JP7029774B2 - Sydnone as a component corresponding to thermosetting resin with excellent heat resistance - Google Patents

Description

The present invention relates to thermosetting resins and, in particular, to the production of ydnone-based thermosetting resins.

Sydnone as a mesoionic heterocyclic aromatic compound [1] is a highly efficient 1,3-bipolar cycloaddition due to simple thermal activation and the sole generation of CO ₂ as an inactive by-product. Receive a reaction. The double cycloaddition reaction with the active alkene yields diazonorbornene, while the Diels-Alder reaction with the alkyne yields aromatic pyrazoles [6, 7] (see Figure 1), respectively. Sydnones are also used for macromolecular synthesis, and low to medium molecular weight linear polymers obtained from cycloaddition reactions of each of these polyfunctional monomers have high glass transition temperatures (T _g ) and Shows thermal stability [8-10]. As an approach corresponding to the cross-linking that produces a polystyrene copolymer, studies on the sidononemaleimide cyclization addition reaction have been conducted, and the polystyrene copolymer is heat-resistant derived from the sidononmaleimide cyclization addition reaction chemistry. Due to the good cycloaddition reactant, it showed excellent thermal stability [11]. These excellent thermal properties and easy formation conditions make sydnone a promising material of great interest for the formation of heat resistant, viaducted thermosetting resin polymers.
There is no teaching in the technical field related to the utilization of ydnone reactions in the formation of new thermosetting materials. Therefore, there is a need for methods and platforms that support the production of ydnone-based thermosetting materials that exhibit high heat resistance. Such materials are of great interest as they provide a scalable and versatile platform for the production of new composites for advanced applications such as thermal conductivity.

Earl, J. C .; Mackney, A. W., Journal of the Chemical Society (Resumed), 1935, 899-900. Sun, K. K., Tetrahedron Letters, 1986, 27, 317-320. Huisgen, R .; Grashey, R .; Gotthardt, H .; Schmidt, R., Angewandte Chemie International Edition in English, 1962, 1, 48-49. Sun, K.K., Macromolecules, 1987, 20, 726-729. Stille, J.K .; Bedford, M.A., Journal of Polymer Science Part B: Polymer Letters, 1966, 4, 329-331. Stille, J.K .; Bedford, M.A., Journal of Polymer Science Part A-1: Polymer Chemistry, 1968, 6, 2331-2342. Intemann, J. J .; Huang, W .; Jin, Z .; Shi, Z .; Yang, X .; Yang, J .; Luo, J .; Jen, A. K. Y., ACS Macro Letters, 2013, 2, 256-259.

The present disclosure provides a synthetic method as a multi-purpose modular platform that accommodates the production of ydnone-based crosslinked materials with selected desirable properties. In one or more embodiments of the present invention, there is provided a method for producing such a thermosetting resin from a heat resistant thermosetting resin and (multi) functional sydnone. In particular, the present invention synthesizes a heat-resistant thermosetting resin via a [4 + 2] cycloaddition reaction between (poly) functional ydnones as 1,3-bipolar and polyfunctional alkene or alkyne moitty. Describe the multipurpose generation method corresponding to. In one or more embodiments, a highly cross-linked network structure with diazonorbornene or pyrazole as a repetitive cross-linking unit is obtained by an efficient two-step B-stage method. In such an embodiment, the initially synthesized soluble oligomer is thermoset in air to produce an insoluble crosslinked thermosetting resin. This approach allows the formation of thermosetting films on solid substrates by heating a simple cross-linked casting oligomer solution.

Embodiments of the present invention include a method for producing a thermosetting resin composition, which comprises providing a monomer mixture containing ydnone and one of an alkene or an alkyne. In certain embodiments of the invention, the sydnone is selected from the group consisting of mono-sydnones, bis-sydnones, and tris-sydnones. The alkene or alkyne is selected from the group consisting of bis-maleimide, tris-maleimide, bis-alkyne, and tris-alkyne.

In one or more embodiments of the invention, a copolymerization of a mixture of different sydnones with a mixture of different alkenes, different alkynes or combinations thereof is provided. In certain embodiments, a mixture of polyfunctional sydnones and mono-sydnones is used to form thermosetting resins with reduced crosslink density in copolymerization with polyfunctional alkene, alkynes or mixtures thereof. ..

The oligomer is formed from a mixture of the thermally activated monomers, where the oligomer is formed by a 1,3-cycladdition reaction of the sydnone to an alkene or alkyne. In one embodiment, the oligomer is formed at a temperature below 90 ° C. The oligomer is then cured at 300 ° C. for up to 5 hours, thus forming a thermosetting resin composition comprising a crosslinked polymer. Prior to curing, the oligomer is partially crosslinked, and the thermosetting resin is completely or fully crosslinked after curing. The soluble oligomer may be coated from solution onto a variety of components (eg, copper, aluminum, stainless steel, polyethylene terephthalate) prior to curing.

In a particular embodiment of the invention, the thermosetting resin is produced by a cycloaddition reaction of a bifunctional sydnone with a bifunctional maleimide or a trifunctional alkyne (see FIG. 3). The resulting thermosetting resin exhibits very high thermal stability from 400 ° C to 520 ° C with a very high glass transition temperature of 370 ° C or higher. In addition, this fully aromatic thermosetting resin containing repeating units of pyrazole was found to have a heat resistance of 300 ° C. over a test period of several hours. The mechanical rigidity of the illustrated example exceeds 5.0 GPa in Young's modulus and the hardness is 0.5 GPa or more. Further, the thermosetting resin has a coefficient of thermal expansion in the temperature range of 25 to 350 ° C. of 51.8 μm / (m. ° C.) or less. These heat resistant high performance thermosetting resins will be used in a number of applications including the microelectronics and aviation industries. The sections of the examples below show the versatility of this modular platform and the impact of different components on the material properties obtained as a result of this study.

It will be clear that the overwhelming advantage of the ydnone-based platform is the high degree of freedom in molecular design. Desirable properties in the application can be achieved without difficulty by introducing the appropriate partial structure of the polymer. Examples of desirable properties are toughness, flexibility and workability. In addition, any combination of functional groups (such as di-sydnone + di-maleimide or tri-sydnone + di-alkyne) can be selected according to the needs of the synthesis or application.

（項目１０）
前記オリゴマーが、３００℃以下の温度で硬化する、上記項目のいずれか一項に記載の前記方法。
（項目１１）
前記オリゴマーが部分的に架橋し及び前記熱硬化性樹脂が完全に架橋する、上記項目のいずれか一項に記載の前記方法。
（項目１２）
前記熱硬化性樹脂組成物が、３００℃を超えるガラス転移温度（Ｔ_ｇ）及び／または４００℃以上の耐熱性を有する、上記項目のいずれか一項に記載の前記方法。
（項目１３）
前記熱硬化性樹脂組成物が、以下の少なくとも１つを含む、上記項目のいずれか一項に記載の前記方法。

（項目１４）
シドノン及びアルケンまたはアルキンの１つを含むモノマー混合物を与え、そのモノマー混合物を熱的に活性化したオリゴマーを形成し、ここで、前記オリゴマーが、前記アルケンまたはアルキンと前記シドノンとの１，３－双極性環化付加反応により形成され、及び、前記オリゴマーを硬化させ、そのため、架橋したポリマーを含む熱硬化性樹脂組成物を形成することを含む、熱硬化性樹脂組成物の生成法。
（項目１５）
前記シドノンが、モノ－シドノン、ビス－シドノン、及びトリス－シドノンから成る群から選ばれる、上記項目のいずれか一項に記載の前記方法。
（項目１６）
前記アルケンまたはアルキンが、ビス－マレイミド、トリス－マレイミド、ビス－アルキン、及びトリス－アルキンから成る群から選ばれる、上記項目のいずれか一項に記載の前記方法。
（項目１７）
前記オリゴマーが、９０℃未満の温度で形成される、上記項目のいずれか一項に記載の前記方法。
（項目１８）
前記オリゴマーが部分架橋し及び前記熱硬化性樹脂が完全架橋している、上記項目のいずれか一項に記載の前記方法。
（項目１９）
前記オリゴマーが、硬化に先立ち、部材にコートされる、上記項目のいずれか一項に記載の前記方法。
（項目２０）
前記部材が、アルミニウムまたは銅部材である、上記項目のいずれか一項に記載の前記方法。
（項目２１）
前記熱硬化性樹脂組成物の熱伝導性を高めるために選ばれた、１つ以上の構成要素の追加をさらに含む、上記項目のいずれか一項に記載の前記方法。
（項目２２）
構成要素が、前記熱硬化性樹脂組成物の物理的強靭性を高めるために添加される、上記項目のいずれか一項に記載の前記方法。
（項目２３）
前記熱硬化性樹脂組成物の接着性を高めるために選ばれた、１つ以上の構成要素の追加をさらに含む、上記項目のいずれか一項に記載の前記方法。
（項目２４）
前記熱硬化性樹脂組成物の浸透性網目構造を形成するために選ばれた、１つ以上の構成要素の追加をさらに含む、上記項目のいずれか一項に記載の前記方法。
（項目２５）
前記熱硬化性樹脂組成物の相分離無機添加物に作用するために選ばれた、１つ以上の構成要素の追加をさらに含む、上記項目のいずれか一項に記載の前記方法。
（項目２６）
任意の１つ以上の上記項目の方法により生成される物質の組成物。
（項目２７）
シドノンモノマーまたはオリゴマーと、第二の商業用熱硬化性樹脂の共レジンとの混合により生成される物質の組成物であって、そのため添加される第二の商業用熱硬化性樹脂に対して、前記シドノンが主要レジンである、前記組成物。
（項目２８）
前述の熱硬化性樹脂の熱機械特性を向上または低下させるために、商業用熱硬化性樹脂とシドノンオリゴマーまたはモノマーとの混合により生成される物質の組成物。
（項目２９）
前記熱機械特性が、Ｔｇ、Ｔｍ、及びＴｄから選ばれる、上記項目のいずれか一項に記載の前記組成物。
（項目３０）
前記商業用熱硬化性樹脂が、Ｔａｃｔｉｘ（商標）、Ｐｒｉｍａｓｅｔ（商標）、 Ｌｏｃｋｔｉｔｅ（商標） 、及び／またはＰＥＴＩ－３３０（商標）組成物である、上記項目のいずれか一項に記載の前記組成物。
（摘要）
シドノン及びアルケンまたはアルキンの１つを含むモノマー混合物を与えることを含む、熱硬化性樹脂組成物の生成法。このモノマー混合物は、熱的に活性化され、そのためオリゴマーが、前記アルケンまたはアルキンと前記シドノンとの１，３－双極性環化付加反応により形成される。次いでこのオリゴマーを硬化させ、その結果、架橋したポリマーを含む熱硬化性樹脂組成物を形成する。 Other objects, features and advantages of the present invention will be apparent to those skilled in the art from the detailed description below. However, it will be appreciated that while detailed descriptions and specific examples are shown and described in some embodiments of the invention, they are not limited thereto. Numerous changes and modifications within the scope of the invention may be made without deviation from the gist of the invention, and the invention includes all such modifications.
For example, the present invention provides the following items.
(Item 1)
A method for producing a thermosetting resin composition, which comprises providing a mixture of at least one monomer of sidonone and alkene or alkyne, forming an oligomer by thermal activation of the mixture, and curing the oligomer and thus a crosslinked polymer. The method comprising forming a thermosetting resin to be contained.
(Item 2)
The method according to the above item, wherein the sydnone is phenylbis-sydnone.
(Item 3)
The phenylbis-sidoneone replaces 1,4-diaminobenzene with ethyl bromide acetate in refluxed ethanol to give a salt, the salt is nitrosylated with an aqueous solution of sodium nitrite at 0 ° C., and the salt thereof. The method according to any one of the above items, which is synthesized by cyclizing a nitrosylated salt in CH ₂ Cl ₂ with anhydrous trifluoroacetic acid.
(Item 4)
The method according to any one of the above items, wherein the alkene is a bifunctional alkene and the alkyne is a tris-alkyne.
(Item 5)
The method according to any one of the above items, wherein the alkene is 1,1'-(methylenedi-4,1-phenylene) bismaleimide.
(Item 6)
The method according to any one of the above items, wherein the alkyne is 1,3,5-tris (phenylethynyl) benzene.
(Item 7)
The method according to any one of the above items, wherein the oligomer is formed by a 1,3-bipolar cycloaddition reaction of the alkene or alkyne with the sydnone.
(Item 8)
The method according to any one of the above items, wherein the oligomer is formed at a temperature of 100 ° C. or lower.
(Item 9)
The method according to any one of the above items, wherein the oligomer comprises at least one of the following, wherein x, y, and z are integers.

(Item 10)
The method according to any one of the above items, wherein the oligomer is cured at a temperature of 300 ° C. or lower.
(Item 11)
The method according to any one of the above items, wherein the oligomer is partially crosslinked and the thermosetting resin is completely crosslinked.
(Item 12)
The method according to any one of the above items, wherein the thermosetting resin composition has a glass transition temperature (T _g ) exceeding 300 ° C. and / or heat resistance of 400 ° C. or higher.
(Item 13)
The method according to any one of the above items, wherein the thermosetting resin composition comprises at least one of the following.

(Item 14)
A monomer mixture containing one of the alkene and alkene or alkyne is given to form an oligomer in which the monomer mixture is thermally activated, wherein the oligomer comprises 1,3- of the alkene or alkyne and the sidonone. A method for producing a thermosetting resin composition, which comprises forming a thermosetting resin composition containing a crosslinked polymer by curing the oligomer, which is formed by a bipolar cyclization addition reaction.
(Item 15)
The method according to any one of the above items, wherein the sydnone is selected from the group consisting of mono-sydnone, bis-sydnone, and tris-sydnone.
(Item 16)
The method according to any one of the above items, wherein the alkene or alkyne is selected from the group consisting of bis-maleimide, tris-maleimide, bis-alkyne, and tris-alkyne.
(Item 17)
The method according to any one of the above items, wherein the oligomer is formed at a temperature of less than 90 ° C.
(Item 18)
The method according to any one of the above items, wherein the oligomer is partially crosslinked and the thermosetting resin is completely crosslinked.
(Item 19)
The method according to any one of the above items, wherein the oligomer is coated on a member prior to curing.
(Item 20)
The method according to any one of the above items, wherein the member is an aluminum or copper member.
(Item 21)
The method according to any one of the above items, further comprising the addition of one or more components selected to enhance the thermal conductivity of the thermosetting resin composition.
(Item 22)
The method according to any one of the above items, wherein the component is added to enhance the physical toughness of the thermosetting resin composition.
(Item 23)
The method according to any one of the above items, further comprising the addition of one or more components selected to enhance the adhesiveness of the thermosetting resin composition.
(Item 24)
The method according to any one of the above items, further comprising the addition of one or more components selected for forming the permeable network structure of the thermosetting resin composition.
(Item 25)
The method according to any one of the above items, further comprising the addition of one or more components selected to act on the phase-separated inorganic additives of the thermosetting resin composition.
(Item 26)
A composition of a substance produced by any one or more of the above methods.
(Item 27)
A composition of a substance produced by mixing a sydnone monomer or oligomer with a co-resin of a second commercial thermosetting resin, with respect to the second commercial thermosetting resin added therein. , The composition, wherein the sydnone is the main resin.
(Item 28)
A composition of a substance produced by mixing a commercial thermosetting resin with a sidnon oligomer or monomer in order to improve or reduce the thermosetting properties of the thermosetting resin described above.
(Item 29)
The composition according to any one of the above items, wherein the thermomechanical properties are selected from Tg, Tm, and Td.
(Item 30)
The composition according to any one of the above items, wherein the commercial thermosetting resin is a Tactix ™, Primacet ™, Locktite ™, and / or PETI-330 ™ composition. thing.
(Summary)
A method for producing a thermosetting resin composition comprising providing a monomer mixture containing ydnone and one of an alkene or an alkyne. The monomer mixture is thermally activated so that oligomers are formed by the 1,3-bipolar cycloaddition reaction of the alkene or alkyne with the sydnone. The oligomer is then cured to form a thermosetting resin composition containing the crosslinked polymer.

References to drawings are shown everywhere in the corresponding part, such as reference numbers ^a . ^a "Note": Only trisubstituted pyrazoles are shown in FIGS. 1, 3, 31, 33, 37, 44, 48, 53, 54, 55 and 56. Potential tetrasubstituted isomers are not clear and are excluded.
FIG. 1 illustrates the reaction pathway of a [4 + 2] cycloaddition reaction between phenylsidenone and each of an alkene and an alkyne according to one or more embodiments of the invention. FIG. 2 is a schematic diagram of a "B-stage approach" utilized in the production of thermosetting resins according to one or more embodiments of the present invention. FIG. 3 illustrates the structure of the monomer constituents used in the production of two sets of thermosetting resins via a cycloaddition reaction of sydnones according to one or more embodiments of the invention. FIG. 4 illustrates a synthetic strategy utilized for the production of phenylbis-sydnone according to one or more embodiments of the invention. FIG. 5 illustrates a synthetic strategy utilized for the production of bis-sydnone 8 according to one or more embodiments of the invention. FIG. 6 illustrates a synthetic strategy utilized for the production of 2,2-bis [4- (4-maleimidephenoxy) -phenyl] propane according to one or more embodiments of the invention. FIG. 7 illustrates a synthetic strategy utilized in the production of 1,3-bis (4-maleimidephenoxy) benzene according to one or more embodiments of the invention. FIG. 8 illustrates the production of 1,3,5-tris (phenylethynyl) benzene 13 according to one or more embodiments of the invention. FIG. 9 illustrates a synthetic scheme for the production of oligomer I according to one or more embodiments of the invention. FIG. 10 is a graph of gel permeation chromatography (GPC) of Oligomer I according to one or more embodiments of the invention. FIG. 11 shows the model compounds MI and O-I. The molecular composition study of oligomer O-I by ¹ H-NMR in the spectral comparison of 2 is illustrated. FIG. 12 illustrates thermogravimetric analysis (TGA) data showing all oligomers stable at T ≦ 350 ° C. according to one or more embodiments of the invention. FIG. 13 illustrates TGA data for OI and the corresponding TS-I according to one or more embodiments of the invention. FIG. 14 illustrates the FT-IR spectra of OI and TS-I according to one or more embodiments of the invention. FIG. 15 is a TGA graph of the crosslinked thermosetting resin polymer TS-I obtained at 300 ° C. for 5 hours according to one or more embodiments of the present invention. FIG. 16 is a differential scanning calorimetry (DSC) graph of the crosslinked thermosetting resin polymer TS-I according to one or more embodiments of the present invention. FIG. 17 is a graph illustrating heating aging of TS-I at 300 ° C. for 5 hours according to one or more embodiments of the present invention. FIG. 18 illustrates the Young's modulus and hardness of the thermosetting resins TS-I, TS-IV and TS-V according to one or more embodiments of the present invention. FIG. 19 illustrates a thermomechanical analysis of a self-supporting thermosetting resin film TS-I, which measures dimensional changes in a film as a function of temperature, according to one or more embodiments of the invention. FIG. 20 illustrates the storage modulus (E'), loss modulus (E'') and tan δ for a freestanding film of TS-I according to one or more embodiments of the present invention. FIG. 21 illustrates the adhesion of TS-I, TS-IV and TS-V according to one or more embodiments of the invention. FIG. 22 illustrates a synthetic scheme corresponding to the production of Oligomer II according to one or more embodiments of the invention. FIG. 23 illustrates a stacked ¹ H-NMR spectrum of initiating monomer and oligomer II according to one or more embodiments of the invention. FIG. 24 illustrates the GPCs of Phenylbis-Sydnone 4 and Oligomer II according to one or more embodiments of the invention. FIG. 25 illustrates a stacked IR spectrum of the produced thermosetting resin II according to one or more embodiments of the present invention. FIG. 26 illustrates TGA data for thermosetting resin II according to one or more embodiments of the invention. FIG. 27 illustrates a synthetic scheme corresponding to the production of Oligomer III according to one or more embodiments of the invention. FIG. 28 illustrates the GPCs of Phenylbis-Sydnone 4 and Oligomer III according to one or more embodiments of the invention. FIG. 29 illustrates the stacked IR spectra of the produced thermosetting resin III according to one or more embodiments of the invention. FIG. 30 illustrates TGA data for thermosetting resin III according to one or more embodiments of the invention. FIG. 31 illustrates a strategy utilized in the production of Oligomer IV according to one or more embodiments of the invention. FIG. 32 is a gel permeation chromatogram of two sets of oligomers in trisalkylbenzene and chloroform, according to one or more embodiments of the invention. FIG. 33 illustrates a comparison of ¹ H-NMR spectra of model compound M-IV and oligomers O-IV and O-V according to one or more embodiments of the invention. FIG. 34 is a TGA graph of oligomers O-IVa and O-IVb according to one or more embodiments of the invention. FIG. 35 is a TGA graph of TS-IV according to one or more embodiments of the invention. FIG. 36 is an isothermal TGA graph of TS-IV according to one or more embodiments of the invention. FIG. 37 illustrates a synthetic scheme corresponding to the formation of oligomer V, according to one or more embodiments of the invention. FIG. 38 illustrates a stacked IR spectrum of TS-Vs produced under different conditions according to one or more embodiments of the invention. FIG. 39 illustrates TGA data of TS-V generated under different conditions according to one or more embodiments of the invention. FIG. 40 illustrates the heating aging of TS-V at 300 ° C. for 5 hours according to one or more embodiments of the invention. FIG. 41 shows a pre-cured film of TS-V suggesting incomplete cross-linking, accompanied by an inset image showing strip pieces of the flexible self-supporting film obtained after partial cross-linking according to one or more embodiments of the invention. Illustrate TGA data. FIG. 42 illustrates a thermomechanical analysis of TS-V according to one or more embodiments of the invention. FIG. 43 illustrates the storage modulus (E'), loss modulus (E'') and tan δ for a TS-V freestanding film according to one or more embodiments of the invention. FIG. 44 illustrates a strategy corresponding to the formation of oligomer VIs according to one or more embodiments of the invention. FIG. 45 illustrates a stacked ¹ H-NMR spectrum of initiating monomer and oligomer VI in one or more embodiments of the invention. FIG. 46 illustrates the GPC of 1,3,5-tris (phenylethynyl) benzene and oligomer VI produced under different conditions according to one or more embodiments of the invention. FIG. 47 illustrates TGA data for oligomers and crosslinked thermosetting resin VIs according to one or more embodiments of the invention. FIG. 48 illustrates a strategy corresponding to the formation of oligomer VII according to one or more embodiments of the invention. FIG. 49 illustrates a stacked ¹ H-NMR spectrum of initiating monomer and oligomer VII in one or more embodiments of the invention. FIG. 50 illustrates TGA data for oligomers and crosslinked Polymer IV according to one or more embodiments of the invention. FIG. 51 provides schematically illustrated example compounds useful in the mechanical properties of thermosetting compounds conditioned by copolymerization reactions containing, for example, linear segments selected to reduce crosslink density. FIG. 52 illustrates a strategy corresponding to the formation of thermosetting resin-I (TS-I) according to one or more embodiments of the present invention. FIG. 53 illustrates a strategy corresponding to the formation of thermosetting resin-IV (TS-IV) according to one or more embodiments of the present invention. FIG. 54 illustrates a strategy corresponding to the formation of thermosetting resin-V (TS-V) according to one or more embodiments of the present invention. FIG. 55 illustrates a strategy corresponding to the formation of thermosetting resin-VI (TS-VI) according to one or more embodiments of the present invention. FIG. 56 illustrates a strategy corresponding to the formation of thermosetting resin-VII (TS-VII) according to one or more embodiments of the invention. FIG. 57 illustrates polyfunctional sydnones and alkene / alkyne monomers that correspond to the formation of thermosetting resins via thermocyclization addition according to one or more embodiments of the invention. FIG. 58 illustrates a strategy corresponding to model compound MI according to one or more embodiments of the invention. FIG. 59 illustrates a strategy corresponding to model compound M-II according to one or more embodiments of the invention. FIG. 60 illustrates characteristic values for a variety of thermosetting resins according to one or more embodiments of the invention.

Numerous techniques and procedures described or referred to herein are well understood by those of skill in the art and are commonly employed in conventional techniques. In the description of the preferred embodiment, the reference may be made by forming a portion of the accompanying drawings, and may be carried out in a particular embodiment of the invention as illustrated. It will be appreciated that other embodiments may be utilized and structural changes may be made without departing from the scope of the invention.

Unless otherwise specified, all technical terms, notations and other specific or technical terms used herein are intended to have meaning generally understood by one of ordinary skill in the art in the art in which the invention relates. ing. In some cases, terms that have a commonly understood meaning are defined herein for clarity and / or quick reference, and the inclusion of such definitions herein is in the art. It does not have to be interpreted as representing a considerable difference beyond what is generally understood in.

Embodiments of the present invention include a method for producing a thermosetting resin composition. Various conventional methods and compositions relating to thermosetting resins are known in the art, and explanatory examples are described below, for example. HANDBOOK OF THERMOSET PLASTICS, Third Edition (Pdl Handbook) 2013, CHEMICAL RESISTANCE, VOL. 2, SECOND EDITION: ELASTOMERS, THERMOSETS & RUBBERS (Plastics Design Library) 1995, THERMOSETS AND COMPOSITES: MATERIAL SELECTION, APPLICATIONS, MANUFACTURING AND COST ANALYSIS (Pdl Handbook) 2013 by Michel Biron, and the HANDBOOK OF THERMOSET RESINS by Debdatta Ratna (Sep 30, 2009). The thermosetting resin forming method of the present invention generally includes the provision of a monomer mixture containing ydnone. In this context, a variety of conventional methods and compositions relating to sydnones are known in the art, and explanatory examples are described, for example, below. SYDNONES: VERSATILE HETEROCYCLES 2014, by Shahrukh Asundaria, METAL COMPLEXES OF SYDNONES, SYDNONE IMINES, AND THEIR INFRARED SPECTRA 1994 by Theresa Shu-Ying Lim Mao, and SYNTHETIC APPLICATIONS OF 1,3-DIPOLAR CYCLOADDITION CHEMISTRY TOWARD HETEROCYCLES AND NATURAL PRODUCTS (Chemistry 2002 ) By Albert Padwa and William H. Pearson.

The invention disclosed herein has a number of embodiments. In one or more embodiments, a method for producing a thermosetting resin composition is provided. The method comprises providing a monomer mixture containing one of ydnone and an alkene or alkyne. In certain embodiments, different sydnone mixtures are provided with copolymerizations of different alkenes, different alkynes or mixtures thereof. Oligomers are formed by thermal activation of the monomer mixture. The oligomer is then cured to form a thermosetting resin composition containing a crosslinked polymer.

In one or more embodiments of the invention, the synthetic procedure corresponding to the production of a ydnone-based thermosetting resin composition is based on three main steps (shown in FIG. 2). In the first step, (poly) functional sydnones are synthesized as monomer components, as are the polyfunctional alkenes and alkynes, respectively. In the second step, thermal activation of the dissolved monomer mixture yields a partially crosslinked low molecular weight oligomer, a pre-curable thermosetting resin that is easily processed from the solution. The third step involves final curing of the oligomer at high temperatures. The three-dimensional (aromatic) network structure of the crosslinked polymer as a thermosetting resin may be obtained from either a solution or a cast film (solid phase).

In one or more embodiments, the sydnone is selected from the group consisting of mono-sydnones, bis-sydnones, and tris-sydnones. In certain embodiments, the sydnone is either a phenylbis-sydnone or an oxygen-bridged bis-sydnone. The phenylbis-sydnone is synthesized in high yield with excellent purity by the following synthetic method which does not require any purification step. First, 1,4-dianobenzene is replaced with ethyl bromide in refluxed ethanol to obtain a salt. The salt is then nitrosylated with an acidic solution of sodium nitrite at 0 ° C. This nitrosylated salt is further cyclized with anhydrous trifluoroacetic acid in CH ₂ Cl ₂ to produce phenylbis-sydnone. Oxygen-bridged bis-sydnones were produced according to the same procedure as described above for phenylbissydnones. In one or more embodiments, the alkene or alkyne is selected from the group consisting of bifunctional alkene, bis-maleimide, tris-maleimide, bis-alkyne, and tris-alkyne. In certain cases, these monomers are described in the literature, and the alkene is 1,1'-(methylenedi-4,1-phenylene) bismaleimide, 1,3-phenylene bismaleimide, 4,4'-. It is (1,3-phenylenedioxy) bismaleimide, and 4,4'-(4,4'-ilopropyridendiphenyl-1,1'-diyldioxy) bismaleimide, and the alkyne is 1,3. 5-Tris (phenylethynyl) benzene and 1,3,5-triethynylbenzene.

In one or more embodiments of the invention, heat is obtained by copolymerizing one or more material properties of the thermosetting resin, eg, a mixture having a selected amount of a particular compound, in order to adjust the crosslink density. A curable resin is formed. In this method, such embodiments of the invention regulate their mechanical properties, eg, through this copolymerization (see, eg, the schematic route diagram shown in FIG. 51). Embodiments include, for example, a mixture of different sydnones and a mixture of different alkenes, different alkynes or combinations thereof. In certain embodiments, the crosslink density of the thermosetting resin varies with the inclusion of linear and / or terminal segments in its network structure. In such embodiments, a mixture of polyfunctional sydnones and mono-sydnones is used for copolymerization with polyfunctional alkenes or alkynes. In one or more embodiments, a mixture of different polyfunctional alkenes, different alkynes or combinations thereof is used for copolymerization with different sydnone mixtures. In certain cases, the mono-sydnone is N-phenylsydnone.

ここで、ｘ、ｙ、及びｚは、整数である。 In one or more embodiments, the oligomer is formed by a 1,3-bipolar cycloaddition reaction of the sydnone to an alkene or alkyne (for alkyne polymers, only 3-substituted pyrazole units are shown. , Potential tetrasubstituted isomers are not clearly excluded). The oligomer is usually formed at a temperature of 80 ° C. or lower. In certain embodiments, the oligomer is typically formed at temperatures above 170 ° C. The oligomer may be one of the following.

Here, x, y, and z are integers.

Generally, the oligomer cures at temperatures up to 300 ° C., not higher. Prior to curing, the oligomer is partially crosslinked, and the thermosetting resin thereof is fully or fully crosslinked after curing. The oligomer may be coated on a member (eg, glass, copper, aluminum) prior to curing. In a particular embodiment, the thermosetting resin composition has a glass transition temperature (T _g ) of 370 ° C. or higher and / or heat resistance of 400 ° C. or higher. The thermosetting resin composition may be one of the following.

In certain embodiments, constituents are added to the sidnon oligomer prior to completion of crosslinking in order to provide enhanced physical properties such as, but not limited to, mechanical toughness, adhesiveness, thermal conductivity, etc. .. In certain embodiments, an inorganic component is added to enhance its thermal conductivity. The above-mentioned additives include, but are not limited to, boron nitride, aluminum nitride, graphene, carbon nanotubes, graphite carbon nitride, and silicon carbide. In certain embodiments, the additive is selected from zinc oxide, graphite oxide, graphene, silica, alumina, carbon nanotubes, fumed oxides and the like to provide enhanced physical toughness. In a further embodiment, co-additives are selected to give the principal components certain actions, such as permeability, phase separability, surface wettability and the like. Co-additives may include, but are not limited to, ionized liquids, epoxys, phenols, oxides and nitrides of graphite, benzoxazines, silanes, polysilsesquioxane, silsesquioxane, imidazoles, triazines, imides. .. For experts in the art, one or more additives may be selected to provide multifunctional properties, and the scope of these constituent additives may not be restrictive or inclusive. Will be recognized.

In one or more embodiments, a multi-component mixture of a sidnon oligomer and a second thermosetting resin is disclosed. In certain embodiments, the sidonone oligomer is conventionally used to enhance the thermal-physical properties of the associated resin, such as Tactix ™, Primacet ™, Locktite ™, PETI-330 ™. It is considered to be an additive (or co-resin) to commercial thermosetting resins. In certain embodiments, any conventionally known polymer or prepolymer and / or monomer is required (or appropriately) to enhance any property except thermal stability or thermal conductivity. It can be added to the sidonone oligomer or monomer. In these cases, all organic co-additives can be blended with the sidnon monomer or associated oligomer.

In the 1,3-bipolar cycloaddition reaction of phenylbis-sydnone with the corresponding aromatic alkene or alkyne derivative, the molecular structure of the cross-linking point of each resin is changed, and two different thermosetting resins are used. It represents a new, easy and versatile synthetic pathway that leads to classification (Fig. 3). As an exemplary embodiment of the invention, eight different thermosetting resins were produced. All of them consist of a viaduct aromatic network structure and thus retain a high _Tg (> 300 ° C) and significantly improved heat resistance (≧ 400 ° C). Corresponding to the illustrated illustrations, the examination of mechanical properties and adhesion to various substrates (eg, copper, aluminum, etc.) are provided. Further, one thermosetting resin in each category serves as an exemplary embodiment corresponding to the curing reaction and detailed study of the molecular structure of the oligomers and thermosetting resins of each thermosetting resin category.

Synthesis of Bis-Sidnon Monomers The exemplary thermosetting resin is based on two different bifunctional sidnon monomers. Efficient synthetic pathways have been developed to provide easy contact with these basic components.

Starting with the substitution of phenylbis-sydnone 4.1,4-diaminobenzene with ethyl bromide acetate, the protected ester 1 was then hydrolyzed to produce zwitterionic compound 2 (FIG. 4). The first prototype for nitrosylation of 2 with aqueous sodium nitrite solution at 0 ° C. gave 3 in 19% yield. The alarmingly low yield of 3 is probably due to the mass formation of unidentified impurities (sticky black solids) with the substance of interest, and then nitrosyl using an acidic solution of sodium nitrite in glacial acetic acid. The conditions for high yield were optimized for the conversion, resulting in a significant improvement in yield (77%) with a purity of 3. Finally, the phenylbis-sydnone 4 was obtained by the cyclization reaction of 3 using anhydrous trifluoroacetic acid at 45 ° C. In particular, the optimized synthesis procedure of 4 improved the yield as a whole and resulted in a high purity that did not require purification at each step.

Phenylbis-Sydnone 8. The bis-sydnone 8 was produced using the same procedure established for phenylbis-sydnone 4 (FIG. 5). Substitution of 4,4'-oxydianiline with ethyl bromide acetate was followed by hydrolysis of the protected ester 5 to yield the zwitterionic compound 6. Then, N-nitrosated compound 7 was obtained through nitrosylation using an acidic solution of sodium nitrite in glacial acetic acid. Finally, a mesoionic substance 8 was obtained by a cyclization hydration reaction of 7 using anhydrous trifluoroacetic acid at 45 ° C.

Synthesis of bis-maleimide monomers Two bis-maleimide monomers were produced by imidization of bisamidic acids corresponding to diamines.

10.30 mmol of bis-maleimide 10.30 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was dissolved in 150 mL of acetone stirring at room temperature at a constant rate. 65 mmol of powdered maleic anhydride was added separately to this solution. A yellow precipitate was formed and it was stirred continuously for 30 minutes. It was filtered and washed with cold acetone and dried. The yield was 80%. The obtained yellow bisamidic acid 9 (FIG. 6) was dispersed in 150 mL of acetone. 40 mmol of sodium acetate and 40 mL of acetic anhydride were added to the reaction mixture and refluxed for 3 hours. The brown solution was poured into ground ice and the title compound was obtained as a yellow precipitate. The 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane was filtered, washed with ice-cold water, and vacuum dried. The yield was 90%.

Bis-maleimide 12. This compound was produced from 4,4'-(1,3-phenylenedioxy) dianiline using the same procedure established for bis-maleimide 10. 30 mmol of diamine was dissolved in 150 mL of acetone stirring at room temperature at a constant rate. 65 mmol of powdered maleic anhydride was added separately to this solution. A yellow precipitate was formed and it was stirred continuously for 30 minutes. It was filtered and washed with cold acetone and dried. The yield was 85%. The obtained yellow bisamidic acid 11 (FIG. 7) was dispersed in 150 mL of acetone. 40 mmol of sodium acetate and 40 mL of acetic anhydride were added to the reaction mixture and refluxed for 3 hours. The brown solution was poured into ground ice and the title compound was obtained as a yellow precipitate. The 1,3-bis (4-maleimide phenoxy) benzene was filtered, washed with cold water and vacuum dried. The yield was 90%.

Synthesis of Tris-Alkyne Monomer 1,3,5-Tris (Phenylethynyl) benzenen 13. A Tris-alkyne monomer corresponding to the Diels-Alder cyclization addition reaction with phenylbis-sydnone 4 was produced in a single step shown in FIG. Sonogashira cross-coupling of 1,3,5-tribromobenzene and phenylacetylene gave 13 in 90% yield.

General procedure for thermosetting resin formation via B-stage approach Step 1: Oligomer formation. The starting monomer was dissolved in anhydrous NMP and then the resulting solution was degassed using a freeze pump thawing cycle. The mixture was reacted at the desired temperature at various times. After the reaction was complete, the reaction mixture was cooled to room temperature and the oligomer was precipitated using methanol. The resulting solid was filtered on a Büchner funnel and dried.

Step 2: Final curing. By drop casting into NMP solution, a solid film of its B-stage oligomer was formed on a glass slide or TGA crucible vessel in air. Simple heating of the film at T = 300 ° C. for 5 hours induced final cross-linking of the reacted precursor oligomers. The resulting thermosetting resin film was found to be insoluble in any solvent, and significant swelling was not visually observable, indicating that the viaduct material was successfully produced.

As described in FIG. 3, the thermosetting resins disclosed herein can be divided into two groups. In the following examples, the A classification comprises TS-I, II and III, and the B classification comprises TS-IV, V, VI and VII. See, for example, FIGS. 52-56, which illustrate strategies for the production of various thermosetting resins according to one or more embodiments of the invention.

Example 1: Thermosetting resin I
Thermosetting resin I (TS-I, A classification) is used for cycloaddition reaction between phenylbis-sydnone 4 and 1,1'-(methylenedi-4,1-phenylene) bismalade as bifunctional alkene 14. Based on.

Oligomer formation in solution. In order to generate the thermosetting resin polymer TS-I by utilizing the above-mentioned B-stage approach, soluble oligomers (O-I) as precursors of the thermosetting resin I are prepared with phenylbis-sidone and bis. -Formed from maleimide 14, the oligomer as a result of which is composed of diazonorbornene cross-linked moities. The main challenge for an efficient B-stage is the development of appropriate reaction conditions for the oligomer formation. All reactive monomers must be consumed to ensure good mixing of reactive groups and to avoid phase separation of the monomers during final curing, while the oligomers allow for easy processing and their. In order for the final crosslink to still contain reactive groups, it must be completely soluble. However, its ultimate goal is a fully cross-linked network structure that can only be achieved by stoichiometric quantities of both functional groups, and one monomer cannot be overused. Therefore, in order to enable the formation of soluble oligomers that completely meet the above criteria, it is essential to study individual reaction conditions such as reaction temperature and time.

１当量のビス－シドノン及び２当量のビス－マレイミドを含む化学量論溶液に対する反応温度の変化で、寡占的なオリゴマー形成が、Ｔ≦８０℃の温度に対してのみ起こることが明らかになった。対照的に、Ｔ＞９０℃の条件に対しては、かなりの程度のモノマーの架橋が見出され、それゆえ不溶性物質がもたらされた。反応時間の影響についてさらに検討を実施し、及びゲル浸透クロマトグラフィー（ＧＰＣ）で、９０℃以下の温度条件においては、可溶性オリゴマーの分子量は、反応温度及び時間と共に増加し、しかし５ｋＤａを超えないことが明らかになった（表２及び図１０）。これらの結果は、多様な極性溶媒に可溶であるＯ－Ｉ前駆体オリゴマーの生成を可能にする、幅広い加工方法の存在を示している。

Diazonorbornene-oligomer I. Phenylbis-sydnone 4 and bis-maleimide 14 were added to the reaction mediated by the (double) 1,3-bipolar cycloaddition reaction in N-methyl-2-pyrrolidone (NMP) under an inert atmosphere. Served. As shown in FIG. 9, this reaction is given by the general substance oligomer I, where the reaction ratio of the crosslinked portion x with the free reaction groups y and z depends on the reaction conditions. In order to examine the effects of reaction temperature and time on the distribution of these structural subunits, the conditions were varied to cover Table 1.

Changes in the reaction temperature to a stoichiometric solution containing 1 equivalent of bis-sydnone and 2 equivalents of bis-maleimide revealed that occupying oligomerization occurred only at a temperature of T ≤ 80 ° C. .. In contrast, for T> 90 ° C. conditions, a significant degree of monomer cross-linking was found, thus resulting in insoluble material. Further studies were conducted on the effects of reaction time, and by gel permeation chromatography (GPC), at temperatures below 90 ° C., the molecular weight of the soluble oligomer increases with reaction temperature and time, but does not exceed 5 kDa. Was clarified (Table 2 and FIG. 10). These results indicate the existence of a wide range of processing methods that allow the production of O-I precursor oligomers that are soluble in a variety of polar solvents.

In order to use soluble oligomers as precursors for the formation of thermosetting resins, it must be ensured that their reactivity is retained. It is known that the first cycloaddition reaction yields a highly active pyrazoline intermediate, which rapidly and occupiedly proceeds to the second cycloaddition reaction, which produces each diazonorbornene unit. Retention of sex is determined solely by the presence of free sydnones (y) and maleimide groups (z). Therefore, the distribution of x, y, and z of different structural units in these low molecular weight materials will be qualitatively examined using ¹ H-NMR (FIG. 11). It has been found that ¹ H-NMR spectra of the different oligomers show the appearance of new peaks in their aromatic and aliphatic regions with the decrease of the peak corresponding to the starting monomer. As expected, no peak corresponding to intermediate pyrazoline was observed from the first participatory reaction. In order to further enable the accurate positioning of newly generated peaks, a small molecule model compound MI was synthesized from the cycloaddition reaction of N-phenylsidenone and N-phenylmaleimide, and its MI. The spectrum corresponding to is shown in the exemplary oligomer O-I. It is shown in FIG. 11 in comparison with 2.

O.I. By spectral comparison of 2 and MI, the apparent spectral similarity indicates structural similarity. The protons Ha', Hb'and Hc'of diazonorbornene in the model compound MI are O.I. It correlates well with a series of peaks in the aliphatic region of 2 and therefore O-I. It shows the presence of protons Ha, Hb and Hc from the diazonorbornene component in 2. In particular, O-I. The series of peaks of each proton of diazonorbornene in 2 may be due to a mixture of different subunits x, y and z. O.I. The 9.05 ppm peak at the most downstream position of 2 appears to emerge from the Hd protons at the unreacted ends of the sidnonmoisties. Furthermore, the 7.1 ppm peak appears to be interrelated with the He protons of the terminal maleimide moietti z. The presence of each signal reveals the retention of reactive end groups in the slightly cross-linked oligomers, even though the quantitative analysis of the ratio of the cross-linked portion x to the free end groups y and z is hindered by the overlap of those peaks. For further curing to a fully crosslinked thermosetting resin, O-I. Guarantees the retention of reactivity in 2.

To examine the thermal properties of the oligomer, a TGA evaluation of each sample was performed and the graphs obtained are shown in FIG. All oligomers obtained under different conditions showed a 2-5% primary weight loss at T-75 ° C, followed by a secondary weight loss of up to approximately 92% starting at 150 ° C. After that, all oligomers showed the start of complete decomposition at T-350 ° C. These data strongly suggest that the two initial weight losses observed can be attributed to the generation of CO ₂ as a result of the cycloaddition reaction of the terminal sydnone with the maleimide group in the slightly crosslinked material. is doing. As proposed, this reaction ultimately results in a highly crosslinked thermosetting resin material that is stable up to T ≤ 350 ° C. Moreover, no significant differences were observed in the thermal behavior of the oligomers produced under different conditions.

Heat curing of precursor oligomers in solid state. O-I. During NMP. 2 (55% solid content) solution was prepared. Since the adhesiveness of TS-I to glass is weak, the solution was poured onto a copper foil wrapping a glass plate. The film was dried at 60 ° C. for 24 hours in an air circulation oven to remove the solvent. The film fixed on the copper foil was started at 100 ° C. for 5 hours and the final temperature was set at intervals of 50 ° C. to almost completely guarantee polymerization to a state without detectable decomposition. Polymerization was carried out until the temperature reached 300 ° C. The film had a black-brown color and its thickness was in the range of 0.1-0.2 mm. Early and homogeneous films of TS-I obtained by polymerization at 300 ° C. for 5 hours were analyzed using FT-IR and TGA (FIGS. 13 and 14). The FT-IR spectrum of the polymer film revealed the consumption / disappearance of the carbonyl expansion and contraction of ydnone at 1750 cm ^-1 , suggesting complete curing at 300 ° C. Furthermore, no series of weight loss was observed in the TS-I TGA, indicating complete cross-linking at 300 ° C. Furthermore, the resulting TS-I film was found to be insoluble in any solvent, and no significant visual swelling was observed, resulting in the successful production of highly crosslinked material. Was showing. In particular, the above-mentioned curing could be carried out in air as well as in an inert atmosphere. No difference was observed in the thermal stability of TS-I obtained under both conditions.

熱重量分析により得られた分解温度は、熱硬化性ポリマーの熱安定性評価に必須なパラメーターであると思われるが、しかし長期にわたる高温での安定性を意味してはいない。したがって、当該熱硬化性ポリマーに対する、経時における熱分解プロセスを特定するために、３００℃での短期間の等温熱重量分析を実施した。等温条件下－不活性雰囲気下の３００℃で３００分－で、熱硬化性樹脂ＴＳ－Ｉの重量減少は、わずかに０．５％であり（図１７）、その結果この材料の高耐熱性を示した。 Thermal evaluation of TS-I. The thermal stability of TS-I was evaluated using TGA in a nitrogen atmosphere and summarized in FIG. 15 and Table 3. The thermosetting resin TS-I has a 5% weight loss temperature (T _d5% ) at 412 ° C. despite the presence of a low content aromatic ring and a thermally unstable aliphatic diazonorbornene moyity. ) Shows a region with good thermal stability. Furthermore, the glass transition temperature of the thermosetting resin was determined by DSC and found to be> 300 ° C. (FIG. 16). This value can be assigned to the relaxation of the highly crosslinked 3D network structure and the concomitantly constrained molecular chains, resulting in high crosslink density.

The decomposition temperature obtained by thermogravimetric analysis appears to be an essential parameter for assessing the thermal stability of thermosetting polymers, but does not imply long-term stability at high temperatures. Therefore, a short-term isothermal gravimetric analysis at 300 ° C. was performed to identify the pyrolysis process over time for the thermosetting polymer. Under isothermal conditions-300 minutes at 300 ° C. under an inert atmosphere-the weight loss of the thermosetting resin TS-I was only 0.5% (FIG. 17), resulting in the high heat resistance of this material. showed that.

Mechanical and thermomechanical properties of TS-I. The applicability of thermosetting resins in materials that require precise dimensional tolerances and eliminate deformation under load depends on the stiffness or rigidity of the crosslinked network structure and its hardness. In order to investigate the thermosetting resin based on the ydnone in relation to these parameters, a nanoindentation test was performed on the cured thermosetting resin film. As shown in FIG. 18, these mechanical measurements indicate that TS-I has a Young's modulus of greater than about 5.0 GPa (Table 4) at room temperature, resulting in general commercially available thermosetting. It was shown that it exhibits excellent mechanical properties that exceed the rigidity of the sex resin. Furthermore, the hardness of the sydnone-based thermosetting resin was as low as 0.6 GPa (Table 4), further indicating that the desired material properties were successfully introduced through individual molecular design. The sydnone-based polymer network structure consists of rigid components that are highly crosslinked and, as a result, exhibit a good combination of high stiffness and hardness.

However, for practical applications, the material must maintain their excellent mechanical properties over a wide temperature range. Since these materials are so tightly crosslinked, only changes in mechanical structural stability can occur due to changes in temperature dependence in the movement of their networked structural segments. An increase in temperature can cause an increase in the mobility of the secondary chain and therefore can cause an expansion of the material at the same time as a decrease in mechanical strength. The direct effect of temperature-induced and increased mobility was determined as the coefficient of thermal expansion of the thermosetting resin TS-I. Correspondingly, thermomechanical analysis (TMA) was performed on each self-supporting film. FIG. 19 shows the dimensional change of the thermosetting resin film as a function of temperature (up to 300 ° C. for TS-I). The thermal expansion rate (CTE) over this temperature range for TS-I is 51.8 μm / (m. ° C.) (Table 5), thus demonstrating excellent dimensional stability at high temperatures.

最終的に、硬化したフィルムとしてのこれら熱硬化性ポリマーの利用は、この材料の基材への接着性に決定的に依存する。したがって、その接着力を、標準化された手順に従った剪断接着試験を実施して評価した。当該反応性前駆体オリゴマー（Ｏ－Ｉ）の溶液を、剪断接着試験の構成において、無研磨の２枚のアルミニウム基材の、重ね合わせ部の表面に塗布した。当該オリゴマーを、空気中で３００℃までの傾斜温度プロファイルを使用して硬化させ、次いで３００℃で５時間の最終硬化ステップで硬化させた。その基材を破壊するまで引っ張り、分析を行い、及びその剪断接着力を、図２１にまとめた。記載のように、熱硬化性樹脂ＴＳ－Ｉは、約０．６ ＭＰａの平均接着力を示した。 In a more direct attempt to measure the effect of temperature on the movement of the link chain, TS-I self-supporting films were tested by dynamic mechanical analysis (DMA). FIG. 20 shows the temperature dependence of storage modulus (E'), loss modulus (E ″) and tan δ. A room temperature storage modulus of 2.7 relative to TS-I sheds light again on the exceptional stiffness of these materials. Moreover, its temperature dependence makes it possible to draw conclusions on thermal dislocations in the network structure of macromolecules. Up to 325 ° C, the E'of TS-I remains constant and then drops sharply. In the combination of the maximum values of tan δ at 376 ° C and E'' at 368 ° C, this change is assigned to the glass transition temperature (Tg) of TS-I. TS-I also revealed a low sub-glass β2 transition that appeared as wide shoulder peaks at tan δ and E'' at ~ 90 ° C and 70 ° C, respectively. These low β2 transitions are probably due to incomplete network structure formation after curing in the bithermosetting polymer. In summary, these results clearly show how the high crosslink density and rigid matrix of the partial or complete aromatic molecular skeleton provided exceptionally good thermomechanical properties for both thermosetting resins. ..

Ultimately, the use of these thermosetting polymers as a cured film depends decisively on the adhesion of this material to the substrate. Therefore, the adhesive strength was evaluated by performing a shear adhesion test according to a standardized procedure. A solution of the reactive precursor oligomer (OI) was applied to the surface of the superposed portion of two unpolished aluminum substrates in the configuration of the shear adhesion test. The oligomer was cured in air using a tilt temperature profile up to 300 ° C. and then cured at 300 ° C. in a final curing step of 5 hours. The substrate was pulled until broken, analyzed, and its shear adhesion was summarized in FIG. As described, the thermosetting resin TS-I showed an average adhesive force of about 0.6 MPa.

Example 2: Thermosetting Resin-II
Thermosetting resin II (TS-II, A classification) is phenylbis-sydnone 4, bis-maleimide 10, a bulk bifunctional alkene monomer, 2,2-bis [4- (4-aminophenoxy) phenyl. ] Based on the cycloaddition reaction with propane.

当該オリゴマーＩＩを、^１Ｈ－ＮＭＲを使用して、特徴付けた。図２３に示すように、新しいピークの出現に伴うモノマーピークの減少で、オリゴマー形成を確認する。５．９及び４．６ｐｐｍ周辺でのプロトンは、シドノンとマレイミド間の環化付加反応の後に形成されたジアゾノルボルネンのプロトンの向きを示している。 Oligomer formation in Solution II. Phenylbis-sydnone 4 and bis-maleimide II are reacted via a (double) 1,3-bipolar cycloaddition reaction in N-methyl-2-pyrrolidone (NMP) under an inert atmosphere. rice field. As shown in FIG. 22, this reaction gave the oligomer II. The effects of reaction temperature and time on the oligomer formation are covered in Table 6. In comparison with the formation of Oligomer I, higher reaction temperatures and longer times are required for the bulk bis-maleimide 10 used.

The oligomer II was characterized using ¹ H-NMR. As shown in FIG. 23, oligomer formation is confirmed by the decrease of the monomer peak with the appearance of the new peak. Protons around 5.9 and 4.6 ppm indicate the orientation of the diazonorbornene protons formed after the cycloaddition reaction between ydnone and maleimide.

Like the GPC data, the disappearance of the two monomers and the appearance of new peaks corresponding to Oligomer II pointed to a complete reaction at 110 ° C. for 6 hours. The average molecular weight (M _n ) was found in the range of 2.0 kDa (FIG. 24, Table 7).

Heat curing of precursor oligomer II in solid state. An O-II (55% solids) solution in NMP was prepared. The obtained solution was poured onto a glass plate in a drip, and then the drip-cast film was heated in air by a gradient curing method. The temperature was increased in an inclined manner from 25 ° C. to 300 ° C. at a rate of 1 ° C./min and then held at an isothermal temperature of 300 ° C. for 5 hours. The FT-IR spectrum of the polymerized film revealed the disappearance of the carbonyl expansion and contraction of ydnone at 1740 cm ^-1 , suggesting complete curing (FIG. 25). The resulting film was found to be insoluble in any solvent and showed cross-linking of oligomers.

Thermal evaluation of TS-II. The thermal stability of TS-II was evaluated using TGA in a nitrogen atmosphere and the results are summarized in FIG. The thermosetting resin TS-II showed a good range of thermal stability with a 5% weight loss temperature (T _{d 5%} ) at 390 ° C.

Example 3: Thermosetting Resin-III
Thermosetting resin-III (TS-III, Class A) is a cyclization of phenylbis-sydnone 4 with bis-maleimide III, a bifunctional alkene monomer, 1,3-bis (4-maleimide phenoxy) benzene. Based on addition reaction.

The reaction of phenylbis-sydnone 4 with the bis-maleimide gave an oligomer III (FIG. 27) based on diazonorbornene, which serves as a precursor for the thermosetting resin III. The reaction was carried out in NMP at 110 ° C. for 5 hours under an inert atmosphere. After precipitation in methanol, the oligomer was isolated.
In the GPC assessment, the disappearance of the two monomers and the appearance of new peaks corresponding to Oligomer III indicated the direction of the complete reaction. The average molecular weight (M _n ) was found within the range of 2.3 kDa (FIG. 28, Table 8).

Heat curing of precursor oligomer III in solid state. A solution of O-III (55% solids) in NMP was prepared. The obtained solution was poured onto a glass plate in a drip, and then the drip-cast film was heated in air by a gradient curing method. The temperature was increased in an inclined manner from 25 ° C. to 300 ° C. at a rate of 1 ° C./min and then held at an isothermal temperature of 300 ° C. for 5 hours. The FT-IR spectrum of the polymerized film revealed the disappearance of the carbonyl expansion and contraction of ydnone at 1740 cm ^-1 , suggesting complete curing (Fig. 29). The resulting film was found to be insoluble in any solvent and showed cross-linking of oligomers.

Thermal evaluation of TS-III. The thermal stability of TS-III was evaluated using TGA in a nitrogen atmosphere and the results are summarized in FIG. The thermosetting resin TS-III showed a good range of thermal stability with a 5% weight loss temperature (T _{d 5%} ) at 390 ° C.

Example 4: Thermosetting Resin IV
The thermosetting resin IV (TS-IV, B classification) is based on the Diels-Alder reaction between phenylbis-sydnone 4 and 1,3,5-tris (phenylethynyl) benzene, which is a tris-alkene 13.

Oligomer formation in solution. The reaction of phenylbis-sydnone with the tris-alkene 13 gave the pyrazole-based oligomer IV, which serves as a precursor corresponding to the complete aromatic network structure of the thermosetting resin IV. Phenylbis-sydnone 4 and 1,3,5-tris (phenylethynyl) benzene 13 were reacted to yield oligomer IV through their respective Diels-Alder cyclization addition reactions (FIG. 31). The reaction was carried out in NMP at 170 ° C. for 12 hours in an inert atmosphere. After precipitation in methanol, the resulting oligomer mixture was found to be soluble in a range of organic solvents including DCM, CHCl ₃ , NMP, DMF and the like.

Two sets of oligomers IVa and IVb with different molecular weights were separated by selective solubility of the small molecule oligomers in acetone. The obtained substances were examined for their molecular weight distribution by GPC analysis, and the results are shown in FIGS. 32 and 9. The molecular weights of all oligomers were found to be ≤3 kDa (Table 9).

両オリゴマーＩＶａ及びＩＶｂの熱的特性を、ＴＧＡを使用して分析し、及び各々のグラフを図３４に示す。ＴＧＡデータにより証明されるように、両オリゴマーは、各々さらなる架橋性を、まだ保持している。当該オリゴマーＩＶａは、～８０℃及び～１８０℃での２つの連続した重量減少と、それに次ぐ～５００℃での分解を示した。対照的に、オリゴマーＩＶｂは、～２１５℃での単一の初期の重量減少と、それに次ぐ～５００℃での分解を受けた。この初期の連続重量減少は、その架橋前の物質における末端シドノンとアルキンモイエティーの環化付加反応からのＣＯ_２の発生に、主として起因していると思われる。この結果は、両オリゴマーが、自由活性末端基を含んでいることを示している。 ¹ Structural analysis of oligomer O-IV using 1 H-NMR showed the emergence of a new aromatic peak set with a decrease in the signal corresponding to the starting monomer, and successfully dealt between the two subunits. It was shown that the Alder reaction was performed. Similar to the study in O-I, the model compound M-IV was synthesized and the peak assignment to the pyrazole cross-linking point in the oligomer O-IV was advanced. As shown in FIG. 33, the set of novel peaks at ~ 9 ppm corresponds well to the pyrazole unit in M-IV, thus indicating the successful incorporation of the pyrazole component in O-IV. In connection with the determination of the free active group, the identification of the terminal protons from the unreacted sidnonmoiety was hampered by duplication with each proton from its pyrazole moyety. Therefore, accurate assignment of free active groups in O-IV could not be performed.

The thermal properties of both oligomers IVa and IVb are analyzed using TGA, and a graph of each is shown in FIG. Both oligomers still retain additional crosslinkability, as evidenced by TGA data. The oligomer IVa showed two consecutive weight losses at ~ 80 ° C and ~ 180 ° C, followed by decomposition at ~ 500 ° C. In contrast, the oligomer IVb underwent a single initial weight loss at ~ 215 ° C, followed by decomposition at ~ 500 ° C. This initial continuous weight loss appears to be primarily due to the generation of CO ₂ from the cycloaddition reaction of terminal sydnones with alkyne moities in the pre-crosslinking material. This result indicates that both oligomers contain free active end groups.

Heat curing of precursor oligomer IV in solid state. A homogeneous slurry of O-IV was dissolved in NMP as a 48% solid and prepared using a high speed stirring mixer. The resulting solution was poured onto copper foil using three different techniques: drop casting, spin coating and blade coating. Curing of the resulting film was performed in an air circulation oven using a gradient heating protocol in which the film was heated to 300 ° C. at a rate of 0.1 ° C./min and then at 300 ° C. for 5 hours. The O-IV was successfully cured under these conditions to produce TS-IV.

A detailed analysis supporting the complete conversion of O-IV to TS-IV was performed as follows. Films of TS-IV were analyzed using FT-IR. Unexpectedly, the FT-IR spectrum revealed the consumption / disappearance of the carbonyl expansion and contraction of ydnone at 1740 cm ^-1 , suggesting complete curing at 300 ° C. In addition, the resulting TS-IV film was found to be insoluble in any solvent, and significant swelling was not visually observable, thus indicating the successful formation of the viaduct material. .. In particular, the above-mentioned curing was carried out in the air as well as in the inert atmosphere. No difference was observed in the thermal stability of TS-IV obtained under both conditions.

熱重量分析により得られた分解温度は、熱硬化性ポリマーの熱安定性評価に必須なパラメーターであると思われるが、しかし長期にわたる高温での安定性を意味してはいない。したがって、両熱硬化性ポリマーに対する、経時における熱分解プロセスを特定するために、３００℃での短期間の等温熱重量分析を実施した。ＴＳ－ＩＶの完全な芳香族網目構造は、等温条件下において、例外的な安定性を示すことが判明した。不活性雰囲気下の３００℃で３００分後に、熱硬化性樹脂ＴＳ－ＩＶの重量減少は、５時間を超えてわずかに０．１ｗｔ％（すなわち、時間当たり０．０２ｗｔ％）であった（図３６）。 Thermal evaluation of TS-IV. The thermal stability of TS-IV was evaluated using TGA under a nitrogen atmosphere, and the results are summarized in FIGS. 35 and 10. Thermosetting resin TS-IV exhibits very high thermal stability with T _{d 5%} at 540 ° C due to its high aromatic content and rigid polymer backbone. Furthermore, it was found that the glass transition temperature determined by DSC was> 300 ° C. This shows the three-dimensional network structure of the viaduct and the resulting relaxation of the restricted molecular chains.

The decomposition temperature obtained by thermogravimetric analysis appears to be an essential parameter for assessing the thermal stability of thermosetting polymers, but does not imply long-term stability at high temperatures. Therefore, short-term isothermic gravimetric analysis at 300 ° C. was performed to identify the pyrolysis process over time for both thermosetting polymers. The complete aromatic network structure of TS-IV has been found to exhibit exceptional stability under isothermal conditions. After 300 minutes at 300 ° C. under the Inactive atmosphere, the weight loss of the thermosetting resin TS-IV was only 0.1 wt% (ie, 0.02 wt% per hour) over 5 hours (FIG. 36).

Mechanical and thermomechanical properties of TS-IV. A nanoindentation test was carried out on the cured thermosetting resin film. As shown in FIG. 18, these mechanical measurements indicate that TS-IV has a Young's modulus of greater than 5 GPa (Table 11) at room temperature, resulting in a generally commercially available thermosetting property. It has been shown that it exhibits excellent mechanical properties that exceed the rigidity of the resin. Further, the hardness of the thermosetting resin based on the ydnone is as low as 0.6 GPa (Table 11).

Finally, the adhesive strength was evaluated by performing a shear adhesion test according to a standardized procedure. As shown in FIG. 21, the thermosetting resin TS-IV has been found to exhibit exceptionally high adhesiveness to aluminum, various and common members in the automobile industry and the like. ¹⁵

Example 5: Thermosetting resin V
The thermosetting resin V (TS-V, B classification) is based on the Diels-Alder reaction between phenylbis-sydnone 4 and tris-alkene 14, 1,3,5-triethynylbenzene.

特定したオリゴマーＶ（Ｏ－Ｖ）を特徴づけるために、プロトンＮＭＲを利用した。図３３に示すように、当該Ｏ－Ｖは、開始モノマーの減少に伴う新規ピークを保有し、オリゴマー形成を確認できる。δ＞８．５ｐｐｍにおける全てのピークは、当該ピラゾールプロトンに対応している。さらに、～４．３ｐｐｍでの１つ以上ピークは、オリゴマーからの未反応アルキンによると思われ、当該オリゴマーは、さらに反応する傾向を、依然として残していることを示唆している。 Oligomer formation in solution. The reaction of phenylbis-sydnone with the tris-alkene 14 gave the pyrazole-based oligomer V, which serves as a precursor corresponding to the complete aromatic network structure of the thermosetting resin V. As shown in FIG. 37, phenylbis-in degassed NMPs using different molar amounts of reaction mixtures as covered in Table 12 at temperatures ranging from 110 ° C to 150 ° C for 15-24 hours. Sydnone 4 and 1,3,5-trisethynylbenzene 14 were reacted together. At 150 ° C. for 15 hours, a soluble oligomer of 0.13 M was obtained, while increasing the concentration of the reaction mixture to 0.2 M resulted in complete polymerization with the formation of insoluble material.

Proton NMR was used to characterize the identified oligomer V (OV). As shown in FIG. 33, the OV has a new peak with a decrease in the starting monomer, and oligomer formation can be confirmed. All peaks at δ> 8.5 ppm correspond to the pyrazole proton. Furthermore, one or more peaks at ~ 4.3 ppm are believed to be due to unreacted alkynes from the oligomer, suggesting that the oligomer still retains a tendency to react further.

Like the GPC data, the disappearance of phenylbis-sydnone 4 and the appearance of new peaks corresponding to O-V indicated the direction of the complete reaction at 150 ° C. for 15 hours. The average molecular weight (M _n ) was found within the range of 4 kDa (Table 13).

Heat curing of precursor oligomer V in solid state. OV heat curing was performed in different temperature ranges corresponding to varying times, ie, step curing at 150 ° C. for 2 hours, 200 ° C. for 4 hours, 250 ° C. for 1.5 hours, and 300 ° C. for 5 hours. IR spectroscopy was used to monitor the progress of cross-linking by tracing the carbonyl expansion and contraction of the sydnone at 1750 cm ^-1 (FIG. 38) as follows. The absence of this expansion and contraction of the heat-curable material represents complete cross-linking. In addition, TGA data for fully cured films also show complete cross-linking at 300 ° C. for 5 hours (FIG. 39).

ＴＳ－Ｖの時間に依存する耐熱性を決定するために、ＴＧＡを利用した３００℃で５時間の、短時間の加熱エージング研究を実施した。図４０に示すように、当該熱硬化性樹脂－Ｖは、３００℃では、時間当たり０．１ｗｔ％の非常にゆっくりとした分解を伴い、安定であることが判明した。これらの結果は、これら材料が、高温用途に適切であることを示唆している。 Thermal evaluation of TS-V. The thermal stability of TS-V was evaluated using TGA in a nitrogen atmosphere and the results are summarized in Table 14. The thermosetting resin TS-V heats up with a 5% weight loss temperature at 507 ° C., slightly lower than TS-IV, which is believed to be due to the slightly lower aromatic content and the resulting slightly less rigid skeleton. It showed a wide range of stability (Fig. 39). Furthermore, as with both TS-I and IV, the glass transition temperature of TS-V was found to be> 300 ° C., as determined by DSC, due to the highly crosslinkable three-dimensional network structure. The direction of the existence of the viaduct density of TS-V was shown.

To determine the time-dependent heat resistance of TS-V, a short heat aging study was performed at 300 ° C. for 5 hours using TGA. As shown in FIG. 40, the thermosetting resin −V was found to be stable at 300 ° C. with a very slow decomposition of 0.1 wt% per hour. These results suggest that these materials are suitable for high temperature applications.

Mechanical and thermomechanical properties of TS-V. In order to enable the mechanical test of TS-V, the conditions for producing the self-supporting film of TS-V were first optimized.

Generation of self-supporting TS-V film for mechanical studies. OV (35 wt%) was dissolved in NMP using a high shear mixer at 3000 rpm for 3 minutes. The obtained homogeneous slurry was dropped and cast onto a glass substrate (preheated at 150 ° C.). The film was heated at the same temperature for 1-2 hours, then the film was cooled, and the pre-cured film pieces were carefully peeled off with a utility knife. This pre-cured film was flexible, non-fragile, and had an inherently homogeneous surface. The flexibility of this film piece was found to be a characteristic of incomplete cross-linking, as suggested by TGA (FIG. 41).

To fully cure the film, the pre-cured piece of film was placed between two glass slides and tightly sandwiched between metal clips to apply pressure and then heated to 300 ° C. for 5 hours. Significant differences could be observed between this pre-cured and fully cured film. It was found that the pre-cured film was flexible, while the fully cured film was stiff. No difference was found in the surface homogeneity of the two films.

A nanoindentation test was carried out on the cured thermosetting resin film. As shown in FIG. 18, these mechanical measurements indicate that TS-V has a Young's modulus of greater than 5 GPa (Table 15) at room temperature, resulting in a generally commercially available thermosetting resin. It has been shown that it exhibits excellent mechanical properties that exceed the rigidity of. Further, the hardness of the thermosetting resin based on the ydnone is as low as 0.6 GPa (Table 15).

In addition, thermomechanical analysis (TMA) was performed on each self-supporting film. FIG. 42 shows the dimensional change of the thermosetting resin film as a function of temperature (up to 350 ° C. for TS-V). The thermal expansion rate (CTE) over this temperature range for TS-V is 47.5 μm / (m. ° C.) (Table 16), thus demonstrating excellent dimensional stability at high temperatures.

最終的に、その接着力を、標準化された手順に従った剪断接着試験を実施して評価した。図２１に示すように、熱硬化性樹脂ＴＳ－Ｖ、アルミニウム、多様な及び自動車産業などで一般的な部材に対して、例外的に高い接着性を示すことが判明した。^１５ To measure the effect of temperature on the movement of the chain, TS-V self-supporting films were tested by dynamic mechanical analysis (DMA). FIG. 43 shows the temperature dependence of the storage modulus (E'), the loss modulus (E ″) and tan δ. The room temperature storage modulus of 3.3 GPa relative to TS-V again sheds light on the exceptional stiffness of these materials. Furthermore, the complete aromatic network structure of TS-V shows a marginal change in E'up to ~ 350 ° C., after which it steadily decreases. In addition to the uncertain sharp decrease in storage modulus, the non-significant maximums of tan δ and E'' suggest that their T _g is higher than 500 ° C. TS-V also revealed a low sub-glass β2 transition as wide shoulder peaks at tan δ and E'' at ~ 90 ° C and 70 ° C, respectively. These low β2 transitions are probably due to incomplete network structure formation after curing. Furthermore, a high sub-glass β1 transition in TS-V was revealed as the maximum value of tan δ and E'' at ~ 480 ° C. In summary, these results clearly show how exceptionally superior thermosetting properties were provided to both thermosetting resins by the high crosslink density and rigid structural matrix of the partial or complete aromatic molecular skeleton. rice field.

Finally, the adhesive strength was evaluated by performing a shear adhesion test according to a standardized procedure. As shown in FIG. 21, it has been found that it exhibits exceptionally high adhesiveness to thermosetting resins TS-V, aluminum, various and general members in the automobile industry and the like. ¹⁵

Example 6: Thermosetting resin VI
In order to introduce flexibility and reduce its brittleness by the system, the phenylbis-sydnone 4 used in the production of TS-IV was replaced with a more flexible 3,3'-(4,4'-, containing an oxygen linker. Diphenyl) bissidedyl ether 8 was replaced. This bis-sydnone 8 was generated using a similar procedure established in correspondence with phenylbis-sydnone 4 and used for the production of oligomer IV. The thermosetting resin VI (TS-VI, B classification) is based on the Diels-Alder reaction between phenylbis-sydnone 8 and Tris-alkene 13.

図４５に示すように、当該オリゴマーＶＩは、開始物質３，３’－（４，４’－ジフェニル）ビスシドニルエーテル８及び１，３，５－トリス（フェニルエチニル）ベンゼン１３の減少に伴う新しいピークを保有しており、オリゴマーＶIの成功裏な生成を確認した。δ＞８．５ｐｐｍにおける全てのピークは、シドノンとアルキンモイエティーの１，３－双極性環化付加反応後に形成されたピラゾール環に対応している。 Oligomer formation in solution. As covered in Table 17, 3,3'-(4,4'-diphenyl) bissidedyl ethers 8 and 1, in degassed NMP at temperatures up to 100 ° C-200 ° C for 15-24 hours. 3,5-Tris (phenylethynyl) benzene 13 (FIG. 44) was reacted together. No reaction was observed at T ≧ 150 ° C., while low molecular weight soluble oligomers were obtained at 0.26 M at 170 and 180 ° C. for 15 hours. In contrast, high temperatures of 0.13M (200 ° C.) resulted in high molecular weight oligomers that were sparingly soluble in polar solvents such as DMSO and DMF.

As shown in FIG. 45, the oligomer VI is new with the reduction of the initiators 3,3'-(4,4'-diphenyl) bissidedyl ether 8 and 1,3,5-tris (phenylethynyl) benzene 13. It possesses a peak, confirming the successful formation of oligomer VI. All peaks at δ> 8.5 ppm correspond to the pyrazole ring formed after the 1,3-bipolar cycloaddition reaction of sydnone and alkyne moitty.

According to the GPC study, the disappearance of 1,3,5-tris (phenylethynyl) benzene 13 and the appearance of a new peak corresponding to the oligomer VI suggest that the reaction is completed in 15 hours at both 170 ° C and 180 ° C. .. The average molecular weight ( _Mn ) was found in the range of 2.5-3.5 kDa (FIG. 46, Table 18).

Heat curing of precursor oligomer VI in solid state. The B-stage oligomer VI was lysed in NMP and then the oligomer solution was degassed using a freeze pump thawing cycle. The obtained solution was dripped into a glass slide / TGA crucible container under severe inert conditions, and then the drip cast film was heated at 150 ° C. for 1 hour and at 300 ° C. for 5 hours. The resulting film was found to be insoluble in any solvent, indicating cross-linking of oligomers.

Thermal evaluation of TS-VI. It was found that the crosslinked polymer TGA showed a significant improvement in thermal stability compared to its initiating oligomer (FIG. 47). The thermosetting resin TS-VI showed a wide range of thermal stability with a 5% weight loss temperature at 515 ° C.

Example 7: Synthesis of Thermosetting Resin VII The thermosetting resin VII (TS-VII, B classification) is based on phenylbis-sydnone 8 and 1,3,5-triethynylbenzene as a bifunctional alkene 14. ..

当該オリゴマーＶIIを、^１Ｈ－ＮＭＲを使用して特徴づけた。図４９に示すように、新ピークの出現に伴うモノマーピークの減少は、オリゴマーの形成を裏付ける。δ＞８．５ｐｐｍにおけるプロトンは、シドノンとアルキン間の環化付加反応後に形成されたピラゾールプロトンの方向を示している。 Oligomer formation in solution. As covered in Table 19, 3,3'-(4,4'-diphenyl) bissidedyl ethers 8 and 1 in NMP under inert conditions at 150 ° C. using different molar amounts of reaction mixtures. , 3,5-Triethynylbenzene 14 (Fig. 48) were reacted together. Complete polymerization was observed at 150 ° C. for 12 hours in the 0.33 M reaction mixture. Complete cross-linking under these conditions was believed to be due to the high concentration of the reaction mixture used. In contrast, reaction molars up to 0.11 M resulted in the formation of soluble low molecular weight oligomers and were soluble in polar solvents such as DMSO and DMF.

The oligomer VII was characterized using ^{1 1} H-NMR. As shown in FIG. 49, the decrease in the monomer peak with the appearance of the new peak supports the formation of the oligomer. The protons at δ> 8.5 ppm indicate the direction of the pyrazole protons formed after the cycloaddition reaction between the sydonone and the alkyne.

Heat curing of precursor oligomer VII in solid state. The oligomer VII was dissolved in NMP and the resulting solution was then added dropwise to a glass slide / TGA crucible vessel under inert conditions. The drop casting film was cured at 150 ° C. for 1 hour and at 300 ° C. for 5 hours.

Thermal evaluation of TS-VII. It was found that the TGA of the crosslinked polymer TS-VII showed a significant improvement in thermal stability as compared to its initiating oligomer (FIG. 50). The decomposition temperature was measured as 400 ° C.

Example 8: Synthesis of Model Compounds In addition to different levels of conjugation, the thermal properties also depend on the three-dimensional structure of the network. Since this factor is decisively determined by the geometrical arrangement of each repeating unit, as a specific example of the present invention, as a model compound corresponding to the trifunctional cross-linking point of the thermosetting resin, a small molecule M -I and M-II were synthesized.

Synthesis of MI.
A mixture of N-phenylsidenone 4 (200 mg, 1 mmol) and N-phenylmaleimide 5 (430 mg, 2 mmol) in toluene (20 ml) was refluxed at 95 ° C. for 6 hours. During reflux, the solid material was condensed from the reaction mixture. The reaction mixture was cooled and filtered to give the substance as a colorless solid (500 mg, 88%). ^{1 1} H-NMR (600 MHz, DMSO-d ₆ ): δ7.37-7.28 (m, 8H), 7.13 (t, J = 7.5 Hz, 2H), 6.86-6.79 (m) , 2H), 6.67 (m, 3H), 5.61 (s, 1H), 4.54 (d, J = 6.8Hz, 2H), 3.61 (d, J = 6.8Hz, 2H) ), ¹³ C-NMR (126MHz, DMSO-d ₆ ): δ174.3, 172.9, 144.3, 131.7, 129.3, 128.6, 128.4, 126.5, 121.1 , 68.2, 62.9, 49.3, MS (ESI) for C ₂₇ H ₂₀ N ₄ O ₄ [M + Na ⁺ ]: calculation 487.15, detection 487.18. See FIG. 58.

Synthesis of M-II.
A mixture of N-phenylsidedone 4 (81 mg, 0.5 mmol) and phenylacetylene 6 (0.11 ml, 1 mmol) in anhydrous NMP (0.5 ml) was stirred at 170 ° C. for 15 hours. The reaction mixture was then cooled to room temperature and purified by column chromatography using hexane: ethyl acetate (9: 1, v / v) as the eluent to give a pure compound as a pale powder (40 mg). , 36% yield). ^{1 1} H-NMR (500 MHz, DMSO-d6): δ7.05 (1H, d, J = 7.1 Hz), 7.31-7.38 (2H, m), 7.46 (2H, m), 7 .53 (2H, m), 7.91-7.94 (4H, m), ¹³ C-NMR (125MHz, DMSO-d ₆ ): δ105.8, 118.7, 125.9, 126.6 128.5, 129.2, 129.8, 130.0, 133.2, 140.1, 152.3, IR, MS. See FIG. 59.

Reference Note: This application refers to a number of different publications indicated throughout the specification by reference numerals enclosed in parentheses, eg [x]. A list of these different publications, organized according to these reference numbers, can be found below. All publications described herein are provided to disclose and describe an exemplary method and / or substance associated with the content cited by that publication.
[1] Earl, JC; Mackney, AW, Journal of the Chemical Society (Resumed), 1935, 899-900.
[2] Stewart, FHC, Chemical Reviews, 1964, 64, 129-147.
[3] McCaustland, DJ; Burton, WH; Cheng, CC, Journal of Heterocyclic Chemistry, 1971, 8, 89-97.
[4] Kier, LB; Roche, EB, J. Pharm. Sci., 1967, 56, 149-168.
[5] Ackermann, E., Pharmazie, 1967, 22, 537-542.
[6] Sun, KK, Tetrahedron Letters, 1986, 27, 317-320.
[7] Huisgen, R .; Grashey, R .; Gotthardt, H .; Schmidt, R., Angewandte Chemie International Edition in English, 1962, 1, 48-49.
[8] Sun, KK, Macromolecules, 1987, 20, 726-729.
[9] Stille, JK; Bedford, MA, Journal of Polymer Science Part B: Polymer Letters, 1966, 4, 329-331.
[10] Stille, JK; Bedford, MA, Journal of Polymer Science Part A-1: Polymer Chemistry, 1968, 6, 2331-2342.
[11] Intemann, JJ; Huang, W .; Jin, Z .; Shi, Z .; Yang, X .; Yang, J .; Luo, J .; Jen, AKY, ACS Macro Letters, 2013, 2, 256 -259.
[12] Songkram, C .; Takaishi, K .; Yamaguchi, K .; Kagechika, H .; Endo, Y., Tetrahedron Letters, 2001, 42, 6365-6368.
[13] Oliver, WC; Pharr, GM, Journal of Materials Research, 1992, 7, 1564-1583.
[14] Martin, SJ; Godschalx, JP; Mills, ME; Shaffer, EO; Townsend, PH, Advanced Materials, 2000, 12, 1769-1778.
[15] Petrie, EM Handbook of Adhesives and Sealants; McGraw Hill: New York, 2007.
[16] DL Browne; JPA Harrity Tetrahedron 2010, 66, 553-568.
[17] KK Sun US Patent # 4,607,093, 1986
[18] JK Stille Makromol. Chem. 1972, 154, 49
[19] DS Breslow, Hercules Inc. US Patent # 3,448,063, 1969;
[20] DL Browne JPA Harrity Tetrahedron 2010, 66, 553

Conclusion This completes the description of the preferred embodiment of the present invention. Descriptions of one or more embodiments of the invention described above are provided for purposes of case and explanation. The present invention is exhaustive and is not intended to be limited to the disclosed details. Many modifications and changes are possible in view of the above teachings.

Claims (34)

A method for producing a film, coating or adhesive made of a thermosetting resin composition, wherein a mixture of at least one monomer of sidonone and alkene or alkyne is provided, oligomer formation by thermal activation of the mixture, and the like. A method comprising curing an oligomer and thus forming a thermosetting resin containing a crosslinked polymer. The method of claim 1, wherein the monomer mixture comprises ydnones and alkynes. The method of claim 1, wherein the sydnone is phenylbis-sydnone. The phenylbis-sidoneone replaces 1,4-diaminobenzene with ethyl bromide acetate in refluxed ethanol to give a salt, the salt is nitrosylated with an aqueous solution of sodium nitrite at 0 ° C., and the salt thereof. The method according to claim 3, wherein the nitrosylated salt is synthesized by cyclizing it in CH ₂ Cl ₂ with anhydrous trifluoroacetic acid. The method of claim 1, wherein the alkene is a bifunctional alkene and the alkyne is a tris-alkyne. The method according to claim 1, wherein the alkene is 1,1'-(methylenedi-4,1-phenylene) bismaleimide. The method of claim 1, wherein the alkyne is 1,3,5-tris (phenylethynyl) benzene. The method of claim 1, wherein the oligomer is formed by a 1,3-bipolar cycloaddition reaction of the alkene or alkyne with the sydnone. The method according to claim 1, wherein the oligomer is formed at a temperature of 100 ° C. or lower. The method of claim 1, wherein the oligomer comprises at least one of the following, wherein x, y, and z are integers.

The method according to claim 1, wherein the oligomer is cured at a temperature of 300 ° C. or lower. The method according to claim 1, wherein the oligomer is partially crosslinked and the thermosetting resin is completely crosslinked. The method according to claim 1, wherein the thermosetting resin composition has a glass transition temperature (T _g ) exceeding 300 ° C. and / or heat resistance of 400 ° C. or higher. The method according to claim 1, wherein the thermosetting resin composition comprises at least one of the following.

A monomer mixture containing one of the alkene and alkene or alkyne is given to form an oligomer in which the monomer mixture is thermally activated, wherein the oligomer comprises 1,3- of the alkene or alkyne and the sidonone. A film made of a thermosetting resin composition, which is formed by a bipolar cyclization addition reaction and comprises curing the oligomer and thus forming a thermosetting resin composition comprising a crosslinked polymer. How to make a coating or adhesive. 15. The method of claim 15, wherein the monomer mixture comprises ydnones and alkynes. 15. The method of claim 15, wherein the sydnone is selected from the group consisting of mono-sydnones, bis-sydnones, and tris-sydnones. 15. The method of claim 15, wherein the alkene or alkyne is selected from the group consisting of bis-maleimide, tris-maleimide, bis-alkyne, and tris-alkyne. 15. The method of claim 15, wherein the oligomer is formed at a temperature below 90 ° C. 15. The method of claim 15, wherein the oligomer is partially crosslinked and the thermosetting resin is completely crosslinked. 15. The method of claim 15, wherein the oligomer is coated on a member prior to curing. 21. The method of claim 21, wherein the member is an aluminum or copper member. 15. The method of claim 15, further comprising the addition of one or more components selected to enhance the thermal conductivity of the thermosetting resin composition. 15. The method of claim 15, wherein the components are added to enhance the physical toughness of the thermosetting resin composition. 15. The method of claim 15, further comprising the addition of one or more components selected to enhance the adhesiveness of the thermosetting resin composition. 15. The method of claim 15, further comprising the addition of one or more components selected to form the permeable network structure of the thermosetting resin composition. 15. The method of claim 15, further comprising the addition of one or more components selected to act on the phase-separated inorganic additives of the thermosetting resin composition. A composition of a substance produced by the method according to any one of claims 1 to 8, 10, 12 to 18 and 20 to 27, wherein the composition of the substance is a film, coating or. A composition of substances that is an adhesive. A composition of a substance produced by mixing a sidonone monomer or oligomer with a co-resin of a second commercial thermosetting resin, for a second commercial thermosetting resin added therein. Where the Sidnon is the primary resin, where the composition of the substance is a film, coating or adhesive, where the Sidnon monomer is mixed with or at least one of Alken or Alkin. The composition of the substance , wherein the sidonone oligomer is formed by thermal activation of a monomer mixture containing sidonone and at least one of an alken or an alkin . 29. The composition of claim 29, wherein the sydnone monomer is mixed with an alkyne, or where the sydnone oligomer is formed by thermal activation of a monomer mixture containing a sydnone and an alkyne. The composition to be. A composition of a substance produced by mixing a commercial thermosetting resin with a sidonone oligomer or monomer in order to improve or reduce the thermomechanical properties of the commercial thermosetting resin, wherein the substance. The composition of is a film, coating or adhesive , wherein the sidonone oligomer is formed by thermal activation of a monomer mixture comprising sidonone and at least one of alkene or alkyne, or where. A composition of a substance in which the sidonon monomer is mixed with at least one of alken or alkin . 31. The composition of claim 31, wherein the sydnone oligomer is formed by thermal activation of a monomer mixture containing a sydnone and an alkyne, or where the sydnone monomer is mixed with an alkyne. The composition to be. The composition according to claim 31 or 32, wherein the thermomechanical properties are selected from Tg, Tm, and Td. The composition according to claim 31 or 32, wherein the commercial thermosetting resin is a Tactix ™, Primacet ™, Locktite ™, and / or PETI-330 ™ composition.

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