジン環、モルホリン環、チオモルホリン環、ピペコリン環などの含窒素６員環、ヘキサメチレンイミン環などの含窒素７員環、又はイミドを挙げることができる。Ｒ１とＲ２が環状基を形成することによって、ジアミノポリスルフィド基本骨格の窒素原子と、その窒素原子に結合する２つの原子の立体構造が固定され、硫黄−硫黄結合の開裂及び結合の温度応答性が最適に規定される。
(Cyclic dynamic covalent bond compound)
The dynamic covalent bond compound used in the present invention may be a dynamic covalent bond compound in which R 1 and R 2 form a cyclic group (hereinafter, may be referred to as a cyclic dynamic covalent bond compound).
That is, R 1 and R 2 may be combined with a nitrogen atom to form a cycloheteroalkyl group having 2 to 8 carbon atoms. Specific examples of the cycloheteroalkyl group include a nitrogen-containing 3-membered ring such as an aziridine ring, a nitrogen-containing 4-membered ring such as an azetidine ring, a pyrrolidine ring, a pyrazolidine ring, an oxazolidine ring, or a nitrogen-containing 5-membered ring such as a thiazolidine ring. Alternatively, a nitrogen-containing 6-membered ring such as a piperidine ring, a piperazine ring, a morpholin ring, a thiomorpholin ring, or a pipecholine ring, a nitrogen-containing 7-membered ring such as a hexamethyleneimine ring, or an imide can be mentioned. By forming a cyclic group between R 1 and R 2, the three-dimensional structure of the nitrogen atom of the diaminopolysulfide basic skeleton and the two atoms bonded to the nitrogen atom is fixed, and the sulfur-sulfur bond is cleaved and the temperature response of the bond is increased. Gender is optimally defined.
また、Ｒ１とＲ２は、窒素原子と一緒になって炭素数２〜８の含窒素複素芳香環基を形成してもよい。具体的な含窒素複素芳香環基としては、ピロール環、トリアゾール環、ピラゾール環、又はイミダゾール環を挙げることができる。Ｒ１とＲ２が環状基を形成することによって、ジアミノポリスルフィド基本骨格の窒素原子と、その窒素原子に結合する２つの原子の立体構造が固定され、硫黄−硫黄結合の開裂及び結合の温度応答性が最適に規定される。 Further, R 1 and R 2 may form a nitrogen-containing heteroaromatic ring group having 2 to 8 carbon atoms together with a nitrogen atom. Specific examples of the nitrogen-containing heteroaromatic ring group include a pyrrole ring, a triazole ring, a pyrazole ring, and an imidazole ring. By forming a cyclic group between R 1 and R 2, the three-dimensional structure of the nitrogen atom of the diaminopolysulfide basic skeleton and the two atoms bonded to the nitrogen atom is fixed, and the sulfur-sulfur bond is cleaved and the temperature response of the bond is increased. Gender is optimally defined.
シクロヘテロアルキル基又は含窒素複素環基の炭素原子に結合している水素原子は、分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されていてもよい。炭化水素基の炭素数は、本発明の効果が得られる限りにおいて特に限定されるものではないが、下限は好ましくは８以上であり、より好ましくは１４以上であり、更に好ましくは２０以上であり、更に好ましくは２６以上である。炭素数の上限は、特に限定されないが、好ましくは５００以下である。炭化水素基としては、例えば、脂肪族炭化水素基（例えば、アルキル基、アルキニル基、又はアルケニル基）、脂環式炭化水素基、又は芳香族炭化水素基を挙げることができる。また、シクロヘテロアルキル基又は含窒素複素環基の炭素原子及び２個の水素原子は、一緒になってカルボニル基に置換されてもよい。
炭化水素基の分子鎖中に含まれてよいヘテロ原子としては、窒素原子、酸素原子、ケイ素原子、フッ素原子、硫黄原子、リン原子、アルミニウム原子、又はセレン原子を挙げることができる。
更に、炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位を含んでもよい。すなわち、本発明に用いる動的共有結合化合物は、高分子化合物でもよい。ヘテロ原子を含む繰り返し単位を含むポリマーとしては、ポリウレタン、ポリエステル、ポリアミド、ポリラクトン、ポリアクリル酸、ポリメタクリル酸、ポリアルキレンオキシド、ポリシロキサン、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリアミドイミド、ポリイミド、ポリフェノール、ポリウレア、ポリウレタンウレア、ポリグルコシド、エポキシ樹脂、及びポリビニルを挙げることができる。また、ヘテロ原子を含まない繰り返し単位を含むポリマーとしては、ポリスチレン、ポリオレフィン、ポリイソブチレン、ポリブタジエン、及びポリアセチレンを挙げることができる。
The hydrogen atom bonded to the carbon atom of the cycloheteroalkyl group or the nitrogen-containing heterocyclic group may be substituted with a hydrocarbon group having 1 to 500 carbon atoms which may contain a heteroatom in the molecular chain. The number of carbon atoms of the hydrocarbon group is not particularly limited as long as the effect of the present invention can be obtained, but the lower limit is preferably 8 or more, more preferably 14 or more, and further preferably 20 or more. , More preferably 26 or more. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 500 or less. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (for example, an alkyl group, an alkynyl group, or an alkenyl group), an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Further, the carbon atom and the two hydrogen atoms of the cycloheteroalkyl group or the nitrogen-containing heterocyclic group may be collectively substituted with the carbonyl group.
Examples of the hetero atom that may be contained in the molecular chain of the hydrocarbon group include a nitrogen atom, an oxygen atom, a silicon atom, a fluorine atom, a sulfur atom, a phosphorus atom, an aluminum atom, and a selenium atom.
Further, the hydrocarbon group may contain a repeating unit containing a hetero atom or a repeating unit containing no hetero atom. That is, the dynamic covalent bond compound used in the present invention may be a polymer compound. Polymers containing repeating units containing heteroatoms include polyurethane, polyester, polyamide, polylactone, polyacrylic acid, polymethacrylic acid, polyalkylene oxide, polysiloxane, polydimethylsiloxane, polycarbonate, polylactide, polyamideimide, polyimide, polyphenol, Examples include polyurea, polyurethane urea, polyglucoside, epoxy resin, and polyvinyl. Examples of the polymer containing a repeating unit containing no heteroatom include polystyrene, polyolefin, polyisobutylene, polybutadiene, and polyacetylene.
また、前記シクロヘテロアルキル基の窒素原子に結合する原子は、限定されるものではないが、炭素原子が好ましい。前記炭素原子に結合している水素原子は、置換されていてもよく、置換基としては、炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、シアノ基、ニトロ基、及びアミノ基からなる群から選択される１又は２の置換基を挙げることができる。 The atom bonded to the nitrogen atom of the cycloheteroalkyl group is not limited, but a carbon atom is preferable. The hydrogen atom bonded to the carbon atom may be substituted, and the substituents include an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a halogen element, a hydroxyl group, and a cyano group. , Nitro groups, and 1 or 2 substituents selected from the group consisting of amino groups.
本発明の組換え方法において用いる具体的な動的共有結合化合物としては、後述の「動的共有結合化合物」の項に記載の化合物を挙げることができる。 Specific examples of the dynamic covalent compound used in the recombinant method of the present invention include the compounds described in the section “Dynamic covalent compound” described later.
《開裂工程（１）》
本発明の組換え方法の開裂工程（１）においては、前記動的共有結合化合物の硫黄−硫黄結合を加熱により開裂することにより、２つの開裂動的共有結合化合物を得ることができる。
前記式（１）において、ｎが０の場合、硫黄−硫黄結合は１である。従って、その１つの硫黄−硫黄結合を加熱により開裂させる。一方、ｎが１〜３０の場合、硫黄−硫黄結合が多数存在する。この場合、任意の硫黄結合間で開裂が生じ、そして硫黄ラジカルが生じることになる。開裂工程（１）においては、いずれの硫黄−硫黄結合間が開裂しても、本発明の効果を得ることができる。
<< Cleavage process (1) >>
In the cleavage step (1) of the recombinant method of the present invention, two cleavage dynamic covalent compounds can be obtained by cleaving the sulfur-sulfur bond of the dynamic covalent bond by heating.
In the above formula (1), when n is 0, the sulfur-sulfur bond is 1. Therefore, the one sulfur-sulfur bond is cleaved by heating. On the other hand, when n is 1 to 30, a large number of sulfur-sulfur bonds are present. In this case, cleavage will occur between any sulfur bonds, and sulfur radicals will be generated. In the cleavage step (1), the effect of the present invention can be obtained regardless of which sulfur-sulfur bond is cleaved.
開裂工程（１）における加熱温度は、動的共有結合化合物の硫黄−硫黄結合間がラジカル的に開裂する温度以上である限りにおいて、特に限定されるものではないが、下限は好ましくは６０℃以上であり、より好ましくは７０℃以上であり、更に好ましくは８０℃以上である。加熱温度の上限は、限定されないが、動的共有化合物の硫黄−硫黄結合以外の構造が破壊されない温度が好ましい。すなわち、動的共有化合物ごとに耐性温度が異なるため、加熱温度の上限はそれぞれの動的共有化合物ごとに決定することができる。しかしながら、一般的には、加熱温度の上限は、好ましくは２００℃以下であり、より好ましくは１６０℃以下であり、更に好ましくは１４０℃以下であり、最も好ましくは１２０℃以下である。 The heating temperature in the cleavage step (1) is not particularly limited as long as it is equal to or higher than the temperature at which the sulfur-sulfur bond of the dynamic covalent bond is radically cleaved, but the lower limit is preferably 60 ° C. or higher. It is more preferably 70 ° C. or higher, and even more preferably 80 ° C. or higher. The upper limit of the heating temperature is not limited, but a temperature at which the structure other than the sulfur-sulfur bond of the dynamic covalent compound is not destroyed is preferable. That is, since the resistance temperature is different for each dynamic covalent compound, the upper limit of the heating temperature can be determined for each dynamic covalent compound. However, in general, the upper limit of the heating temperature is preferably 200 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower, and most preferably 120 ° C. or lower.
《結合工程（２）》
本発明の組換え方法の結合工程（２）においては、前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを可逆的に結合させる。すなわち、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとの硫黄−硫黄結合が可逆的に形成される。
結合工程（２）においては、１つの動的共有結合化合物から得られた２つの動的共有結合化合物が結合することがある。しかしながら、異なる動的共有結合化合物から得られた２つの開裂動的共有結合化合物が結合する交換反応が好ましい。交換反応が起きることによって、動的共有結合化合物の組換え方法を、後述の成形体の結合方法などに用いることができるからである。また、実施例に示すように、２種類の動的共有結合化合物を混合して、動的共有結合化合物の組換え方法を実施することによって、組換えが生じた新たな動的共有結合化合物を製造することができる。
<< Bonding process (2) >>
In the binding step (2) of the recombinant method of the present invention, the sulfur radicals and sulfur radicals of the two cleavage dynamic covalent compounds are reversibly bonded by cooling the cleavage dynamic covalent bond compound. That is, a sulfur-sulfur bond between the sulfur radicals of the two cleavage dynamic covalent compounds and the sulfur radicals is reversibly formed.
In the binding step (2), two dynamic covalent compounds obtained from one dynamic covalent compound may be bonded. However, an exchange reaction in which two cleavage dynamic covalent compounds obtained from different dynamic covalent compounds are bonded is preferred. This is because when the exchange reaction occurs, the method for recombining the dynamic covalent bond compound can be used for the method for binding the molded product, which will be described later. Further, as shown in Examples, a new dynamic covalent bond compound in which recombination has occurred is obtained by mixing two kinds of dynamic covalent bond compounds and carrying out a recombination method of the dynamic covalent bond compound. Can be manufactured.
前記結合工程（２）における冷却温度は、硫黄ラジカルと硫黄ラジカル間での硫黄−硫黄結合が形成される限りにおいて、特に限定されるものではないが、好ましくは８０℃以下であり、より好ましくは８０℃未満であり、更に好ましくは６０℃以下であり、最も好ましくは４０℃以下である。前記の温度であることにより、ジアミノポリスルフィド基本骨格の硫黄ラジカルと硫黄ラジカルとが、可逆的に硫黄−硫黄結合を形成することができる。 The cooling temperature in the bonding step (2) is not particularly limited as long as a sulfur-sulfur bond is formed between the sulfur radicals, but is preferably 80 ° C. or lower, more preferably 80 ° C. or less. It is less than 80 ° C., more preferably 60 ° C. or lower, and most preferably 40 ° C. or lower. At the above temperature, the sulfur radicals and sulfur radicals of the diaminopolysulfide basic skeleton can reversibly form a sulfur-sulfur bond.
〔２〕成形体の結合方法
本発明の組換え方法は、例えば２つの成形体の結合方法に用いることができる。すなわち、本発明の成形体の結合方法は、前記動的共有結合化合物の組換え方法を用いる結合方法であって、前記動的共有結合化合物を含む２つ以上の成形体を接触させる工程、前記動的共有結合化合物の硫黄−硫黄結合間を加熱により開裂することにより開裂動的共有結合化合物を得る開裂工程、及び前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを結合させる工程、を含む。
[2] Method for binding molded bodies The recombinant method of the present invention can be used, for example, for a method for joining two molded bodies. That is, the method for binding the molded product of the present invention is a binding method using the method for recombining the dynamic covalent bond compound, and is a step of bringing two or more molded bodies containing the dynamic covalent bond compound into contact with each other. A cleavage step of obtaining a cleavage dynamic covalent bond by cleaving the sulfur-sulfur bond of the dynamic covalent compound by heating, and a cleavage step of cooling the cleaving dynamic covalent bond to obtain two cleaving dynamic covalent bonds. The step of binding the sulfur radical of the compound to the sulfur radical is included.
すなわち、２つの成形体の接触面において、両方の成形体に含まれる動的共有結合化合物の硫黄−硫黄結合が開裂し、開裂動的共有結合化合物が生じる。そして、片方の成形体に含まれる開裂動的共有結合化合物の硫黄ラジカルと、他方の成形体に含まれる開裂動的共有結合化合物の硫黄ラジカルとが硫黄−硫黄結合を形成する。２つの成形体の接触面において、成形体間に多数の硫黄−硫黄結合が形成されることによって、２つの成形体が結合することができる。 That is, on the contact surfaces of the two molded bodies, the sulfur-sulfur bond of the dynamic covalent bond compound contained in both molded bodies is cleaved to generate a cleaved dynamic covalent bond compound. Then, the sulfur radical of the cleaving dynamic covalent bond compound contained in one of the molded bodies and the sulfur radical of the cleaving dynamic covalent bond compound contained in the other molded body form a sulfur-sulfur bond. By forming a large number of sulfur-sulfur bonds between the molded bodies on the contact surface of the two molded bodies, the two molded bodies can be bonded.
本発明の成形体の結合方法においては、限定されるものではないが、２つの成形体の接触面に圧力を印加することが好ましい。圧力を印加することによって、成形体間の硫黄−硫黄結合を効率よく、形成することができる。印加する圧力は、特に限定されるものではないが、例えば０．１〜１０ＭＰａの圧力を印加することができる。 The method for joining the molded products of the present invention is not limited, but it is preferable to apply pressure to the contact surfaces of the two molded products. By applying pressure, a sulfur-sulfur bond between the compacts can be efficiently formed. The pressure to be applied is not particularly limited, but for example, a pressure of 0.1 to 10 MPa can be applied.
本発明の組換え方法は、成形体の修復方法に用いることもできる。すなわち、動的共有結合化合物を含む成形体（材料）が損傷を受けた場合に、その動的共有結合化合物を含む損傷面を接触させ、前記動的共有結合化合物の硫黄−硫黄結合を加熱により開裂することにより開裂動的共有結合化合物を得る開裂工程、及び前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを結合させる工程を実施することにより、成形体を修復することができる。 The recombinant method of the present invention can also be used as a method for repairing a molded product. That is, when the molded body (material) containing the dynamic covalent compound is damaged, the damaged surface containing the dynamic covalent compound is brought into contact with the damaged surface, and the sulfur-sulfur bond of the dynamic covalent compound is heated. A cleavage step of obtaining a cleavage dynamic covalent bond compound by cleavage and a step of binding sulfur radicals and sulfur radicals of the two cleavage dynamic covalent bond compounds by cooling the cleavage dynamic covalent bond compound are carried out. By doing so, the molded product can be repaired.
〔３〕動的共有結合化合物
本発明の動的共有結合化合物は、下記式（１）：
（Ａ）動的共有結合化合物Ａ
前記動的共有化合物Ａは、前記式（１）中、ｎは３〜３０の整数であり、Ｒ１及びＲ２は、それぞれ独立して、分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基、又はＲ１とＲ２は、窒素原子と一緒になって形成する炭素数２〜８のシクロヘテロアルキル基であって、前記シクロヘテロアルキル基の水素原子は分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されてもよく、前記炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマーを含んでもよい。前記「炭素数１〜５００の炭化水素基」、「炭素数２〜８のシクロヘテロアルキル基」、及び「ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマー」などは、前記「動的共有結合化合物の組換え方法」に記載の動的共有結合化合物と同じものを含むことができる。更に、具体的なＲ１及びＲ２に関しては、後述の動的共有結合化合物Ｂ又は動的共有結合化合物ＣのＲ１及びＲ２と同じ基を含むものでもよい。
(A) Dynamic covalent bond compound A
In the above formula (1), n is an integer of 3 to 30, and R 1 and R 2 have 1 carbon atoms which may independently contain a heteroatom in the molecular chain. Hydrocarbon groups of ~ 500, or R 1 and R 2, are cycloheteroalkyl groups having 2 to 8 carbon atoms formed together with nitrogen atoms, and the hydrogen atoms of the cycloheteroalkyl groups are in the molecular chain. May be substituted with a hydrocarbon group having 1 to 500 carbon atoms which may contain a heteroatom, and the hydrocarbon group comprises a polymer composed of a repeating unit containing a heteroatom or a repeating unit containing no heteroatom. It may be. The "hydrocarbon groups having 1 to 500 carbon atoms", "cycloheteroalkyl groups having 2 to 8 carbon atoms", and "polymers composed of repeating units containing heteroatoms or repeating units not containing heteroatoms" are used. , The same as the dynamic covalent compound described in the above-mentioned "Method for recombining a dynamic covalent compound" can be included. Further, the specific R 1 and R 2 may contain the same group as R 1 and R 2 of the dynamic covalent bond compound B or the dynamic covalent bond compound C described later.
（Ｂ）動的共有結合化合物Ｂ
前記動的共有化合物Ｂは、非環状動的共有結合化合物である。具体的には、動的共有化合物Ｂは、前記式（１）中、ｎは０〜２の整数であり、Ｒ１及びＲ２は、それぞれ独立して、分子鎖中にヘテロ原子を含んでもよい炭素数１４〜５００の炭化水素基であって、前記炭素数１３〜５００の炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマーを含んでもよい。前記「炭素数１４〜５００の炭化水素基」は、炭素数が１４〜５００であることを除いては、前記「動的共有結合化合物の組換え方法」に記載の動的共有結合化合物の「炭素数１〜５００の炭化水素基」と同じものを含むことができる。また、「ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマー」などは、前記「動的共有結合化合物の組換え方法」に記載の動的共有結合化合物と同じものを含むことができる。
(B) Dynamic covalent bond compound B
The dynamic covalent compound B is an acyclic dynamic covalent bond compound. Specifically, in the dynamic covalent compound B, n is an integer of 0 to 2 in the above formula (1), and R 1 and R 2 may independently contain a heteroatom in the molecular chain. A good hydrocarbon group having 14 to 500 carbon atoms, the hydrocarbon group having 13 to 500 carbon atoms, may contain a polymer composed of a repeating unit containing a heteroatom or a repeating unit containing no heteroatom. The "hydrocarbon group having 14 to 500 carbon atoms" is a "recombinant method of a dynamic covalent bond compound" described in the above "method for recombining a dynamic covalent bond compound", except that the "hydrocarbon group having 14 to 500 carbon atoms" has 14 to 500 carbon atoms. It can contain the same hydrocarbon group having 1 to 500 carbon atoms. Further, the "polymer composed of a repeating unit containing a heteroatom or a repeating unit not containing a heteroatom" is the same as the dynamic covalent bond compound described in the above-mentioned "Method for recombining a dynamic covalent bond compound". Can include.
（Ｃ）動的共有結合化合物Ｃ
前記動的共有化合物Ｃは、環状動的共有結合化合物である。具体的には、動的共有化合物Ｃは、前記式（１）中、ｎは０〜２の整数であり、Ｒ１とＲ２は、窒素原子と一緒になって形成する炭素数２〜８のシクロヘテロアルキル基又は含窒素複素芳香環基であって、前記シクロヘテロアルキル基又は含窒素複素芳香環基の水素原子は分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されており、前記炭素数１〜５００の炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマーを含んでもよい。前記「炭素数２〜８のシクロヘテロアルキル基」、「炭素数１〜５００の炭化水素基」、及び「ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマー」などは、前記「動的共有結合化合物の組換え方法」に記載の動的共有結合化合物と同じものを含むことができる。
(C) Dynamic covalent bond compound C
The dynamic covalent compound C is a cyclic dynamic covalent bond compound. Specifically, in the dynamic covalent compound C, n is an integer of 0 to 2 in the above formula (1), and R 1 and R 2 have 2 to 8 carbon atoms formed together with the nitrogen atom. Cycloheteroalkyl group or nitrogen-containing heteroaromatic ring group, and the hydrogen atom of the cycloheteroalkyl group or nitrogen-containing heteroaromatic ring group may contain a heteroatom in the molecular chain. The hydrocarbon group having 1 to 500 carbon atoms, which is substituted with a group, may contain a polymer composed of a repeating unit containing a heteroatom or a repeating unit containing no heteroatom. The "cycloheteroalkyl group having 2 to 8 carbon atoms", the "hydrocarbon group having 1 to 500 carbon atoms", and the "polymer composed of a repeating unit containing a heteroatom or a repeating unit not containing a heteroatom" are used. , The same as the dynamic covalent compound described in the above-mentioned "Method for recombining a dynamic covalent compound" can be included.
本発明の動的共有結合化合物には、ポリマー鎖を含む化合物及びポリマー鎖を含まない化合物が含まれる。ポリマー鎖を含まない動的共有結合化合物は、そのまま本発明の動的共有結合化合物として用いることができる。また、ポリマー鎖を含む動的共有結合化合物の製造原料として用いることもできる。動的共有結合化合物Ｃを例として、ポリマー鎖を含む動的共有結合化合物及びポリマー鎖を含まない動的共有結合化合物について説明する。 The dynamic covalent bond compound of the present invention includes a compound containing a polymer chain and a compound not containing a polymer chain. The dynamic covalent bond compound containing no polymer chain can be used as it is as the dynamic covalent bond compound of the present invention. It can also be used as a raw material for producing a dynamic covalent bond compound containing a polymer chain. The dynamic covalent bond compound containing a polymer chain and the dynamic covalent bond compound not containing a polymer chain will be described by taking the dynamic covalent bond compound C as an example.
（ポリマー鎖を含まない環状動的共有結合化合物Ｃ）
ポリマー鎖を含まない環状動的共有結合化合物Ｃとして、例えば
下記式〔４〕：
これらの動的共有結合化合物は、いずれも加熱によりジスルフィド結合が開裂し、冷却により硫黄ラジカルが結合することによって、交換反応が起きた。すなわち、本発明の動的共有結合化合物の組換え方法に用いることができた。
(Cyclic dynamic covalent bond compound C containing no polymer chain)
As the cyclic dynamic covalent bond compound C containing no polymer chain, for example, the following formula [4]:
In all of these dynamic covalent bond compounds, a disulfide bond was cleaved by heating, and a sulfur radical was bonded by cooling, resulting in an exchange reaction. That is, it could be used in the method for recombining the dynamic covalent compound of the present invention.
（ポリマー鎖を含む環状動的共有結合化合物）
本発明の動的共有結合化合物は、ポリマー鎖を含む高分子化合物（ポリマー）でもよい。すなわち、シクロヘテロアルキル基又は含窒素複素芳香環基の置換基である「炭素数１〜５００の炭化水素基」にポリマー鎖を含んでもよい。ポリマー鎖を含む炭素数１〜５００の炭化水素基の置換基の位置は、特に限定されるものではないが、シクロヘテロアルキル基又は含窒素複素芳香環基の窒素原子の隣接する炭素原子を除く炭素原子の置換基であるのが好ましい。また、動的共有結合化合物全体をポリマーと考えた場合、前記ジアミノポリスルフィド基本骨格が、ポリマーの主鎖、又はポリマーの架橋点に含まれることが好ましい。
(Cyclic dynamic covalent bond compound containing polymer chain)
The dynamic covalent bond compound of the present invention may be a polymer compound (polymer) containing a polymer chain. That is, the polymer chain may be contained in the "hydrocarbon group having 1 to 500 carbon atoms" which is a substituent of the cycloheteroalkyl group or the nitrogen-containing heteroaromatic ring group. The position of the substituent of the hydrocarbon group having 1 to 500 carbon atoms including the polymer chain is not particularly limited, but excludes the carbon atom adjacent to the nitrogen atom of the cycloheteroalkyl group or the nitrogen-containing heteroaromatic ring group. It is preferably a substituent of a carbon atom. When the entire dynamic covalent bond compound is considered as a polymer, it is preferable that the diaminopolysulfide basic skeleton is contained in the main chain of the polymer or the cross-linking point of the polymer.
本明細書において、ポリマー鎖を含む動的共有結合化合物におけるポリマー鎖の繰り返し部分を「繰り返し単位」と称する。繰り返し単位としては、限定されるものではないが、ポリウレタン、ポリエステル、ポリアミド、ポリラクトン、ポリスチレン、ポリアクリル酸、ポリメタクリル酸、ポリアルキレンオキシド（例えば、ポリプロピレンオキシド、ポリエチレンオキシド、ポリテトラメチレンオキシド）、ポリシロキサン、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリオレフィン、ポリイソブチレン、ポリアミドイミド、ポリイミド、ポリウレア、ポリウレタンウレア、ポリフェノール、ポリグルコシド、ポリブタジエン、エポキシ樹脂、ポリアセチレン、又はポリビニルを挙げることができる。 In the present specification, the repeating portion of the polymer chain in the dynamic covalent bond compound containing the polymer chain is referred to as a “repeating unit”. The repeating unit is, but is not limited to, polyurethane, polyester, polyamide, polylactone, polystyrene, polyacrylic acid, polymethacrylic acid, polyalkylene oxide (for example, polypropylene oxide, polyethylene oxide, polytetramethylene oxide), poly. Examples thereof include siloxane, polydimethylsiloxane, polycarbonate, polylactide, polyolefin, polyisobutylene, polyamideimide, polyimide, polyurea, polyurethane urea, polyphenol, polyglucoside, polybutadiene, epoxy resin, polyacetylene, and polyvinyl.
本発明のポリマー鎖を含む動的共有結合化合物は、例えば、前記ポリマー鎖を含まない動的共有結合化合物から、既知の反応を工夫して合成をすることができる。
例えば、原料となる下記式（７）：
For example, the following formula (7), which is a raw material:
前記ＢｉＴＥＭＰＳ−ＯＨを用いて合成できるポリマーとしては、ポリウレタン、ポリエステル、ポリラクトン、ポリアミド、ポリアルキレンオキシド（ポリプロピレンオキシド、ポリエチレンオキシド、ポリテトラメチレンオキシド）、ポリジメチルシロキサン、ポリカーボネート、ポリラクチド、ポリアミドイミド、ポリイミド、ポリウレア、ポリウレタンウレア、ポリフェノール、ポリグルコシド、ポリシロキサン、ポリオレフィン、ポリイミド、又はエポキシ樹脂を挙げることができる。ＢｉＴＥＭＰＳ−ＯＨを修飾したビニル化合物を用いて得られるポリマーとしては、ビニル系ポリマー（例えば、ポリスチレン誘導体、ポリアクリル酸誘導体、ポリメタクリル酸誘導体）又はポリオレフィンを挙げることができる。また、ＢｉＴＥＭＰＳ−ジアルキンを用いて合成できるアジド末端を有するポリマーとしては、アジド末端を有するビニル系ポリマー（例えば、ポリスチレン誘導体、ポリアクリル酸誘導体、ポリメタクリル酸誘導体）、ポリスチレン、ポリアルキレンオキシド（ポリプロピレンオキシド、ポリエチレンオキシド、ポリテトラメチレンオキシド）、ポリシロキサン、ポリジメチルシロキサン、ポリビニル、ポリイソブチレン、ポリブタジエン、又はポリアセチレンを挙げることができる。 Examples of the polymer that can be synthesized using BiTEMPS-OH include polyurethane, polyester, polylactone, polyamide, polyalkylene oxide (polypropylene oxide, polyethylene oxide, polytetramethylene oxide), polydimethylsiloxane, polycarbonate, polylactide, polyamideimide, and polyimide. Examples thereof include polyurea, polyurethane urea, polyphenol, polyglucoside, polysiloxane, polyolefin, polyimide, or epoxy resin. Examples of the polymer obtained by using the vinyl compound modified with BiTEMPS-OH include vinyl-based polymers (for example, polystyrene derivatives, polyacrylic acid derivatives, polymethacrylic acid derivatives) or polyolefins. Examples of the polymer having an azide terminal that can be synthesized using BiTEMPS-dialkyne include vinyl-based polymers having an azide end (for example, polystyrene derivative, polyacrylic acid derivative, polymethacrylic acid derivative), polystyrene, and polyalkylene oxide (polypropylene oxide). , Polystyrene oxide, polytetramethylene oxide), polysiloxane, polydimethylsiloxane, polyvinyl, polyisobutylene, polybutadiene, or polyacetylene.
本発明のポリマー鎖を含む動的共有結合化合物として、より具体的には、下記式〔８〕：
前記式〔８〕の具体的な化合物として、下記式〔９〕のポリマー（ポリウレタン）を挙げることができる。下記式〔９〕のポリマーは、ＢｉＴＥＭＰＳ−ＯＨと、末端がジイソシアネート基で修飾されたポリプロピレングリコール及びヘキサメチレンジイソシアネートとを用いて、合成することができる。
更に前記式〔８〕の具体的な化合物として、下記式〔１０〕のポリマーを挙げることができる。下記式〔１０〕のポリマーは、末端に２つのアルキニル基を有するＢｉＴＥＭＰＳ−ジアルキンと、アジド末端を有するポリスチレンとを反応させることで、合成することができる。
前記式〔８〕におけるＲ３の繰り返し単位を、他のポリマーの繰り返し単位に置き換えるように、公知の方法を用いて合成することによって、本発明のポリマー鎖を含む動的共有結合化合物を合成することが可能である。更に、前記式〔８〕以外の構造を有し、且つＢｉＴＥＭＰＳ基本骨格を有するポリマーも、公知の方法を用いて合成することができる。 The repeating units of R 3 in the formula (8), to replace the repeating units of the other polymers, by synthesized using known methods, to synthesize a dynamic covalent compound containing a polymer chain of the present invention It is possible. Further, a polymer having a structure other than the above formula [8] and having a BiTEMPS basic skeleton can also be synthesized by a known method.
また、ポリマーの架橋点にＢｉＴＥＭＰＳ基本骨格を含む動的共有結合化合物として、下記式〔１１〕：
以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but these do not limit the scope of the present invention.
下記の反応式（１２）に、実施例１〜３の化合物の反応を示す。
《実施例１》
本実施例では、前記反応式（１２）に記載の化合物（１）ＢｉＴＥＭＰＳ−ＯＨを合成した。
反応容器に１，１，１，３，３，３−ヘキサメチルジシラザン２０．８ｇ（１２９ｍｍｏｌ）、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン２０．２ｇ（１２９ｍｍｏｌ）、ニトロメタン１３０ｍＬを加え、窒素雰囲気下５０℃で１時間反応を行った。その後、真空下溶媒留去を行い、十分に乾燥を行った。
次に、酢酸ナトリウム（１０．５ｇ、１２９ｍｍｏｌ）および脱水ジメチルホルムアミド（１０３ｍＬ）を加えた反応容器に、窒素雰囲気下、０℃で二塩化二硫黄（約４．１ｍＬ）を滴下した。滴下完了後０℃にて１０分間撹拌した後、反応溶液を氷水に注いで生じた沈殿をろ過にて回収した。沈殿をヘキサンに溶解させ、硫酸ナトリウムを用いて乾燥した後に減圧下で濃縮し、ヘキサン／エタノール混合溶媒からの再結晶によってＢｉＴＥＭＰＳ−ＯＴＭＳ１１．８ｇ（２２．７ｍｍｏｌ）を得た。
続いて、ＢｉＴＥＭＰＳ−ＯＴＭＳを炭酸カリウム６．２５ｇ（４５．３ｍｍｏｌ）とメタノール２２６ｍＬ中、室温で反応させた。４時間後、反応溶液を水中に注いだ後に生じた沈殿をろ過にて回収し、メタノールから再結晶を行うことでＢｉＴＥＭＰＳ−ＯＨを無色透明固体として得た（収量６．９６ｇ、収率８０％）。
1H NMR (300 MHz, MeOD) : δ/ppm 3.95 (m, 2H, -C(CH3)2CH2CH<), 1.90 (dd, J = 4.0 Hz, 12.4 Hz, 4H, -C(CH3)2CH2CH<), 1.45 (s, 12H, -C(CH3)2CH2CH<), 1.50 (t, J = 12.4 Hz, 4H, -C(CH3)2CH2CH<),1.20 (s, 12H, -C(CH3)2CH2CH<). ; 13C NMR (75 MHz, CDCl3) : δ/ppm 60.92, 59.12, 49.49, 34.60, 26.69.
本実施例で測定を行った１Ｈ−ＮＭＲスペクトル測定の結果を図１に示す。
<< Example 1 >>
In this example, the compound (1) BiTEMPS-OH described in the reaction formula (12) was synthesized.
In the reaction vessel, 1,1,1,3,3,3-hexamethyldisilazane 20.8 g (129 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine 20.2 g (129 mmol), nitromethane 130 mL Was added, and the reaction was carried out at 50 ° C. for 1 hour in a nitrogen atmosphere. Then, the solvent was distilled off under vacuum, and it was sufficiently dried.
Next, disulfur dichloride (about 4.1 mL) was added dropwise at 0 ° C. under a nitrogen atmosphere in a reaction vessel containing sodium acetate (10.5 g, 129 mmol) and dehydrated dimethylformamide (103 mL). After the dropping was completed, the mixture was stirred at 0 ° C. for 10 minutes, the reaction solution was poured into ice water, and the precipitate formed was collected by filtration. The precipitate was dissolved in hexane, dried over sodium sulfate and then concentrated under reduced pressure to give 11.8 g (22.7 mmol) of BiTEMPS-OTMS by recrystallization from a mixed hexane / ethanol solvent.
Subsequently, BiTEMPS-OTMS was reacted with 6.25 g (45.3 mmol) of potassium carbonate in 226 mL of methanol at room temperature. After 4 hours, the precipitate formed after pouring the reaction solution into water was recovered by filtration and recrystallized from methanol to obtain BiTEMPS-OH as a colorless transparent solid (yield 6.96 g, yield 80%). ).
1 H NMR (300 MHz, MeOD): δ / ppm 3.95 (m, 2H, -C (CH 3 ) 2 CH 2 CH <), 1.90 (dd, J = 4.0 Hz, 12.4 Hz, 4H, -C (CH) 3 ) 2 CH 2 CH <), 1.45 (s, 12H, -C (CH 3 ) 2 CH 2 CH <), 1.50 (t, J = 12.4 Hz, 4H, -C (CH 3 ) 2 CH 2 CH < ), 1.20 (s, 12H, -C (CH 3 ) 2 CH 2 CH <).; 13 C NMR (75 MHz, CDCl 3 ): δ / ppm 60.92, 59.12, 49.49, 34.60, 26.69.
The results of the 1H-NMR spectrum measurement measured in this example are shown in FIG.
《実施例２》
本実施例では、前記反応式（１２）に記載の化合物（２）ＢｉＴＥＭＰＳ−ＯｎＢｕを合成した。
反応容器にＢｉＴＥＭＰＳ−ＯＨ４９３ｍｇ（１．３１ｍｍｏｌ）および脱水ジメチルアセトアミド（ＤＭＡｃと略称する）６．５ｍＬを加え、０℃にて水素化ナトリウム２６２ｍｇ（６．５４ｍｍｏｌ、６０ｗｔ％suspension in mineral oil）をゆっくりと加えた。その後、室温で３０分反応させ、再度０℃とした後、臭素化ｎ−ブチル１．４３ｇ（１０．５ｍｍｏｌ）を滴下した。滴下後、室温で８時間反応させ、０℃で水を加えることによって反応を停止させた。反応溶液からヘキサンを用いて抽出し、溶媒留去し、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝９５：５）で単離した（収量５５４ｍｇ、収率８６％）。
1H NMR (300 MHz, CDCl3) : δ/ppm 3.54 (m, 2H, -C(CH3)2CH2CH<), 3.44 (t, J = 6.6 Hz, 4H, -OCH2CH2CH2CH3), 1.77 (dd, J = 3.8 Hz, 12.5 Hz, 4H, -C(CH3)2CH2CH<), 1.52 (m, 4H, -OCH2CH2CH2CH3), 1,43 (s, 12H, -C(CH3)2CH2CH<), 1.41-1.31 (m, 8H, -OCH2CH2CH2CH3 and -C(CH3)2CH2CH<), 1.18 (s, 12H, -C(CH3)2CH2CH<), 0.92 (t, J = 7.3 Hz, 6H, -OCH2CH2CH2CH3). ; 13C NMR (75 MHz, CDCl3) : δ/ppm 70.81, 68.00, 59.78, 46.94, 35.19, 32.56, 27.11, 19.60, 14.02.
本実施例で測定を行った１Ｈ−ＮＭＲスペクトル測定の結果を図２に示す。
<< Example 2 >>
In this embodiment, a synthesized compound (2) BiTEMPS-O n Bu according to the reaction formula (12).
Add 493 mg (1.31 mmol) of BiTEMPS-OH and 6.5 mL of dehydrated dimethylacetamide (abbreviated as DMAc) to the reaction vessel, and slowly add 262 mg (6.54 mmol, 60 wt% suspension in mineral oil) of sodium hydride at 0 ° C. added. Then, the reaction was carried out at room temperature for 30 minutes, the temperature was adjusted to 0 ° C. again, and then 1.43 g (10.5 mmol) of brominated n-butyl was added dropwise. After the dropping, the reaction was carried out at room temperature for 8 hours, and the reaction was stopped by adding water at 0 ° C. The reaction solution was extracted with hexane, the solvent was distilled off, and the mixture was isolated by silica gel column chromatography (hexane: ethyl acetate = 95: 5) (yield 554 mg, yield 86%).
1 H NMR (300 MHz, CDCl 3 ): δ / ppm 3.54 (m, 2H, -C (CH 3 ) 2 CH 2 CH <), 3.44 (t, J = 6.6 Hz, 4H, -OCH 2 CH 2 CH 2 CH 3 ), 1.77 (dd, J = 3.8 Hz, 12.5 Hz, 4H, -C (CH 3 ) 2 CH 2 CH <), 1.52 (m, 4H, -OCH 2 CH 2 CH 2 CH 3 ), 1 , 43 (s, 12H, -C (CH 3 ) 2 CH 2 CH <), 1.41-1.31 (m, 8H, -OCH 2 CH 2 CH 2 CH 3 and -C (CH 3 ) 2 CH 2 CH <) , 1.18 (s, 12H, -C (CH 3 ) 2 CH 2 CH <), 0.92 (t, J = 7.3 Hz, 6H, -OCH 2 CH 2 CH 2 CH 3 ).; 13 C NMR (75 MHz, CDCl 3 ): δ / ppm 70.81, 68.00, 59.78, 46.94, 35.19, 32.56, 27.11, 19.60, 14.02.
The result of 1H-NMR spectrum measurement measured in this Example is shown in FIG.
《実施例３》
本実施例では、前記反応式（１２）に記載のＢｉＴＥＭＰＳ−ジメタクリレートを合成した。
反応容器にＢｉＴＥＭＰＳ−ＯＨ２７４ｍｇ（０．７２８ｍｍｏｌ）、触媒量のジラウリル酸ジブチル錫と脱水ＤＭＡｃ７．３ｍＬを加え、０℃の下メタクリル酸２−イソシアナトエチル３３８ｍｇ（２．１８ｍｍｏｌ）をゆっくり滴下した。滴下後、反応溶液を室温に戻し４時間反応を行った。その後、再度メタクリル酸２−イソシアナトエチル１１３ｍｇ（０．７２８ｍｍｏｌ）を滴下し、２４時間反応を行った。その後、反応溶液を８０ｍＬの水に注ぎ、ジエチルエーテルを用いて抽出し、有機層を飽和食塩水で洗浄を行い、溶媒留去の後に、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）にて単離し、無色透明固体を得た。収量は４４８ｍｇ、収率は９０％であった。
1H NMR (300 MHz, CDCl3) : δ/ppm 6.12 (s, 2H, CH2C(CH3)COO-), 5.61 (s, 2H, CH2C(CH3)COO-), 4.98 (m, 2H, -C(CH3)2CH2CH<), 4.89 (s, -OCH2CH2NHCOO-), 4.23 (t, J = 5.1 Hz, 4H, -OCH2CH2NHCOO-), 3.50 (m, 4H, -OCH2CH2NHCOO-), 1.96-1.95 (m, 10H, -C(CH3)2CH2CH< and CH2C(CH3)COO-), 1.48 (t, J = 12.4 Hz, 4H, -C(CH3)2CH2CH<), 1.43 (s, 12 H, -C(CH3)2CH2CH<), 1.23 (s, 12H, -C(CH3)2CH2CH<). ; 13C NMR (75 MHz, CDCl3) : δ/ppm 167.37, 156.08, 136.02, 126.18, 67.74, 63.83, 59.60, 46.00, 40.15, 34.87, 26.79, 18.42.
図３に１Ｈ−ＮＭＲスペクトル測定の結果を示す。
<< Example 3 >>
In this example, BiTEMPS-dimethacrylate described in the reaction formula (12) was synthesized.
274 mg (0.728 mmol) of BiTEMPS-OH, a catalytic amount of dibutyltin dilaurate and 7.3 mL of dehydrated DMAc were added to the reaction vessel, and 338 mg (2.18 mmol) of 2-isocyanatoethyl methacrylate was slowly added dropwise at 0 ° C. After the dropping, the reaction solution was returned to room temperature and the reaction was carried out for 4 hours. Then, 113 mg (0.728 mmol) of 2-isocyanatoethyl methacrylate was added dropwise again, and the reaction was carried out for 24 hours. Then, the reaction solution is poured into 80 mL of water, extracted with diethyl ether, the organic layer is washed with saturated brine, the solvent is distilled off, and then silica gel column chromatography (hexane: ethyl acetate = 2: 1) To obtain a colorless transparent solid. The yield was 448 mg and the yield was 90%.
1 H NMR (300 MHz, CDCl 3 ): δ / ppm 6.12 (s, 2H, CH 2 C (CH 3 ) COO-), 5.61 (s, 2H, CH 2 C (CH 3 ) COO-), 4.98 ( m, 2H, -C (CH 3 ) 2 CH 2 CH <), 4.89 (s, -OCH 2 CH 2 NHCOO-), 4.23 (t, J = 5.1 Hz, 4H, -OCH 2 CH 2 NHCOO-), 3.50 (m, 4H, -OCH 2 CH 2 NHCOO-), 1.96-1.95 (m, 10H, -C (CH 3 ) 2 CH 2 CH <and CH 2 C (CH 3 ) COO-), 1.48 (t, J = 12.4 Hz, 4H, -C (CH 3 ) 2 CH 2 CH <), 1.43 (s, 12 H, -C (CH 3 ) 2 CH 2 CH <), 1.23 (s, 12H, -C (CH) 3 ) 2 CH 2 CH <).; 13 C NMR (75 MHz, CDCl 3 ): δ / ppm 167.37, 156.08, 136.02, 126.18, 67.74, 63.83, 59.60, 46.00, 40.15, 34.87, 26.79, 18.42.
FIG. 3 shows the results of 1H-NMR spectrum measurement.
《実施例４》
本実施例では、実施例１で得られた化合物（１）ＢｉＴＥＭＰＳ−ＯＨ及び実施例２で得られた化合物（２）ＢｉＴＥＭＰＳ−ＯｎＢｕの交換反応を行った。
反応容器にＢｉＴＥＭＰＳ−ＯＨ２６．２ｍｇ（６９．４μｍｏｌ）、ＢｉＴＥＭＰＳ−ＯｎＢｕ３４．２ｍｇ（６９．４μｍｏｌ）およびＤＭＡｃ１．４ｍＬを加え、大気下８０℃または１００℃で交換反応を行い、任意の時間で液体クロマトグラフィーを測定することで交換反応の進行を追跡した。下記式（１３）に反応式を示し、図４に液体クロマトグラフィーの結果及び反応時間ごとの化合物（１）ＢｉＴＥＭＰＳ−ＯＨ、化合物（２）ＢｉＴＥＭＰＳ−ＯｎＢｕ、及び交換反応によって得られた化合物（３）の割合を示す。いずれの温度においても交換化合物に基づくシグナルが観測され、熱により交換反応が進行することが示された。
In this embodiment, it carried out exchange reaction of Example compound obtained in 1 (1) BiTEMPS-OH and the compound obtained in Example 2 (2) BiTEMPS-O n Bu.
A reaction vessel BiTEMPS-OH26.2mg (69.4μmol), added BiTEMPS-O n Bu34.2mg (69.4μmol) and DMAc1.4ML, to exchange reaction at 80 ° C. or 100 ° C. under atmospheric, at any time The progress of the exchange reaction was followed by measuring liquid chromatography. Formula (13) shows the reaction scheme results and compounds of each reaction time of the liquid chromatography in FIG. 4 (1) BiTEMPS-OH, compound (2) BiTEMPS-O n Bu , and compounds obtained by the exchange reaction The ratio of (3) is shown. Signals based on the exchange compound were observed at all temperatures, indicating that the exchange reaction proceeds with heat.
《実施例５》
本実施例では、実施例１で得られた化合物（１）ＢｉＴＥＭＰＳ−ＯＨ及び４，４−ジチオモルフォリン（４）の交換反応を行った。
反応容器にＢｉＴＥＭＰＳ−ＯＨ８．８ｍｇ（２３．４μｍｏｌ）、ジチオジモルホリン（１４）５．５ｍｇ（２３．４μｍｏｌ）およびＤＭＡｃ１．２ｍＬを加え、大気下１００℃、１時間交換反応を行い、薄層クロマトグラフィーを用いて交換反応の進行を確認した。下記式（１４）に反応式を示す。反応後の混合物（図５中３）にはいずれの化合物からも見られなかった新たな反応点の出現が観測され、熱により交換化合物が得られることが明らかになった。
In this example, the exchange reaction of the compound (1) BiTEMPS-OH and 4,4-dithiomorpholin (4) obtained in Example 1 was carried out.
Add 8.8 mg (23.4 μmol) of BiTEMPS-OH, 5.5 mg (23.4 μmol) of dithiodimorpholine (14) and 1.2 mL of DMAc to the reaction vessel, and carry out an exchange reaction at 100 ° C. for 1 hour in the air to perform thin layer chromatography. The progress of the exchange reaction was confirmed using imaging. The reaction formula is shown in the following formula (14). In the mixture after the reaction (3 in FIG. 5), the appearance of a new reaction point, which was not seen in any of the compounds, was observed, and it was clarified that an exchange compound was obtained by heat.
《実施例６》
本実施例では、トリスルフィド形のＢｉＴＥＭＰＳ−ＯＨ及びポリスルフィド形のＢｉＴＥＭＰＳ−ＯＣＯＮＨｎＢｕの交換反応を行った。
反応容器にトリスルフィド形ＢｉＴＥＭＰＳ−ＯＨ（６）１０．０ｍｇ（１５．６μｍｏｌ）、ポリスルフィド形ＢｉＴＥＭＰＳ−ＯＣＯＮＨｎＢｕ（７）６．３９ｍｇ（１５．６μｍｏｌ）およびＤＭＡｃ０．３ｍＬを加え、大気下１００℃、１時間交換反応を行い、薄層クロマトグラフィーを用いて交換反応の進行を確認した。下記式（１５）に反応式を示す。反応後の混合物（図６中３）にはいずれの化合物からも見られなかった新たな反応点の出現が観測され、熱により交換化合物（８）が得られることが明らかになった。
In this example, the exchange reaction of the trisulfide type BiTEMPS-OH and the polysulfide type BiTEMPS-OCONH n Bu was carried out.
To the reaction vessel, 10.0 mg (15.6 μmol) of trisulfide type BiTEMPS-OH (6), 6.39 mg (15.6 μmol) of polysulfide type BiTEMPS-OCONH n Bu (7) and 0.3 mL of DMAc were added, and the temperature was 100 ° C. in the air. The exchange reaction was carried out for 1 hour, and the progress of the exchange reaction was confirmed by using thin layer chromatography. The reaction formula is shown in the following formula (15). In the mixture after the reaction (3 in FIG. 6), the appearance of a new reaction point which was not seen in any of the compounds was observed, and it was clarified that the exchange compound (8) was obtained by heat.
《参考例１》
本参考例では、実施例２で得られた化合物（２）ＢｉＴＥＭＰＳ−ＯｎＢｕ及びＢｉＴＥＭＰＳ−ＯＣＯＮＨｎＢｕ（９）の光照射による交換反応を行った。
反応容器にＢｉＴＥＭＰＳ−ＯｎＢｕ９．２ｍｇ（１９μｍｏｌ）、ＢｉＴＥＭＰＳ−ＯＣＯＮＨｎＢｕ１１ｍｇ（１９μｍｏｌ）およびＤＭＡｃ１．４ｍＬを加え、光照射下（３６５ｎｍ、２ｍＷ／ｃｍ２）室温で交換反応を行い、約２２時間後に液体クロマトグラフィー測定により交換反応の進行を確認した。下記式（１６）に反応式を示し、図６に液体クロマトグラフィーにより、化合物（２）ＢｉＴＥＭＰＳ−ＯｎＢｕ、化合物（９）ＢｉＴＥＭＰＳ−ＯＣＯＮＨｎＢｕ、及び交換反応によって得られた化合物（１０）が検出されたことを示す。いずれの温度においても交換化合物に基づくシグナルが観測され、紫外光照射により交換反応が進行することが示された。
In this reference example was subjected to exchange reaction by light irradiation of the compound obtained in Example 2 (2) BiTEMPS-O n Bu and BiTEMPS-OCONH n Bu (9) .
The reaction vessel BiTEMPS-O n Bu9.2mg (19μmol) , added BiTEMPS-OCONH n Bu11mg (19μmol) and DMAc1.4ML, under light irradiation (365nm, 2mW / cm 2) to exchange reaction at room temperature, about 22 hours Later, the progress of the exchange reaction was confirmed by liquid chromatography measurement. Shows the reaction scheme the following equation (16), by liquid chromatography in FIG. 6, the compound (2) BiTEMPS-O n Bu , compound (9) BiTEMPS-OCONH n Bu , and compounds obtained by exchange reaction (10) Indicates that was detected. Signals based on the exchange compound were observed at all temperatures, indicating that the exchange reaction proceeds by irradiation with ultraviolet light.
《実施例７》
本実施例では、実施例３で得られたＢｉＴＥＭＰＳ−ジメタクリレートを用いて、ＢｉＴＥＭＰＳ基本骨格を有する架橋高分子を合成した。
反応容器にメタクリル酸ｎ−ヘキシル１．００ｇ（５．８８ｍｍｏｌ）、ＢｉＴＥＭＰＳ−ジメタクリレート０．０２０２ｇ（０．０２９４ｍｍｏｌ）および脱水ＤＭＡｃ１．０ｍＬを加え、脱気を十分に行い、反応系を窒素雰囲気とした。その後、アゾ系の開始試薬Ｖ−７０を９．１ｍｇ（０．０２９４ｍｍｏｌ）を加え、再度窒素置換を行い、３０℃で反応を行った。得られたＢｉＴＥＭＰＳ含有架橋高分子は塩化メチレンを用いたソックスレー抽出によって精製を行い、減圧乾燥することで無色透明固体を得た（収量０．５２５ｇ、収率５０％）。
<< Example 7 >>
In this example, the BiTEMPS-dimethacrylate obtained in Example 3 was used to synthesize a crosslinked polymer having a BiTEMPS basic skeleton.
To the reaction vessel, 1.00 g (5.88 mmol) of n-hexyl methacrylate, 0.0202 g (0.0294 mmol) of BiTEMPS-dimethacrylate and 1.0 mL of dehydrated DMAc were added, and degassing was carried out sufficiently to make the reaction system a nitrogen atmosphere. did. Then, 9.1 mg (0.0294 mmol) of the azo-based starting reagent V-70 was added, nitrogen substitution was carried out again, and the reaction was carried out at 30 ° C. The obtained BiTEMPS-containing crosslinked polymer was purified by Soxhlet extraction using methylene chloride and dried under reduced pressure to obtain a colorless transparent solid (yield 0.525 g, yield 50%).
《比較例１》
本比較例では、ブタン１，４−ビス［Ｎ−［２−（メタクリロイルオキシ）エチル］アミノカルボナート］を用いて、ＢｉＴＥＭＰＳ基本骨格を持たない架橋高分子を合成した。
反応容器にメタクリル酸ｎ−ヘキシル１．００ｇ（５．８８ｍｍｏｌ）、ブタン１，４−ビス［Ｎ−［２−（メタクリロイルオキシ）エチル］アミノカルボナート］０．０１１８ｇ（０．２９４ｍｍｏｌ）および脱水ＤＭＡｃ１．０ｍＬを加え、脱気を十分に行い、反応系を窒素雰囲気とした。その後、アゾ系の開始試薬Ｖ−７０を９．１ｍｇ（０．０２９４ｍｍｏｌ）を加え、再度窒素置換を行い、３０℃で反応を行った。得られた非ＢｉＴＥＭＰＳ含有架橋高分子は塩化メチレンを用いたソックスレー抽出によって精製を行い、減圧乾燥することで無色透明固体を得た（収量０．８５５ｇ、収率７６％）。
<< Comparative Example 1 >>
In this comparative example, butane 1,4-bis [N- [2- (methacryloyloxy) ethyl] aminocarbonate] was used to synthesize a crosslinked polymer having no BiTEMPS basic skeleton.
In the reaction vessel, 1.00 g (5.88 mmol) of n-hexyl methacrylate, 0.0118 g (0.294 mmol) of butane 1,4-bis [N- [2- (methacryloyloxy) ethyl] aminocarbonate] and dehydrated DMAc1 .0 mL was added and degassed sufficiently to give the reaction system a nitrogen atmosphere. Then, 9.1 mg (0.0294 mmol) of the azo-based starting reagent V-70 was added, nitrogen substitution was carried out again, and the reaction was carried out at 30 ° C. The obtained non-BiTEMPS-containing crosslinked polymer was purified by Soxhlet extraction using methylene chloride and dried under reduced pressure to obtain a colorless transparent solid (yield 0.855 g, yield 76%).
《実施例８》
本実施例では、実施例７で得られたＢｉＴＥＭＰＳ含有架橋高分子を用いて交換反応を行った。対照として、比較例１で得られた非ＢｉＴＥＭＰＳ含有架橋高分子を用いた。
実施例７で得られたＢｉＴＥＭＰＳ含有架橋高分子、又は比較例１で得られた非ＢｉＴＥＭＰＳ含有架橋高分子５０ｍｇにＢｉＴＥＭＰＳ−ＯｎＢｕ３．５ｍｇ（架橋剤のＢｉＴＥＭＰＳに対して５等量）および脱水ＤＭＡｃ５．０ｍＬを加え、１００℃で二時間反応させた。ＢｉＴＥＭＰＳ含有架橋高分子は溶媒であるＤＭＡｃに完全に溶解したが、非ＢｉＴＥＭＰＳ含有架橋高分子はＤＭＡｃに溶解しなかった。図８に、実施例６において作製したＢｉＴＥＭＰＳ含有架橋高分子（ａ）（ＢｉＴＥＭＰＳ−ジメタクリレートで架橋）、及び比較例１で作製した非ＢｉＴＥＭＰＳ含有架橋高分子（ｂ）（ブタン１，４−ビス［Ｎ−［２−（メタクリロイルオキシ）エチル］アミノカルボナート］で架橋）の加熱前後の様子を示す。
<< Example 8 >>
In this example, the exchange reaction was carried out using the BiTEMPS-containing crosslinked polymer obtained in Example 7 . As a control, the non-BiTEMPS-containing crosslinked polymer obtained in Comparative Example 1 was used.
And dried (5 equivalents to BiTEMPS crosslinker) BiTEMPS containing crosslinked polymer, or obtained in Comparative Example 1 Non BiTEMPS containing crosslinked polymer 50mg to BiTEMPS-O n Bu3.5mg obtained in Example 7 5.0 mL of DMAc was added and reacted at 100 ° C. for 2 hours. The BiTEMPS-containing crosslinked polymer was completely dissolved in the solvent DMAc, but the non-BiTEMPS-containing crosslinked polymer was not dissolved in DMAc. FIG. 8 shows the BiTEMPS-containing crosslinked polymer (a) prepared in Example 6 (crosslinked with BiTEMPS-dimethacrylate) and the non-BiTEMPS-containing crosslinked polymer (b) (butane 1,4-bis) prepared in Comparative Example 1. The state before and after heating of [crosslinked with N- [2- (methacryloyloxy) ethyl] aminocarbonate] is shown.
《実施例９》
本実施例では、実施例７で得られたＢｉＴＥＭＰＳ含有架橋高分子を用いて、本発明の成形体の結合方法を実施した。対照として、比較例１で得られた非ＢｉＴＥＭＰＳ骨格架橋高分子を用いた。
実施例７で得られたＢｉＴＥＭＰＳ含有架橋高分子からなる成形体、又は比較例１で得られた非ＢｉＴＥＭＰＳ含有架橋高分子からなる成形体をナイフによって切断し、切断面を合わせ上部より加重をかけながら１００℃で６時間処理を行った。ＢｉＴＥＭＰＳ含有架橋高分子からなる成形体は、熱処理後には切断跡の消失と扁平状への形状変化が観測された。一方非ＢｉＴＥＭＰＳ含有架橋高分子からなる成形体は、切断跡は修復されず、形状変化も見られなかった。図９に、本発明のＢｉＴＥＭＰＳ含有架橋高分子を用いた成形体（ａ）及び比較例１の非ＢｉＴＥＭＰＳ含有架橋高分子を用いた成形体の熱圧縮前後の様子を示す。
<< Example 9 >>
In this example, the method for binding the molded product of the present invention was carried out using the BiTEMPS-containing crosslinked polymer obtained in Example 7 . As a control, the non-BiTEMPS skeletal cross-linked polymer obtained in Comparative Example 1 was used.
The molded product made of the BiTEMPS-containing crosslinked polymer obtained in Example 7 or the molded product made of the non-BiTEMPS-containing crosslinked polymer obtained in Comparative Example 1 is cut with a knife, the cut surfaces are aligned, and a load is applied from above. The treatment was carried out at 100 ° C. for 6 hours. In the molded product made of the BiTEMPS-containing crosslinked polymer, disappearance of cutting marks and a change in shape to a flat shape were observed after the heat treatment. On the other hand, in the molded product made of the non-BiTEMPS-containing crosslinked polymer, the cutting marks were not repaired and no shape change was observed. FIG. 9 shows the state before and after heat compression of the molded product (a) using the BiTEMPS-containing crosslinked polymer of the present invention and the molded product using the non-BiTEMPS-containing crosslinked polymer of Comparative Example 1.
本発明の動的共有結合化合物の組換え方法は、大気中における成形体の結合、又は破損した成形体の修復に用いることができる。本発明の動的共有結合化合物の組換え方法は、異なる架橋高分子からなる２つの成形体の接着に用いることができる。更に、２種類の架橋高分子から製造された成形体において、２種類の架橋高分子が組み替えられた架橋高分子複合体を含む成形体を製造することができる。 The method for recombining a dynamic covalent bond compound of the present invention can be used for binding a molded product in the air or repairing a damaged molded product. The method for recombining a dynamic covalent bond compound of the present invention can be used for bonding two molded articles made of different crosslinked polymers. Further, in a molded product produced from two types of crosslinked polymers, it is possible to produce a molded product containing a crosslinked polymer composite in which two types of crosslinked polymers are recombined.
Claims (9)
Ｒ１及びＲ２は、それぞれ独立して、分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基、又は
Ｒ１とＲ２は、窒素原子と一緒になって形成する炭素数２〜８のシクロヘテロアルキル基又は含窒素複素芳香環基であって、前記シクロヘテロアルキル基又は含窒素複素芳香環基の水素原子は分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されてもよく、
前記炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマーを含んでもよい〕
で表されるジアミノポリスルフィド基本骨格を有する動的共有結合化合物の硫黄−硫黄結合間を６０〜２００℃の加熱により開裂することにより開裂動的共有結合化合物を得る開裂工程、及び
前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを結合させる工程、
を含む動的共有結合化合物の組換え方法。 The following formula (1):
R 1 and R 2 are each independently a hydrocarbon group having 1 to 500 carbon atoms which may contain a hetero atom in the molecular chain, or R 1 and R 2 are carbons formed together with a nitrogen atom. A cycloheteroalkyl group or a nitrogen-containing heteroaromatic ring group having the number 2 to 8, and the hydrogen atom of the cycloheteroalkyl group or the nitrogen-containing heteroaromatic ring group may contain a heteroatom in the molecular chain. May be substituted with 500 hydrocarbon groups,
The hydrocarbon group may include a polymer composed of repeating units containing heteroatoms or repeating units not containing heteroatoms.]
A cleavage step of obtaining a cleavage dynamic covalent bond compound by cleaving between sulfur and sulfur bonds of a dynamic covalent bond compound having a diaminopolysulfide basic skeleton represented by the above by heating at 60 to 200 ° C., and the cleavage dynamic covalent bond. A step of binding sulfur radicals and sulfur radicals of two cleaving dynamic covalent bond compounds by cooling the binding compound.
A method for recombining a dynamic covalent compound containing.
窒素原子に結合するＲ１及びＲ２の原子は炭素原子であり、前記炭素原子が、炭素数１〜２０のアルキル基、炭素数１〜２０のヘテロアルキル基、ハロゲン元素、水酸基、シアノ基、ニトロ基、及びアミノ基からなる群から選択される１又は２の置換基によって置換さ
れている、請求項１に記載の動的共有結合化合物の組換え方法。 When R 1 and R 2 do not combine with a nitrogen atom to form a cycloheteroalkyl group or a nitrogen-containing heteroaromatic ring group.
The atoms of R 1 and R 2 bonded to the nitrogen atom are carbon atoms, and the carbon atoms are an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a halogen element, a hydroxyl group, a cyano group, and the like. The method for recombining a dynamic covalent compound according to claim 1, wherein the dynamic covalent compound is substituted with a substituent of 1 or 2 selected from the group consisting of a nitro group and an amino group.
前記動的共有結合化合物を含む２つ以上の成形体を接触させる工程、
前記動的共有結合化合物の硫黄−硫黄結合間を加熱により開裂することにより開裂動的共有結合化合物を得る開裂工程、及び
前記開裂動的共有結合化合物を冷却することにより、２つの開裂動的共有結合化合物の硫黄ラジカルと硫黄ラジカルとを結合させる工程
を含む成形体の結合方法。 A method for binding a molded product by the method for recombining a dynamic covalent bond compound according to any one of claims 1 to 5.
A step of bringing two or more molded articles containing the dynamic covalent compound into contact with each other.
A cleavage step of obtaining a cleavage dynamic covalent bond by cleaving between the sulfur and sulfur bonds of the dynamic covalent bond by heating, and a cleavage step of cooling the cleavage dynamic covalent bond to obtain two cleavage dynamic covalent bonds. A method for binding a molded product, which comprises a step of binding sulfur radicals and sulfur radicals of a binding compound.
で表される架橋高分子。 The following formula (1 1 ):
In represented Ru cross-linking polymer.
式中、ｎは０〜３０の整数であり、
Ｒ１とＲ２は、窒素原子と一緒になって形成する炭素数２〜８のシクロヘテロアルキル基又は含窒素複素芳香環基であって、前記シクロヘテロアルキル基又は含窒素複素芳香環基の水素原子は分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されてもよく、
Ｒ ３ とＲ ４ は、窒素原子と一緒になって形成する炭素数２〜８のシクロヘテロアルキル基又は含窒素複素芳香環基であって、前記シクロヘテロアルキル基又は含窒素複素芳香環基の水素原子は分子鎖中にヘテロ原子を含んでもよい炭素数１〜５００の炭化水素基で置換されてもよく、
前記炭化水素基は、ヘテロ原子を含む繰り返し単位又はヘテロ原子を含まない繰り返し単位によって構成されるポリマーを含んでもよい動的共有結合化合物であって、
前記Ｒ１及びＲ２で形成される基と、前記Ｒ３及びＲ４で形成される基が異なる、動的共有結合化合物。 The following formula (17):
In the formula, n is an integer from 0 to 30
R 1 and R 2 are cycloheteroalkyl groups or nitrogen-containing heteroaromatic ring groups having 2 to 8 carbon atoms formed together with the nitrogen atom, and are the cycloheteroalkyl groups or nitrogen-containing heteroaromatic ring groups. The hydrogen atom may be substituted with a hydrocarbon group having 1 to 500 carbon atoms, which may contain a heteroatom in the molecular chain.
R 3 and R 4 are cycloheteroalkyl groups or nitrogen-containing heteroaromatic ring groups having 2 to 8 carbon atoms formed together with the nitrogen atom, and are the cycloheteroalkyl groups or nitrogen-containing heteroaromatic ring groups. The hydrogen atom may be substituted with a hydrocarbon group having 1 to 500 carbon atoms, which may contain a heteroatom in the molecular chain.
The hydrocarbon group is a dynamic covalent compound which may contain a polymer composed of repeating units containing heteroatoms or repeating units not containing heteroatoms.
A dynamic covalent bond compound in which the group formed by R 1 and R 2 and the group formed by R 3 and R 4 are different.
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| JP2022037478A (en) * | 2020-08-25 | 2022-03-09 | 株式会社Adeka | Compound, composition containing the same, and cured product |
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| WO2022268662A1 (en) | 2021-06-25 | 2022-12-29 | Sabic Global Technologies B.V. | Vitrimer polymers derived from functionalized polyolefins |
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