TW591067B - Polymers having backbones with reactive groups employed in crosslinking as precursors to nanoporous thin film structures - Google Patents

Abstract

Nanoporous materials are fabricated from polymers having backbones with reactive groups used in crosslinking. In one aspect of preferred methods and compositions, the reactive groups in the backbone comprise a diene and a dienophile. The diene may advantageously comprise a tetracyclone, and the dienophile may advantageously comprise an ethynyl. In another aspect of preferred methods and compositions, the reactive groups in the backbone are included in a conjugated system. Especially preferred polymeric strands comprise a poly(arylene ether) synthesized from a difluoroaromatic portion and an aromatic bisphenolic portion. It is still more preferred that the difluoroaromatic portions of the poly(arylene ether) are modified in such a way that some difluoroaromatic portions carry a thermolabile portion. In still other aspects crosslinking may advantageously occur without reliance on an exogenous crosslinker.

Description

V. Description of the invention (1) This application declares the benefits of April 9, 1999 > 60/128, 465, and the eighth US provisional application JLg · < /, which is incorporated herein by reference in its entirety. The field of the invention is nanoporous materials. Background, the increase in functional components in integrated circuits. In order to adapt to the modern integrated circuit circuit and interconnection degree layer metal conductor circuit.多 Multi-wire gates in low-dielectric constant materials • ", r, reduce capacitance effects, which often cause conductors, ', β crosstalk and lower drive integrated circuit voltage.: = Insulation materials / materials Materials with a low dielectric constant and constant dielectric constant. Often, in recent years, two or two materials: inorganic oxides and organic polymers have been used. Inorganic oxides have a dielectric constant of ▲ and have been widely used. For interconnections with greater than 0.25 a ^ rule. As the interconnection size shrinks, materials with lower dielectric = numbers become more desirable. Organic polymers have shown many benefits I 'which include high heat Stability, ease of handling, low stress / TCE, low dielectric constant and high resistance 'and are therefore considered as alternative low dielectric constant polymers for smaller and smaller sizes of 0.18 and future generations. About other properties 'The desired dielectric should also be free of moisture and outgassing problems, have suitable friction and interstitial qualities, and be suitable for thermal cycling, etching, and 591067 V. Description of the invention (2) CMP process (ie, chemical mechanical polishing) has Suitable size stability. Suitable The dielectric should also have a D-g value (glass transition temperature) of at least 3,000, and preferably 50,000 or higher. Inferred design rules for 0 · 0 7 // m and below The demand has emerged for the strong demand for materials with a dielectric constant less than 2.2. It has led to the development of dielectric materials with a designed nanoporosity. Since air has a dielectric constant of about 1.0, the main goal is In order to reduce the dielectric constant of nanoporous materials to a theoretical limit below 1. This technique is known for many methods of manufacturing nanoporous materials. In one method, 'thermostatic polymer blended with thermosensitive (thermally decomposable) polymerization The blended mixture is then crosslinked and the thermosensitive part is pyrolyzed. An example is described in Hedrick et al. Patent 776'990. In another method, the thermostable block and the thermostable block are in a monoblock polymer. Interleaved. Then the block copolymer is heated to pyrolyze the thermal block. In the third method, the thermal block and the thermally stable block carrying the thermal block are mixed and polymerized to produce the copolymer. The copolymer is then heated Sensitive thermal block with pyrolysis. In the fourth method, small hollow glass spheres are introduced into the material. Examples are shown in U.S. Patent 5,458 " 709, Kamezaki, and U.S. Patent 5,593,526, Yokouchi. 'What are the methods for introducing pores? In the manufacture, structural problems are often encountered. Among them, the porosity is increased beyond a critical range ^ (the known pen microporous material is usually about 30%) tends to cause the porosity solution. By adding a coupling thermal stabilizer And other hot additives thus make a harder network, and-this part of the coupling is energized, in this technology two different types of cross-linking heat in nanoporous materials are known

Page 6 591067 V. Description of the invention (3) Technology of the stability part. In one technique, specific cross-linking functional groups have been added to the polymer. This functional group reacts together to cross-link the polymer before pyrolyzing. For example, it is known to include diphenylacetylene functional groups in block copolymers and use ethyl functional groups to cross-link polyfluorene imine polymers. The diagram is shown in Figure 1. Figure 1 'Two of the two independent polymer bundles 10AA, ι〇β carry the parent functional groups X1 and X2 as side groups, and the heat-sensitive part L as side groups as Part of the skeleton. As the cross-linking progresses, XI reacts with X2 to form a parent cross-linking gamma, thus covalently linking two bundles of 10 A, 10 β into a single cross-linked polymer 10 C. In f f techniques, 'foreign cross-linking molecules are used for cross-linking. The crosslinked polymer is then heated to pyrolyze the heat-sensitive portion. For example, in Streckle, Jr's ΓΠΓ?:, 1, two, the use of a multifunctional fluorenyl- or fluorenyl function two U in advanced technology ®2, where two independent polymerizations carry cross-linking functional groups χι and χ2 As a side-linking group, and: = Λ-side Λ-group and as-part of the skeleton. With the cross-linking of the cross-linking molecule χ3, cross-linking γ is formed, and the nano-Non-U: r-Beddi linking into a single cross-linked polymer 20c. In the use of foreign cross-linking molecules, it is necessary to account for one part: s Λ $ system without disturbing the polymerization reaction. This r specifically reacts in the same solvent system as the thermal stabilizer or monomer. The agent: must be dissolved in ... The chemical structure and reactivity of the polymer are: the thermal stability part and the heat sensitive part are limited to the complexity of using bio-polymers in the polymer, so =: Canada; 1 \ Defining cross-linking functional groups to increase the difficulty of early body synthesis. Adding 591067 V. Description of the invention (4) Functional groups also interfere with the polymerization reaction and adversely change the polymerization properties, especially when using relatively complex cross-linking In short, it is known that polymerization in various crosslinked nanoporous materials, and the current methods often complicate monomer synthesis, or the polymerization reaction or physicochemical properties of porous materials. Amazingly improved nanoporous materials Various properties, and the cross-linking of expensive materials, there is still no general method to cross-link (a); cross-linking molecules' and (b) do not add pendant functional groups to the monomer. E. Methods and combinations that pass these restrictions Needs of things. Summary of invention The invention provides a method and a composition, wherein a nanoporous material is produced from a fluoride containing a skeleton having and having a reactive group for a cross-linking reaction. In a state of a preferred embodiment, the skeleton is dilute and hydrophilic. Diene. In a more preferred embodiment, the di- and di-dienes comprise ethynyl in the form of diphenylethynyl. In another state of the preferred embodiment, the backbone is enclosed in a co-light system. In the preferred embodiment, the polymerized mono-aromatic aromatic moiety and the fluorinated aromatic resorcinol moiety are synthesized.) In a more preferred embodiment, the poly (aryl ether) is two | Modification of the method with a heat-sensitive part In other states of the preferred embodiment, cross-linking occurs. Various purposes, characteristics, states, and advantages of the present invention are determined by the mechanism and time of the compound. It tends to interfere with the house, even though it is modified by Nu Zhangdi: it depends on external interactions, but it still has more flexible structural parts and non-fluorinated polymerization. The reactive group contains fluorene, which contains the reactive group in tetracyclone. The bundle contains a polyfluoride The following is a copy of the present invention, which does not rely on the following. The present invention is more obvious than 591067. 5. Detailed description of the invention (5) The detailed description of the specific embodiment and the accompanying drawings are obvious, and similar numbers indicate similar components. Brief description. Figure 1 is a description of the prior art of thermosensor-containing polymer bundles. Figure 2 is a view of the prior art of thermosensor-based polymer bundles using foreign molecules. Figure 3 is a description of thermosensor-based polymer bundles. The cross-linking diagram of the state of the subject of the present invention. Figure 4 is a diagram describing the cross-linking of the thermo-group-containing polymer bundle according to another state of the subject of the invention. A-6 J is the structure of the intended difluoroaromatic compound according to the subject of the present invention. Fig. 7 is a synthesis diagram of a tetracyclic ketone for producing an aromatic ether-containing polymer. Fig. 8 is a synthesis diagram of grafting a thermosensitive component to a polymer bundle. . Figures 9A and 9B show the structure of a difluoroaromatic monomer containing a tetracyclone-containing poly (aryl ether) according to the subject invention. Figures 10 and 11 are structures of difluoroaromatic monomers that make tetracyclone and ethynyl poly (aryl ether) according to the subject invention. Figures 1 2 A-1 2 I show the structure of the repeating portion of the aggregated bundle according to the subject invention. DETAILED DESCRIPTION In Fig. 3, two polymer bundles 30A, 30B carry a plurality of thermosensitive groups L. Each converging bundle defines a skeleton, and each skeleton includes a reactive group \ 1 and Y2. Beam 30A with

O: \ 63 \ 63739.ptd Page 9 591067 V. Description of the invention (6) 3 0 B is cross-linked in the cross-linking reaction between the reactive groups Xi and X2 without the addition of external cross-linked molecules. The cross-linking reaction generates cross-linking Z and thus covalently connects, or the bundles 30A, 30B may be further connected to form a polymer 30C. In a further step (not shown), the thermosensitive L is pyrolyzed, leaving voids. When the pores are small enough and dispersed, the resulting material thus becomes a nanoporous polymer. Figure 4 is quite similar to Figure 3, except that the reactive group Xi forms part of the skeleton in the beam 40A, and the reactive group X2 flanks the skeleton in the beam 4 0 B. However, the cross-linking reaction proceeds to generate cross-linked Z and a cross-linked polymer 4 0 C. The diagrams described in FIGS. 3 and 4 are intended to be viewed in a general manner. For example, the term π polymeric bundle π as used herein refers to any monomer composition that is covalently bonded to define a backbone, and may include any pendant groups other than crosslinked couplers. The term π monomer π as used herein refers to any chemical compound that can form a covalent bond with a compound that is different from itself or chemically in a repeatable manner. The formation of multiple bonds between monomers can result in linear, branched, hyperbranched, or three-dimensional products. Monomers can be molecules of various chemical types, including inorganic, organometallic or inorganic molecules. Examples of organic monomers are acrylamide, vinyl chloride, bifenol or 3,31-dihydroxydiphenylacetylene. Examples of organosilicon monomers are octamethylcyclotetrasiloxane, fluorenylbenzylcyclotetrasiloxane and the like. Examples of the inorganic monomer that causes the structure of inorganic Si 02 or A 1 2 03 include tetraethoxysilane (TEOS) and ethoxy aluminum oxide which are most commonly used. The molecular weight of the monomer can vary greatly from about 40 Daltons to 20,000 Daltons. The monomer may also include a thermosensitive group or a functional group for crosslinking. For example, the monomer may include poly (propylene oxide), polycarbonate, poly (fluorenyl acrylate), various styrene polymers, or ethynyl- or tetracyclone groups. It is also intended that the monomer is halogenated, and the preferred halogen is fluorine. Halogenation, especially fluorine

O: \ 63 \ 63739.ptd Page 10 591067 V. Description of the invention (7) ^ The dielectric constant of the monomer and the dielectric constant of the polymer can be advantageously reduced.丨 r Low penetrating pore branching, super branching, and polymeric bundles can belong to any organic polymeric bundle. Under these definitions, the polymeric bundles can therefore be linear or three-dimensional, and they can include heat-sensitive parts and reactive groups Chemical species, including organic or inorganic compositions. Examples are polyimide, polyester, or hydrazone. Examples are various substituted polysiloxanes. 7:] ::. Silica or oxidized inscription of silicone polymer bundles. Polymer bundles can also include: Pan; r 5: Examples include oxides, which include aromatic systems, and by Lunengji or structural group. Polymeric bundles can have chemistry that can participate; "= or -cf3 The molecular weight of the polymeric bundles is spread over a wide range of: additional reactive groups. The intended range is between 400 000 Daltons or higher. The target range is typically 400 Daltons to

Particularly preferred polymer bundles are those having a ring Z backbone cross-linking group. A particularly preferred species has a ketene bundle comprising a diene and a dienophile. This bundle may advantageously contain cyclopentanedione in which the diene is a tetracyclone, and a gasified difluoride may be prepared from a fluorinated or non-gas containing, fluorinated or non-fluorinated polydiphenylethylene aromatic biphenol compound. Aromatic compounds and fluorinated or non-fluorinated compounds include biphenyls, and in preferred embodiments, aromatic biphenols are even more preferred. In particular embodiments, the D-group f compounds include diphenylacetylene. In other preferred embodiments: the Group 2 compound comprises tetracyclone. Modifications, or the aromatic portion of a difluoroaromatic compound that is an aromatic biphenol compound, may include isomerization changes, or modification of the aromatic portion of an aromatic compound. This modification is the addition or removal of cycline, amidine, and alcohol. For example, the tetraethenyl diphenylacetylene's aromatic intestinal or aromatic substituents can be introduced into 3,3, -di77. 591067 for 4, 4'-difluorodiphenyldione 5. Description of the invention (8 ) The aromatic part is also intended for similar changes. In another variation, the sβ2 · mixed carbon atom may be replaced by any other suitable atom, including sulfur, oxygen, nitrogen, and the like. In the modification including the introduction of halogens, particularly fluorine, it is intended to covalently bond one or more fluorine atoms to aromatic carbon atoms, or to covalently bond one or more fluorine atoms to non-aromatic carbon atoms. Alternatively, at least one fluorine atom may be covalently bonded to a non-aromatic carbon atom, while at least one fluorine atom is covalently bonded to an aromatic carbon atom. In a further alternative embodiment, the polymeric bundle may be completely different from polydiethylene glycol. Alternative polymeric bundles include organic, organometallic, or inorganic polymers. Examples of intended organic polymeric bundles are polyimide, polyester, and polycyanurate. Examples of intended organometallic polymers are poly (dimethylsiloxane) and poly (vinylsiloxane). Examples of intended inorganic polymers are polysilicates and polyaluminates. In fact, the intended polymerization bundle need not include monomers of a single type, but may include a mixture of various monomers. As used herein, the term "π skeleton" refers to the covalent bonding of consecutive bonds of atoms or moieties forming a polymeric bundle, so that any atom or part of the chain is removed. Preferred skeletons include an aromatic ring system, or at least one Conjugate groups. However, many other combinations are also intended. For example, the intended skeleton may include any element, which specifically includes C, N, 0, S, P, Si, and A1. In addition, the intended skeleton may include aromatic Groups, which include phenyl-, substituted or unsubstituted cyclopentadienyl, thermolyl, aromatic ring systems, and fluorinated or other reactive groups. The term π cross-linking reaction as used herein refers to at least two A process in which two parts of a molecule or a long-chain molecule are bound together by a chemical reaction. This interaction

591067 V. Description of the invention (9) In a way that can be formed in many ways, the molecular crosses multiple molecules, and the intermolecular aggregation is different. The aqueous and hydrophilic interaction characteristics can be combined with this at least temporarily. Its inclusiveness, Ionicity is also at least one physical connection. Body cross-linked. Including covalent bonds or electrostatic interactions between molecules and this, the intention is to form, hydrogen bonds interact. This or two or more cross-linking reactions according to the present invention are generally conducted by various reactive groups, and can occur by many types of mechanisms. If a covalent bond is formed between two reactive groups, it can be formed by many chemical reaction mechanisms, including addition, exclusion, or substitution. Examples are nucleophilic or, electronic addition, Eb or E2-type exclusion, nucleophilicity and aromatic substitution. Paternity reactions can be spontaneous or require energy or catalyst. Examples of this energy are thermal energy, radiation, mechanical, electrical, or electromagnetic energy. Examples of catalysts are acid, test, and paste activated carbon. In further alternative embodiments, the cross-linking may or may not involve an epitaxial cross-linking agent, and any epitaxial cross-linking agent may comprise two molecules. The cross-linking molecules themselves may also be recruited or even polymerized. The number of reactive groups used in the beam of cross-linking reactions can also vary widely. It generally depends on the required crosslinking strength and the strength of the individual crosslinking bonds. For example, 'to form a stable cross-link between two single-stranded nucleic acids at room temperature, a minimum of about 25 to 30 hydrogen bonds are required. In contrast, only one covalent bond is required to obtain a crosslink with even higher stability. It is also intended that the number of reactive groups involved in the cross-linking reaction can be varied within a wide range. For example, the cross-linking reaction can involve as low as 5% of the reactive groups, but can also involve more than 90% of all available reactive groups in the polymer bundle. Although the preferred reactive groups are different from each other, it is also intended that all the reactive groups can the same.

The term "reactive group" as used herein refers to any

Page 13 591067 V. Explanation of the invention (10) = ㈡ reaction! Element or combination of elements. Reactive base intent-coal; 7 op injuries, including terminal. In a preferred embodiment, the tetracyclone and the dienophile may include an ethynyl group. In its m-generation reactive group may include a nucleophilic or electrophilic center: in the range of 300t to 45 (TC. In the preferred and "= trend, generally the stable part contains polydiphenylenedione ' ; =: =: = 物 的 热 = ί difluoroaromatic compounds and aromatic ageing compounds are prepared, the compounds in the pot contain thorium, and the second group of wuyne. In a further preferred embodiment, j '上Two-two-two upper ring _. The compound of a tetragonal group contains four-ΐ = Λ name: .Thermal "refers to the property of the material to degrade above high temperature, generally in the range of 25 0 C to 400 C. It should be understood that any Part, j: Including the thermosensitive group of Figure 3 故 4, which can be propylene oxide, polylactide, and polycarbonate. The thermosensitive group includes polydiphenylene, polymer, and chain: two = part ester). In a more specific embodiment t, difluoromono-poly (with an average molecular weight of 300). Dalton's ethylene glycol: poly (parts to j5; 25% heat-sensitive thermal base may advantageously include a linker) It should be interpreted broadly here to mean the chemical part of the reactable nouns " connecting part " class. Many types of anti ## compound: any formation of reactive groups in the matter may involve Formation = Two cases 2: Substitution, exclusion, and addition examples are esterification, amidation, and epoxidation

591067 V. Description of Invention (11) Special. The size of the connecting part can be greatly changed by the amount of approximation. Quite small links to nuclear and electrophilic groups. For example, R-C0-R ,, R-NH2, R-SH, and R- are tetracyclone, cyclopentadienyl or di1,2-diaminobenzene or 1,3-diphenyl. The part does not need to have a single type to be an alternative connecting part. It can also be a variety of alternative linking agents that are further intended to make the alternative connecting part suitable for participation.-Electrostatic-ionic interaction. Leucine-like structure, high polarity. Base, and multidentate base. The connection part is formed at various positions in the polymerization bundle, and the connection part can also be located on the thermal base. The term used here, 'degradation' refers to many ways, including uneven cracks, which do not need to be complete, that is, not all some bonds occur The bond breakage is more unstable than others, so the same fragments are released at a faster rate. The energy of apparent degradation and pyrolysis can include heat and electromagnetic radiation. For example, examples of suitable energy fractions of? 20 Daltons to about 50 Daltons are acid groups, bases, and the parent's small linking moiety is R-CO2H, halogen, and the like. Examples of larger linking moieties are Benyl aliphatic groups, which specifically include propan-2-one. It is still further intended to substitute functional groups or monomorphic substituents without a mixture of identical linking moieties. Copies do not need to participate in the formation of covalent bonds. Non-covalent coupling, which includes hydrophobicity, complex formation, or hydrogen bonding. An example is the position where the chemical bond between the group's polycationic or polyanionic moiety and the polymer can be included at the end of the intermediate. Any part, including the terminal. The covalent bond is broken. This kind of bond cleavage can be free radical, and even cleavage. Breakable bonds must be broken. Also, in fast. For example, ester bonds are usually more cleaved than amido bonds. Bond cleavage can also result in chemical compositions that are not part of each other. Involved, mechanical energy, granulated or non-granulated radiation-Fortunately, delta radiation, ultrasound, microwave or

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Page 15

591067 V. Description of the invention (12) a'- It is therefore intended that the method disclosed herein can be advantageously used in the manufacture of many nanoporous materials-the general method includes steps ... providing multiple polymeric bundles, each of which includes a thermal Part, and defines a frame comprising a plurality of reactive groups; providing a first energy to cross-link the polymeric beam using at least one reactive group, and providing two energy to at least partially degrade the heat-sensitive portion. ', Material borrowing = method of polymer bundles, can produce many kinds of nanoporous materials. The term " nanoporous material " as used herein refers to any pore with a diameter ranging from Z 1 ΠΠ1 to about 100 nm, and the meaning of the spoon includes synthetic polymers and inorganic materials. 4 -微 ^ 物. Examples of binary polymers are polyethers, and examples of: organic :: silicon compounds include silica or aluminosilicate 2. Examples of inorganic materials include poly (dimethylformaldehyde), pottery materials, organic silicon compounds (trifluoropropylsiloxane), soil emulsion, poly (vinylsiloxane), and poly (vinylsiloxane).

Nanoporous materials are characterized by the degree to which dt gas substitution is usually not a temporary B, a combination mixture. Air (mainly ^ rolling body includes fairly pure gases and their "pores", but a mixture of ,, 2, and 2) is often configured in nanopure gases. Nanoporous materials; gas, atmosphere, Argon, or ⑶, includes spherical pores, but or: 2 gap structure. Nanoporous materials-shape, and pores with other shapes can include tube, sheet, and pores can be substantially larger or smaller One of the many different forms of nanoporous materials, including two ... nanoporous materials can have a body. Nanoporous materials also; :: in thin slabs, plates, balls: active agents and plasticizers. 3 additional Village materials, which includes filling u

Page 16 591067 V. Description of the invention (13) Regarding the step of providing the first energy, the energy is preferably Baodan: Er'an. The embodiment would heat the beam to about 250. . In his view, the first energy is preferably sufficient to obtain at least 20% of the reactive group. However, plus should cover all < degrees, including 150. (: To 2 50 its strict sound.% Feng Du ,,,,, ^ μ degree. In a further alternative embodiment, the heating period can be changed from a few seconds or less to a few hours or to further replace the specific implementation For example, the first energy need not be thermal energy, but may involve any suitable form of energy, including various electromagnetic radiation such as UV-, laser, X-ray, or infrared radiation, mechanical energy (such as ultrasound or Physical pressure), and particle radiation (for example, α-or radiation). Regarding the degradation step, the energy is again preferably thermal energy. In certain embodiments, such heating may advantageously reach about 3 50. (; The temperature is about 20 minutes. In alternative embodiments, the temperature can be greatly changed, which depends on the nature of the heat-sensitive and heat-stabilizing part of the cross-linked polymer chain. The intended temperature range is 2000 ° C Or lower to about 450 ° C or higher. In a further alternative embodiment, the time required to degrade the heat-sensitive portion is intended to change from less than a few seconds to at least a few hours. It is again intended to make the energy used different from Pure thermal energy.

The nanoporous polymers described are somewhat similar to those described in Burgoyne et al., U.S. Patent No. 5, 8 74, 5 1 6 (February, 1999), which is incorporated herein by reference 'and may be so incorporated They are used in substantially the same way. For example, the nanoporous polymers described herein are intended to be used in the manufacture of multi-chip modules, interlayer dielectrics, protective coatings, and as substrates in circuit boards or printed wiring boards. In addition, the films or coatings of nanoporous polymers described herein may be

Page 591067

V. Description of the invention (14) --- It is formed by solution technology, such as spraying, spin coating or casting. Spin coating is preferred. The best solvents are 2-ethoxyethyl ether, cyclohexanone, cyclopentanone, toluene, diphenyl, chlorobenzene, N-methylpyrrolidone, N, dimethylformamide, & n-dioxine Acetylamine, methyl isobutyl ketone, 2-monomethoxyethyl ether, methyl-hexanone, T-butyrolactone, and mixtures thereof. Generally, the coating thickness is from about 0.1 to about 15 microns. As for the dielectric interlayer, the film thickness is less than 2 microns. Additives can also be used to enhance or impart specific target properties, as known in polymer technology, including stabilizers, flame retardants, pigments, plasticizers, interfacial agents, and the like. Compatible or incompatible polymers can be blended to produce the desired properties. Adhesion promoters can also be used. This accelerator is exemplified by hexamethyldioxazine, which can be used to interact with exposed hydroxyl functional groups that may be present on the surface, such as silica, to wet or wet it. Polymers used in microelectronics are expected to contain low levels of ionic impurities (usually less than i ppm, preferably less than 10 to ppb), especially for dielectric intermediate examples. The following examples demonstrate the principle of the subject matter of the present invention . The general synthetic diagram for the manufacture of poly (aryl ether) polymer bundles is described in Figure 50. AR and AR can independently contain any suitable thermally stable structure with two aromatic or molten aromatic moieties, and In the example of FIG. 5, no-QHrAR-CA-OH is a biphenyl, and AR'-CA-F is a difluoroaromatic such as biphenyl and 4-fluoro-3, which contains at least one diphenylacetylene moiety,- The general synthetic steps of the nucleophilic aromatic substitution as exemplified by the reaction between (4-fluorobenzyl) and dibenzylacetylene are as follows: a magnetic stirrer, thermocouple, Dean-Stark trap, and reflux condensation are installed to wash 2 and n

Page 18591067 V. Description of the invention (15) 1 liter 3-neck RB flask connected to the outlet for several hours and feeding 0.2 liters of inlet one by one ~ ^ one by one, one by one ------- ^ Λ 7Γ ^ Wenhuan Ding Feng. At 70-8 0 ° C, 35.042 g (0.100 mol) of terphenylphenol (FBP) and 31.320 g (0.1 100 mol) of 4-fluoro- 3 '-(4-fluorobenzyl) methylphenyl diphenylacetylene (FBZT) and 27.64 g (0.2 mol) of carbonic acid are unloaded, and cyclamidine and 165 5 ml Wash with ml of toluene. The refractory block was heated to 140 ° C and azeotroped at this temperature for 1-2 hours, and then the temperature was gradually raised to 175 ° C by removing ^ benzene, and the reaction continued at 175 ° C for 15-20 hours . The temperature was reduced to 165 ° C, 4-fluorodiphenyl ketone was added and capped for 5 hours. The reaction mass was diluted with 165 ml of NMp and left overnight. Then the cold reaction block was filtered through squeegee paper, in 5 x μe 〇Η (0 · 〇3% Η N 03), Youdian, redissolved in NMP and in 5xMe0H (〇〇1% ΗΝ〇3). ) Precipitation. The material was filtered with filter paper, washed three times on the filter, each time used] liter of eOH, and in a vacuum oven at 60. 〇70〇 It is dry. Example 1 Figures 6A-6J are exemplary compounds of difluoroaromatic compounds due to the fact that they are based on unhardened poly (pure). // ^ two novel combinations of hexanone) and benign aromatic ethers (such as methoxy: in high-efficiency / capacitors (such as ring to facilitate solution preparation and spin coating, /, phenylbenzene), high solubility A homogeneous physical blend of any of these compounds with the target surface, and then thermally activated to advance ~; soil silicon [said round surface or other objects at a temperature of 300 ℃ to form thermal safety ^ Mo 仃 Ασ and the parent Response, so in low, as described in Figure 4), and into-疋 罔 · Road. If the heat-sensitive group is grafted (eg, decomposition, volatilization, and in the network # = the generated polymer is heated, pores are generated in the heat-sensitive group. The generation network is affected by the crosslinking reaction and

591067 V. Description of the invention (16) Its high-temperature polymer structure has a high glass transition temperature exceeding 400 ° C. The general synthetic diagrams of the structures described in Figures 6A and 6B are as follows: The general synthetic diagrams of the structures described in Figures 6C, 6E, 6F and 6G are as follows:

Chapter 20591067

Page 591067

V. Description of the invention (18) Example 2 FIG. 7 illustrates a synthetic diagram for the production of tetracyclone-containing poly (aromatic mystery). Successful poly-8 is performed at 1 40-1 60 ° C for 24 hours, and the polymer is processed using the same steps as other polyethers). The color of the tetracyclone-containing polymerization product was ochre red 7. It showed a final Mη of 3,000, a Mw of 5,600, a Mp of 5,200, and a PD of 1.9. Molecular weight can be improved by polymerizing directly at 160 ° C for 24 hours instead of 24 hours at 1 40-160 ° C. However, since the polymer and FLARE polymer 'w can be more effectively crosslinked when hardened to form a hexaphenyl structure with a relatively low density, intermediate molecular weight species are more advantageous. Example 3 Figure 8 is a synthesis diagram including general reaction conditions for grafting thermosensitive components to a polymeric bundle, in which 4-fluoro-4'-hydroxydiphenyl ketone is reacted with ethylene glycol-polyethylene in THF (dead, PPh3). (Caprolactone) to make a 4-fluorodiphenylketone terminated thermosensitive polymer. The thermosensitive 4-fluorodiphenyl ketone terminated thermosensitive polymer can then be added to the poly (arylene ether) together with the aromatic biphenol compound. Example 4 Figures 9A and 9B show the intended structure of a difluoroaromatic monomer containing a tetraketone poly (aryl ether). Example 5 In Figs. 10 and 11, the intended cross-linkable units and heat-sensitive units are combined into a single polymerized bundle. After synthesizing each of these difluoroaromatic polymers, the above-mentioned thermosensitive units can be grafted onto the polymers. Alternatively, the polymerization can be carried out with 4-fluorodiphenylketone-terminated thermosensitive units and difluoroaromatic monomers which can be reacted with bifenol.

Page 22 591067 V. Description of the invention (19) Example 6 In Fig. 1 2 A-1 2 I, the structures of various fluorinated repeating unit portions in the polymer bundle are shown. The introduction of fluorine into the polymeric beam is particularly advantageous because the dielectric constant of the dielectric material can be modified according to the specific requirements of a particular application. It should be understood that fluorine can be added directly to the backbone through covalent bonds of the para-aromatic ring system to produce a fluoroaromatic polymeric bundle. Alternatively, fluorine may be added to the skeleton in the form of a -CF3 group to which an aromatic or non-aromatic carbon atom may be attached. Fluorine is usually added to the polymer bundles in accordance with the general agreement described in Figure 5 using fluorinated biphenol compounds and / or highly fluorinated aromatic compounds. Typical Synthesis of Highly Fluorinated Aromatic Monomers The following reactions were performed in a standard unit. In the first Heck reaction, 1-halo-3,4,5-trifluorobenzene (R = H, X diBr, 1) was reacted with ethynyltriamidine in a triethylamine solvent at 80 ° C under palladium catalysis. Silyl, producing the intermediate product 1- (tris (fluorenylethynyl) ethynyl) -3,4,5-trifluorobenzene, which is then subjected to a reverse Favorskii reaction in methanol in the presence of potassium carbonate to produce 1-ethynyl -3,4,5-trifluorobenzene. Similarly, 1-halo-2,3,4,5,6-pentafluorobenzene (R = F, X = Βγ, I) is reacted with ethynyltriphenylamine in triethylamine solvent at 80 ° C under palladium catalysis. Fluorenylsilane to produce intermediate (trimethylsilylethynyl) -2,3,4,5,6-pentafluorobenzene, which is then subjected to a reverse Favorskii reaction in methanol in the presence of potassium carbonate to produce 1 -Ethynyl-2,3,4,5,6-pentafluorobenzene. Between 3-bromo-4'-fluorodiphenyl ketone and 1-ethynyl-3, 4, 5-trifluorobenzene or 1-ethynyl-2,3,4,5,6-pentafluorobenzene The second Heck reaction synthesizes 3,4,5-trifluoro-3 '-(4-fluorophenylfluorenyl) diphenylacetylene or 2,3,4,5,6-pentafluoro-3'-(4 -Fluorophenylfluorenyl) diphenylacetylene.

O: \ 63 \ 63739.ptd Page 23 591067 V. Description of Invention (20)

ΧΒΒ, Ι R-F, H

1. Pd (? Pfe3) 4-> 2 · CH3OH, K2CO3

Or 'may be in 3- / stinky ~ 2,, 3,4,5,, 6, -pentafluorodiphenyl ketone with 1 ~ ethoxy-3,4,5-difluorodiphenyl ketone or A group of two reactions similar to the listed Heck reactions are carried out between ethynyl-2,3,4,5,6-pentafluorobenzene, each of which results in 3, 4, 5 -trifluoro-3-(2, 3 , 4, 5, 6-pentafluorobenzylidene) diphenylacetylene or 2, 3, 4, 5, 6-pentagas-3 '-(2, 3, 4, 5, 6-pentafluorophenylhydrazone) Group) diphenylacetylene. Amended to be easy to understand the scope of the patent 'all in particular, the elements of the absolute side, reference to it has been revealed without layered dielectric. However, many ideas beyond the narrative are obvious to those skilled in the art Unless it is explained in the broadest possible way beyond the scope of the attached application description and patent application. The inclusion of compr i s i ngn should be interpreted as a non-step, which means reference or utilization, or the combination is not explicitly step. Determine specific embodiments and applications. Capable without departing from the invention. Therefore, the spirit of the present invention is not limited. In addition, in the interpretation of the nouns, the nouns should be consistent with the text " comprise1, and reference elements, ingredients, or Γ! Steps can exist, ', 疋', ingredients, or steps

Claims (1)

591067 VI. Scope of Patent Application, 1. A method for manufacturing a countersunk material 2 comprising: providing a plurality of polymeric bundles, wherein each polymeric bundle includes a thermally sensitive portion and defining a skeleton including a plurality of reactive groups; providing a first Energy to cross-link the polymeric beam using at least one reactive group; and providing a second energy to at least partially degrade the heat-sensitive portion. 2. The method according to item 1 of the scope of patent application, wherein all the reactive groups are the same as each other. 3. The method according to item 1 of the patent application, wherein the backbone comprises a conjugated group. 4. The method according to item 1 of the patent application, wherein the backbone comprises an aromatic ring system. 5. The method according to item 1 of the patent application, wherein the skeleton is fluorinated. 6. The method according to item 5 of the patent application, wherein at least one fluorine atom is covalently bonded to the aromatic carbon atom. 7. The method according to item 5 of the patent application, wherein at least one fluorine atom is covalently bonded to a non-aromatic carbon atom. 8. The method according to item 5 of the patent application, wherein at least one fluorine atom is covalently bonded to a non-aromatic carbon atom, and at least one fluorine atom is covalently bonded to an aromatic carbon atom. 9. The method according to item 1 of the scope of patent application, wherein at least one reactive group comprises a nucleophilic_heart. 10. The method according to item 1 of the patent application, wherein at least one of the reactive groups comprises an electrophilic center. 11. The method according to item 1 of the scope of patent application, which further comprises to Page 25 591067 VI. Scope of patent application One cross-linking reaction between one polymer bundle and itself. 12. The method according to item 1 of the scope of patent application, wherein a crosslinking reaction occurs without the addition of an external crosslinking agent. 13. The method according to item 1 of the scope of patent application, wherein at least one polymer bundle crosslinks at least one other polymer bundle without generating free radicals. 14. The method according to item 1 of the scope of patent application, wherein at least one of the reactive groups comprises dilute. 15. The method according to item 1 of the patent application, wherein at least one of the reactive groups comprises a dienophile. 16. A method according to claim 1 in which the backbone comprises a ring system and at least one reactive group comprises a diene. 17. A method according to claim 1 in which the backbone comprises a ring system and at least one reactive group comprises a dienophile. 18. The method according to item 1 of the scope of patent application, further comprising manufacturing a skeleton using a biphenyl and a difluoroaromatic compound, and at least one of the reactive groups thereof comprises a tetracyclone. 19. The method according to item 1 of the scope of patent application, further comprising manufacturing a skeleton using a biphenyl and a difluoroaromatic compound, and at least one of the reactive groups includes an ethynyl functional group. 20. The method according to item 1 of the scope of patent application, wherein the skeleton is made of a fluorinated terpineol compound and a fluorinated difluoroaromatic compound, and a plurality of the reactive groups thereof include at least one tetracyclone and at least one ethynyl group. O: \ 63 \ 63739.ptd Page 26