Crosslinkable siloxane compounds for the preparation of dielectric materials

Abstract

The present invention relates to novel siloxane oligomers and polymers and crosslinkable compositions that may be used to prepare dielectric materials with excellent barrier, passivation, and / or planarization properties. Monomer compositions from which the siloxane oligomers or polymers may be obtained, and methods for preparing the siloxane oligomers or polymers, are also provided. The present invention also relates to a manufacturing method for preparing microelectronic structures, in which a crosslinkable composition is applied to the surface of a substrate and then cured, and to electronic devices containing the microelectronic structures obtained by the manufacturing method.

Description

[Technical Field]

[0001] Technical field of the present invention The present invention relates to novel siloxane oligomers and polymers and crosslinkable compositions, which may be used for the preparation of dielectric materials having excellent barrier, passivation, and / or planarization properties. These dielectric materials may be used for various applications in the electronics industry, such as for the electronic packaging or preparation of field-effect transistors (FETs) or thin-film transistors (TFTs). The dielectric materials may form barrier coatings, passivation layers, planarization layers, or combined passivation and planarization layers on conductive or semiconducting structures. Furthermore, the materials may be used for the preparation of substrates for printed circuit boards.

[0002] The siloxane oligomer or polymer of the present invention is a co-oligomer or copolymer obtained from a specific monomer composition comprising at least two different siloxane monomers. The oligomers and polymers are photostructureable and may be used for the preparation of passivation layers or barrier coatings for packaged electronic devices, or for passivation and optional planarization of semiconductor structures in FET or TFT devices. Here, the cured dielectric material is obtained from a siloxane polymer exhibiting excellent film-forming ability, excellent thermal properties, excellent mechanical properties, and easy handling and processing from conventional solvents. Furthermore, the material is characterized by a low dielectric constant and a low coefficient of thermal expansion (CTE). Due to the favorable and balanced relationship between the stiffness and elasticity of the material, thermal stresses that may occur during device operation can be easily compensated for.

[0003] Methods for preparing the siloxane oligomer or polymer, and crosslinkable oligomer or polymer compositions comprising the siloxane oligomer or polymer are further provided. Beyond this, the present invention relates to a method for preparing a microelectronic structure, wherein the crosslinkable oligomer or polymer composition is applied to the surface of a substrate and then cured, and to an electronic device comprising the microelectronic structure obtained or obtainable by the method.

[0004] The manufacturing method of the present invention enables cost-effective and reliable production of microelectronic devices, significantly reducing the number of defective products caused by mechanical deformation (warping) due to undesirable thermal expansion. Because polymerization can be carried out at lower temperatures, thermal stress during manufacturing is reduced, decreasing the amount of waste from defective microelectronic devices, thereby enabling resource-efficient and sustainable production. [Background technology]

[0005] Background of the present invention Various materials have been described for the preparation of dielectric coatings or layers in the electronics industry. For example, US2012 / 0056249A1 relates to polycycloolefins, which are norbornene-type polymers and are used for the preparation of dielectric interlayers applied to fluoropolymer layers in electronic devices.

[0006] WO2017 / 144148A1 provides a positive-type photosensitive siloxane composition that can form a cured film such as a planarization film or an intermediate layer insulating film for a TFT substrate. The positive-type photosensitive siloxane composition comprises (I) a polysiloxane having substituted or unsubstituted phenyl groups, (II) a diazonaphthoquinone derivative, (III) a hydrate or solvate of a photobase generator, and (IV) a solvent.

[0007] US2013 / 0099228A1 is, [ka] The present invention relates to a passivation layer solution composition containing an organic siloxane resin represented by the following: Here, R is at least one substituent selected from saturated or unsaturated hydrocarbons having 1 to about 25 carbon atoms, and x and y may each be independently 1 to about 200, and each dashed line indicates a bond to an H atom, or a bond to an x ​​siloxane unit or a y siloxane unit, or a bond to an x ​​siloxane unit or a y siloxane unit of another siloxane chain containing an x ​​siloxane unit or a y siloxane unit, or a combination thereof. The passivation layer solution composition is used to prepare a passivation layer on an oxide semiconductor in a thin-film transistor (TFT) array panel.

[0008] Polyfunctional polyorganosiloxanes, described in DE4014882A1, can be used for the production of polymers with liquid crystalline side chains or for the preparation of photosensitive resists or photocrosslinkable coatings.

[0009] Furthermore, US2007 / 0205399A1 relates to functionalized cyclic siloxanes useful as thermosetting adhesive resins for the electronics packaging industry, and US2011 / 0319582A1 relates to curable compositions comprising reaction products obtained by reacting alkoxysilane compounds and inorganic oxide fine particles in the presence of water and organic solvents.

[0010] As is evident from the above discussion, organopolysiloxanes are a very interesting class of compounds due to their thermal stability and mechanical hardness, and they are used for a variety of different applications, such as for the formation of cured films with high heat resistance, transparency, and resolution. Organopolysiloxanes with methyl and / or phenyl side groups are used as dielectric materials in the electronics industry (primarily front-end-of-line (FEOL)) where thermally stable materials are required. These materials must withstand temperatures up to 600°C. However, known materials are too hard and brittle to be used in back-end-of-line (BEOL) applications, i.e., redistribution, stress buffering, or passivation layers, where the temperature requirements are somewhat lower (250-300°C), but mechanical properties such as elongation and thermal expansion are becoming far more important.

[0011] To prevent device cracking or coating delamination, flexible material systems are required. Typically, such material systems are modified to suit specific application conditions through complex blending concepts of more than ten different compounds, currently used to tune desired mechanical, thermal, and / or electrical properties. Advantageously, organopolysiloxane polymers can be tuned to overcome potential drawbacks such as low adhesion, low elongation, and high thermal expansion / contraction, potentially preventing the development of complex multi-component solutions.

[0012] Therefore, there is a continuing demand for the development of new compounds that may be used as dielectric or barrier coating materials for various applications in the electronics industry, such as packaging microelectronic devices or preparing field-effect transistors (FETs) or thin-film transistors (TFTs).

[0013] Objective of the present invention The object of the present invention is to overcome the defects and shortcomings of the prior art and to provide novel compounds that enable the preparation of dielectric materials having excellent barrier, passivation, and / or planarization properties, which can be used in a variety of applications in the electronics industry. Preferred applications include, for example, electronic packaging or preparation of FET or TFT devices. The dielectric material may form a barrier coating, a passivation layer, a planarization layer, or a combination of a passivation layer and a planarization layer on a conductive or semiconducting structure.

[0014] Furthermore, the present invention aims to provide a novel dielectric material that exhibits excellent film-forming ability, excellent thermal properties such as a low coefficient of thermal expansion, and excellent mechanical properties such as excellent flexibility, when used for forming passivation layers in packaged electronic devices. Another objective of the present invention is to provide a novel dielectric material that enables easy handling and processing from conventional solvents.

[0015] Furthermore, an object of the present invention is to provide novel compounds that are photostructureable and particularly suitable for various applications in the electronics industry, such as preparing passivation layers or barrier coatings on conductive or semiconducting structures of packaged electronic devices, or for passivating and / or planarizing semiconductor layers in FETs or TFTs.

[0016] More specifically, the object of the present invention is to provide a novel crosslinkable composition that enables the preparation of dielectric materials for structuring redistribution layers (RDLs) of packaged microelectronic devices prepared by wafer-level packaging or panel-level packaging, or for passivating and optionally planarizing semiconductor layers in FET or TFT devices.

[0017] Therefore, the first aspect of the present invention is to provide monomer compositions for the preparation of oligomers or polymers which may be used for the purposes described above.

[0018] A second aspect of the present invention is to provide a method for preparing the oligomer or polymer.

[0019] A third aspect of the present invention is the provision of the oligomer or polymer.

[0020] A fourth aspect of the present invention is to provide a crosslinkable oligomer or polymer composition containing the oligomer or polymer.

[0021] A fifth aspect of the present invention is to provide a method for manufacturing a microelectronic structure.

[0022] A sixth aspect of the present invention is to provide an electronic device including the microelectronic structure. [Overview of the project]

[0023] Summary of the present invention The inventors have surprisingly found that the above objective can be achieved by providing a monomer composition for the preparation of siloxane oligomers or polymers, wherein the monomer composition is: (a) the first siloxane monomer; and (b) Second siloxane monomer; Includes, Here, the first siloxane monomer contains a substituted or unsubstituted maleimide group.

[0024] The monomer composition is used for the preparation of photostructureable siloxane oligomers or polymers that may form crosslinked dielectric materials exhibiting excellent film-forming ability, excellent thermal properties such as a low coefficient of thermal expansion, and excellent mechanical properties such as excellent flexibility, when used for forming a passivation layer in packaged electronic devices.

[0025] Therefore, the present invention further provides a method for preparing a siloxane oligomer or polymer, the method comprising the following steps: (i) To provide the monomer composition of the present invention; and (ii) React the monomer composition provided in step (i) to obtain a siloxane oligomer or polymer.

[0026] Furthermore, siloxane oligomers or polymers that can be obtained or are obtained by the above-described method for preparing siloxane oligomers or polymers are also provided.

[0027] Furthermore, a siloxane oligomer or polymer comprising or derived from a first repeating unit is also provided, wherein the first repeating unit is derived from a first siloxane monomer comprising a substituted or unsubstituted maleimide group.

[0028] Otherwise, a crosslinkable oligomer or polymer composition is provided, comprising one or more of the siloxane oligomers (one or more) or polymers (one or more) described above.

[0029] Ultimately, a method for manufacturing a microelectronic structure, preferably a packaged microelectronic structure, an FET structure, or a TFT structure, is provided, comprising the following steps: (1) Applying the crosslinkable oligomer or polymer composition of the present invention to the surface of a substrate, preferably to the surface of a conductive or semiconducting substrate; and (2) Curing the crosslinkable oligomer or polymer composition to form a layer that passivates and optionally planarizes the surface of the substrate.

[0030] Also provided are electronic devices, preferably packaged microelectronic devices, FET array panels, or TFT array panels, which include a microelectronic structure that can be obtained or are obtained by the manufacturing method of the present invention.

[0031] Preferred embodiments of the present invention are described thereafter and in dependent claims. [Brief explanation of the drawing]

[0032] [Figure 1] Figure 1: Cross-sectional view of the substrate for capacitance measurement. [Figure 2] Figure 2: Top view of the substrate for capacitance measurement, showing the points where film thickness was measured.

[0033] Detailed description Electronics packaging As solid-state transistors began to replace vacuum tube technology, it became possible to directly mount electronic components such as resistors, capacitors, and diodes onto the printed circuit board of a card using their leads, thus forming the basic building blocks or levels of packaging still used today. Complex electronic functions often require too many individual components to be interconnected on a single printed circuit card. The capability of multilayer cards has been accompanied by the development of techniques for three-dimensionally packaging daughter cards on multilayer motherboards. In integrated circuits, many discrete circuit elements such as resistors and diodes can be incorporated into individual, relatively small components known as integrated circuit chips or dies. However, despite the incredible circuit integration, due to the technology of integrated circuits themselves, more than one level of packaging is typically required. Integrated circuit chips are very fragile and have very small terminals. The first level of packaging achieves its primary function of providing mechanical protection, cooling, and the ability to provide electrical connectivity to the delicate integrated circuit. Some components (high-power resistors, mechanical switches, capacitors) are difficult to integrate on a chip, so at least one additional level of packaging, such as a printed circuit card, is utilized. For extremely complex applications, such as those on mainframe computers, multiple package-level hierarchies are required.

[0034] As a result of Moore's Law, advanced electronics packaging strategies play an increasingly important role in the development of more powerful electronic products. In other words, as the demand for smaller, faster, and more functional mobile and portable electronic devices increases, so does the demand for more cost-effective packaging technologies. A wide variety of advanced packaging technologies exist to meet the demands of today's semiconductor industry. Representative advanced packaging technologies such as wafer-level packaging (WLP), fan-out wafer-level packaging (FOWLP), 2.5D interposers, chip-on-chip stacking, package-on-package stacking, and embedded ICs all require the structuring of other components such as thin substrates, redistribution layers, and high-resolution interconnects. The end consumer market is constantly demanding smaller, thinner devices at lower prices and with higher functionality. This necessitates next-generation packaging that offers more refined features and improved reliability at competitive manufacturing costs.

[0035] Wafer-level packaging (WLP) is a technique that packages integrated circuits while they are still part of a wafer, in contrast to conventional chip-scale packaging methods that slice the wafer into individual circuits (dies) before packaging. WLP offers several key advantages over chip-scale packaging technologies and is essentially a true chip-scale packaging (CSP) technology, as the resulting package is virtually the same size as the die. Wafer-level packaging enables the integration of wafer fab, packaging, testing, and wafer-level burn-in, streamlining the manufacturing process from silicon start to customer shipment. Key applications of WLP include size-constrained smartphones and wearables. WLP capabilities offered to smartphones or wearables include compasses, sensors, power management, wireless connectivity, and more. Wafer-level chip-scale packaging (WL-CSP) is one of the smallest packages currently available on the market. WLP can be categorized into fan-in and fan-out WLP. Both utilize redistribution techniques to form connections between the chip and solder balls.

[0036] Fan-out wafer-level packaging (FOWLP) is one of the latest packaging trends in microelectronics, and it has high miniaturization potential in terms of both package volume and packaging thickness. The technical basis of FOWLP is a reconfigured and painted wafer with embedded chips and a thin film redistribution layer, which together form a surface mount device (SMD) compatible package. The main advantages of FOWLP are its outstanding thinness due to the substrate-less packaging, low thermal resistance, and good high-frequency characteristics due to short, planar electrical connections with bumpless chip connections instead of wire bonds or soldering, for example.

[0037] With current materials, the WLP process is limited to medium-sized chip applications. This limitation stems primarily from the current material selection, which can degrade performance and stress the die due to thermal mismatch with the silicon die. There is a strong demand for new materials with superior mechanical properties (particularly a CTE close to that of silicon). Currently, redistribution layers (RDLs) are fabricated from copper layers electroplated onto polymer passivation layers such as polyimide (PI), butylcyclobutane (BCB), or polybenzoxazole (PBO). For such materials, low curing temperatures, in addition to photopatterning capability, are two further important requirements.

[0038] Thin-film transistor (TFT) Thin-film transistor (TFT) array panels are typically used as circuit boards for independently driving pixels in liquid crystal displays, electrophoretic particle / liquid, organic electroluminescent (EL) display devices, quantum dot electroluminescent displays, and light-emitting diodes. A TFT array panel includes scan lines or gate lines for transmitting scan signals, image signal lines or data lines for transmitting image signals, thin-film transistors connected to the gate and data lines, and pixel electrodes connected to the thin-film transistors. A TFT includes a gate electrode, which is part of the gate wire, a semiconductor layer that forms a channel, a source electrode, which is part of the data wire, and a drain electrode. The TFT is a switching element that controls the image signal transmitted to the pixel electrode via the data wire in response to the scan signal transmitted via the gate line.

[0039] Currently, two methods are used for depositing silicon nitride / silicon oxide layers onto silicon or oxide semiconductor substrates: • Low-pressure chemical vapor deposition (LPCVD) techniques that operate at relatively high temperatures and are performed in either vertical or horizontal tubular furnaces; or • Plasma-excited chemical vapor deposition (PECVD), which operates at relatively low temperatures and under vacuum conditions.

[0040] SiNx films with a thickness of 200 nm or more, fabricated by LPCVD, have been shown to be prone to cracking under pressure or temperature changes. The process temperature is too high for application to glass substrates and hydrogenated amorphous silicon or oxide semiconductors. SiNx films fabricated by PECVD exhibit low tensile stress, but curling of the glass substrate still occurs as the size of the glass substrate increases. Electrical properties also deteriorate. Furthermore, plasma can damage thin-film semiconductors, especially oxide semiconductors, degrading the performance of TFTs.

[0041] The photostructuring of SiN layers requires many steps, including photoresist coating, photopatterning, SiNx etching, photoresist stripping, and cleaning. These procedures are time-consuming and costly. Therefore, a new type of material is needed to passivate the semiconductor layer of TFTs that form part of a TFT array panel.

[0042] definition The term “polymer” includes, but is not limited to, homopolymers, copolymers, e.g., block, random, and alternating copolymers, terpolymers, quarterpolymers, etc., and blends and modifications thereof. Furthermore, unless specifically limited, the term “polymer” shall include all possible constituent isomers of the material. These constituents include, but are not limited to, isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule with high relative molecular mass, and its structure essentially consists of multiple repetitions of units (i.e., repeating units) that are actually or conceptually derived from molecules with low relative molecular mass (i.e., monomers). In the context of this invention, a polymer is composed of more than 60 monomers.

[0043] The term "oligomer" refers to a molecular complex consisting of several monomer units, in contrast to polymers, which in principle have an unlimited number of monomers. For example, dimers, trimers, and tetramers are oligomers consisting of two, three, and four monomers, respectively. In the context of this invention, an oligomer may consist of up to 60 monomers.

[0044] As used herein, the term "monomer" refers to a polymerizable compound that, through polymerization, contributes constituent units (repeating units) to the essential structure of a polymer or oligomer. A polymerizable compound is a functional compound having one or more polymerizable groups. In a polymerization reaction, a large number of monomers are combined to form a polymer. A monomer with one polymerizable group is also called a "monofunctional" or "monoreactive" compound, a compound with two polymerizable groups is also called a "difunctional" or "direactive" compound, and a compound with more than two polymerizable groups is also called a "polyfunctional" or "polyreactive" compound. A compound without polymerizable groups is also called an "afunctional" or "nonreactive" compound.

[0045] As used herein, the term “homopolymer” means a polymer obtained from one type of monomer (real, implicit, or hypothetical).

[0046] As used herein, the term "copolymer" generally means any polymer derived from one or more monomers, where the polymer contains one or more corresponding repeating units. In one embodiment, the copolymer is a reaction product of two or more monomers and therefore contains two or more corresponding repeating units. The copolymer preferably contains two, three, four, five, or six repeating units. A copolymer obtained by copolymerizing three monomer species may also be called a terpolymer. A copolymer obtained by copolymerizing four monomer species may also be called a quarterpolymer. The copolymer may exist as a block copolymer, a random copolymer, and / or an alternating copolymer.

[0047] As used herein, the term "block copolymer" refers to a copolymer in which adjacent blocks are constitutively different, that is, a copolymer containing repeating units derived from different types of monomers, or repeating units derived from the same type of monomer but with different compositions or arrangement distributions.

[0048] Furthermore, the term "random copolymer" as used herein refers to a polymer formed from macromolecules in which the probability of finding a given repeating unit at any given site in the chain is independent of the properties of adjacent repeating units. Typically, in random copolymers, the sequence distribution of repeating units follows Bernoulli statistics.

[0049] As used herein, the term "alternating copolymer" refers to a copolymer consisting of macromolecules containing two types of repeating units arranged alternately.

[0050] "Siloxane" is a compound of the general formula R3Si[OSiR2]. n OSiR3 or (RSi) n O 3n / 2 A chemical compound in which R is a hydrogen atom or an organic group, and n is an integer. > The silicon atoms in siloxanes are not directly linked to each other, but are linked via intermediate oxygen atoms: Si-O-Si. Depending on the chain length, siloxanes may arise as linear or branched, cubic or ladder-like, or random oligomers or polymers (i.e., oligosiloxanes or polysiloxanes). Siloxanes in which at least one substituent R is an organic group are called organosiloxanes.

[0051] As used herein, "halogen" refers to elements belonging to Group 17 of the periodic table. Group 17 of the periodic table includes the chemically related elements fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).

[0052] As explained above, "electronics packaging" is a major area within the field of electronics engineering and encompasses a wide variety of technologies. It refers to inserting discrete components, integrated circuits, and MSI (medium-scale integrated circuits) and LSI (large-scale integrated circuits) chips (usually mounted on lead frames with beam leads) into a plate through holes in a multilayer circuit board (also called a card) that are soldered in place. Packaging of electronic systems must take into account mechanical damage, cooling, protection from high-frequency noise emission, protection from electrostatic discharge maintenance, operator convenience, and cost.

[0053] As used herein, the term “microelectronic device” refers to electronic devices of extremely small electronic designs and components. Usually, but not always, this means on a micrometer scale or smaller. These devices typically contain one or more microelectronic components, fabricated from semiconductor materials and interconnected in a packaged structure to form a microelectronic device. Many electronic components of a normal electronics design are available as microelectronic equivalents. These include transistors, capacitors, inductors, resistors, diodes, and, of course, insulators and conductors, all of which can be found in microelectronic devices. Due to the extremely small size of components, leads, and pads, unique wiring techniques, such as wire bonding, are also often used in microelectronics.

[0054] As used herein, the terms “field-effect transistor” or “FET” refer to a transistor that uses an electric field to control the electrical behavior of a device. FETs are also known as unipolar transistors because they involve single-carrier operation. Many different implementations of field-effect transistors exist. Field-effect transistors generally exhibit extremely high input impedance at low frequencies. The conductivity between the drain and source terminals is controlled by the electric field within the device, generated by the voltage difference between the device body and gate.

[0055] As used herein, the terms “thin-film transistor” or “TFT” refer to a specific type of transistor fabricated by depositing thin films of an active semiconductor layer, a dielectric layer, and metal contacts onto a supporting (but non-conductive) substrate. Since the primary application of TFTs is liquid crystal displays (LCDs), the substrate is typically glass. This differs from conventional transistors where the semiconductor material is typically a substrate such as a silicon wafer. TFTs may also be used to form TFT array panels for liquid crystal display (LCD) devices.

[0056] Preferred embodiment Monomer composition In its first aspect, the present invention is (a) the first siloxane monomer; and (b) Second siloxane monomer; The present invention relates to monomer compositions for the preparation of siloxane oligomers or polymers containing, Here, the first siloxane monomer contains a substituted or unsubstituted maleimide group.

[0057] The maleimide group has the following structure: [ka] It is a functional group represented by, Here R 1 and R 2are the same or different from each other and each independently represents H or a substituent. R 1 and R 2 both represent H, the maleimide group is an unsubstituted maleimide group. R 1 and R 2 at least one of which is a substituent different from H, the maleimide group is a substituted maleimide group.

[0058] The synthesis of the maleimide-functionalized trialkoxysilane is described in CN104447849A.

[0059] The first siloxane monomer In a preferred embodiment, the first siloxane monomer (a) contained in the monomer composition of the present invention has the formula (1):

Chemical formula

[0060] L 1 , L2 and L 3 They are either the same or different from each other, and each is independently selected from R, OR, F, Cl, Br, and I, where L 1 , L 2 and L 3 Preferably, at least one of them is OR, F, Cl, Br, or I.

[0061] more, Condition (1) or (2): (1) L 1 =L 2 =L 3 =OR; or (2) L 1 =L 2 =R, and L 3 =Cl, One of these will apply.

[0062] In a preferred embodiment, R is selected from the group consisting of H, a linear alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, and where one or more H atoms are optionally replaced by F.

[0063] In a more preferred embodiment, R is selected from the group consisting of H, a linear alkyl having 1 to 12 carbon atoms, a branched alkyl having 3 to 12 carbon atoms, a cyclic alkyl having 3 to 12 carbon atoms, and an aryl having 6 to 14 carbon atoms.

[0064] In its most preferred embodiment, R is H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C6H 11 Selected from the group consisting of , and -Ph.

[0065] In a preferred embodiment, R 1 and R 2 These are either the same or different from each other, and each is independently selected from H, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, and aryl having 6 to 14 carbon atoms, where one or more H atoms are optionally replaced by F or R 1 and R 2 Together, they form a monocyclic or polycyclic aliphatic ring system, a monocyclic or polycyclic aromatic ring system, or a polycyclic aliphatic and aromatic ring system, where one or more H atoms are optionally replaced by F.

[0066] A preferred monocyclic or polycyclic aliphatic ring system has 3 to 20, preferably 5 to 12, ring carbon atoms. A preferred monocyclic or polycyclic aromatic ring system has 5 to 20, preferably 6 to 12, ring carbon atoms. A preferred polycyclic aliphatic and aromatic ring system has 6 to 30, preferably 10 to 20, ring carbon atoms.

[0067] In a more preferred configuration, R 1 and R 2 These are either the same or different from each other, and are selected from H, -CH3, -CF3, -CH2CH3, -CF2CF3, -CH2CH2CH3, -CH(CH3)2, or -Ph.

[0068] In a more preferred embodiment, R 1 and R 2 The same and selected from -CH3, -CF3, -CH2CH3, -CF2CF3 or -Ph.

[0069] Most preferably, in this embodiment, R1 and R 2 It is -CH3.

[0070] In a preferred embodiment, Z represents a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 3 to 12 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F.

[0071] In a more preferred embodiment, Z is -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -,-(CH2) 11 -, and -(CH2) 12 - Represents a linear alkylene group having 1 to 12 carbon atoms, selected from the options below.

[0072] In a preferred embodiment, R 0 and R 00 These are either the same or different from each other, and each is independently selected from H, a linear alkyl having 1 to 12 carbon atoms, and a branched alkyl having 3 to 12 carbon atoms, which are optionally fluorinated.

[0073] In a more preferred configuration, R 0 and R 00 These are either the same or different from each other, and each is independently selected from H, -CH3, -CF3, -CH2CH3, and -CF2CF3.

[0074] A particularly preferred first siloxane monomer is formula (2): [ka] It is represented as, Here: L 1 =-OCH3, -OCF3, -OCH2CH3, -OCF2CF3, -OCH2CH2CH3, -OCH(CH3)2, -OC6H 11 , or -Ph; Z = -(CH2) n -, where n=1~10; and R 1 =H, -CH3, -CF3, -CH2CH3, -CF2CF3, or -Ph.

[0075] In its most preferred embodiment, the first siloxane monomer is of formula (3): [ka] It is represented as follows.

[0076] Second siloxane monomer In a preferred embodiment, the second siloxane monomer contained in the monomer composition of the present invention is represented by one of the following structures S1 to S5: [ka] Here: L 11 , L 12 , L 13 , and L 14 They are either the same or different from each other, and each is independently selected from OR' and halogen; R' is selected from the group consisting of linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 is replaced by - or -C≡C-, and here, one or more H atoms are optionally replaced by F; R 11 , R 12 and R 13 are the same or different from each other, and each is independently selected from the group consisting of H, linear alkyl having 1 to 30 carbon atoms, branched alkyl having 3 to 30 carbon atoms, cyclic alkyl having 3 to 30 carbon atoms, and aryl having 6 to 20 carbon atoms, which is -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 -, and optionally contains one or more functional groups selected from - and -C≡C-, and here one or more H atoms are optionally replaced by F; Z 1 represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 is replaced by - or -C≡C-, and here, one or more H atoms are optionally replaced by F; W1 represents a divalent, trivalent, or tetravalent organic part; R 0 , R 00 , Y 1 , and Y 2 It is defined as shown above; and n1 = 2, 3, or 4.

[0077] L 11 , L 12 , L 13 , and L 14 Preferably, these elements are the same or different from each other, and each is independently selected from OR', F, Cl, Br, and I.

[0078] L 11 , L 12 , L 13 , and L 14 They are either the same or different from each other, and each is independently selected from OR', which is preferable.

[0079] In a preferred embodiment, R' is selected from the group consisting of a linear alkyl having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms; a branched alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms; a cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms; and an aryl having 6 to 14 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F.

[0080] In a more preferred embodiment, R' is selected from the group consisting of linear alkyls having 1 to 12 carbon atoms, branched alkyls having 3 to 12 carbon atoms, cyclic alkyls having 3 to 12 carbon atoms, and aryls having 6 to 14 carbon atoms.

[0081] In a particularly preferred embodiment, R' is -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 -C5H4F7, -C6H 13 -C6H4F9, -C7H 15 -C7H4F 11 -C8H 17 -C8H4F 13 The group is selected from -CH=CH2, -C(CH3)=CH2, -C6H5, and -C6F5.

[0082] In the most preferred embodiment, R' is selected from -CH3 or -C2H5.

[0083] In a preferred embodiment, R 11 , R 12 and R 13 These are either the same or different from each other, and each is independently selected from the group consisting of H, a linear alkyl having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a branched alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, a cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and an aryl having 6 to 14 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 The system optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F.

[0084] In a more preferred configuration, R 11 , R 12 and R 13 These are selected from the group consisting of H, linear alkyls having 1 to 12 carbon atoms, branched alkyls having 3 to 12 carbon atoms, cyclic alkyls having 3 to 12 carbon atoms, and aryls having 6 to 14 carbon atoms, and these are -C(=O)-, -C(=O)-O-, -OC(=O)-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, and -CY 1 =CY 2 - optionally contains one or more functional groups selected from, where one or more H atoms are optionally replaced by F.

[0085] In a particularly preferred embodiment, R 11 , R 12 and R 13 -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 -C5H4F7, -C6H 13 -C6H4F9, -C7H 15 -C7H4F 11 -C8H 17 -C8H4F 13 The group is selected from -CH=CH2, -C(CH3)=CH2, -C3H6-OC(=O)-CH=CH2, -C3H6-OC(=O)-C(CH3)=CH2, -C6H5, and -C6F5.

[0086] In the most preferred configuration, R 11 , R 12 and R 13 This is selected from -CH3 or -C2H5.

[0087] In a preferred embodiment, Z 1represents a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 3 to 12 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F.

[0088] In a more preferred embodiment, Z 1 -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -,-(CH2) 11 -, and -(CH2) 12 - Represents a linear alkylene group having 1 to 12 carbon atoms, selected from the options below.

[0089] In a preferred embodiment, W 1 It can be represented by one of the following structures W1 to W4: [ka] Here: L is H, -F, -Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -OH, -R 0 , -OR 0 , -SR 0 -C(=O)R 0 , -C(=O)-OR 0 -OC(=O)-R 0 -NH2, -NHR 0 , -NR 0 R 00 -C(=O)NHR 0 -C(=O)NR0 R 00 , -SO3R 0 , -SO2R 0 , selected from alkyl groups with 1 to 20 carbon atoms, preferably 1 to 12 atoms, or aryl groups with 6 to 20 carbon atoms, preferably 6 to 14 atoms, which are optionally -F, -Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -OH, -R 0 , -OR 0 , -SR 0 -C(=O)-R 0 , -C(=O)-OR 0 -OC(=O)-R 0 -NH2, -NHR 0 , NR 0 R 00 , -OC(=O)-OR 0 -C(=O)-NHR 0 , or -C(=O)-NR 0 R 00 It may be replaced by:

[0090] R 0 and R 00 The above definition applies accordingly.

[0091] In a preferred embodiment, L is selected from H, -F, -Cl, -NO2, -OCH3, -CH3, CF3, -CH2CH3, -CH2CH2CH3, and -CH(CH3)2, -Ph, and C6F5.

[0092] A preferred second siloxane monomer is represented by one of the following structures: [ka] Here: R 11 It has one of the meanings defined above; L 11 , L 12 , and L 13 They are either the same or different from each other, and each is independently selected from OR' and halogen; and R', Z 1 And L has one of the meanings defined above.

[0093] A more preferred second siloxane monomer is represented by one of the following structures: [ka]

[0094] The third siloxane monomer In a preferred embodiment, the monomer composition of the present invention: (c) Third siloxane monomer; It further includes, Here, the third siloxane monomer is different from the first and second siloxane monomers.

[0095] Preferably, the third siloxane monomer is represented by one of the following structures T1 to T5: [ka] Here: L 21 , L 22 , L 23 , and L 24 They are either the same or different from each other, and each is independently selected from OR'' and halogens; R'' is selected from the group consisting of linear alkyl groups having 1 to 30 carbon atoms, branched alkyl groups having 3 to 30 carbon atoms, cyclic alkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2- or -C≡C- is used to replace C, and where one or more H atoms are optionally replaced by F; R 21 , R 22 and R 23 These are either the same or different from each other, and each is independently selected from the group consisting of H, linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 It optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F; Z 2 represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; W 2 represents a divalent, trivalent, or tetravalent organic part; R 0 , R 00 , Y 1 , and Y 2It is defined as shown above; and n² = 2, 3, or 4.

[0096] L 21 , L 22 , L 23 , and L 24 Preferably, these elements are the same or different from each other, and each is independently selected from OR'', F, Cl, Br, and I.

[0097] L 21 , L 22 , L 23 , and L 24 It is more preferable that they are the same or different from each other, and each is independently selected from OR''.

[0098] With respect to R'', the preferred, more preferred, particularly preferred, and most preferred definitions of R' disclosed above apply accordingly.

[0099] In a preferred embodiment, R 21 , R 22 and R 23 These are either the same or different from each other, and each is independently selected from the group consisting of H, a linear alkyl having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a branched alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, a cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and an aryl having 6 to 14 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 The system optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F.

[0100] In a more preferred configuration, R 21 , R 22 and R 23 These are selected from the group consisting of H, linear alkyls having 1 to 12 carbon atoms, branched alkyls having 3 to 12 carbon atoms, cyclic alkyls having 3 to 12 carbon atoms, and aryls having 6 to 14 carbon atoms, and these are -C(=O)-, -C(=O)-O-, -OC(=O)-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, and -CY 1 =CY 2 - optionally contains one or more functional groups selected from, where one or more H atoms are optionally replaced by F.

[0101] In a particularly preferred embodiment, R 21 , R 22 and R 23 -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 -C5H4F7, -C6H 13 -C6H4F9, -C7H 15 -C7H4F 11 -C8H 17 -C8H4F 13 The group is selected from -CH=CH2, -C(CH3)=CH2, -C3H6-OC(=O)-CH=CH2, -C3H6-OC(=O)-C(CH3)=CH2, -C6H5, and -C6F5.

[0102] In the most preferred configuration, R 21 , R 22 and R 23 This is selected from -CH3 or -C2H5.

[0103] In a preferred embodiment, Z 2represents a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 3 to 12 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F.

[0104] In a more preferred embodiment, Z 2 -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -,-(CH2) 11 -, and -(CH2) 12 - Represents a linear alkylene group having 1 to 12 carbon atoms, selected from the options below.

[0105] In a preferred embodiment, W 2 As defined above, it is represented by one of the structures W1 to W4.

[0106] A preferred third siloxane monomer is represented by one of the following structures: [ka] Here: R'' and R 21 It has the meaning defined above.

[0107] A more preferred third siloxane monomer is represented by one of the following structures: [ka]

[0108] The fourth siloxane monomer In a more preferred embodiment, the monomer composition of the present invention is: (d) A fourth siloxane monomer; It further includes, Here, the fourth siloxane monomer is different from the first, second, and third siloxane monomers.

[0109] Preferably, the fourth siloxane monomer is represented by one of the following structures F1 to F5: [ka] Here: L 31 , L 32 , L 33 , and L 34 They are either the same or different from each other, and each is independently selected from OR''' and halogen; R''' is selected from the group consisting of linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, and where one or more H atoms are optionally replaced by F; R 31 , R 32 and R 33These are either the same or different from each other, and each is independently selected from the group consisting of H, linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 It optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F; Z 3 represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; W 3 represents the divalent, trivalent, and tetravalent organic parts; R 0 , R 00 , Y 1 , and Y 2 It is defined as shown above; and n3 = 2, 3, or 4.

[0110] L 31 , L 32 , L33 , and L 34 Preferably, these elements are the same or different from each other, and each is independently selected from OR''', F, Cl, Br, and I.

[0111] L 31 , L 32 , L 33 , and L 34 It is more preferable that they are the same or different from each other, and each is independently selected from OR'''.

[0112] With respect to R''', the preferred, more preferred, particularly preferred, and most preferred definitions of R' disclosed above apply accordingly.

[0113] In a preferred embodiment, R 31 , R 32 and R 33 These are either the same or different from each other, and each is independently selected from the group consisting of H, a linear alkyl having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a branched alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, a cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and an aryl having 6 to 14 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, -CY 1 =CY 2 The molecule optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F.

[0114] In a more preferred configuration, R 31 , R 32 and R 33These are selected from the group consisting of H, linear alkyls having 1 to 12 carbon atoms, branched alkyls having 3 to 12 carbon atoms, cyclic alkyls having 3 to 12 carbon atoms, and aryls having 6 to 14 carbon atoms, and these are -C(=O)-, -C(=O)-O-, -OC(=O)-, -CR 0 =CR 00 -, -CR 0 =CR 00 2, and -CY 1 =CY 2 - optionally contains one or more functional groups selected from, where one or more H atoms are optionally replaced by F.

[0115] In a particularly preferred embodiment, R 31 , R 32 and R 33 -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 -C5H4F7, -C6H 13 -C6H4F9, -C7H 15 -C7H4F 11 -C8H 17 -C8H4F 13 The group is selected from -CH=CH2, -C(CH3)=CH2, -C3H6-OC(=O)-CH=CH2, -C3H6-OC(=O)-C(CH3)=CH2, -C6H5, and -C6F5.

[0116] In the most preferred configuration, R 31 , R 32 and R 33 This is selected from -CH3 or -C2H5.

[0117] In a preferred embodiment, Z 3 represents a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 3 to 12 carbon atoms, where one or more non-adjacent and non-terminal CH2 groups are optionally -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F.

[0118] In a more preferred embodiment, Z 3 -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -,-(CH2) 11 -, and -(CH2) 12 - Represents a linear alkylene group having 1 to 12 carbon atoms, selected from the options below.

[0119] In a preferred embodiment, W 3 It is represented by one of the structures W1 to W4 as defined above.

[0120] A preferred fourth siloxane monomer is represented by one of the following structures: [ka] Here: R''' and R 31 It has one of the meanings defined above.

[0121] More preferably, the fourth siloxane monomer is represented by one of the following structures: [ka]

[0122] It is preferable that the molar ratio between the first siloxane monomer and all the further siloxane monomers (including at least the second siloxane monomer in the monomer composition of the present invention) is in the range of 1:0.1 to 1:10, more preferably 1:0.1 to 1:5, particularly preferably 1:0.5 to 1:4, and most preferably 1:1 to 1:3.

[0123] The monomer composition of the present invention preferably contains one or more solvents.

[0124] Method for preparing siloxane polymers In a second aspect, the present invention provides a method for preparing a siloxane oligomer or polymer, the method comprising the following steps: (i) To provide the monomer composition of the present invention; and (ii) Reacting the monomer composition provided in step (i) to obtain a siloxane oligomer or polymer.

[0125] The monomer composition provided in step (i) preferably contains a solvent. Preferred solvents are polar solvents such as alcohol solvents and ester solvents, for example. Preferred alcohol solvents are ethanol, propan-1-ol, propan-2-ol, and propylene glycol methyl ether (PGME). A preferred ester solvent is 1-methoxy-2-propyl acetate (PGMEA).

[0126] In step (ii), the monomer composition is preferably reacted in the presence of a base such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, alkali metal hydroxide, and diazabicycloundecene (DBU).

[0127] In step (ii), the monomer composition is preferably reacted under an inert gas atmosphere, such as a nitrogen and / or argon atmosphere.

[0128] The reaction temperature for step (ii) is preferably controlled not to exceed 50°C, and more preferably not to exceed 25°C.

[0129] The reaction time required for step (ii) is determined by turnover control. The reaction time is typically up to 6 hours, preferably up to 4 hours, and more preferably up to 2 hours.

[0130] Siloxane oligomers and polymers In a third aspect, a siloxane oligomer or polymer is provided that can be obtained or obtained by a method for preparing a siloxane oligomer or polymer of the present invention.

[0131] Further provided are siloxane oligomers or polymers comprising or derived from a first repeating unit, wherein the first repeating unit is derived from a first siloxane monomer, and wherein the first siloxane monomer comprises a substituted or unsubstituted maleimide group. The above definitions consequently apply to the first siloxane monomer.

[0132] The siloxane oligomer or polymer preferably comprises a first repeating unit and a second repeating unit, wherein the first repeating unit is derived from a first siloxane monomer, and the second repeating unit is derived from a second siloxane monomer, wherein the first siloxane monomer comprises a substituted or unsubstituted maleimide group; and wherein the second siloxane monomer is different from the first siloxane monomer. The above definition consequently applies to the second siloxane monomer.

[0133] The siloxane oligomer or polymer more preferably further comprises a third repeating unit, wherein the third repeating unit is derived from a third siloxane monomer, which is different from the first and second siloxane monomers. The above definition consequently applies to the third siloxane monomer.

[0134] Ultimately, the siloxane oligomer or polymer more preferably further comprises a fourth repeating unit, where the fourth repeating unit is derived from a fourth siloxane monomer, where the fourth siloxane monomer is distinct from the first, second, and third siloxane monomers. The above definition consequently applies to the fourth siloxane monomer.

[0135] The phrase "derived from a siloxane monomer" means that the repeating units in question are formed by the condensation reaction of a siloxane monomer with another monomer, while usually maintaining the characteristic structural features of the siloxane monomer in the repeating units that form part of the siloxane oligomer or polymer.

[0136] The siloxane oligomer or polymer of the present invention is preferably obtained or can be obtained by a method for preparing the siloxane oligomer or polymer of the present invention.

[0137] Depending on the number of different repeating units present in the oligomer or polymer, the compound may be a homopolymer or a copolymer.

[0138] The siloxane oligomer or polymer of the present invention may have a linear and / or branched structure. The branched structure includes, for example, ladder, closed cage, open cage, and amorphous structures.

[0139] Preferably, the siloxane oligomer or polymer of the present invention has a molecular weight M of at least 500 g / mol, more preferably at least 1,000 g / mol, and even more preferably at least 2,000 g / mol, as determined by GPC. w It has a molecular weight M of a siloxane oligomer or polymer. w The concentration is less than 50,000 g / mol, more preferably less than 30,000 g / mol, and even more preferably less than 10,000 g / mol.

[0140] crosslinkable composition In a fourth aspect, the present invention provides a crosslinkable oligomer or polymer composition comprising one or more siloxane oligomers or polymers of the present invention.

[0141] The crosslinkable composition preferably contains one or more solvents.

[0142] The crosslinkable composition preferably contains one or more initiators, such as photochemical initiators or thermal initiators. Preferred photochemical initiators are photoinitiators that, when exposed to radiation such as UV or visible light, create reactive species such as free radicals, cations, or anions. Preferred photoinitiators include Omnipol TX and Speedcure 7010.

[0143] A preferred thermal initiator is one that, when exposed to heat, creates a reactant species such as a free radical, cation, or anion.

[0144] In a particularly preferred embodiment of the present invention, the crosslinkable oligomer or polymer composition comprises a photoinitiator.

[0145] The total amount of initiator in the crosslinkable composition is preferably in the range of 0.01 to 10 wt.-%, more preferably 0.5 to 5 wt.-%, based on the total weight of the siloxane polymer.

[0146] The crosslinkable composition of the present invention may contain one or more additives selected from diamines, diols, dicarboxylic acids, polyhedral oligomers of silsesquioxane (POSS), edge-modified silsesquioxanes, small aromatic or aliphatic compounds, and nanoparticles, which may be optionally modified with maleimide- or dimethylmaleimide groups.

[0147] Modified POSS compounds can be readily prepared from readily available precursors and readily incorporated into crosslinkable compositions under appropriate mixing conditions. For example, maleimide-substituted POSS compounds and their preparations are described in US2006 / 0009578A1, which is incorporated by reference into this specification.

[0148] Preferred additives are: [ka] [ka] [ka] [ka] Selected from, Here: R= [ka] X = -OH, -NH2, -CO2H, or [ka] Sp=-CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, or -Si(CH3)2-CH2-CH2-CH2-; R x =H, -CH3, CF3, CN, or -CH2CH3; and n = 1 to 36, preferably 1 to 20, and more preferably 1 to 12.

[0149] Method for fabricating microelectronic structures In the fifth aspect, the present invention relates to the following steps: (1) Applying the crosslinkable oligomer or polymer composition of the present invention to the surface of a substrate, preferably to the surface of a conductive or semiconducting substrate; and (2) Curing the crosslinkable oligomer or polymer composition to form a layer that passivates and optionally planarizes the surface of the substrate. The present invention provides a method for manufacturing a microelectronic structure, preferably a packaged microelectronic structure, an FET structure, or a TFT structure, including the above.

[0150] The surface of the substrate to which the crosslinkable oligomer or polymer composition is applied in step (1) is preferably made of a conductive or semiconducting material. Preferred conductive materials are metals such as aluminum, molybdenum, titanium, nickel, copper, silver, and metal alloys, for example. Preferred semiconducting materials are metal oxides such as indium gallium zinc oxide (IGZO), indium zinc oxide (IZO), amorphous silicon, and polysilicon.

[0151] The crosslinkable composition applied in step (1) preferably contains one or more initiators. Preferred initiators are listed above.

[0152] The crosslinkable composition preferably further comprises one or more inorganic filler materials. Preferred inorganic filler materials are selected from nitrides, titanates, diamonds, oxides, sulfides, sulfites, silicates, and carbides, which may optionally be surface-modified with a capping agent. More preferably, the filler material is selected from the list consisting of AlN, Al2O3, BN, BaTiO3, B2O3, Fe2O3, SiO2, TiO2, ZrO2, PbS, SiC, diamonds, and glass particles.

[0153] Preferably, the total content of the inorganic filler material in the crosslinkable composition is in the range of 0.001 to 90 wt.-%, more preferably 0.01 to 70 wt.-%, and most preferably 0.01 to 50 wt.-%, based on the total weight of the composition.

[0154] If the crosslinkable composition contains a solvent, it is preferable that the solvent be removed by heating, more preferably to 80-120°C, after the composition has been applied to the surface of the substrate.

[0155] The method by which the crosslinkable composition is applied in step (1) is not particularly limited. Preferred application methods for step (1) include dispensing, dipping, screen printing, stencil printing, roller coating, spray coating, slot coating, slit coating, spin coating, stereolithography, gravure printing, flexographic printing, or inkjet printing.

[0156] The crosslinkable oligomer or polymer composition of the present invention may be provided in the form of a formulation suitable for gravure printing, flexographic printing, and / or inkjet printing. For the preparation of the formulation, ink-based formulations known from the art may be used.

[0157] Alternatively, the crosslinkable oligomer or polymer composition of the present invention may be provided in the form of a formulation suitable for photolithography. The photolithography process allows for the creation of a photopattern by using light to convert a geometric pattern into a photopatternable composition by means of a photomask. Typically, such a photopatternable composition contains a photochemically activated initiator. Photoresist-based formulations known from the art may be used for the preparation of such formulations.

[0158] In step (1), the crosslinkable composition is preferably applied as a layer having an average thickness of about 0.1 to 50 μm, more preferably about 0.5 to 20 μm, and most preferably about 1 to 5 μm.

[0159] The curing in step (2) is preferably carried out photochemically by exposure to radiation such as UV or visible light, and / or thermally by exposure to heat. More preferably, the curing in step (2) is carried out photochemically by exposure to UV light and thermally by exposure to heat.

[0160] Exposure to radiation includes exposure to visible light and / or UV light. Visible light is preferably electromagnetic radiation with wavelengths >380 to 780 nm, more preferably >380 to 500 nm. UV light is preferably electromagnetic radiation with wavelengths ≤380 nm, more preferably 100 to 380 nm. More preferably, UV light is selected from UV-A light having wavelengths of 315 to 380 nm, UV-B light having wavelengths of 280 to 315 nm, and UV-C light having wavelengths of 100 to 280 nm.

[0161] For UV light sources, Hg vapor lamps or UV lasers are possible; for IR light sources, ceramic emitters or IR laser diodes are possible; and for light in the visible region, laser diodes are possible.

[0162] In a preferred embodiment, the light source is a xenon flash. Preferably, the xenon flash has a broad emission spectrum with short wavelength components extending down to about 200 nm.

[0163] Exposure to heat includes exposure to high temperatures, preferably in the range of 100 to 300°C, more preferably 150 to 250°C, and most preferably 180 to 230°C.

[0164] Electronic devices In a sixth aspect, the present invention provides electronic devices, preferably packaged microelectronic devices, FET array panels, or TFT array panels, which include microelectronic structures that can be obtained by methods for manufacturing microelectronic structures according to the present invention.

[0165] For electronic devices, the cured layer obtained from the crosslinkable composition is preferably passivated and optionally planarized on the surface of a substrate that forms part of the microelectronic structure. The formed layer is a dielectric layer that plays a role in electronically isolating one or more electronic components of the electronic device from each other.

[0166] In a preferred embodiment, the dielectric layer forms part of the redistribution layer in the packaged microelectronic device.

[0167] The siloxane oligomer or polymer of the present invention is also preferably used for preparing dielectric materials for redistribution layers (RDLs) in wafer-level packaging or panel-level packaging.

[0168] The present invention is further illustrated by the following examples, which should not be construed as limiting. Those skilled in the art will recognize that various modifications, additions, and changes may be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.

[0169] example Measurement method NMR spectroscopy: The NMR sample is a 5 mm (O) sample containing CD3CN in a ring space. A ) A 3.7 mm (O) thin-walled precision glass NMR tube (Wilmad 537 PPT) placed inside A ) Measured in an FEP inliner or 5mm(O AThe measurement was performed internally as a dry solvent in a precision glass NMR tube. The measurement was performed at 25°C on a Bruker Avance III 400 MHz spectrometer equipped with a 9.3980 T cryomagnet. 1 The 1H NMR spectra were obtained using a 5mm combination operating at 400.17 and 376.54 MHz, respectively. 1 H / 19 Obtained using an F probe. 13 C, and 29 Si NMR spectra were obtained using a 5 mm wideband inverse probe operating at 100.62 and 79.50 MHz, respectively. The linewidth expansion parameter used for the exponential multiplication of free induction decay was set to be equal to or less than the resolution of each data point or the natural linewidth of the resonance. All linear functions were of the Lorentz type unless otherwise specified. In some cases, a Gaussian function was multiplied by the free induction decay to improve resolution during the Fourier transform. 1 The 1H NMR chemical shifts are based on tetramethylsilane (TMS), and the solvents used—CDCl3 (7.23 ppm), DMSO-d6 (2.50 ppm), and CD2HCN (1.96 ppm)—result in the following chemical shifts. 13 The 13C NMR spectra were obtained for the solvents CDCl3 (77.2 ppm), DMSO-d6 (39.5 ppm), and CD3. C For N (118.7 ppm), the chemical shift was used, with tetramethylsilane (TMS) as the reference. 29 The Si NMR chemical shifts were referenced to SiCl4. The positive (negative) sign indicates the chemical shift of the reference compound to higher (lower) frequencies.

[0170] Thermal analysis data was achieved on a TA Instruments DSCQ100 operating in the temperature range of -90 to 725°C using the DSC:Tzero cell design, with a temperature accuracy of ±0.1°C and a calorific accuracy of ±1%. Samples were placed in sealed aluminum pans and heated using a temperature program. Typical programs consist of a 5k / min ramp from 25°C to 450°C, or a 10k / min ramp from 0°C to 450°C.

[0171] FT-IR: The FT-IR spectrum was recorded using a Bruker ALPHA Platinum-ATR FT-IR with a diamond crystal.

[0172] Flexible low-load measurements were performed on the E2B:Zwick Roell Zwicki 500N system. Elongation to fracture was measured with a preload of 0.1N, and the elongation rate was set to 50 mm / min. Suitable specimens for measurement should be 15 mm wide and 25 mm long.

[0173] CTE (thermomechanical analysis) was performed on a Netzsch TMA 402 F1 / F3 Hyperion equipped with a high-precision induction displacement sensor, a precise force control system, and a vacuum-tight constant temperature measurement system. Suitable specimens for measurement should be uniform, independent films. Measurements were performed in nitrogen at a flow rate of 50 mL / min. The static force of the instrument used was 0.05 N, and the sampling rate was 75 points / min. The temperature for each measurement ranged from 20°C to 300°C, with a heating rate of 5 K / min. Each temperature lamp was measured twice, and the second measurement was evaluated.

[0174] GPC Analysis: Gel permeation chromatography (GPC) analysis was performed on an Agilent 1260 Infinity II liquid chromatography system equipped with a refractive index detector. The column (Agilent MesoPore PL1113-6325) was set to a flow rate of 1.0 cm³. 3 Elution was performed with tetrahydrofuran at a rate of 1 / min and a temperature of 40°C. A series of 12 narrow-dispersibility polystyrene standard samples were used to calibrate the GPC system.

[0175] Mechanical properties: Polysiloxane oligomers were prepared fresh in PGMEA solvent at different concentrations (20-50 wt.%). These solutions were then applied to various forms by spin coating, doctor blade cutting, or drop casting. The materials were subsequently thermocured and / or irradiated with ultraviolet light in various ways. Test specimens or self-supporting films were then measured using the aforementioned apparatus.

[0176] Surface topography analyzer (stylus type): High-resolution 2D profiling of developed specimens was performed on a KLA Tencor Alpha-step D-500 equipped with optical lever sensor technology. The 140 mm sample stage supports scan lengths of up to 30 mm in a single scan and up to 80 mm using the stitching function. The D-500 offers a maximum vertical range of 1200 μm and low-force sensor technology at 0.03 mg, ensuring scan accuracy on a variety of applications including thin films, flexible materials, Toll steps, bows, and stressed surfaces. The specimens shown here were measured with a stylus radius of 2 μm and a stylus force of 1 mg.

[0177] UV lamps: 365nm and 254nm. The material was cured using an Analytic Jena UVP Transilluminator with 8-watt UV bulbs at 302nm and 365nm, and a 20cm x 20cm filter size.

[0178] Monomer synthesis 1-Allyl-3,4-dimethylpyrrole-2,5-dione:

number

[0179] In a 250 mL round-bottom flask equipped with a Dean-Stark trap, 3,4-dimethylfuran-2,5-dione (160.0 g; 1243.4 mmol; 1.0 eq.) was dissolved in anhydrous toluene (1040 mL; 9.8 mol; 7.90 eq.). The mixture was stirred at RT until completely dissolved. A solution of allylamine (139.9 mL; 1865.0 mmol; 1.5 eq.) in anhydrous toluene (160.0 mL; 1.5 mol; 1.2 eq.) was added using a dropping funnel at 23°C. This solution was heated (140°C, reflux) and stirred at 140°C for 5 hours. Over time, a white solid precipitated. Subsequently, the mixture was cooled to RT, and toluene was removed under vacuum (10 mbar) at 70°C. A clear, pale orange crude product (222 g) was isolated in liquid form. Vacuum (10 mbar) at 120°C -2 After fractionation and concentration in mbar, 1-allyl-3,4-dimethylpyrrole-2,5-dione (201.2 g; 1.169 mmol), a clear, colorless product, was isolated in 94% yield and 96% purity. This product was stored at low temperature (4°C).

[0180] 1 ¹H-NMR (δ at 400.17 MHz, DMSO, ppm): 1.92 (s, 6H, CH3); 4.01 (dt, 3 J HH = 5.1 Hz, 4 J HH = 1.7, 2H, CH2);5.05 (ddt, 3 J trans-HH = 17.1 Hz, 2 J HH = 3.1 Hz, 4 J HH = 1.5 Hz, 1H, CH2=CH);5.08 (ddt, 3 J cis-HH = 10.3 Hz, 2 J HH = 3.1 Hz, 4 J HH = 1.5 Hz, 1H, CH2=CH);5.79 (ddt, 3 J trans-HH = 17.1 Hz, 3 Jcis-HH = 10.3 Hz, 3 J HH = 5.1 Hz, 1H, CH2=CH). 13 ¹³C-NMR (100.62 MHz, CDCl3, δ at ppm): 8.62 (q, 1 J CH = 129.5 Hz, CH3);39.92 (td, 1 J CH = 140.3 Hz, 2 J CH = 8.0 Hz, 2 J CH = 5.5 Hz, CH2);117.18 (ddt, 1 J CH = 159.4 Hz, 1 J CH = 155.3 Hz, 3 J CH = 5.5 Hz, CH2);132.01 (dtd, 1 J CH = 157.7 Hz, 2 J CH = 5.5 Hz, 2 J CH = 3.0 Hz, CH); 137.18 (qq, 2 J CH = 7.5 Hz, 3 J CH = 5.7 Hz, C=C);171.6 (m, C=O).

[0181] 3,4-Dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione:

number

[0182] In a 500 mL round-bottom flask equipped with a reflux condenser, pale yellow and liquid 1-allyl-3,4-dimethylpyrrole-2,5-dione (100.0 g; 851.2 mmol; 1.0 eq.) was presented, and platinum(IV) oxide (25.0 mg; 0.110 mmol; 1.15 eq.) and triethoxysilane (129.9 g; 668.3 mmol; 1.15 eq.) were added under strict stirring at RT. The solution was warmed (80°C) and stirred at 80°C for 190 hours. Completion of the reaction was confirmed by: 1 The reaction was monitored by 1H NMR spectroscopy. The solution was subsequently cooled to RT. Chloroform (100 mL) and activated carbon (8.0 g) were added and the mixture was stirred at RT for 1 hour. The suspension was subsequently filtered (paper filter and 0.45 μm PTFE filter), and the mother liquor was distilled at 60°C under vacuum (20 mbar) to remove the solvent. The product, 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (162 g), was isolated as a clear, pale brown liquid. After fractionation and concentration at 130-140°C under vacuum (0.2-0.35 mbar), β3,4-dimethyl-1-(2-triethoxysilylpropyl)pyrrole-2,5-dione (11.93 g; 36.2 mmol), a clear, deep yellow material, was isolated in 6.2% yield and 96% purity. The desired product, γ-3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (147.6 g; 448 mmol), was isolated as a colorless, clear liquid in a vacuum (0.2 mbar) at 160°C with a yield of 77% and purity of 99%. The material was stored at a low temperature (4°C).

[0183] 1 ¹H-NMR (400.17 MHz, CD3CN film, δ at ppm): -0.05 (m, 2H, CH2); 0.61 (t, 3 J HH = 7.0 Hz, 9H, CH3);1.04 (tt, 3 J HH = 7.3 Hz, 3 J HH = Resolution τ 1 / 2= 2.5 Hz, 2H, CH2);1.36 (s, 6H, CH3);2.85 (t, 3 J HH = 7.3, 2H, CH2); 3.21 (q, 3 J HH (= 7.0 Hz, 6H, CH2). 13 ¹¹C-NMR (100.62 MHz, CD3CN film, δ at ppm): 6.69 (tt, 1 J CH = 117.1 Hz, 2 J CH = 2.9 Hz, CH2); 6.97 (q, 1 J CH = 128.9 Hz, CH3);17.08 (qt, 1 J CH = 125.8 Hz, 2 J CH = 2.3 Hz, CH3); 21.19 (tc, 1 J CH = 128.8 Hz, 2 J CH = Resolution τ 1 / 2 = 12 Hz, CH2); 39.10 (tt, 1 J CH = 139.7 Hz, 2 J CH = 4.4 Hz, CH2); 57.04 (tq, 1 J CH = 141.8 Hz, 2 J CH = 4.5 Hz, CH2); 135.65 (qq, 2 J CH = 7.5 Hz, 3 J CH = 5.7 Hz, C=C);170.33 (m, C=O). 29 Si{ 1 ¹H-NMR (79.5 MHz, CDCl3, ppm, δ): -46.0 (s).

[0184] Octakis(3,4-dimethylpyrrole-2,5-diionicpropyldimethylsiloxy)-T8-silsesquioxane:

number

[0185] In a two-necked 50 mL round-bottom flask equipped with a reflux condenser and a nitrogen inlet, pale yellow liquid 1-allyl-3,4-dimethylpyrrole-2,5-dione (2.705 g; 15.7 mmol; 8.00 eq.) was presented and stirred at 400 rpm. In a separate flask, white solid octakis(dimethylsiloxy)-T8-silsesquioxane (2.000 g; 1.97 mmol; 1.00 eq.) was dissolved in dry toluene (20.0 ml; 0.189 mol; 96 eq.) and added in a single addition to 1-allyl-3,4-dimethylpyrrole-2,5-dione. The solution was heated to 80°C. At 50°C, a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt ~2%; 100 μl) in xylene was added using a Hamilton syringe. The solution was stirred at 80°C for 2 hours. The solution turned yellow depending on the reaction time. Completion of the reaction was monitored by NMR spectroscopy. Subsequently, toluene and all volatile materials were removed under vacuum at 70°C using a rotary evaporator (20 mbar) to obtain a highly viscous yellow liquid. The product, octakis(3,4-dimethylpyrrole-2,5-diionicpropyldimethylsiloxy)-T8-silsesquioxane (4.6 g, 1.96 mmol), was isolated in nearly 100% yield.

[0186] 1 H-NMR (δ at 400.17 MHz, CDCl3, ppm): 0.1 (s, 6H, CH3); 0.54 (m, 2H, CH2); 1.55 (m, 2H, CH2); 1.91 (s, 6H, CH3); 3.41 (t, 3 J HH = 7.3 Hz, 2H, CH2). 13 ¹³C-NMR (100.62 MHz, CDCl3, δ at ppm): -0.27 (q, 1 J CH= 118.19 Hz, CH3); 8.77 (q, 1 J CH = 128.9 Hz, CH3);14.82 (m, CH2);22.5 (ttt, 1 J CH = 128.7 Hz, 2 J CH = 5.0 Hz, 3 J CH = 3.0 Hz, CH2); 40.84 (ttt, 1 J CH = 139.5 Hz, 2 J CH = 4.6 - 5.0 Hz, CH2);137.04 (qq, 2 J CH = 7.5 Hz, 3 J CH = 5.7 Hz, C=C);172.32 (m, C=O).

[0187] Tetrakis(3,4-dimethyl-pyrrole-2,5-diionicpropyldimethylsiloxy)tetrakis(2-propyloxymethyl-oxiran)-T8-silsesquioxane:

number

[0188] In a two-necked 50 mL round-bottom flask equipped with a reflux condenser and a nitrogen inlet, pale yellow liquid 1-allyl-3,4-dimethylpyrrole-2,5-dione (1.352 g; 7.86 mmol; 4.00 eq.) and 2-allyloxymethyloxirane (0.932 ml; 7.86 mmol; 4.0 eq.) were presented and stirred at 400 rpm. In a separate flask, white solid octakis(dimethylsiloxy)-T8-silsesquioxane (2.000 g; 1.97 mmol; 1.0 eq.) was dissolved in dry toluene (20.0 ml; 0.189 mol; 96 eq.) and added to 1-allyl-3,4-dimethylpyrrole-2,5-dione in a single addition. The solution was heated to 80°C. At 50°C, a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt ~2%; 100 μl) in xylene was added using a Hamilton syringe. The solution was stirred at 80°C for 2 hours. The solution turned yellow depending on the reaction time. Completion of the reaction was monitored by NMR spectroscopy. Subsequently, toluene and all volatile materials were removed under vacuum at 70°C using a rotary evaporator (20 mbar) to obtain a highly viscous yellow liquid. The product, tetrakis(3,4-dimethyl-pyrrole-2,5-diionicpropyldimethylsiloxy)tetrakis(2-propyloxymethyl-oxirane)-T8-silsesquioxane (4.2 g, 1.97 mmol), was isolated in nearly 100% yield.

[0189] 1 1H-NMR (400.17 MHz, CDCl3, ppm, δ): 0.0 (m, 48H, CH3) DMMI / エポキシ );0.44 (m, 16H, CH2 DMMI / エポキシ ) o ;1.45 (m, 8H, CH2 DMMI );1.52 (m, 8H, CH2 エポキシ ) o ;1.82 (s, 24H, CH3 DMMI );3.0 (m, 4H, CH エポキシ );3.3 (m, 8H, CH2 エポキシ ) o;3.3 (m、4H、H'' エポキシ ) o ;3.31 (t、 3 J HH = 7.3、8H、CH2 DMMI ) o ;3.55 (d、 3 J HH 11.2 Hz、4H、HOUSE'' エポキシ )。( o overlaid) 13 C-NMR (100.62 MHz、CDCl3、ppmでのδ): -0.26 (q、 1 J CH = 118.8 Hz、CH3 DMMI / エポキシ );-0.21 (q、 1 J CH = 118.8 Hz、CH3 DMMI / エポキシ );8.8 (q、 1 J CH = 130.0 Hz、CH3 DMMI );13.8 (t、 1 J CH = 117.3 Hz、CH2 エポキシ );14.9 (t、 1 J CH = 117.3 Hz、CH2 DMMI );22.5 (tm、 1 J CH = 128.7 Hz、CH2 DMMI );23.34 (tm、 1 J CH = 126.6 Hz、CH2 エポキシ );40.8 (low、 1 J CH = 139.6 Hz、 2 J CH = 4.5 Hz、CH2 DMMI );44.5 (t、 1 J CH = 175.1 Hz、CH2 エポキシ );51.0 (dm、 1 J CH = 174.1 Hz、CH2 エポキシ );71.6 (t、 1 J CH= 140.6 Hz、CH2 エポキシ );74.3 (tqui、 1 J CH = 140.4 Hz、 2 J CH = 4.1 Hz、CH2 エポキシ );137.1 (whi、 2 J CH = 6.6 Hz、C DMMI );172.3 (s、CO DMMI ). 29 Si-NMR (79.5 MHz、CDCl3、ppmでのδ): -109.1 (m、8 SiO 1.5 );12.5 (m、4 Si DMMI );12.9 (m、Si エポキシ ).

[0190] T7iBu7(Si(CH3)2H)3: In a 250 mL round-bottom flask, 1,3,5,7,9,11,14-heptisobutyltricyclo[7.3.3.15,11]heptasiloxane-endo-3,7,14-triol (5.0 g, 6.3 mmol) was cooled (0°C) and dissolved in dry cold THF (50 mL, 0°C) under an N2 atmosphere. Chlorodimethylsilane (2.02 g, 21.34 mmol) was added, followed by the dropwise addition of triethylamine (2.20 g, 21.73 mmol). The reaction was exothermic, forming a white precipitate. The mixture was stirred at 0°C for 2 hours. The suspension was then heated to RT and stirred for a further 20 hours. Subsequently, the suspension was filtered, and all volatile materials were condensed under vacuum (150-200 mbar) at 25°C. A white, viscous solid was obtained and washed with CH3OH (3 × 10 mL). The solid material was finally dried in a vacuum (10–40 mbar) at 35°C. The desired product, 3,7,14-tris[(dimethylsilyl)oxy]-1,3,5,7,9,11,14-heptakis(2-methylpropyl)tricyclo[7.3.3.15,11]heptasiloxane (4.567 g; 4.73 mmol), was isolated as a white solid in 74.8% yield. Further purification can be achieved by recrystallization from CH3OH / CHCl3 (3:2). [ka]

[0191] 1 1H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.19 (d, 3 J HH = 2.8 Hz, 18H d ), 0.54 (d, 3 J HH = 6.9 Hz, 14H c,c’,c’’ ) o , 0.93 (dm, 3 J HH = 6.7 Hz, 4 J HH = 2.7 Hz, 42H a,a’,a’’ ) o , 1.81 (sepm,3 J HH = 6.7 Hz, 7H b,b’,b’’ ) o , 4.71 (sep, 3 J HH = 6.7 Hz, 3H e (overlaid)

[0192] T7iBu7(Si(CH3)2propylDMMI)3: A solution of 3,7,14-tris[(dimethylsilyl)oxy]-1,3,5,7,9,11,14-heptakis(2-methylpropyl)tricyclo[7.3.3.15,11]heptasiloxane (3.44 g, 3.56 mmol) and 3,4-dimethyl-1-(propa-2-en-1-yl)-2,5-dihydro-1H-pyrrole-2,5-dione (1.69 g, 10.25 mmol) in dry toluene (20 mL) were stirred under an N2 atmosphere and at RT. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt~2%, 0.23 mL, 0.51 mmol) (Karstedt catalyst) in xylene was added to the solution and heated to 90°C. The solution should be heated at 90°C for 1 hour, or FTIR (904 cm⁻¹). -1The reaction was refluxed until completion, monitored by the disappearance of the Si-H signal. The post-reaction mixture was cooled to room temperature before activated carbon (0.5 g) was added and stirred at RT for several hours. The mixture was filtered through a Celite bed, the filtrate was separated, and all volatile materials were condensed under vacuum (150-200 mbar) at 25°C. The crude product appeared as a golden liquid. Purification can be achieved using column chromatography (CH2Cl2 / Light Petrol 40-60 (7:3) solvent system). All volatile materials were again condensed from the relevant fractions under vacuum (150-200 mbar) at 25°C and further dried under vacuum (10-40 mbar) at 35°C. The desired product, 1-[3-({[7,14-bis({[3-(3,4-dimethyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-1-yl)propyl]dimethylsilyl}oxy)-1,3,5,7,9,11,14-heptakis(2-methylpropyl)tricyclo[7.3.3.15,11]heptasiloxane-3-yl]oxy}dimethylsilyl)propyl]-3,4-dimethyl-2,5-dihydro-1H-pyrrole-2,5-dione (2.8 g, 1.92 mmol), was isolated as a colorless liquid in 53.9% yield. [ka]

[0193] 1 1H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.07 (s, 18H) d ), 0.48 (m, 6H e ), 0.53 (m, 14H c ), 0.95 (dd, 3 J HH = 6.6 Hz, 4 J HH = 1.6 Hz, 42H a ), 1.52 (m, 6H f ), 1.78 (dec, 3 J HH = 6.7 Hz, 7H b ), 1.95 (s, 3H h)、3.39 (t, 3 J HH = 7.5 Hz, 6H g ). 13 C-NMR (100.62 MHz, CDCl3, δ in ppm): 0.41 (q, 1 J CH = 119.1 Hz, 6C 7 ), 8.88 (q, 1 J CH = 129.1 Hz, 6C 1 ), 15.39 (t, 1 J CH = 116.7 Hz, 3C 6 ), 22.87 (t, 1 J CH = 125.7 Hz, 6C 5 ), 21.5 - 28.5 (i-Bu group, 28C a-c,a’-c’,a’’-c’’ ). o , 41.05 (t, 1 J CH = 139.8 Hz, 3C 4 ), 137.09 (q, 2 J CH = 7.4 Hz, 6C 2 ), 172.43 (m, 6C 3 ).

[0194] T7Ph7(Si(CH3)2H)3: In a 250 mL round-bottom flask, 1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.15,11]heptasiloxane-endo-3,7,14-triol (5.0 g, 5.37 mmol) was dissolved in dry toluene (25 mL) at 0°C under an N2 atmosphere. Chlorodimethylsilane (1.72 g, 18.20 mmol) was added to this solution at 0°C, followed by the dropwise addition of triethylamine (1.87 g, 18.48 mmol). The reaction was exothermic, forming a white precipitate. The suspension was stirred at 0°C for 2 hours. The suspension was then heated to RT and stirred for a further 20 hours at RT. Subsequently, the suspension was filtered, and all volatile substances were condensed under vacuum (150-200 mbar) at 25°C. A white, viscous solid was obtained and washed with CH3OH (3 × 10 mL). The solid material was finally dried in a vacuum (10–40 mbar) at 35°C. The desired product, 3,7,14-tris[(dimethylsilyl)oxy]-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.15,11]heptasiloxane (4.200 g; 3.80 mmol), was isolated as a white solid in 70.7% yield. Further purification can be achieved by recrystallization from CH3OH / CHCl3 (3:2). [ka]

[0195] 1 1H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.35 (d, 3 J HH = 2.8 Hz, 18H b ), 4.93 (sep, 3 J HH = 2.8 Hz, 3H a ), 7.12 (tm, 3 J HH = 8.0 Hz, 14H ma,b,c ) o , 7.28 (tm, 3 J HH = 8.0 Hz, 6H pa,b ) o , 7.32 (dm,3 J HH = 8.0 Hz, 6H oa ), 7.42 (tm, 3 J HH = 8.0 Hz, 1H pc ), 7.45 (dm, 3 J HH = 8.0 Hz, 6H ob ), 7.59 (dm, 3 J HH = 8.0 Hz, 2H oc ).( o (overlaid)

[0196] T7Ph7(Si(CH3)2propylDMMI)3: In a 250 mL round-bottom flask, (3r,7s,11s)-3,7,14-tris[(dimethylsilyl)oxy]-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.15,11]heptasiloxane (2.78 g, 2.52 mmol) and 3,4-dimethyl-1-(propa-2-en-1-yl)-2,5-dihydro-1H-pyrrole-2,5-dione (1.20 g, 7.26 mmol) were dissolved in dry THF (20 mL) under strict stirring in an N2 atmosphere of RT. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt ~2%, 0.16 mL, 0.36 mmol) (Karstedt catalyst) was added to xylene and heated to 90°C. The solution was heated at 90°C for 1 hour, or until the Si-H signal disappeared in FTIR (904 cm⁻¹). -1The mixture was refluxed until completion was monitored by a meter. The post-reaction mixture was cooled to room temperature before all volatile materials were condensed in a vacuum at 25°C (150–200 mbar). The residue was redissolved in CHCl3 (20 mL) and treated with 0.1 wt.-% activated carbon (0.021 g, 1.75 mmol). The mixture was heated to reflux temperature and refluxed further at 60°C for 18 hours. The mixture was then filtered through a bed of Celite supported by cotton in a microcolumn. Subsequently, all volatile substances were condensed in a vacuum at 25°C (150–200 mbar). The crude product appeared as a golden viscous liquid. Purification can be achieved using column chromatography (CH2Cl2 / Light Petrol 40–60 (7:3) solvent system). All volatile materials were condensed again from the relevant fractions in a vacuum at 25°C (150–200 mbar) and further dried in a vacuum at 35°C (10–40 mbar). The desired product, 1-{3-[dimethyl({[(7r,9r,11s,14r)-7,14-bis({[3-(3,4-dimethyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-1-yl)propyl]dimethylsilyl}oxy)-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.15,11]heptasyloxan-3-yl]oxy})silyl]propyl}-3,4-dimethyl-2,5-dihydro-1H-pyrrole-2,5-dione (0.800 g, 0.50 mmol), was isolated in 20% yield as a colorless viscous liquid. [ka]

[0197] 1 1H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.25 (s, 18 H) e ), 0.56 (m, 6 H b ), 1.53 (m, 6H c ), 1.93 (s, 18 H a ), 7.10 (tm, 3 J HH = 8.0 Hz, 6H ma)、7.15 (tm、 3 J HH = 8.0 Hz、6H mb )、7.26 (tm、 3 J HH = 8.0 Hz、3H pa )、7.29 (tm、 3 J HH = 8.0 Hz、3H pb )、7.31 (dm、 3 J HH = 8.0 Hz、6H oa )、7.41 (tm、 3 J HH = 8.0 Hz、1H pc )、7.37 (dm、 3 J HH = 8.0 Hz、6H ob )、7.54 (dm、 3 J HH = 8.0 Hz、2H oc )。( o overlaid) 13 C-NMR (100.62 MHz、CDCl3、ppmでのδ): 0.5 (q、 1 J CH = 119.1 Hz、6C 7 )、8.9 (q、 1 J CH = 129.1 Hz、6C 1 )、15.4 (t、 1 J CH = 116.7 Hz、3C 6 )、22.8 (t、 1 J CH = 125.7 Hz、3C 5 )、40.5 (t、 1 J CH = 141 Hz、C 5 )、127.7 (dm、 1 J CH = 161.1 Hz、2C 10 )、127.8 (dm、 1 J CH = 161 Hz、2C 14 )、128.1 (m、2C 18 )、130.2 (m、2C11 ) o , 130.8 (m, 2C 15 ) o , 131.3 (m, 2C 19 ) o , 132.8 (m, 2C 17 ) o , 134.1 (dm, 1 J CH = 157 Hz, 2C 9 ), 134.2 (dm, 1 J CH = 158 Hz, 2C 13 ), 137.1 (s, 6C 2 ), 172.4 (s, 6C 3 ). ( o (overlaid)

[0198] Priamine-bis(3,4-dimethylpyrrole-2,5-dione):

number

[0199] In a 250 mL round-bottom flask equipped with a dropping funnel and a Dean Stark trap, [2-(8-amino-octyl)-3-hexyl-4-octyl-cyclohexyl]-octylamine (priamine) (81.00 g; 149.9 mmol; 1.00 eq.) was dissolved in dry toluene (max. 75 ppm H2O) SeccoSolv® (480.00 ml; 4.5 mol; 30.2 eq.) and stirred at RT using a magnetic stirrer until dissolved. A solution of 3,4-dimethylfuran-2,5-dione (DMMA) (38.58 g; 299.78 mmol; 2.00 eq.) in dry toluene (max. 75 ppm H2O) SeccoSolv® (400.0 ml; 3.78 mol; 25.20 eq.) was presented in a dropping funnel and added to the priamine solution at RT, where a white solid precipitated over time. The reaction suspension was heated (refractory) to 140°C and stirred at 140°C for 5 hours. Water was separated in a Dean Stark trap. The reaction mixture was cooled to RT before residual toluene was removed under vacuum at 70°C (~10 mbar). The product, 1-[8-[2-[8(3,4-dimethyl-2,5-dioxo-pyrrole-1-yl)octyl]-3-hexyl-4-octyl-cyclohexyl]octyl]-3,4-dimethyl-pyrrole-2,5-dione (109.43 g; 145.7 mmol; 97% yield), was isolated as a clear, orange liquid.

[0200] 1 ¹H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.74 bis 0.95 (m, 8H, CH und CH3); 1.03 bis 1.41 (m, 52H, CH2); 1.54 (q, 3 J HH = 6.6, 6H, CH und CH2);1.94 (s, 12H, CH3);3.45 (t, 3 J HH = 7.3, 4H, CH2). 13 ¹³C-NMR (100.62 MHz, CDCl3, δ at ppm): 8.6 (q,1 J CH = 129.0 Hz, CH3); 14.1 (qm, 1 J CH = 124.7 Hz, CH2); 22.6 (tm, 1 J CH = 125.7 Hz, CH2); 26.8, 28.7, 29.2, 29.3, 29.5, 29.6, 29.66, 29.7 (m, CH2) o ;37.9 (tm, 1 J CH = 139.6 Hz, CH2);136.95 (q, 2 J CH = 6.6 Hz, C); 172.3 (s, CO).

[0201] Pyromelitbis[3-(trimethoxysilyl)propyl]imide:

number

[0202] In a 100 mL round-bottom flask equipped with a reflux condenser and a nitrogen inlet, a premix of benzo[1,2-c;4,5-c']difuran-1,3,5,7-tetraone (4.570 g; 20.950 mmol; 1.00 eq.) and urea (9.322 ml; 208.0 mmol; 9.93 eq.) was heated to 200°C. The solution was stirred at 200°C for 2 hours. Over time, a white solid precipitated. After 2 hours, the solid was filtered and ground into a powder. The powder was stirred at 200°C for another hour. After cooling to RT, the powder was washed several times with distilled water. Subsequently, the white powder was dried in a vacuum (10 mbar) at 100°C for several hours. The desired product A, pyrrolo[3,4-f]isoindole-1,3,5,7-tetraone (4.49 g; 20.8 mmol; 99%), was isolated as a white solid. In a 250 mL three-necked round-bottom flask equipped with a condenser and nitrogen inlet, pyrrolo[3,4-f]isoindole-1,3,5,7-tetraone (13.927 g; 0.063 mol; 1.00 eq.) was dissolved at 100 °C in dried dimethyl sulfoxide (max. 50 ppm H2O) SeccoSolv® (31.250 mL; 0.440 mol; 7.04 eq.). A solution of potassium hydroxide (3.438 ml; 0.125 mol; 2.00 eq.) in dry ethanol (max. 20 ppm H2O) SeccoSolv® (62.500 ml; 1.072 mol; 17.15 eq.) was added dropwise over 10 minutes at 100°C. A white solid precipitated over time. The suspension was stirred for another 30 minutes. The suspension was filtered at 100°C, washed several times with dry ethanol, and subsequently dried under vacuum (10 mbar) at 100°C for 4 hours. The desired product B (17.54 g; 60.0 mmol) was isolated as a white solid in 95% yield.

number

[0203] In a 250 mL round-bottom three-neck flask equipped with a reflux condenser, pyrrolo[3,4-f]isoindole-2,6-dide-1,3,5,7-tetron potassium (7.000 g; 24 mmol; 1.0 eq.) was dissolved in dimethylformamide (40.0 mL; 514 mmol; 21.5 eq.), and 3-iodopropyl(trimethoxy)silane (14.628 g; 48 mmol; 2.0 eq.) was added. The suspension was heated to 100°C and stirred at 100°C for 2 hours. The suspension was further heated (110°C), followed by the addition of more DMF (10 mL), and stirred for another 4 hours until all materials were dissolved. The solution was stirred at 110°C for another 1 hour and then cooled to RT. The solvent (DMF) was removed under vacuum (~10 mbar) at 50°C. A yellow / orange suspension was isolated. This suspension was resuspended in chloroform (70 mL). The solid, presumably KI, was filtered and dried (7.41 g; 45 mmol, 93% yield). The solvent was removed under vacuum (~10 mbar) at 50°C. The desired crude product, pyromellites[3-(trimethoxysilyl)propyl]imide (7.82 g; 14.5 mmol; 60.4%), was obtained as a pale yellow solid. The crude product could be purified by crystallization from methanol. After crystallization, a pure compound (6.18 g; 11.4 mmol; 47.5%) was obtained.

[0204] 1 H-NMR (δ at 400.17 MHz, DMSO, ppm): 0.63 (m, 4H, Si-CH2-); 1.69 (m, 4H, -CH2-); 3.45 (s, 18H, O-CH3); 3.6 (t, 3 J HH = 7.1, 4H, N-CH2-);8.17 (s, 2H, CH). 13 ¹¹C-NMR (100.62 MHz, DMSO film, δ at ppm): 6.37 (t, 2 CH2); 21.73 (t, 1 J CH = 128.0 Hz, 2 CH2);24.26 (q, 1 JCH = 140.2 Hz, 2 CH2);50.46 (q, 1 J CH = 143.0 Hz, 6 CH3);117.41 (dt, 2 J CH = 173.4 Hz, J = 7.4 Hz, 2 CH);137.46 (dd, J = 14.9 Hz, 2 J CH = 6.1 Hz, 4 C);166.85 (q, J = ~3-4 Hz, 4 CO).

[0205] DDSQ-T8Ph8 Silsesquioxane:

number

[0206] In a 1000 mL three-necked round-bottom flask, T8Ph8(OH)4 (87.45 g; 81.77 mmol) was suspended in THF (850 mL). Triethylamine (41.14 g; 408.83 mmol) was added, yielding a clear solution. Dichloromethylsilane (94.06 g; 817.66 mmol) was added within 45 minutes. An exothermic reaction was observed, and a white solid precipitated. The suspension was stirred at RT for 20 hours. Subsequently, the suspension was filtered, and the isolated white crude product was recrystallized from toluene or a mixture of toluene and methanol at high temperature (75°C). The desired product, DDSQ-T8Ph8(Si(CH3)H)2 (53.26 g; 46.16 mmol), was isolated as a white solid in 56.5% yield. [ka]

[0207] 1 1H-NMR (400.17 MHz, CDCl3, δ at ppm): 0.42 (d, 3 J HH = 1.5 Hz, 6H a cisおよびtrans ), 5.03 (q, 3 JHH = 1.5 Hz、2H b cisおよびtrans )、7.22 (tm、 3 J HH = 7.6 Hz、8H m’ cisおよびtrans )、7.30 (t、 3 J HH = 7.6 Hz、8H m )、7.38 (tm、 3 J HH = 7.6 Hz、4H p’ cisおよびtrans )、7.44 (tt、 3 J HH = 7.6 Hz、 4 J HH = 1.4 Hz、4H p )、7.47 (dm、 3 J HH = 8.0 Hz、8H o’ cisおよびtrans )、7.6 (dd、 3 J HH = 8.0 Hz、 4 J HH = 1.4 Hz、8H o )。( o overlaid) 13 C-NMR (100.62 MHz、CDCl3、ppmでのδ): 0.9 (qd、 1 J CH = 119.5 Hz、 2 J CH = 20.5 Hz、2C 1 cisおよびtrans )、127.9 (dm、 1 J CH = 159.8 Hz、8C 3’ cisおよびtrans )、128.0 (dd、 1 J CH = 159.8 Hz、 2 J CH = 7.2 Hz、8C 3 )、130.6 (dm、 1 J CH = 159.8 Hz、4C 5’ cisおよびtrans )、130.7 (dm、1 J CH = 159.8 Hz, 4C 5 ), 131.0 (m, 4C 2’ cisおよびtrans ), 131.8 (m, 4C 2 ), 134.2 (dm, 1 J CH = 159.5 Hz, 8C 4 ), 134.3 (dm, 1 J CH = 159.5 Hz, 8C 4’ cisおよびtrans ). 29 Si-NMR (79.50 MHz, CDCl3, ppm in δ): -32.82 (dq, 1 J SiH = 250.5 Hz, 2 J SiH = 7.8 Hz, 2Si(H)CH3 trans ), -32.84 (dq, 1 J SiH = 250.5 Hz, 2 J SiH = 7.8 Hz, 2Si(H)CH 3 cis ), -77.8 (tm, 3 J SiH = 6.3 Hz, 4 SiO 1.5 ), -79.3 (tm, 3 J SiH = 6.3 Hz, 4 SiO 1.5 cisおよびtrans ).

Number

[0208] In a 1000 mL three-necked round bottom flask, T8Ph8(Si(CH3)H)2 was dissolved in toluene (280 mL) at 60 °C. A 2% xylene solution of Karstedt catalyst and 1-allyl-3,4-dimethyl-pyrrole-2,5-dione (6.01 g; 36.40 mmol) were added and stirred at 60 °C for 6 hours and at RT for 18 hours. A white solid precipitated. Subsequently, the suspension was filtered and the isolated white crude product was recrystallized from hot acetonitrile. The desired product (15.82 g; 10.66 mmol) was isolated as a white solid in 88% yield. [Chemical formula]

[0209] 1 H-NMR (400.17 MHz, CDCl3; δ in ppm): 0.28 (s, 6H d )、0.66 (m, 4H e )、1.62 (m, 4H f )、1.93 (s, 12H h )、3.40 (t, 3 J HH = 7.3 Hz, 4H g )、7.22 (t, 3 J HH = 7.5 Hz, 8H m )、7.26 (t, <[ 3 J HH = 8.2 Hz, 8H m’ )、7.36 (tt, 3 J HH = 7.5 Hz, 3 J HH = 1.4 Hz, 4H p )、7.40 (tt, 3 J HH = 7.5 Hz, 3 J HH = 1.4 Hz, 4H p’ )、7.46 (d, 3 J HH = 7.5 Hz, H o )、7.54 (d, 3 J HH = 7.5 Hz, Ho’ ). 13 C{ 1 ¹H-NMR (100.65 MHz, δ at CDCl3 ppm): -0.8 (C5), 8.8 (C 11 ), 14.1 (C6), 22.4 (C7), 40.7 (C8) 127.8 (C3), 127.9 (C3'), 130.5 (C4), 131.1 (C1), 132.1 (C1'), 134.1 (C2), 134.2 (C2'), 137.0 (C10), 172.3 (C9) ppm. 29 Si{ 1 H}-NMR (δ at 79.50 MHz, CDCl3; ppm): -18.1 (s, 2Si(H)CH3), -78.5 (4 SiO 1.5 ), -79.5 (4 SiO 1.5 ). FTIR (ATR) (ν in cm -1 ): 3050 (CH aromat.), 2929 (CH aliphat.), 1700 (C=O), 1594 and 1432 (CC aromat.), 1084 (Si-O-Si).

[0210] Synthesis of siloxane oligomers or polymers Example 1 - MPDMMIQ-453510: Methyltrimethoxysilane (2.72 g, 20.0 mmol), phenyltrimethoxysilane (3.17 g, 16.0 mmol), tetraethyl orthosilicate (0.83 g, 4.00 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (1.46 g, 4.44 mmol), and propan-2-ol (14.0 g) were added to the reaction vessel and purged with nitrogen. Tetramethylammonium hydroxide (3.66 g, 10.0 mmol, 25% in water) was added to the reaction with rapid stirring for 5 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred at 23°C under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (17.0 g), 35% hydrochloric acid (1.09 g, 10.5 mmol), and n-propyl acetate (17.0 g, 166 mmol). The mixture was stirred at 23°C for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (17.0 g) and then rinsed to approximately 10 cm. 3 The solution was vacuum concentrated to the volume. Propylene glycol methyl ether acetate (20 g) was added to the organic phase, and the solution was vacuum concentrated to obtain siloxane 1 (14.0 g, 98% in 32 wt.% propylene glycol methyl ether acetate). GPC (THF, 40℃): M n = 1498 g / mol, M w = 2318 g / mol.

[0211] Example 2 - MPDMMIQ-403020: Methyltrimethoxysilane (1.63 g, 12.0 mmol), phenyltrimethoxysilane (1.90 g, 9.60 mmol), tetraethyl orthosilicate (0.50 g, 2.40 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (1.98 g, 6.00 mmol), and propan-2-ol (8.39 g) were added to the reaction vessel and purged with nitrogen. Tetramethylammonium hydroxide (2.20 g, 6.02 mmol, 25% water) was added dropwise to the reaction with rapid stirring for 3 minutes. During the addition, the temperature was controlled to <25°C. The reaction mixture was stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (10.0 g), 35% hydrochloric acid (0.66 g, 6.30 mmol), and n-propyl acetate (10.2 g, 99.6 mmol). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (10.0 g) and then allowed to rise for approximately 10 cm. 3 The solution was vacuum concentrated to volume. Propylene glycol methyl ether acetate (20.0 g) was added to the organic phase, and the solution was vacuum concentrated to obtain siloxane 2 (12.0 g, 98% in 29 wt.-% propylene glycol methyl ether acetate). GPC (THF, 40°C): M n = 1550 g / mol, M w = 2352 g / mol.

[0212] Example 3 - MPDMMIQ-332730: Methyltrimethoxysilane (3.18 g, 23.4 mmol), phenyltrimethoxysilane (3.70 g, 18.7 mmol), tetraethyl orthosilicate (1.46 g, 7.00 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (6.92 g, 21.0 mmol), and propan-2-ol (18.2 g) were added to the reaction vessel and purged with nitrogen. Tetramethylammonium hydroxide (5.77 g, 15.8 mmol, 25% in water) was added dropwise to the reaction with rapid stirring for 3 minutes. During the addition, the temperature was controlled to <25°C. The reaction was stirred for 2 hours at ambient temperature under nitrogen. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (23.8 g), 35% hydrochloric acid (1.81 g, 17.4 mmol), and n-propyl acetate (23.8 g, 233 mmol). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (23.8 g) and then rinsed for approximately 15 cm. 3 The solution was vacuum concentrated to volume. Propylene glycol methyl ether acetate (30.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 3 (15.3 g, 47 wt.-% in propylene glycol methyl ether acetate, 92% yield). GPC (THF, 40°C): M n = 1718 g / mol, M w = 2727 g / mol.

[0213] Example 4 - MPDMMIQ-282240: Methyltrimethoxysilane (2.65 g, 19.4 mmol), phenyltrimethoxysilane (3.08 g, 15.6 mmol), tetraethyl orthosilicate (1.46 g, 7.00 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (9.23 g, 28.0 mmol), and propan-2-ol (18.2 g) were added to the reaction vessel and purged with nitrogen. Tetramethylammonium hydroxide (5.77 g, 15.8 mmol, 25% in water) was added dropwise to the reaction with rapid stirring for 3 minutes. During the addition, the temperature was controlled to <25°C. The reaction was stirred for 2 hours at ambient temperature under nitrogen. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (23.8 g), 35% hydrochloric acid (1.81 g, 17.4 mmol), and n-propyl acetate (23.8 g, 233 mmol). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (23.8 g) and then rinsed for approximately 15 cm. 3 The solution was vacuum concentrated to volume. Propylene glycol methyl ether acetate (30.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 4 (16.9 g, in 46 wt.-% propylene glycol methyl ether acetate, 92% yield). GPC (THF, 40℃): M n = 1753 g / mol, M w = 2609 g / mol.

[0214] Example 5 - MPDMMIQ-221850: Methyltrimethoxysilane (2.12 g; 15.6 mmol; 2.22 eq.), phenyltrimethoxysilane (2.47 g; 12.4 mmol; 1.78 eq.), tetraethyl orthosilicate (1.46 g; 7.00 mmol; 1.00 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (11.53 g; 35.0 mmol; 5.00 eq.), and propan-2-ol (18.2 g; 0.30 mol; 43.3 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (5.77 g; 15.8 mmol; 2.26 eq.) was added dropwise to the reaction with rapid stirring for 4 minutes. During the addition, the temperature was controlled to <25°C. The reaction was stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (23.8 g), 35% hydrochloric acid (1.81 g; 17.4 mmol; 2.49 eq.), and n-propyl acetate (23.8 g; 233 mmol; 33.3 eq.). The mixture was stirred at ambient temperature for 40 minutes, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (23.8 g) and then vacuum concentrated to approximately 15 mL. PGMEA (40.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 5 (30.5 g, in 34.3 wt.-% propylene glycol methyl ether acetate, yield: 97.5%). GPC (THF, 40°C): M n 1464, M w 1795, PDI 1.23.

[0215] Example 6 - MDMMIQ-4050: Methyltrimethoxysilane (1.64 g; 12.0 mmol; 1.00 eq.), tetraethyl orthosilicate (0.63 g; 3.0 mmol; 0.25 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (4.94 g; 15.0 mmol; 1.25 eq.), and propan-2-ol (7.8 g; 130 mmol; 11 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (2.47 g; 6.78 mmol; 0.565 eq.) was added to the reaction with rapid stirring for 5 minutes. During the addition, the temperature was controlled to <25°C. The reaction was stirred for 2 hours at ambient temperature under nitrogen. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (10.0 g), 35% hydrochloric acid (0.74 g; 7.1 mmol; 0.59 eq.), and n-propyl acetate (10.2 g; 99.9 mmol; 8.32 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (10.0 g) and then vacuum concentrated to approximately 10 mL. PGMEA (20.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 6 (14.2 g, in 27.0 wt.-% propylene glycol methyl ether acetate, yield: 90.0%), GPC (THF, 40°C): M n 1511, M w 2219, PDI 1.47.

[0216] Example 7-MADMMIQ-502020: Example 7.1-MADMMIQ502020: In a 1000-mL three-necked round-bottom flask, methyltrimethoxysilane (38.70 g; 281.3 mmol; 1 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (37.82 g; 112.5 mmol; 0.40 eq.), trimethoxy(octyl)silane (26.37 g; 112.5 mmol; 0.40 eq.), and tetraethoxysilane (11.84 g; 56.3 mmol; 0.20 eq.) were dissolved in 2-propanol (186 mL; 2433 mmol) and cooled to ice (5°C) under an argon atmosphere (X1). The condensation reaction was initiated by adding tetramethylammonium hydroxide solution (25% water; 46.35 g; 127.1 mmol; 0.45 eq.) within 5 minutes. The exothermic reaction must be controlled so that the temperature of the reaction mixture does not exceed 25°C. The clear, colorless solution was heated to RT and stirred for 2 hours (magnetic stirrer 400 rpm). In a separate 1000-mL round-bottom flask, an emulsion (X2) (two-phase system) of deionized water (191.25 g), hydrochloric acid (15.20 g; 133.43 mmol; 0.47 eq.), and n-propyl acetate (191.25 g; 1872.6 mmol; 6,66 eq.) was prepared to quench the reaction. Solution X1 was added to X2 to obtain a two-phase system. The turbid emulsion was stirred for 1 hour until the two phases separated. The oligomer dissolved in the upper organic phase was washed three times with deionized water (pH 4-5). Propylene glycol monomethyl ether acetate (225.0 g) was added to the solution, and the oligomer solution was finally concentrated to a solid content of approximately 20-45 wt.% under vacuum (~10 mbar) at 50°C. Any solid precipitates can be removed by filtration. A clear, colorless solution can be used for further reactions.

[0217] GPC (THF, International Standard: Toluene, 40°C); M n = 2245 g / mol; M w = 5157 g / mol; M z = 11652 g / mol, PDI = 2.30.

[0218] The self-supporting film was prepared by filling a silicone mold (moldstar) with MADMMIQ502020 solution (in 40% PGMEA) and cured using the following procedure: Curing conditions: 90℃ for 10 minutes 68 minutes UV (365nm; 10J / cm2) 90℃~120℃(3K / min) 20 minutes at 120℃ 120℃~175℃ (3.6K / min) Bake at 175℃ for 30 minutes.

[0219] measurement: Film thickness: 410 μm TGA:386℃(47% loss) CTE: 209 ppm / K(T) g (less than) | 299 ppm / K(T g super) T g :30.08℃ E2B: 9.71% F max = 5.85 MPa.

[0220] The self-supporting membrane was prepared by filling a silicone mold (moldstar) with a mixture of MADMMIQ502020 solution (3.6 g (solid content); ~28.8 mmol) in 40% PGMEA and Priamin-DMMI2 (1.8 g; ~2.3 mmol).

[0221] Curing conditions: 90℃ for 10 minutes 68 minutes UV (365nm; 10J / cm2) 90℃~120℃(3K / min) 20 minutes at 120℃ 120℃~175℃ (3.6K / min) 30 minutes at 175℃

[0222] measurement: Film thickness: 362 μm TGA:466.7℃(60% loss) E2B: 19.9% Fmax = 0.99 MPa.

[0223] Example 7.2-MADMMIQ-502020: Methyltrimethoxysilane (4.087 g; 30.00 mmol; 1.000 eq.), tetraethyl orthosilicate (1.250 g; 6.00 mmol; 0.200 eq.), trimethoxy(octyl)silane (2.813 g; 12.00 mmol; 0.400 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.954 g; 12.00 mmol; 0.400 eq.), and propan-2-ol (14.600 g; 242.95 mmol; 8.098 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (4.944 g; 13.56 mmol; 0.452 eq.) was added dropwise to the reaction with rapid stirring for 4 minutes. During the addition, the temperature was controlled to <25°C. The reaction was stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (20.00 g), 35% hydrochloric acid (1.481 g; 14.22 mmol; 0.474 eq.), and n-propyl acetate (20.000 g; 195.83 mmol; 6.528 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (20.0 g) and then vacuum concentrated to approximately 15 mL. PGMEA (25.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 7.2 (20.5 g, in 33.1 wt.-% propylene glycol methyl ether acetate, yield: 96.8%), GPC (THF, 40℃): M n 1910, M w A result of 3054 and a PDI of 1.60 was obtained.

[0224] Example 8 - MPDMMI-483220: Methyltrimethoxysilane (1.64 g; 12.0 mmol; 1.00 eq.), phenyltrimethoxysilane (1.59 g; 8.00 mmol; 0.667 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (1.65 g; 5.00 mmol; 0.417 eq.), and propan-2-ol (6.00 g; 99.8 mmol; 8.32 eq.) were added to the reaction vessel and purged with nitrogen. Tetramethylammonium hydroxide (2.06 g; 5.65 mmol; 0.471 eq.) was added dropwise to the reaction with rapid stirring for 3 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred under nitrogen at ambient temperature for 4 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (8.0 g), 35% hydrochloric acid (0.619 g; 5.94 mmol; 0.495 eq.), and n-propyl acetate (8.0 g; 78 mmol; 6.5 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (8.0 g) and then vacuum concentrated to approximately 10 mL volume. PGMEA (20.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 8 (9.7 g, 27.9 wt.-% in propylene glycol methyl ether acetate, yield: 92.8%), GPC (THF, 40°C): M n 1193, M w 1553, PDI 1.30 was obtained.

[0225] Example 9 - MDMMIQ-56204: Methyltrimethoxysilane (1.91 g; 14.0 mmol; 1.00 eq.), tetraethyl orthosilicate (1.25 g; 6.0 mmol; 0.429 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (1.65 g; 5.00 mmol; 0.357 eq.), and PGME (6.00 g; 66.6 mmol; 4.76 eq.) were added to the reaction vessel and purged with nitrogen. 50% choline hydroxide (2.399 g; 9.90 mmol; 0.707 eq.) was added dropwise to the reaction with rapid stirring for 4 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred under nitrogen at ambient temperature for 1 hour. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (8.0 g), citric acid (1.99 g; 10.4 mmol; 0.740 eq.), and n-propyl acetate (8.00 g; 78.3 mmol; 5.60 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (8.0 g) and then vacuum concentrated to approximately 10 mL. PGME (20.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 9 (7.9 g, in 26.0 wt.-% propylene glycol methyl ether acetate, yield: 85.9%), GPC (THF, 40°C): M n 1345, M w In 1839, a PDI of 1.37 was obtained.

[0226] Example 10-MPDMMI-502525: Methyltrimethoxysilane (1.36 g; 10.00 mmol; 1.00 eq.), phenyltrimethoxysilane (0.99 g; 5.00 mmol; 0.50 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (1.37 g; 5.00 mmol; 0.50 eq.), and PGMEA (6.08 g; 46.00 mmol; 4.60 eq.) were added to the reaction vessel and purged with nitrogen. Sodium hydroxide (0.60 g; 15.00 mmol; 1.50 eq.) was dissolved in water (1.44 g; 80.00 mmol; 8.00 eq.) and added to the vessel in one step, and the reaction mixture was then stirred under nitrogen at ambient temperature for 1 hour. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (6.0 g), hydrochloric acid (1.64 g; 15.75 mmol; 1.58 eq.), and n-propyl acetate (6.08 g; 59.50 mmol; 5.95 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed three times with deionized water (6.0 g) and then vacuum concentrated to approximately 5 mL volume. PGMEA (20.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 10 (4.5 g, in 28.2 wt.-% propylene glycol methyl ether acetate, yield: 54%), GPC (THF, 40°C): M n 974, M w A PDI of 1.24 was obtained for 1203.

[0227] Example 11-MDMMIQ-6525: Methyltrimethoxysilane (2.724 g; 20.00 mmol; 1.000 eq.), tetraethyl orthosilicate (0.642 g; 3.08 mmol; 0.15 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (2.537 g; 7.70 mmol; 0.38 eq.), and propan-2-ol (7.993 g; 0.13 mol; 6.65 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (2.534 g; 6.95 mmol; 0.35 eq.) was added dropwise to the reaction with rapid stirring for 4 minutes. During the addition, the temperature was controlled to <25°C. The reaction mixture was stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (10.00 g), 35% hydrochloric acid (0.760 g; 7.30 mmol; 0.365 eq.), and n-propyl acetate (10.213 g; 100.00 mmol; 5.000 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed three times with deionized water (10.0 g) and then vacuum concentrated to approximately 1.5 mL. PGMEA (12.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 11 (3.3 g, 13.9 wt.-% propylene glycol methyl ether acetate, yield: 11.6%), GPC (THF, 40°C): M n 1108, M w A PDI of 1.48 was obtained for 1635.

[0228] Example 12 - MDMMIQ-7020: Methyltrimethoxysilane (34.328 g; 252.00 mmol; 1.000 eq.), tetraethyl orthosilicate (7.502 g; 36.01 mmol; 0.143 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (23.720 g; 72.00 mmol; 0.286 eq.), and propan-2-ol (93.600 g; 1557.53 mmol; 6.181 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (29.665 g; 81.36 mmol; 0.323 eq.) was added to the reaction with rapid stirring for 5 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (122.00 g), 35% hydrochloric acid (8.900 g; 85.43 mmol; 0.339 eq.), and n-propyl acetate (122.400 g; 1198.45 mmol; 4.756 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (122.0 g) and then vacuum concentrated to approximately 100 mL. PGMEA (72.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 12 (85.4 g, in 39.9 wt.-% propylene glycol methyl ether acetate, yield: 97.6%), GPC (THF, 40°C): M n 1498, M w A result of 2322 and a PDI of 1.55 was obtained.

[0229] Example 13-MPVDMMIQ-28222020: Methyltrimethoxysilane (2.838 g; 20.83 mmol; 1.39 eq.), phenyltrimethoxysilane (3.305 g; 16.67 mmol; 1.111 eq.), tetraethyl orthosilicate (1.562 g; 7.50 mmol; 0.50 eq.), vinyltrimethoxysilane (2.223, 15.00 mmol, 1.00 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (4.942 g; 15.00 mmol; 1.00 eq.), and propan-2-ol (19.000 g; 316.17 mmol; 21.08 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (6.180 g; 16.95 mmol; 1.130 eq.) was added to the reaction with rapid stirring for 5 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (25.00 g), 35% hydrochloric acid (1.855 g; 17.81 mmol; 1.187 eq.), and n-propyl acetate (25.000 g; 244.78 mmol; 16.319 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (25.0 g) and then vacuum concentrated to approximately 15 mL. PGMEA (30.0 g) was added to the organic phase, and the solution was again vacuum concentrated to obtain siloxane 13 (22.4 g, in 31.8 wt.-% propylene glycol methyl ether acetate, yield: 96.6%), GPC (THF, 40℃): M n 1275, M w 1586, PDI 1.24 was obtained.

[0230] Example 14-MDMMI-5050: Methyltrimethoxysilane (2.724 g; 20.00 mmol; 1.000 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (6.589 g; 20.00 mmol; 1.000 eq.), and propan-2-ol (10.500 g; 174.72 mmol; 8.736 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (3.296 g; 9.04 mmol; 0.452 eq.) was added dropwise to the reaction with rapid stirring for 3 minutes. During the addition, the temperature was controlled to <25°C. The reaction mixture was stirred at ambient temperature under nitrogen for 2 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (13.00 g), 35% hydrochloric acid (0.983 g; 9.44 mmol; 0.472 eq.), and n-propyl acetate (13.000 g; 127.29 mmol; 6.364 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed three times with deionized water (13.0 g) and then vacuum concentrated to approximately 15 mL. PGMEA (20.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 14 (16.6 g, in 30.4 wt.-% propylene glycol methyl ether acetate, yield: 99.0%), GPC (THF, 40°C): M n 1454, M w In 1909, a PDI of 1.31 was obtained.

[0231] Example 15-MFDMMIQ-202050: Methyltrimethoxysilane (1.362 g; 10.00 mmol; 1.000 eq.), tetraethyl orthosilicate (1.042 g; 5.00 mmol; 0.500 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (8.237 g; 25.00 mmol; 2.500 eq.), trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane (3.683 g; 10.00 mmol; 1.000 eq.), and propan-2-ol (13.000 g; 216.32 mmol; 21.632 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (4.120 g; 11.30 mmol; 1.130 eq.) was added dropwise to the reaction with rapid stirring for 2 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred under nitrogen at ambient temperature for 3.5 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (17.00 g), 35% hydrochloric acid (1.240 g; 11.90 mmol; 1.190 eq.), and n-propyl acetate (17.000 g; 166.45 mmol; 16.645 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (17.0 g) and then vacuum concentrated to approximately 10 mL volume. PGMEA (22.0 g) was added to the organic phase, and the solution was again vacuum concentrated to obtain siloxane 15 (30.4 g, in 29.0 wt.-% propylene glycol methyl ether acetate, yield: 93.6%), GPC (THF, 40℃): M n 1382, M w 1814, PDI 1.26 was obtained.

[0232] Example 16 - MDMMIQ-2070: Methyltrimethoxysilane (1.090 g; 8.00 mmol; 1.000 eq.), tetraethyl orthosilicate (0.833 g; 4.00 mmol; 0.500 eq.), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (9.225 g; 28.00 mmol; 3.500 eq.), and propan-2-ol (10.400 g; 173.06 mmol; 21.632 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (3.296 g; 9.04 mmol; 1.130 eq.) was added dropwise to the reaction with rapid stirring for 2 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred under nitrogen at ambient temperature for 3.5 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (13.60 g), 35% hydrochloric acid (0.938 g; 9.52 mmol; 1.190 eq.), and n-propyl acetate (13.600 g; 133.16 mmol; 16.645 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed with deionized water (13.0 g) and then vacuum concentrated to approximately 15 mL volume. PGMEA (40.0 g) was added to the organic phase, and the solution was vacuum concentrated again to obtain siloxane 16 (23.0 g, in 27.0 wt.-% propylene glycol methyl ether acetate, yield: 90.0%), GPC (THF, 40°C): M n 1254, M w 1583, PDI 1.23 was obtained.

[0233] Example 17-DMMI-100: 3,4-Dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (2.88 g; 8.75 mmol; 1.00 eq.) and propan-2-ol (5.00 g; 83.2 mmol; 9.51 eq.) were added to the reaction vessel and purged with nitrogen. 25% tetramethylammonium hydroxide (0.72 g; 1.98 mmol; 0.23 eq.) was added dropwise to the reaction with rapid stirring for 2 minutes. During the addition, the temperature was controlled to <25°C. The reactants were stirred under nitrogen at ambient temperature for 3.5 hours. The reaction mixture was rapidly stirred and poured into a second flask containing deionized water (15.0 g), 35% hydrochloric acid (0.22 g; 2.08 mmol; 0.24 eq.), and n-propyl acetate (15.0 g; 147 mmol; 16.8 eq.). The mixture was stirred at ambient temperature for 1 hour, after which the aqueous phase was removed. The organic phase was washed twice with deionized water (13.0 g) and then vacuum concentrated to approximately 5 mL volume. Yield: 90%, GPC (THF, 40°C): M n 1723, M w 2029, PDI 1.18.

[0234] Photo Patterning Negative type | UV | No initiator The substrate (glass or Si wafer) was cleaned according to a standard process of sequential ultrasonic treatment in acetone and isopropyl alcohol for 10 minutes each. The oligomer or polymer solution (20-40% total solid content) was spin-coated at a speed of 1000-2000 rpm to obtain a uniform film with a target thickness of 1-3 μm. The residual solvent was removed by annealing at 90-110°C for 2 minutes.

[0235] The coated substrate is subjected to UV irradiation through a mask (λ=254nm, 2~10J / cm²). 2 The sample was then subjected to UV irradiation. After UV irradiation, the sample was gently wiped with a lint-free cloth soaked in a solubilizing solvent such as propylene glycol monomethyl ether acetate (PGMEA) to remove any uncured oligomer or polymer residue, revealing a pattern consisting of crosslinked material.

[0236] After UV crosslinking, the oligomer or polymer film may undergo an additional thermal bake step at 230°C for 60 minutes to crosslink thermally active groups.

[0237] Photopatterning of Example 18-Example 7 (MADMMIQ-502020): UV curing, 8J / cm 2 254nm, UV lamp power 3mW / cm 2 A simple shadow mask pattern was used. The irradiated film was wiped with a lint-free cloth soaked in PGMEA to remove uncured areas and reveal the pattern.

[0238] The substrate (glass or Si wafer) was cleaned according to a standard process of sequential ultrasonic treatment in acetone and isopropyl alcohol for 10 minutes each. An oligomer solution (20-40% total solid content) with 2 phr (based on the solid content of the oligomer) of Omnipol TX was spin-coated at a speed of 1000-2000 rpm to obtain a uniform film with a target thickness of 1-3 μm. The residual solvent was removed by annealing at 90-110°C for 2 minutes.

[0239] The oligomer-coated substrate is subjected to UV irradiation through a mask (λ=365nm, irradiation dose 2-10J / cm²). 2 The sample was then subjected to UV irradiation. After UV irradiation, the sample was lightly wiped with a lint-free cloth soaked in a solubilizing solvent such as propylene glycol monomethyl ether acetate (PGMEA) to remove uncured oligomer residue and reveal a pattern consisting of crosslinking material. After UV crosslinking, the oligomer film may undergo an additional thermal bake step of 60 minutes at 230°C to crosslink thermally active groups.

[0240] Example 19 - Measurement of photopatterning and film retention The substrate (glass or Si wafer) was cleaned according to the standard process of sequential ultrasonic wave treatment in acetone and isopropyl alcohol for 10 minutes each. An oligomer solution (20 - 40% total solid content) with optionally 0 - 2 phr (based on the solid content of the oligomer) of Omnipol TX or Speedcure 7010 was spin-coated at a speed of 1000 - 2000 rpm to obtain a uniform film. The residual solvent was removed by annealing at 90 - 110 °C for 2 minutes. The substrate coated with the oligomer was UV irradiated (λ = 254 nm, 1 - 10 J / cm 2 dose, see Table 1) (λ = 365 nm, 1 - 10 J / cm 2 dose, see Table 2). The film thickness was determined by measuring the step height of the scratch applied through the film using a stylus profilometer.

[0241] A layer of solubilizing solvent such as propylene glycol monomethyl ether acetate (PGMEA) was dispensed onto the polymer-coated substrate, immersed for 1 minute, and then spin-dried with an optional annealing at 80 - 120 °C for 1 - 2 minutes. The film thickness was determined by measuring the step height of the scratch applied through the residual film using a stylus profilometer. The ratio of the film retained after solvent exposure was calculated.

Table 1

[0242]

Table 2

[0243] Example 20 - Measurement of the relative permittivity of the dielectric film The ITO glass was sequentially washed with acetone and isopropyl alcohol. The oligomer of interest was then spin-coated from the solution (20-40% solid content) at a speed of 1000-2000 rpm to obtain a uniform film with a thickness of 500-2000 nm. The residual solvent was removed by annealing at 90-100°C for 2 minutes. Optionally, the film was then UV-cured (λ=254 nm, 2 J / cm²) to crosslink the reactive groups within the film. 2 The process may also involve dose-based curing or thermosetting (165°C, 30 minutes).

[0244] The electrodes (60 nm, Ag) were vapor-deposited through a shadow mask with circular openings, so that nine circular electrodes were formed per inch of substrate, as shown in Figures 1 and 2.

[0245] The capacitance of the film was measured as a function of frequency (21 Hz to 1000 Hz) using a precision LCR meter (Keysight, E4980AL). The film thickness was measured at three different locations using a stylus surface profile measuring device (KLA-tencorD-500). The relative permittivity of the polymer was then calculated using the following relationship.

number

[0246] A specific example of the dielectric constant after thermal curing is shown below. The dielectric constant value was measured at 1000 Hz and is the average value of three data points (see Table 3). [Table 3]

Claims

1. A monomer composition for the preparation of siloxane oligomers or polymers, (a) The first siloxane monomer; Here, the first siloxane monomer contains a substituted or unsubstituted maleimide group. The first siloxane monomer is given by formula (1): 【Chemistry 1】 Here: L 1 , L 2 and L 3 They are either the same or different from each other, and each is independently selected from R, OR, and halogen, where L 1 , L 2 and L 3 At least one of them is either an OR or a halogen; R is selected from the group consisting of H, linear alkyl having 1 to 30 carbon atoms, branched alkyl having 3 to 30 carbon atoms, cyclic alkyl having 3 to 30 carbon atoms, and aryl having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH 2 groups may optionally be replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms may optionally be replaced by F; R 1 and R 2 These are either the same or different from each other, and each is independently selected from alkyl groups having 1 to 20 carbon atoms, where one or more H atoms are optionally replaced by F; Z represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH groups. 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; Y 1 and Y 2 They are either the same or different from each other, and each is independently selected from H, F, Cl, and CN; R 0 and R 00 These are either the same or different from each other, and each is independently selected from H, a linear alkyl having 1 to 20 carbon atoms, and a branched alkyl having 3 to 20 carbon atoms, which are optionally fluorinated; It is represented as, (b) Second siloxane monomer; Here, the second siloxane monomer is different from the first siloxane monomer, and (c) Third siloxane monomer; Includes, Here, the third siloxane monomer is the monomer composition, which is different from the first siloxane monomer and the second siloxane monomer.

2. Condition (1) or (2): (1) L 1 =L 2 =L 3 =OR; or (2) L 1 =L 2 =R, and L 3 =Cl, A monomer composition according to claim 1, to which one of the following is applied.

3. R 1 and R 2 However, they are either the same or different from each other, and each is independently selected from alkyl groups having 1 to 12 carbon atoms, where one or more H atoms are optionally replaced by F. The monomer composition according to claim 1 or 2.

4. The second siloxane monomer is represented by one of the following structures S1 to S5: 【Chemistry 2】 Here: L 11 , L 12 , L 13 , and L 14 They are either the same or different from each other, and each is independently selected from OR' and halogen; R' is selected from the group consisting of linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, where one or more non-adjacent and non-terminal CHs are present. 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; R 11 , R 12 and R 13 These are either the same or different from each other, and each is independently selected from the group consisting of H, linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CR 0 =CR 00 2 -, -CY 1 =CY 2 It optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F; Z 1 This represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH groups. 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; W 1 represents a divalent, trivalent, or tetravalent organic part; R 0 , R 00 , Y 1 , and Y 2 is as defined in claim 1; and n1 = 2, 3, or 4. A monomer composition according to any one of claims 1 to 3.

5. W 1 However, it can be represented by one of the following structures W1 to W4: 【Transformation 3】 Here: L is H, -F, -Cl, -NO 2 , -CN, -NC, -NCO, -NCS, -OCN, -SCN, -OH, -R 0 , -OR 0 , -SR 0 , -C(=O)R 0 , -C(=O)-OR 0 , -O-C(=O)-R 0 , -NH 2 , -NHR 0 , -NR 0 R 00 , -C(=O)NHR 0 , -C(=O)NR 0 R 00 , -SO 3 R 0 , -SO 2 R 0 , an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, which is optionally, F, -Cl, -NO 2 , -CN, -NC, -NCO, -NCS, -OCN, -SCN, -OH, -R 0 , -OR 0 , -SR 0 , -C(=O)-R 0 , -C(=O)-OR 0 , -O-C(=O)-R 0 , -NH 2 , -NHR 0 , NR 0 R 00 , -O-C(=O)-OR 0 , -C(=O)-NHR 0 , or -C(=O)-NR 0 R 00 and may be substituted by; and R 0 and R 00 This is as defined in claim 1, The monomer composition according to claim 4.

6. The third siloxane monomer is represented by one of the following structures T1 to T5: 【Chemistry 4】 Here: L 21 , L 22 , L 23 , and L 24 They are either the same or different from each other, and each is independently selected from OR'' and halogens; R'' is selected from the group consisting of linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, where there is one or more non-adjacent and non-terminal CH 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, and where one or more H atoms are optionally replaced by F; R 21 , R 22 and R 23 These are either the same or different from each other, and each is independently selected from the group consisting of H, linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CR 0 =CR 00 2 -, -CY 1 =CY 2 It optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F; Z 2 This represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where there is one or more non-adjacent and non-terminal CH groups. 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; W 2 represents a divalent, trivalent, or tetravalent organic part; R 0 , R 00 , Y 1 , and Y 2 is as defined in claim 1; and n² = 2, 3, or 4. The monomer composition according to claim 5.

7. (d) A fourth siloxane monomer; It further includes, Here, the fourth siloxane monomer is different from the first, second, and third siloxane monomers. The monomer composition according to claim 5 or 6.

8. The fourth siloxane monomer is represented by one of the following structures F1 to F5: 【Transformation 5】 Here: L 31 , L 32 , L 33 , and L 34 They are either the same or different from each other, and each is independently selected from OR''' and halogen; R''' is selected from the group consisting of linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, where there is one or more non-adjacent and non-terminal CH 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, and where one or more H atoms are optionally replaced by F; R 31 , R 32 and R 33 These are either the same or different from each other, and each is independently selected from the group consisting of H, linear alkyls having 1 to 30 carbon atoms, branched alkyls having 3 to 30 carbon atoms, cyclic alkyls having 3 to 30 carbon atoms, and aryls having 6 to 20 carbon atoms, which are -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CR 0 =CR 00 2 -, -CY 1 =CY 2 It optionally contains one or more functional groups selected from - and -C≡C-, where one or more H atoms are optionally replaced by F; Z 3 This represents a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, where one or more non-adjacent and non-terminal CH groups. 2 The base can be any of the following: -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- is used to replace C, where one or more H atoms are optionally replaced by F; W 3 represents the divalent, trivalent, and tetravalent organic parts; R 0 , R 00 , Y 1 , and Y 2 is as defined in claim 1; and n3 = 2, 3, or 4. The monomer composition according to claim 7.

9. The molar ratio between the first siloxane monomer and the total of all further siloxane monomers is in the range of 1:0.1 to 1:

10. A monomer composition according to any one of claims 1 to 8.

10. A method for preparing a siloxane oligomer or polymer, wherein the method comprises the following steps: (i) To provide a monomer composition according to any one of claims 1 to 9; and (ii) React the monomer composition provided in step (i) to obtain a siloxane oligomer or polymer. including, The aforementioned method.

11. A siloxane oligomer or polymer that can be obtained by the method described in claim 10.

12. A crosslinkable composition comprising one or more siloxane oligomers or polymers as described in claim 11.

13. A method for manufacturing microelectronic structures, The following steps: (1) Applying the crosslinkable composition described in claim 12 to the surface of a substrate; and (2) Curing the crosslinkable composition to form a layer that passivates and optionally planarizes the surface of the substrate. including, The aforementioned method.

14. An electronic device comprising a microelectronic structure that can be obtained by the manufacturing method described in claim 13.

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