TW200900458A - Methods of preparing polymer-organoclay composites and articles derived therefrom - Google Patents

Abstract

A method for preparing a polymer-organoclay composite composition comprises combining a solvent and an unexfoliated organoclay to provide a first mixture, wherein the unexfoliated organoclay comprises alternating inorganic silicate layers and organic layers, and has an initial spacing between the silicate layers; exposing the first mixture to an energized condition of a sufficient intensity and duration to increase the initial spacing of the inorganic silicate layers, to provide a second mixture; contacting the second mixture with a polymer composition so that the polymer composition fills at least one region located between at least one pair of silicate layers, wherein the polymer composition is at least partially soluble in the solvent; and removing at least a portion of the solvent from the second mixture, wherein the inorganic silicate layers remain separated by the polymer after removal of the solvent.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Priority of Provisional Patent Application No. 60/945, filed on Jan. 5, the entire disclosure of which is incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of preparing a polymer-organic clay composite and the use of such composite materials, for example, in forming a solvent cast film. The present invention also discloses a solvent cast film comprising polyimine and a method of making the same. The film is formed by polymerization of a dianhydride component and a diamine component and has a relationship between 180 ° C and 450 ° C, particularly 19 (TC or greater Tg, and wherein the film has: a) is less than 7 〇ppm/°C, especially CTE less than 60 ppm/°C; b) between 0.1 and 250 microns 'in particular 5 to 250 microns thickness; and, c) containing less than 5% by weight residual Solvent. [Prior Art] Background of the Invention Thermoplastic sheets and films have a wide range of applications. For example, thermoplastic films and sheets can be found in automotive applications, electronic applications, military applications, appliances, industrial equipment, and furniture. An important use of the film is as a substrate or flexible circuit application -5-200900458 coating. In order to play this role, the novel film should meet the decisive requirements of two flexible circuit substrates, namely low coefficient of thermal expansion (CTE) and high temperature residual (especially when high temperature steps are employed). The low CTE must meet (as close as possible) the CTE of copper (CTE = 17 PPm/°C). When the film is a substrate or copper circuit traces for a copper layer, this low CTE prevents the film from curling as the temperature changes. The low CTE also prevents inconsistent changes in the dimensions between the copper and substrate layers during thermal cycling, which increases the lifetime of the final flexible circuit board by reducing stress and fatigue of the patterned copper wiring. In other words, the properties of the flexible circuit board are beneficial when the film substrate of the flexible circuit board and the applied conductive metal layer expand and contract at the same rate. When these layers do not expand and contract at the same rate, controversy about the adhesion and orientation of the layers can and does occur. A CTE of less than 70 ppm/°C, especially less than 60 ppm/°C, and even more specifically less than 30 ppm/t will allow for low warpage during thermal cycling and is a common goal when the CTE of the film becomes close to copper. Better results will be achieved at CTE. CTE is tested by TMA or thermomechanical analysis. The change in size of the film sample is measured as a function of temperature and the slope of the change is calculated from the CTE. Typically, C TE must measure the temperature range in which the film is expected to be seen during processing of the flexible circuit board. The temperature range of 20 to 25 °C is a reasonable temperature range for determining CTE. The high temperature residual property can also be an important property of the substrate film remaining in the soldering process during the manufacture of the flexible circuit board. For novel lead-free soldering methods, the film should exhibit short-term residual properties at, for example, a high temperature of 260 °C. Temperature Residual The standard test for 200900458 is a solder float test in which a small piece of film is attached to a cork stopper and immersed in molten solder for 0.25 seconds. Then remove the film, wipe off the solder, and inspect the film. If there is any visible warpage or blistering, the film test fails. Although this test does not have a standard thickness, the minimum thickness of the film through the float welding test can be reported. 26 (TC and 2 8 8 °c are the standard float soldering temperatures for lead eutectic and lead-free solder respectively. The low CTE and high temperature requirements of flexible circuit substrates have been treated with polyimine membranes. Many commercial poly Amine (PI) films have high glass transition temperatures (greater than 350 ° C) and can be partially crosslinked, resulting in anomalous temperature remnants. The polymer molecules in these films are slightly stressed when they are prepared, resulting in polymers. The alignment of the molecules and the low CTE of the given PI film. Since the film never sees a temperature above the glass transition temperature (Tg) of the material, the stress can never be relaxed and the film is dimensionally stable at soft manufacturing temperatures. Materials and films are used in a wide variety of applications. 'The thermoplastic sheets and films need to be resistant to high temperatures for a suitable period of time without substantial degradation. Continue to need to have: a) at 70 ppm/〇c' special It is a CTE at 30 ppm/°C and technically as close as possible to the CTE of copper; and b) a film with high heat residual. SUMMARY OF THE INVENTION The present invention is directed to a method of making a polymer-organic clay composite and articles derived therefrom, such as thermoplastic sheets and films. The 200900458 sheets and films are available for a wide range of applications, sub-applications, military applications, appliances, and industrial systems, in a system for preparing polymeric colorants comprising: combining a 丨unexfoliated organic clay to provide The _ peel-off type organic clay comprises alternating initial inorganic citrate layers having an initial spacing; the first and the period of the excitation conditions are increased to increase the inorganic cerium to provide a second mixture; and the second mixing is made to The polymer composition is filled in a region between at least one layer, wherein the polymer constitutes the solvent; and from the second mixture, the inorganic silicate layer is in another system after removal of the solvent, and a preparation is performed The method of the composition comprises: combining a solvent soil to provide a first mixture, wherein the citrate layer and the organic layer, and the formula (1) 2 R9 R*-Q-R10

I R7 wherein Q is phosphorus or nitrogen; and R7, R8, R9 aliphatic hydrocarbon, c5-c2Q cycloaliphatic, c2-c20 organoclay additionally have an initial exposure between the citrate layers to form a second Hybrid-8 - for example for automotive applications, electrical equipment and furniture. J-organic clay composite compatibilizer and a non-peeling type (the mixture, wherein the non-salt layer and the organic layer, and the cerium mixture is exposed to a sufficient spacing between the layers of the acid salt, the polymer and the polymer composition The at least one pair of sulphate systems are at least partially dissolved in at least a portion of the solvent which remains separated by the polymer. The mash-organic clay composite and the non-peeling organic viscous clay comprise alternating An inorganic grade 3 organic cation and R1() are independently an aromatic or polymer chain 'and a spacing; a first mixture, wherein the excitation condition 200900458 has sufficient strength and period to produce an organic clay composition of inorganic cerium a net increase in the initial spacing between the acid salt layers; contacting the second mixture with a polyamidene separating the inorganic silicate layer to form a third mixture, wherein the polyamidene is at least partially dissolved in the solvent And removing at least a portion of the solvent from the third mixture, wherein the citrate layer remains separated by the polymer after removal of the solvent. The method of organic clay composite comprises combining a solvent and a non-peeling type organic clay to form a first mixture, wherein the organic clay comprises alternating inorganic silicate layers and an organic layer with an initial layer between the citrate layers a spacing; exposing the first mixture to a sufficient strength and period of excitation to increase the initial spacing between the inorganic bismuth silicate layers to form a second mixture; contacting the first or second mixture with the polymer precursor And polymerizing the polymer precursor to form a polymer; and removing at least a portion of the solvent from the second mixture, wherein the inorganic silicate layer remains separated by the polymer after removal of the solvent. In another system, a preparation The method of polymer-organic clay composite composition comprises a combined solvent, a non-peeling organic clay, a dianhydride component and a diamine component to form a first mixture, wherein the organic clay comprises alternating inorganic silicate layers and organic a layer having an initial spacing between the citrate layers; exposing the first mixture to a sufficient strength and period of excitation to increase An initial spacing between the inorganic silicate layers to form a second mixture; polymerizing the dianhydride component and the diamine component to form a poly-proline; and removing at least a portion of the solvent from the polyamid acid mixture to provide a polyimine The inorganic tellurite layer remains separated by the polyimine after removal of the solvent. -9- 200900458 In another system the article comprises a white organic clay composite. DETAILED DESCRIPTION OF THE INVENTION When thermoplastic sheets and films are used Reference will be made to a number of indicators that are defined in the form "a (a)" and "an", unless the context clearly dictates otherwise the technical and scientific knowledge used herein is the same. The use of quantity numbers or representations of ingredients in addition to those in the operating examples or the scope of the claims and claims should be understood to mean that one or more of the listed ingredients are present in the term "about". The range of various numbers is because each of these ranges is continuous, so each one between them. Unless explicitly indicated, the various numerical ranges are approximate. With respect to the endpoint of the circumference including the endpoint and independently for the present invention, the term "film" is a thin thermoplastic resin or other material. The term "casting" means a molding impression by smoothing or dissolving it. The polymer prepared by the above method is hardened in the mold or on the sheet - the following description and the scope of the patent application have the following meanings. Single, and "the" include plural designations. Unless otherwise defined, the term has a compound that is described in the standard nomenclature of those skilled in the art. In addition, all the 'modifications' used in the instructions, reaction conditions, and the like. The term "combination of any of these" is arbitrarily combined with one or more of those listed in the present patent application. They include all combinations of the same components or properties as specified in the minimum and maximum indications. It is compared to its length and width as a pole section. Or a forming method in which a type (a molten material is injected into a mold or a sheet or cured). -10-200900458 "Solvent cast film" is a type formed by casting a fluid on a surface to form a sheet or mesh. A film formed by removing solvent from a casting fluid. All ASTM tests and data are from the 1991 edition of the ASTM Standard, unless otherwise indicated. “Coefficient of expansion” is the temperature at a fixed pressure per unit volume of polymer. An increase in volume of 1 ° C was added. For the purposes of the present invention, CTE measurements were carried out by thermomechanical analysis (TMA) using a thermal ramp rate of 5 ° C/min. The sample size was 23 mm long x 5 mm 寛. First, the heating rate from 0 ° C to 250 ° C at a heating rate of 5 ° C / min and the CTE lanthanum are measured at a pressure of 0.05 Newton from the slope of the temperature range from 30 ° C to 2 ° C. Chemical resistance is the ability of a solid material to resist damage due to chemical reactivity or solvent action and can be determined according to ASTM Test D 5 4 3 - 0 6. "Dielectric Constant" (permittivity constant): Any two charged bodies There is a force (attraction or repulsion) based on the charge strength 'q 1 and q2, the distance between the charged bodies, r, and the dielectric (dielectric) characteristics of the separate charged body called the dielectric constant (S). Change. This force is generated by the equation: F = ql.q2/(e.r2). "Flexing modulus" (flex modulus) is the static of the sample at three points within the elastic limit The ratio of the applied stress in the outermost fiber of the buckling to the calculated stress in the outermost fiber and can be determined according to ASTM test D790 or D790M 湏fj. The flexural strength (fracture modulus of the fracture) is a test with two points of load. The maximum calculated stress at the moment of cracking or breaking in the outermost fiber of the rod. ASTM tests D 7 90 and D 790M are widely used to measure this property. For most -11 - 200900458 plastics, the flexural strength is usually substantially higher than Straight tensile strength. "Glass transfer" is a reversible change that occurs when an amorphous polymer or an amorphous region of a partially crystalline polymer is heated from a very low temperature to a certain range (specific to each polymer). 'It is characterized by hard, glass or easy Conditions change quite abruptly to soft or elastic conditions. Physical properties (such as coefficient of thermal expansion, specific heat, and density) are usually changed simultaneously with their temperature derivatives. During the transfer, the molecular chains (normally coiled at low temperatures, The entanglement, and immobility) become free to rotate and slide over each other. The "glass transition temperature" (Tg) is approximately the midpoint of the temperature range in which the glass transition occurs. Tg is not obvious (like the melting point), and in the second Properties (eg, varying rates as a function of temperature or electrical or mechanical properties of a particular volume) are detected by changes in elevated temperature. Moreover, the observed Tg can vary significantly depending on the particular properties selected for medical observation and based on experimental details such as heating rate or electrical frequency. The reported Tg should therefore be considered as an assessment. The most reliable assessment is normally obtained from the loss peaks in the dynamic-mechanical test or from the expansion data. For the purposes of the present invention, the glass transition temperature (Tg) is determined by the maximum point of the enthalpy curve. Tg can also be determined by the inflection point of the DSC (Differential Scanning Thermal Method) trace (ASTM Test D3 148). The "melting temperature" (identified by its symbol "Tm" hereinafter) is the temperature at which the thermal energy in the solid material is sufficient to overcome the intermolecular attraction in the crystal lattice, causing the lattice to collapse and the material to become liquid, i.e., its melting temperature. The Tm system -12-200900458 according to the present invention is measured in accordance with ASTM test D3 148. "Fused viscosity" is the shear resistance in molten resin, and the quantitative is the quotient divided by the shear rate at any point of the flowing material. Similarly, the long viscosity is applied to the drawing of the extrudate. In the polymerization, the viscosity depends not only on the temperature but also on the pressure, and also on the degree of stress (or shear rate). For the purposes of the present invention, the melt viscosity is measured at 380 ° C by capillary rheometry according to ASTM D3 8 3 5: "hygroscopicity" is absorbed by the time interval when the material is exposed to the specified humidity and temperature. steam. There is no test for this A STM test. At 5 〇 % relative humidity and by immersion in water, the wetness is measured by weight gain. The "tensile modulus" or "elastic modulus" is the ratio of the material to the ratio of the tensile stress to the corresponding elongation. The relevant ASTM test is: 抗 "Tensile strength" is the maximum nominal stress maintained at a specified temperature and at a specified tensile rate. When the maximum nominal stress volts occurs, it will be specified as the drop point tensile strength. When it occurs, it will be designated as the tensile strength at break. The ASTM of the plastic is D63 8 (metric, D63 8M). The SI unit of tensile strength is pascal (N/m2). "Organic clay" means a nano silicate (also known as nano-clay) which has undergone ion exchange to replace metal ions with organic cations. The organic clay used in this article contains the term modified organically modified nano-clay nano-clay, modified clay, modified citrate, modified nano-nanoic acid, and the modified excision. The D638 end of the suction of the medium quality was tested by the drop-break test, the salt, the -13-200900458 nano composite, and the modified nano-filler. "Modifier" means an organic cation that can be ion exchanged with a metal ion of a nanoclay to form an organic clay, including a polymeric organic cation.

The gallery spacing or d-spacing is the distance between the various microplates that make up the nanoclay or organic clay. The change in spacing seems to depend on the composition of the organic clay and solvent. By "inter-clip" is meant a method by which the d-spacing is increased by the incorporation of modifiers, solvents or polymers between the sheets. The modified nanoclay has a d-spacing greater than the d-spacing of the same unmodified nanoclay. "Peeling" refers to the complete separation of the sheets that make up the clay structure. Smaller structures with multilayer sheets called tactoids sometimes have incomplete peeling. "Polyuric acid solution" (also known as poly-guanamine-acid, poly(proline), lysine, polylysine, poly(proline), poly(deamine-acid) or poly The indoleamine-acid) is a solution comprising a proline unit having the ability to react with the surrounding organic moiety to form a quinone imine group. "Polyimine" as used herein refers to a polymer comprising a repeating quinone imine functional group and any additional functional groups such as guanamines and/or ethers. "Polyimine" thus includes polyamidoenimines and polyetherimines in its scope. The term "inert" means that the atmosphere within the container is replaced with an inert gas such as nitrogen. "Recycled" means that all or a portion of the polymer according to the present invention can be reused for the initial use of the polymer. For example, if the original use of polymer -14-200900458 is used as a solvent cast film for flexible circuit boards, all or a portion of the polymer is recovered and redissolved in the solvent, with or without the use of additional monomers or polymers. Recycling can also mean that the polymer can be partially or completely reused by other processing methods to form parts using other processes such as injection. When the structural unit of the chemical moiety is said to be formally derived from the precursor moiety, it is not meant to limit the actual chemical reaction that can be used to produce the chemical moiety. For example, when a chemical moiety such as a polyetherimine is said to have a structural unit derived formally derived from a dianhydride and a diamine, any known method can be used to prepare a polyetherimine, including a reaction of a dianhydride and a diamine, or The displacement reaction between the phenoxide species and the quinone imine having a displaceable group, or other known methods, requires only the chemical moiety to comprise a structural unit that can be represented by the precursor moiety. In one system, the polymer is a polyimine formed by the polymerization of a dianhydride component and a diamine component and having a Tg between about 180 ° C and 45 ° C. An article derived from the polymer-organic clay composite is a solvent cast film having: a) a CTE of less than 70 ppm/° C; b) a thickness of between about 0.1 and 1000 microns; , c ) contains less than 5% residual solvent. The present invention relates to an article comprising a solvent cast film comprising a dianhydride component and a diamine component and a Tg between 180 ° C and 450 ° C, particularly 190 ° C or more, and Wherein the film has: a) a CTE of less than 70 ppm/° C. (especially less than 60 ppm/° C.); b) a thickness between 0.1 and 250 microns (eg, 5 to 250 microns); c) contains less than 5% by weight residual solvent. The solvent cast film according to the present invention may be made of at least one polyimine having a Tg of between 1 80 -15 and 200900 458 ° C and 450 ° C. In another system, the polyimine has a temperature of 190 ° C or greater, especially 190. (: Tg to 500 ° C, more particularly 190 ° C to 400 ° C. Those skilled in the art should be aware that the Tg of any particular polyimine may include the choice of dianhydride monomer, different dianhydride monomers ( The number of the structure of the unit, the choice of the diamine monomer, the number of different diamine monomers (not the structure of the unit), the processing conditions during the preparation of the film, the type of the amidation method used to harden the polymer, etc. The factors vary widely, and those skilled in the art will be aware of the ability to produce polymers having any desired Tg within the above Tg range, depending on the monomer, structure and/or end cap used, etc. The type of polyimine constituting the film is likewise variable. The invention is particularly encompassed by all compositions of one or more dianhydrides and one or more diamines from which the polyimines of the invention can be made. Random and block polymers and co-polymers. There may be more than one type of polyimine, such as a combination of polyamidoximine and polyetherimine, or two different types of polyether Imine. That is, the present invention relates to A solvent cast film of various polyimine films, including other options including PPSU (polyphenylene), PSU (poly), PC (polycarbonate), PPO (polyphenylene ether), PMMA (polymethyl) Amorphous thermoplastic polymer of methyl acrylate), ABS (acrylonitrile-butadiene-styrene tri-copolymer), PS (polystyrene), PVC (polyvinyl chloride), including PFA (perfluoroalkoxyalkylene) ), MFA (copolymer of TFE (tetrafluoroethylene) and PFVE (perfluorinated vinyl ether)), FEP (fluorinated ethylene propylene polymer), PPS (polyphenylene sulfide), PEK (polyether ketone), PEEK (Polyether-ether ketone), ECTFE (ethylene-chlorotrifluoroethylene copolymer-16- 200900458), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PET (polyethylene terephthalate) ), POM (polyacetal), PA (polyamide), UHMW-PE (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene), LDPE (low Density polyethylene) crystalline thermoplastic resins, and advanced engineering resins such as PBI (polybenzimidazole), poly (ether milling), poly (aryl milling), polyphenylene ether, poly And benzoxazoles, and polybenzothiazoles, and polymers of blends and copolymers thereof. The measured c TE of the film may be inherent in the material due to the chemical composition of the material. Or 'via the use of additives and or The CTE from the processing step can be significantly lower than the inherent CTE of the film material. The CTE of the solvent cast film can be any CTP' below 70 ppm/°C, especially below 60 ppm/T: and the film acts on the desired Usability. For example, for a flexible circuit board, the CTE can be chosen to be close enough to the CTE of the connected metal conductive layer, and the film can be used as a dielectric substrate (a layer of a laminate and/or a layer of a flexible circuit board). . In a separate system, the CTE is less than 70 ppm/°C, less than 50 ppm/°C, less than 40 ppm/°c, less than 35 ppm/°C, less than 30 ppm/°C, or less than 20 ppm / °C. According to other systems, the film has a CTE of at least 5 ppm/°C. The film may also have a CTE' of 5 ppm/t: to 60 ppm/°C and more particularly a coefficient of thermal expansion of ppm/° (: to 30 ppm/°C ' and even more particularly 10 ppm/°c to 20 ppm) /t: 〇 or 'adjust the CTE of the film to match the substrate material on which the film is disposed. In one system, the film has copper, tantalum, aluminum, gold, silver, -17-200900458 nickel, glass, ceramic or The CTE of the polymer has a CTE within ±20 ppm/°C, especially within ±20 ppm/T of the CTE of copper, tantalum, aluminum, gold, silver or nickel. In another system, the film has copper in , C, TE, aluminum, gold, silver or nickel (especially copper) thermal expansion coefficient of ± 15 PpnW ° C CTE. In an advantageous feature, the CTE of the film is found to be very stable. For example, the film from 2 5 After laminating to the substrate at a temperature of 0 to 4500 °C, the film has a thickness of ±1〇0?111/° (: within ±1. The application, the method of making the film, the solids content of the casting solution, and the few nominal parameters of the appointment vary widely. The thickness can vary from 0.1 micron to the maximum. Up to 10,000 microns, or more specifically from 5 microns up to looo microns, however it is generally expected that the most likely thickness to be used in a flexible circuit board will be between 0.1 and 250 microns. Finally the solvent cast film may contain residues The solvent can act for its intended purpose. The minimum amount of residual solvent will be the maximum residual solvent content under which the film will still have the desired effect. On the other hand, the solvent cast film may also contain as much A low residual solvent content achieved. For example, solvents are expensive and can be hazardous to the environment. Both cost savings and environmental improvements can be achieved by minimizing the amount of solvent contained in the final product. The residual solvent content will be less than the film. 5% of the total weight. In another system, the amount of residual solvent will be less than 1% of the total weight of the film. ^ The solvent used in the process may include any solvent from which the solvent casting film can be made. The solvent may be polyfluorene. A good solvent for imines, for example, having a relatively boiling point to aid in the formation of a solution film or direct venting via extrusion. Using a solvent for film formation from -18 to 200900458 It may be the same as the solvent used to produce the following polyamic acid solution. Examples of suitable solvents include, but are not limited to, N-methyl 11 succinyl ketone (NMP), Sanqi Yiyuan, N, N_ Methylacetone fl female (DMAc), N-methylpyrrolidone (NMP), dimethyl hydrazine (DMSO), cyclobutyl milling, tetrahydrofuran (THF), diphenyl ketone, cyclohexanone, benzoquinone, a mixture of o-, p-, and m-cresols, a mixture of cresol and phenol, acetol, isopropyl phenol, tri-butyl phenol, xylenol, 2, 4, 6 - 3 Toluene, chlorophenols, dichlorophenols, o-dichlorobenzene (o-DCB), phenylphenols, monoalkyl ethers, alkyl groups of ethylene glycol having 1 to 4 carbon atoms in the alkyl group a monoalkyl ether having a diethylene glycol of 1 to 4 carbon atoms, a monoaryl ether glycol, a monoaryl ether of propylene glycol, N,N-dimethylformamide, tetramethylurea, a phenoxy group Ethanol, propylene glycol phenyl ether, anisole, cucurbit ether, o-dichlorobenzene, chlorobenzene, trichlorobenzene, trichloroethane, dichloromethane, chloroform, pyridine, N-cyclohexyl pyrrolidone, lactate B Ester, ion Thereof, and mixtures comprising one or more of their solvent. Ionic liquids typically include salts having a lower (below 100 °C) melting point. Examples of the ionic liquid include, but are not limited to, ammonium, imipenone, scaly-, pyridinium-, pyrrole-indene-, and sulfonium-based salts. The relative ions in the liquid may include, but are not limited to, the following: bromine anion, chloride anion, tetrafluoroborate ion, acetate ion, phosphate ion, carbonate ion, sulfate ion, sulfate ion , nitrate ions, thiocyanate ions and combinations thereof. $gastric sputum I page S operator should be aware that the particular solvent used will include, for example, the solubility of the polyimine and precursor monomers in the solvent, and any number of factors of solvent -19-200900458 volatility. Set, for example. The solvent cast film according to the present invention can be produced by any method known in the art. The following patents assigned to GE disclose the general methods for making solvent cast films and casting solutions: 4,115,341; 4,157,996; 4,307,226; 4,360,633; 4,374,972; and 3,847,867. A manufacturing method can include the steps of: forming a polyamic acid solution comprising a monomer component comprising one or more dianhydrides and one or more organic diamines at least partially dissolved in a solvent system; The polyamic acid solution is cast on the substrate such that the polyaminic acid solution is in the form of length, width and depth on the surface of the substrate; the solvent is removed, and the polyamic acid solution is hardened to form less than 70 ppm/°C. (especially less than 60 ppm/°C) CTE and films from 0.1 microns to 250 microns (especially 5 to 250 microns). Alternatively, the method may comprise producing a solvent cast film comprising: preparing a casting solution comprising a polyamic acid solution consisting of a monomer component and a solvent component; casting a film of the casting solution on the carrier base; The cast film removes the solvent for a predetermined period of time to form a CTE having less than 70 ppm/° C. (especially less than 60 ppm/° C.) and between 0.1 μm and 25 μm (especially between 5 and 2 50) A solvent cast film having a thickness between micrometers; and an additional step on the solvent cast film to produce a CTE of a film of 30 ppm/° C. or less. The polyaminic acid solution can be prepared by stirring and mixing one or more dianhydrides, water, and a solvent until one or more dianhydride components are dissolved. One or more monomeric diamines and a stirred solution can then be added until the amines are dissolved. The components constituting the dianhydride component and the diamine component may include 1, 2, 3, 4, 5 or more non--20- 200900458 homo-dianhydrides and diamines. The scope of the invention is particularly intended to include substitutions and combinations of the numbers and types of all dianhydride and diamine monomers. For example, in a monolithic system, the polyaminic acid solution will consist of two different dianhydrides and two different diamines. In another system, one of the one or more dianhydrides is ODPA. In general, the 'organoamine component can be included in an amount from 0.5 moles to 2.0 moles, or ' more specifically, from 1 to 1.3 moles per gram of dianhydride component. In the case where more than one compound is included in the solution component of the present invention, the ingredient, mole or other amount of the ingredient is taken as the sum of the parts, the molars or the other amounts of the respective compounds of the ingredient, respectively. Thus, for example, the total amine content is calculated by adding the equivalent amounts of the respective diamines in the amine component, for example, 2 (the number of moles of the first diamine) + 2 (the number of moles of the second diamine) = total amine equivalent. The total anhydride content was calculated in a similar manner. A slight excess of amine can be used to impart additional film elasticity or possible crosslinking. The polyamidene enamel may be found to have 5 to 500 repeating dianhydride-diamine reaction product units and preferably from 1 to 200. Terminal amine groups and capric acid or phthalic anhydride or various suitable terminal groups may also be present. Experience has shown that sufficient solvent should be utilized to provide a solids content that provides a workable viscosity for solution agitation and handling. In a system, the solids content will be from 1 to 65 wt%. In other systems the solids content will be 1-4%, 1-25% '1-15% or 1-12.5% by weight. The solution having a high proportion of the monomer reactant to the organic solvent component advantageously minimizes the amount of the organic solvent during the formation and hardening of the polyether oximine resin in the solvent cast film. These solutions having a high amount of monomer reaction -21 - 200900458 may have a higher viscosity than those of some solvent cast films. Typically, the inclusion of water reduces the viscosity of the solution. A given viscosity reduction can be produced using an amount of added water that is lower than the amount of organic solvent component required to produce the same viscosity reduction. The water may or may not be part of a polyaminic acid solution. Water can be present in any amount up to the maximum amount of solution substantially free of precipitates. Although water can be mixed with the organic solvent component in substantially all proportions, the inclusion of too much water in the monomer solution of the present invention results in the formation of precipitates or other complex phases. The amount of water which may be present depends on the specific dianhydride and diamine component, the specific organic solvent component, and the weight ratio of the monomer reactant to the organic solvent. Advantageously, the poly-proline solution of the present invention may comprise a total of 40 or more weight percent (e.g., 40 to 75 or more weight percent) of the monomer reactant based on the weight of the solution. In general, the high monomer content solution (which may include water if desired) has an appropriate viscosity at a temperature range (e.g., 15 ° C to 200 ° C) which is normally used to produce a solvent cast film. The liquid solution including water can be more easily prepared by adding a monomer reactant component to a solution of water and an organic solvent component and stirring. The preparation of the solution is usually accelerated at high temperatures. The additive may be present in the polyimide film, for example by addition to a polyamine solution to reduce C T E to below the C T E of the material without the additive. These additives include those which will help reduce the CTE of the solvent cast film, and those which may help to produce another desirable property in the film of the present invention. These ingredients can be used in any amount of 0.001 to 60 parts by weight of the additive (per 1 part by weight of the polyimine) to impart the desired properties. Alternatively, these additives may be added in an amount of from 0.01 to 30 parts by weight per 100 parts by weight of the polyimine, and more particularly from 1 to 1 part by weight of the additive. Types of additives that can be used to reduce the CTE of the solvent cast polyimine film include modified nano-composite silicates (nano clays). Suitable nano-clay includes kaolinite, dick stone, pearl stone, Hele stone, leaf serpentine, serpentine, pyrophyllite, microcrystalline kaolinite, aluminum bentonite, iron bentonite, saponite, and saponite , strontite, hectorite, tetrasilylic mica, sodium mica, muscovite, pearl mica, talc, vermiculite, phlogopite, green fragile mica, chlorite, synthetic silicate, and A combination of at least one of the foregoing nano clays. In a particular system, the method of forming a nano-clay composite (particularly a polymer-organic clay composite) and an article (e.g., a film) comprising the polymer-organic clay composite are not described herein. The polymer-organic clay composite can be formed into a film by solution casting. These organic clays are thermally stable at film forming processing temperatures. The polymer-organic clay composite can be formed using different polymers, including thermoset and thermoplastic polymers. Typical polymers include such polymers as described above, particularly polyvinyl chlorides, polyolefins, polyesters (including aromatic polyesters), polyamines, poly-stripes, poly-imines, Including polyamidoquinones and polyetherimines, polyether oximes, polyphenylenes, polyether ketones, polyetheretherketones, ABS, polystyrenes, polybutadienes, Polyacrylates, polyalkyl acrylates, polyacrylonitriles, polyacetals, polycarbonates, polyphenylene ethers, ethylene-vinyl ethyl ester copolymers, polyvinyl acetates, liquid crystal polymers Class, ethylene-tetrafluoroethylene copolymerization-23- 200900458 A material, a polyvinyl fluoride, a polyvinylidene fluoride, a polyvinylidene chloride, a polytetrafluoroethylene, and a combination comprising at least one of the foregoing polymers. The specific polymer is polyimine. The polymer-organic clay composite further comprises an organic clay. Organic clay is an organically modified nano-clay with a plurality of inorganic silicate layers that are usually alternating with organic layers. Organic clay can be prepared by ion exchange of metal cations in organic clay with organic cations. For example, the nano ions in the microcrystalline kaolinite nanoclay can be exchanged with organic cations such as tetrakiles or tetrahydrocarbon cations. Ion exchange is usually carried out by a known method in water or a combination of water and a water-miscible organic solvent. In a system, the organic cation is a quaternary organic cation, such as ammonium or scaly ion of formula (1) R9 R®-Q-R10

I R7 (1) wherein Q is nitrogen or pity; and R7, R8, R9 and R1G are each independently an I-C2 oxime hydrocarbon group, an h-Cu cycloaliphatic hydrocarbon group, an aromatic group or a polymer chain. The aforementioned group may be unsubstituted or, for example, a Cl_C^ hydrocarbon and/or one or more functional groups such as a trans group, a sulfhydryl group, a nitro group, a cyano group, a dentate, a carboxylic acid, a carboxylic acid ester, a carbonyl group, a decylamine, Substituted by quinone imine and anhydride. In another system, the organic cation is a quaternary cation of formula (2) -24- 200900458

Wherein Ar1, Ar2, Ar3 and Ar4 are each independently a C6-C5〇 aromatic group; "a" is a number from 1 to about 200; "c" is a number from 0 to 3; R1 is independent at each occurrence The ground is a halogen atom, a Ci-C^ aliphatic hydrocarbon group, a C5-C2Q cycloaliphatic hydrocarbon group or a C2-C20 aromatic group; and 112 is a CrCn aliphatic hydrocarbon group, a c5-c20 cyclohexyl hydrocarbon group, a C2-C5Q aromatic group or a polymer. chain. The child is separated from the phoenix scale, and the third type is the detachable yang machine.

ΑΓ1AI, 4ui_JI 011 ΑΓ1 (3) wherein Ar12, Ar13, Ar14 and Ar15 are independently a C6-C5〇 aromatic group; and Ar16 is a Ca-C^o aromatic group or a polymer chain containing at least one aromatic group. Typical quaternary ammonium cations include pyridinium cations of formula (4)

Wherein Ar6 'Ar7, and Ar8 are independently a c6-C5G aromatic group; "b" is from 〇-25-200900458 to 2; R3 is independently a cryptin atom, a C^Czo aliphatic hydrocarbon group at each occurrence, a C5-C2Q cycloaliphatic or C6-C2 fluorene aromatic group; and Ar11 is a C6-C2 fluorene aromatic group or a polymer chain comprising at least one aromatic group. A specific example of this type of cation is the cation of formula (5)

Wherein Ar6, Ar7, and Ar8 are independently a C2-C5〇 aromatic group; "b" is from 0 to 2; "d" is from 0 to 4; and R3 and R4 are independently halogen at each occurrence. Atom, C^-Cm aliphatic hydrocarbon group, C5-C2G cycloaliphatic hydrocarbon group, or C2-C2 fluorene aromatic group; Z is bonded, divalent (: 丨-(:2() aliphatic hydrocarbon group, divalent C5-C20 ring An aliphatic hydrocarbon group 'divalent C2-C2G aromatic group, an oxygen bond group, a sulfur bond group, an S〇2 bond group or a Se bond group; and Ar9 is an aromatic group or an aggregation comprising at least one aromatic group After the ion exchange, the spacing between the inorganic citrate layers ("d-spacing") is greater than 15, 20, 25, 30, 40 or 75 angstroms. The organic clay is then stripped to produce the polymer-organic clay composite. Material. Peeling occurs when the organic clay is exposed to sufficient strength and excitation conditions during the period, and results in an increase in the spacing ("d-spacing") between the inorganic citrate layers. The d-spacing in the exfoliated organic clay can be any Greater than the initial d-spacing, that is, the d-spacing distance in the non-peeled organic clay. In a system, the d_-spacing is sufficient to effectively provide a reduction in the CTE of the polyimide film. Polymer-organic clay composites. In some systems, exfoliated organic clays have a 5 to 90 angstroms, especially large -26-200900458 at the beginning of 15, 5, 25, 30, 40 or 7 5 angstroms. d - increase in spacing. After increasing in other systems, the d-spacing in the exfoliated organic clay is random. When the d-spacing increases, resulting in a random distribution, the sheets are no longer measurable at d-spacing. Mode orientation. In other systems, the net increase in d-spacing of organic clay is from about 1 〇 to about 5%. One method of stripping is sonic vibration processing. Peeling can also be done by high-energy mixing. The treatment and high energy mixing are in a solvent system (for example in a solvent system comprising from 1 to 90% by weight of organic clay and from 1 to 99% by weight, in particular from 1 to 50% by weight of organic clay and from 50 to 99% by weight % solvent system, more particularly 1 to 15% by weight of organic clay and 85 to 99% by weight of solvent system). Suitable solvent systems allow good dispersion, effective stripping, and dissolution of organic clay as described below. Polymer or poly Precursor. Suitable solvents include N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyridinone, dimethyl hydrazine, cyclobutane, tetrahydrofuran, Phenyl ketone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, phenol, acetol, isopropyl phenol, tri-butyl phenol, xylenol, 2, 4, 6 a trimethylphenol, a chlorophenol, a dichlorophenol, a phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, and a diethylene group having from 1 to about 4 carbon atoms in the alkyl group. Alcohol monoalkyl ether, monoaryl ether glycol, propylene glycol aryl ether, tetramethyl urea, phenoxyethanol, propylene glycol phenyl ether, anisole, veratrol, o-dichlorobenzene, chlorobenzene , trichlorobenzene, trichloroethane, dichloromethane, chloroform, pyridine, N-cyclohexyl pyrrolidone, ethyl lactate, ionic liquids, and combinations thereof. -27- 200900458 In a system, the first mixture is obtained by combining (for example, homogenizing) an organic clay into a solvent system of choice, followed by stripping, that is, exposing the first mixture to an excitation condition. To form a second mixture. The excitation conditions are at a sufficient strength and duration to increase the initial spacing between the inorganic tellurite layers, for example, sonic vibration processing. Typical sonic vibrators are ultrasonic liquid processors available from Misonix, fixed-frequency SONOPUSH MONO HD® ultrasonic transducers from Weber Ultrasonics, and tubular diving converters sold by MPI. The sonic vibration processing can be performed in batch or continuous mode. In the batch process, homogenization of the first mixture occurs when it comes into contact with the source of the sound wave. The mixture was stirred evenly to determine the uniform sonic vibration treatment of the entire mixture. In a continuous process, the first mixture flows through the sonic vibration processing zone at a rate that is imparted. The mixture was stirred evenly to determine a uniform dispersion of the nanocaprate. In batch or continuous processes, the sonic vibration processing conditions required for stripping (ie, flow velocity, sonic vibration processing force, sonic vibration processing time) depend on the type of modifier used, solvent, batch capacity, and sonic source. The configuration and size, and the temperature at which the sonic vibration treatment occurs. Those skilled in the art will appreciate that other devices and methods can be used to impart an excitation condition. In another system, for example, a silversontm mixer can be used. Different modes can be used depending on the specific needs of the present. Any functionally equivalent shear/grinding mixer can be used. The sandwich and peeling between the organic clays can be observed by X-ray diffraction (XRD) of the resulting solution. Peeling can also be accomplished by combining a sonicated organic clay mixture with a polymer, removing the solvent, for example, by evaporating, precipitating or passing through a venting extruder, and then casting or pressing the film, and -28 - 200900458 Perform TEM analysis and observation. Exfoliation can be carried out prior to combination with the polymer, after combination with the polymer, prior to combination with the polymer precursor, or after combination with the polymer precursor. In other words, the polymer or polymer precursor can be added to the first mixture (solvent and non-peeled nano-clay) or to the second mixture (solvent and exfoliated nano-clay). Thus, in a particular system, the stripping is carried out after combining the non-exfoliating nanoclay with a polymer such as polyimine. In other specific systems, the exfoliation is carried out prior to combination with the polyimine. In this system, the third mixture is formed by combining exfoliated nano clay with polyimine (or other polymer). The polyimine (or other polymer) may be pre-dissolved in a solvent (e.g., DM Ac or hydrazine) or directly added to the mixture comprising the exfoliated organic clay to provide a solids content in the range of 5 to 25 wt%. The polyimine (or other polymer) is at least partially dissolved in the solvent, and the citrate layer in the organic clay is further separated. The solvent is then at least partially removed from the third mixture. Alternatively, exfoliation occurs prior to merging with the polyamic acid solution (or other polymeric precursor) to provide a second mixture having a solids content of, for example, from 5 to 25 wt% solids. The polylysine solution is then polymerized as described above. In one system, polymerization occurs during removal of the solvent from the exfoliated nanoclay and polylysine compositions. The polyimine thus formed is at least partially dissolved in a solvent, and further separates the silicate layer in the organic clay. The solvent can then be removed continuously from the polyimide-organic clay composite. The silicate layer of organic clay remains separated after solvent removal. -29- 200900458 In another system, the polymer precursor is combined with the non-peelable organic clay in a solvent system prior to exposure of the mixture to the excitation conditions. The polymer precursor can be at least partially polymerized prior to stripping, during stripping, and/or after stripping to provide a polymer. The polymer thus formed is at least partially dissolved in a solvent, and further separates the silicate layer in the organic clay. The solvent is then removed at least partially to provide the polymer-organic clay composite composition. For example, the hydrazine dianhydride component and the organic diamine component and the organic clay are in a solvent system (eg, DM Ac ) to provide a solid having, for example, 2 to 15% by weight, or more specifically, 1 to 5% by weight. a mixture of solids solids. Sonicated organic clay and monomer to increase the initial d-spacing of organic clay. The organic clay and monomer mixture are then heat stripped to form polylysine. The polylysine thus formed is at least partially dissolved in a solvent. The polyamine acid is converted to the polyimine by at least partially removing the solvent from the second mixture. The polymerization of diamines and dianhydrides in the presence of organic clays was found to produce a good dispersion of organic clay. In another system, the organic clay is stripped prior to combining with the dianhydride component and the organic diamine component in a solvent system (eg, DM Ac ) to provide, for example, 2 to 15 wt% solids, or In particular, a mixture of solids content of 1 to 5% by weight solids. The dianhydride and the organic diamine are then polymerized to provide a poly-proline, and then a polyimine. The polyimine thus formed is at least partially dissolved in a solvent and further separates the silicate layer in the organic clay. The solvent is then at least partially removed from the polyaminic acid or polyamidiamine mixture. The silicate layer of organic clay remains separated after the solvent has been removed -30-200900458. Removal of the solvent in any of the foregoing systems can be accomplished by venting or precipitating in a non-solvent. The peeling was maintained after the solvent was removed. The resulting polymer-organic clay composition can be formed into a film by solution casting or melt extrusion. The use of organic clays (especially exfoliated organic clays) is found to provide unexpected advantages. The film comprising the organic clay may have a lower CTE than the film of the same composition without the organic clay. Alternatively, or in addition, the film containing the machine clay may have the same Tg as the film of the same composition without the organic clay. Films containing organic clay can also be transparent. The amount of organic clay used in the film will vary depending on the nature of the film desired. For example, the film may comprise from 0.1 to 10% by weight of organic clay, especially from i to 10% by weight of organic clay, based on the total weight of the film. A monomer (at least one dianhydride monomer and at least one diamine monomer) is added to the clay dispersion to form a modified polyaminic acid solution. Moreover, instead of adding polyamic acid to the clay dispersion, in another system, the dry film has a solution of 1% by weight in dimethylacetamide or N-methylpyrrolidone greater than 〇_05 Intrinsic viscosity of dl/g. The polyimine solution can then be combined with the clay dispersion and cast as described above. Another type of additive that can be used to reduce the CTE of the solvent cast polyimine film includes a soluble nanoparticle precursor such as aluminum (acetylacetonoate) 3 . Another additional filler which can be used to reduce the CTE of the solvent cast polyimine film is a metal oxide nanoparticle which can be formed from an organic-metal precursor. Metal oxide nanoparticles can be produced in situ by decomposing organometallic precursors -31 - 200900458. An example of such a material is (acetylthiopyruvate) 3 Ming ( ). The pyrolysis of (Al(acac)3) produces alumina. A12 Ο 3 nm when carried out in a dilute molecular solvent or polymer melt). Aligning the 1% by weight of the loaded ai2o3 and the diamine monomer in the final polymer (especially the oxydiphthalic anhydride and the diaminodiphenyl group were added to the precursor in advance. The obtained fluorene A1203 nanoparticle showed a ratio CTE less than 15% lower than the unfilled sample. In addition to the addition of the organometallic precursor to the polymer, the propolyamine solution or the finished soluble polyimine solvent is blended, polymer blended and extruded to produce An entanglement system in which a solution can be cast into a film and hardened to produce a entangled film. Other precursors include a metal (acac) complex, and a ceramic precursor molybdenum. Other types of additives for the CTE or properties of the film include enamels and fortifiers, glass, glass beads, flakes, etc. Minerals, ash, mica, kaolinite or microcrystalline kaolinite may be added. , fumed silica, perlite, quartz, and barite may also be used in an effective amount of an inorganic chelating agent, such as, for example, carbon fiber tubes, glass fibers, metal fibers, metal powders, conductive carbons, and agents including naphthalenes. Meter-grade The metal oxide can be added to the polymerization of the present invention. In some examples, the metal oxide can further improve the fire resistance (FR) performance by reducing heat release and increasing the release time.

The polymerization of the poly(acac)3 solution (small particle formation, in the dianhydride oxime) can be used with or in the finished product. ί Organic-gold, such as sulfur, such as fiberglass such as talc, white carbon. Compositions and nanoparticles are added to other additives. The peak heat release oxidation is -32- 200900458 I have to pay attention. Other metal oxides include zinc oxides, boron oxides, cerium oxides, iron oxides, and transition metal oxides. In some cases a white metal oxide is required. Metal oxides can be used alone or in combination with other metal oxides. The metal oxide can be used in any effective amount & in some examples from 0.01 to 20% by weight of the polymer. Other effective additives include smoke suppressants such as metal borates (e.g., zinc borate), alkali metal or alkaline earth metal borates or other borates. Additional boron-containing compounds, such as boric acid, borate esters, boron oxides or other boron oxygen compounds, may be useful. Additional flame retardant additives can be used, such as aryl phosphates and brominated aromatic compounds, including polymers comprising linkages made from brominated aryl compounds. Examples of the halogenated aromatic compound are brominated phenoxy resins, halogenated polystyrenes, guanidinium halides, brominated polycarbonates, brominated epoxy resins, and mixtures thereof. In some instances, a flame-retardant composition of substantially halogen-free atoms (especially bromine and chlorine) may be required. Substantially halogen-free atoms means that in some systems the composition has less than 3% halogen (especially chlorine and/or bromine), based on the weight of the composition, and in other systems less than 1% by weight of the composition contains a halogen atom' Especially chlorine and / or bromine. The amount of halogen atoms can be determined by ordinary chemical analysis. The composition may also optionally be included in the weight of the composition. 〇 1 to 5.0% by weight of the fluoropolymer of the fluoropolymer. The fluoropolymer can be used in any effective amount to provide anti-drip properties of the resin composition. Examples of suitable fluoropolymers and methods of making the fluoropolymers are disclosed in, for example, U.S. Patent Nos. 3,671,487, 3,723,373 and 3,383,092. Suitable fluoropolymer packages -33- 200900458 include homopolymers and copolymers comprising structural units derived from one or more fluorinated "-olefin monomers." The term "fluorinated alpha-olefin monomer" means an alpha-olefin monomer comprising at least one fluorine atom substituent. Some suitable fluorinated alpha-olefin monomers include, for example, fluoroethylenes such as, for example, cf2 = cf2, CHF = CF2, CH2 = CF2, and CH2 = CHF and fluoropropene such as, for example, cf3cf = cf2, cf3cf =chf , cf3ch=cf2 ' CF3CH-CH2 ' CF3CF = CHF ' CHF2CH = CHF ' fn CF3CF = CH2. Some suitable fluorinated a-olefin copolymers include copolymers comprising structural units derived from two or more fluorinated alpha-olefin monomers such as, for example, poly(tetrafluoroethylene-hexafluoroethylene), and the derivatives are derived from a copolymer of one or more fluorinated monomers and one or more structural units of a non-fluorinated monoethylenically unsaturated monomer copolymerized with a fluorinated monomer such as, for example, poly(tetrafluoroethylene-ethylene-propylene) Copolymer. Suitable non-fluorinated monoethylenically unsaturated monomers include, for example, alpha-olefin monomers such as, for example, ethylene, propylene, butylene, acrylate monomers such as, for example, methyl methacrylate, butyl acrylate, etc. Etc., and a poly(tetrafluoroethylene) homopolymer (PTFE) is preferred. Other additives which may be added to the solvent cast film include antioxidants such as phosphites, linoleic acid vinegars, and hindered benzoquinones. Phosphorus-containing stabilizers, including triaryl phosphites and aryl phosphonates, are noted as effective additives. Difunctional dish-containing compounds can also be used. Stabilizers having a molecular weight greater than or equal to 300 Daltons are preferred. Phosphorus-containing stabilizers having greater than or equal to 500 Daltons are useful in other examples. The phosphorus-containing stabilizer is typically present in the composition at from 0.5 to 0.5% by weight of the formulation. Also available are -34- 200900458 colorants as well as light stabilizers and UV absorbers. Flow aids and mold release compounds are also contemplated. Examples of the release agent are alkyl carboxylates such as pentaerythritol tetrastearate, glyceryl tristearate, and ethylene glycol distearate. The release agent and processing aid are typically present in the composition at from 0.5 to 0.5% by weight of the formulation. The preferred release agent will have a high molecular weight, typically greater than 300 Daltons, to prevent loss during melt processing if the release agent is from the molten polymer mixture. The composition used to form the article according to the invention also includes various additives such as nucleating agents, fining agents, stiffnessing agents and/or crystallization rate agents. These reagents can be used in conventional materials and in conventional amounts. The composition can be blended with the above ingredients by a variety of methods including uniform blending of the materials and additional additives required in any formulation. A preferred procedure involves solution blending, although melt blending can be used after the solvent cast film is made. Illustrative examples of equipment used in such melt processing methods include co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, disc-pack processors, and various other types The extrusion equipment. The liquid coating solution can be formed using the above polyimine composition and a film forming solution. Liquid coating solutions have many and different uses. The coating solution can be applied to various substrates using any suitable coating method (e.g., dipping, brushing, spraying, wiping, etc.), and thereafter heated to evaporate the solvent system and form a hardened polyetherimide resin coating. It is preferred to gradually increase the temperature to prepare a smooth resin coating. The polymerization and hardening are advantageously carried out at a temperature of from 125 ° C to 300 ° C or more. -35- 200900458 Polyammonic acid solution can also be used as a coating solution which can be prepared or stored immediately before use. In general, the maximum shelf life can be obtained by storing the solution in the absence of light in a nitrogen atmosphere. The polymers used to make the solvent cast film and coating are polyamidomines and in some specific examples are polyetherimine. The polyimines according to the present invention have the general formula (6):

Ο 0 ” a (6) wherein a is greater than 1, typically 10 to 1,000 or more, or more specifically 10 to 500; and wherein V is a tetravalent linker but is not limited as long as the linker does not hinder the poly Synthesis or use of amines. Suitable linkers include, but are not limited to, (a) substituted or unsubstituted saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, (b) having 1 to 3 0 A substituted or unsubstituted linear or branched saturated or unsaturated alkyl group of one carbon atom; or a composition comprising at least one of the foregoing. Suitable substituents and/or linkers include, but are not limited to, ethers, epoxides, amines, esters, and compositions comprising at least one of the foregoing. In a system, at least a portion of the linker V comprises a moiety derived from bisphenol. In another system, no linker V must contain a portion derived from a double enthalpy. Desirably, the linker includes, but is not limited to, a tetravalent aromatic group of the formula: -36-200900458)0〇c) wherein w is one including -〇-, -s-, -c(o)-, -so2-, a divalent moiety of -so-, -CyH2y- (y is an integer from 1 to 5), and a halogenated derivative thereof, including a perfluoroalkylene group, or a group of the formula -0-Z-0-, wherein The divalent bond of the -0- or -0-2-0- group is at the 3,3', 3,4', 4,3' or 4,4' position, and wherein Z is included but not limited to Divalent group =

Wherein Q includes, but is not limited to, one including -〇-, -S-, -C(0)-, -S02--37-200900458, -SO-, -CyH2y- (y is an integer from 1 to 5) a divalent moiety, and a halogenated derivative thereof, including a perfluoroalkylene group. R in the formula (6) includes, but is not limited to, a substituted or unsubstituted divalent organic group such as: (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof; (b) a linear or branched alkyl group having 2 to 20 carbon atoms; (c) a cycloalkyl group having 3 to 20 carbon atoms, or (d) a divalent group of the formula (7)

(7) wherein Q includes, but is not limited to, a divalent moiety comprising -〇-, -S-, -c(0)-, -so2-, -SO-, -CyH2y- (y is an integer from 1 to 5) And its halogenated derivatives, including perfluoroalkylene groups, typical classes of polyamidiamines include polyamidoximines and polyetherimines, especially such melt-processable polyethers The imines, such as their preparation and properties, are described in U.S. Patent Nos. 3,8,3, 〇8 5 and 3,9,5,9,42. Typical polyetherimide resins comprise more than one, typically from 1 to 1,000 or more specifically from 10 to 500, structural units of formula (8)

Wherein T is a group of -〇- or formula - 0-Z- 0-, wherein the -〇- or _〇_/_〇_yl-38-200900458 group has a divalent bond at 3,3', 3, 4, 4, 3, or 4, 4, position, and wherein Z includes, but is not limited to, a divalent group as described above. In one system, the polyether quinone imine may be a copolymer which additionally comprises a polyamidimide structural unit of the formula (9) in addition to the above-mentioned acid amide amine unit Ο 0

A A —Ν Μ ^Ν—R— Υ Ο Ο Ο (9) wherein R is as defined in the above formula (6) and μ includes (but is not limited to) the following groups:

H2n-r-nh2 (11) -39 200900458 wherein R and T are as defined in relation to the above formulas (6) and (8). Examples of specific aromatic bis(ether anhydride) and organic diamines are disclosed in, for example, U.S. Patent Nos. 3,972,902 and 4,45 5,410. Illustrative examples of dianhydride include = 2.2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)di Phenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Keto dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphoric dianhydride; 2.2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane Dihydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide Anhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ketone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenylphosphoric anhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxybenzene Oxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxybenzene Oxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ketone dianhydride; 4-(2 ,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl -40- 200900458 milled dianhydride; 1.3-bis(2,3-dicarboxyphenoxy)phthalic anhydride; 1,4-bis(2,3-dicarboxyphenoxy)phthalic anhydride; 1.3- double ( 3,4-dicarboxyphenoxy)phthalic anhydride; 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride; 3,3',4,4'-diphenyltetracarboxylic acid Anhydride; 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride; naphthalic dianhydrides, such as 2,3,6,7-naphthalenedihydride, etc.; 3,3',4,4 '-Biphenyl sulfonate ("1?11〇1^(〇tetracarboxylic dianhydride; 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; 3,3',4,4'-dimethyl Diphenyl decane tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy Diphenyltriamine; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride; 3,3',4,4'-biphenyltetracarboxylic dianhydride; Sulphur sulphate dianhydride; p-phenyl-bis(triphenylphosphonium) dianhydride; m-phenyl-bis(triphenylphosphonium) dianhydride; Phenylhydrazine)-4,4'-diphenyl ether dianhydride; bis(triphenylphosphonium)-4,4'-diphenylmethane dianhydride; , 2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-oxydiphthalic anhydride; pyromellitic dianhydride; 3,3',4,4'- Diphenyl maple tetracarboxylic acid dianhydride; -41 - 200900458 4',4'-bisphenol A dianhydride; hydroquinone dianhydride; 6,6'-bis(3,4-dicarboxyphenoxy)- 2,2',3,3'-tetrahydro-3,3,3',3' tris-tetramethyl-1,1'-spirobis[1H-indole] dianhydride; 7,7,-double (3,4-dicarboxyphenoxy)-3,3,,4,4,-tetrahydro-4,4,4,,4,-tetramethyl-2,2'-spiro[2H-1 -benzophenanthrene dianhydride; 1,1'-bis[1-(3,4-dicarboxyphenoxy)-2-methyl-4-phenyl]cyclohexane dianhydride; 3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride; 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride; 3,3',4,4'-diphenylarylene Tetracarboxylic acid dianhydride; 4,4'-oxydiphthalic anhydride; 3,4'-oxydiphthalic anhydride; 3,3'-oxydiphthalic anhydride; 3,3'-diphenyl ketone Tetracarboxylic acid dianhydride; 4,4'-carbonyldiphthalic anhydride; 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride; 2.2-bis(4-(3,3-dicarboxyphenyl) Propane dianhydride; 2.2-bis(4-(3,3-dicarboxyphenyl)hexafluoropropane dianhydride (3,3',4,4'-diphenyl)phenylphosphinetetracarboxylic dianhydride; (3,3',4,4'-diphenyl)phenylphosphine oxide tetracarboxylic dianhydride; , 2'-dichloro-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-dicyano-3,3',4,4'-biphenyltetracarboxylic dianhydride; -42- 200900458 2,2'-dibromo-3,3',4,4'-biphenyl Tetracarboxylic acid dianhydride 2,2'-diiodo-3,3',4,4'-biphenyltetracarboxylic dianhydride 2,2,-di. Trifluoromethyl_3,3',4,4'- Biphenyltetracarboxylic dianhydride; 2,2,-bis(;!_methyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride> 2,2,-double (1-Trifluoromethyl-2-phenyl)-3,3',4,4'-biphenyltetracarboxylic acid - 0T, 2,2,-bis(1-trifluoromethyl-3-phenyl) -3,3',4,4'-biphenyltetracarboxylic acid-O, 2,2,-bis(1-trifluoromethyl-4-phenyl)-3,3',4,4'-biphenyl Tetraformic acid--ST, 2,2,-bis(1-phenyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride 4.4 '-bisphenol A dianhydride; 3.4 '-bisphenol A dianhydride; 3,3 '-bisphenol A dianhydride; 3,3',4,4'-diphenylarylene Formic acid dianhydride; 4,4'-carbonyldiphthalic anhydride; 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride; 2,2'-bis(1,3-trifluoromethyl- 4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, and all of its isomers, as well as the foregoing combinations. The bis(ether anhydride) can be prepared by hydrolysis of a reaction product of a nitro-substituted phenyl dinitrile with a metal salt of a bisphenol compound (for example, BPA) in the presence of a dipolar aprotic solvent, followed by dehydration. . Typical classes of aromatic bis(ether anhydrides) included in the above formula (7-43-200900458) include, but are not limited to, wherein T has the formula (12);

〇— (12) a compound linked to an ether (for example) at the 3, 3 ', 3, 4 ', 4, 3 ' or 4, 4 ' position, and a mixture comprising at least one of the foregoing, and wherein Q is as described above definition. Any diamine based compound can be used. Examples of suitable compounds are: m-phenylenediamine; p-phenylenediamine; 2,4-diamine toluene; 2,6-diamine toluene; m-xylylenediamine; p-xylylenediamine; benzidine 3,3 '-dimethylbenzidine; 3,3'-dimethoxybenzidine; 1,5-diaminonaphthalene; bis(4-aminophenyl)methane; bis(4-aminophenyl) Propane; bis(4-aminophenyl) sulfide; bis(4-aminophenyl)anthracene; bis(4-aminophenyl)ether; -44- 200900458 4,4'-diaminodiphenylpropane 4,4'-diaminodiphenylmethane (4,4,-methylenediphenylamine); 4,4'-diaminodiphenyl sulfide; 4,4'-diaminodiphenyl Base, 4,4'-diaminodiphenyl ether (4,4,-oxydiphenylamine); 1,5-diaminonaphthalene; 3,3'dimethylbenzidine; 3-methyl Heptanediamine; 4,4-dimethylheptanediamine; 2,2,3,3'-tetrahydro-3,3,3',3,-tetramethyl-1,1,-spiro[ 1H-茚]-6,6,-diamine; 3,3,,4,4'-tetrahydro-4,4,4,,4,-tetramethyl-2,2,-spirobis[2H- 1-benzopyran]-7,7 '-diamine; 1,1'-biguanide-amino-2-methyl-4-phenyl]cyclohexane, and isomers thereof Comprising at least one of the mixtures and blends thereof. Desirably, the 'diamine-based compound is an aromatic diamine, particularly m- and p-phenylenediamine, and a mixture comprising at least one of the foregoing. In one system, the 'polyether phthalimide resin comprises a structural unit according to formula (8), wherein each R is independently a p-phenylene or meta-phenylene group or a mixture comprising at least one of the foregoing and T is a formula ( 13) Divalent group

Included in U.S. Patent Nos. 3,850,885, 3, 852, 242, 3, 855, 178, 3, 983, 093, 4, 443, 591, the disclosure of which is incorporated herein by reference. The reaction can be carried out using a solvent such as o-dichlorobenzene, m- or the like to cause a reaction between the formula ((1 1 ) diamine at a temperature of from 1 ° C to 250 ° C, and the chain is stopped. In the reaction of the agent and the branching. When using a poly(fluorene) containing an ether- and a non-ether-containing subunit, a dianhydride (for example, pyromellitic anhydride) and a bis(ether anhydride) combination imine can be optionally obtained from the aryl group. a bis(ether anhydride) and an organic limb, wherein the diamine is present in a molar excess of less than or equal to 0.2 molar. Under these conditions, the polyether quinone imide resin may have a small equivalent of one microgram per gram (micro equivalent weight) / gram) acid titratable group, or less than or equal to 1 〇 microequivalent per gram of acid titratable group, such as percent by weight (% by weight) of solution titration of hydrobromic acid in glacial acetic acid. The acid titratable group is essentially due to the amine end group in the polyacid. One of the synthetic polyamidiamine pathways has a squat! The bis (4-haloquinone imine) is carried out: 3,847,867, , and cresol/toluene, etc. 1 0) Anhydride and a formula can also be used for the use of an amine copolymer. Preparation of the reaction mixture of polyfluorene ί or equal to 1 5 , more particularly [has 33 weight: chloroform solution: quinone imine resin ί structure (1 4 )

Wherein R is as described above and X is a halogen. Among them, R is a bis(4-haloininimide) of 1,3-phenyl group as shown in (15), which is particularly useful.

X (15) bis(haloinin) (14) and (15) are typically employed by amines (eg, '1,3-diaminobenzene) and anhydrides (eg, 4 halophthalic anhydride (16) )) The condensation formed: 〇

(16) Polyether oximines may be obtained by the alkali metal salt of bis(haloinin) and bisphenol such as bisphenol A or the alkali metal salt of bisphenol and the base of another dihydroxy-substituted aromatic hydrocarbon The composition of the metal salt is synthesized in the presence or absence of a phase transfer catalyst. Suitable phase transfer catalysts are disclosed in U.S. Patent No. 5,229,4,82. Suitable dihydroxy-substituted aromatic hydrocarbons include those having the formula (17) H〇-A2-〇H (17) wherein A is a divalent aromatic hydrocarbon group. Suitable A2 groups include m-phenyl, p-phenyl, 4,4, biphenyl, and the like. As mentioned above, the poly-@55月安类' can' $ & open more than $丨容齐流* Μ % of the imine film. However, in a particular system, the polyimine film contains up to -47 to 200900458 to 50% by weight (especially up to 30% by weight) of recycled polyimine, wherein the recycled polyimide film is recovered prior to recovery. It has a glass transition temperature of 210 °C to 450 °C. In a system, the unused polyisoimine is melt mixed with a recycled polyimine (e.g., a film-forming polyimine). In another embodiment, the polyimine is not solvent mixed with the recovered polyimine (e.g., a film-forming polyimine as described above). The polyimine composition comprising recycled polyimine may then form a cast composition and, as described herein, for example, from a composition comprising from 1 to 30% by weight solids. In the foregoing system, the CTE containing the film of the recovered polyimine may be within ±10 PPm/°C of the film having the same composition without recovering the polyimide. - an alternative to producing a solvent cast film having a CTE of less than 70 ppm/°c, less than 60 ppm/°C in another system, or 'less than 35 ppm/°C in another system, possibly adding one An additional step to reduce the CTE of a solvent cast film having a CTE of 70 ppm/°C or more, 60 ppm/°C or more or 35 Cpm/°C or more in another system to 60 ppm/°C or less In another system less than 35 ppm/°C, especially less than 30 PPm/°C. The CTE of the solvent cast film can be reduced by biaxial stretching as described in U.S. Patent No. 5,460,890. Similarly, the CTE of the melt extruded film or the fully yttrium imidized solvent cast film can be reduced by thermal biaxial stretching as described in U.S. Patent No. 5,260,407. Those skilled in the art will be familiar with other known methods for lowering the CTE of polyimine films. For example, a film having a low in-plane CTE can be obtained from a polyimide resin composition because the resin exhibits partial crystallinity after annealing, and The crystal phase can be biaxially stretched in two directions after extrusion at -48-200900458. The film is then thermally fixed while confined to a frame, returning the amorphous portion of the film to a random unoriented configuration while preserving the alignment of the crystal phases (and also including more aligned crystalline regions). The alignment of the crystal phases produces a film with a low CTE. Since the amorphous portion of the material returns to its random state, the film will not exhibit shrinkage, even when it is above the Tg of the material. This can result in dimensionally stable films at flex fabrication temperatures because the crystalline regions are stable to temperatures above 400 °C. The film has high temperature residual properties due to the high Tg and partial crystallinity of the material. The Tg of the material is above the temperature of the float solder test, which also causes the material to remain in this test. The polymer crystals did not melt until the temperature exceeded 400 ° C, which was good above the temperature seen during soft manufacturing. Crystallization acts as an effective crosslink below Tm, and the materials are bonded together for high temperature residual. The crystallization kinetics of the compositions identified below were rather slow 'the material was melt extruded into a film before significant crystallization occurred. The film can then be thermally fixed above Tg to induce crystallinity. A wide range of monomers including 4,4'-oxydiphthalic anhydride (〇DPA), bisphenol A dianhydride (BPADA), m-phenylenediamine (mPD), and p-phenylenediamine (PPD) The polyetherimine copolymer shows that the film exhibits the desired partial crystallinity and high heat for the desired properties. The polymer can be capped with, for example, aniline. The scope of the present invention is particularly intended to include monomers and endcaps which are required to have partial crystallinity and to maintain processability. - A specific example may be 80-100% ODPA as a dianhydride and 30-100% pPD as a diamine, and 3.5-5% aniline as a blocking agent.

Varying these compositions changes the crystallization kinetics to achieve a desired balance that reduces the processability and achievable crystallinity of CTE-49-200900458. In a system, the optimum composition according to processability, ductility, slow crystallization kinetics, and maximum achievable crystallinity is a dianhydride component comprising 95% ODPA and 5% BP ADA, based on one equivalent, and A diamine component comprising 70% mPD and 3 % pPD, based on one equivalent, based on the total equivalents of the dianhydride component and the diamine component, together with 5% aniline. Very good film properties are obtained when a particular combination of dianhydrides is used, especially when a particular dianhydride is used in combination with a particular diamine. In the monolith, the dianhydride comprises 3,4'-oxydianic anhydride, 3,3'-oxydianic anhydride, 4,4'-oxydianic anhydride, and combinations thereof. In addition, additional dianhydrides may be present to adjust the properties of the film. However, in one system, the polyimine has less than 15 mole % of a structure derived from biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and members thereof. unit. Alternatively, the polyimines consist essentially of a combination of 3,4'-oxyphthalic anhydride, 3,3'-oxy-dianic anhydride, 4,4'-oxydianic anhydride, and combinations thereof. The dianhydride component is formed. In another system, the polyamidiamines are selected from the group consisting of 3,4'-oxydic phthalic anhydride, 3,3'-oxydianic anhydride, 4,4'-oxydianic anhydride, and combinations thereof. The composition of the dianhydride component is formed. Further, it was found that when the diamine component contains 4,4'-diaminodiphenyl maple, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydiphenylamine, 1,3_bis (4) When a combination of monoaminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and the like, a film having excellent properties is obtained. In a system, the 'diamine component consists essentially of 4,4,monodiaminodiphenylphosphonium, m-phenylenediamine, p-phenylenediamine, 4,4,monooxydiphenylamine, 1,3- Bis(4-monoaminophenoxy)-50-200900458 Benzene, 1,3-bis(3-aminophenoxy)benzene and combinations thereof. In another system, the 'diamine component consists of 4,4 'monodiaminodiphenyl maple, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydiphenylamine, 1,3_double (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy), and combinations thereof, and no other diamines are present. The poly-imines are further advantageously formed from the structural monolayers. The female component in January contains 4,4'-diaminodiphenylphosphonium, which is greater than or equal to 10 mol%, and the total molar amount of the diamine component is Benchmark. In one system, the diamine component comprises 10 to 1 mole % of 4,4'-diaminodiphenyl milling. Films can have a number of advantageous properties in addition to low CTE 'effective Tg, and low solvent retention. In one system, the film is stable, that is, after 24 hours of storage at 25t, the loss is less than 5% of its initial weight, especially after storage at 25 °C for 24 hours, the loss is less than 2% of its initial weight. In an unexpected feature, the inventors have discovered that polyimines, particularly polyetherimines containing units derived from specific diamines, can be formulated to exhibit a relatively fixed CTE while achieving from 220 to 375. Tg of °C. This result is unexpected because the 'CTE' typically changes linearly with Tg in a thermoplastic amorphous film. It is therefore possible to choose Tg while maintaining a specific CTE. The liquid coating solution, film casting solution, coating, and solvent cast film of the present invention have many and various uses. The coating solution can be applied to various substrates using any suitable coating method (eg, dipping, brushing, spraying, wiping, etc.) and thereafter heated to evaporate the solvent system and form a hardened poly-Asian-51 - 200900458 amine resin coating. And / or solvent cast film. The temperature is preferably gradually increased to produce a smooth resin coating. The polyimine-forming reaction is advantageously carried out at a temperature of from 1 25 to 450 C or more. Various substrates can be used, such as copper, ruthenium, aluminum, gold, silver, nickel, glass, ceramics, and polymers, including polymeric release layers. The first and second substrates having the same or different compositions may be disposed on opposite sides of the solvent cast polyimide film. In a system, the coating and casting solution is used to produce a laminate comprising a solvent-casting polyimide film comprising a conductive layer of a metal, wherein one side of the film is adhesively disposed on one side of the conductive layer. The conductive metal may be copper, silver, gold, aluminum or an alloy comprising at least one of the foregoing metals. In a particular system, the metal is copper and the solvent cast film thereof has a coefficient of thermal expansion of less than 35 ppm/t. In another system, the present coating and casting solution can be used to make a film of a circuit board (including a flexible circuit board). In this system, a solvent cast polyimide film is adhesively disposed on a conductive substrate, such as a metal layer such as a side of copper where the metal is tacted to provide circuitry. The second substrate (e.g., another layer of conductive metal such as copper, tantalum, aluminum, gold, silver or nickel) may be disposed on the film side opposite the first substrate. The flexible printed circuit may additionally comprise a dielectric layer comprising a second dielectric material of a non-film polyimine. Other specific articles that can be fabricated using solvent-casting polyimide membranes include capacitors, which in their simplest system contain solvent-casting polyimine disposed between two conductive layers (eg, two copper layers) membrane. In another system, the solution can be used as an enamelled wire lacquer to form a resin insulating coating on copper and aluminum wires. In this system, the polyimide film forms a coating around at least a portion of the radial surface of the wire on the conductive line -52-200900458. The solution can also be used as a varnish for coating or impregnating various substrates such as the aforementioned insulated wire coils (e.g., in motors and generator coils), as well as fabrics and non-wovens'. The solvent cast film of the present invention can also be used for flexible printed circuit board (FPC), chip on TFT (COF), and tape automated bonding (TAB) applications. The "object" may also include a s p e a k e r C ο n e , an audio tape and a label, a wire sleeve, and the like. [Embodiment] EXAMPLES Without further elaboration, the skilled artisan will be able to make and use the invention as described herein. The following examples are included to provide additional guidance to those skilled in the art to implement the claimed invention. These examples are provided as representative of the work and contribute to the teachings of the present invention. Therefore, the examples are not intended to limit the scope of the invention in any way. Unless otherwise indicated below, 'all parts are expressed in degrees Celsius by weight and all temperatures. The material ODPA is a dianhydride monomer, also known as 4,4'-oxy-dianic anhydride (CAS No. 1823-59-2), which can be produced as described in US 6,028,203, US 4,870,194 or US 5,〇21,168. . 〇DPA (99% purity) was obtained from Chriskev Corporation of Lenexa, Kansas, USA. BPDA is a bis-53-200900458 anhydride monomer, also known as 3,3',4,4,-biphenyltetracarboxylic dianhydride, commercially available from Chriskev, Inc., Leawood, Kansas. PMD A is a dianhydride monomer, also known as pyromellitic dianhydride, commercially available from Aldrich Chemical Company, Milwaukee, Wisconsin. BPADA is a dianhydride monomer also known as 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride commercially available from Aldrich Chemical Company, Wisconsin State Erwaji office. BTDA is a dianhydride monomer also known as 3,3'-diphenyl ketone tetracarboxylic dianhydride, which is commercially available from TCI, Portland, OR. BPhDA is also known as 4,4'-bis(3,4-dicarboxyphenoxy)

a dianhydride of a biphenyl dianhydride, which can be, for example, the Journal of Polymer Science, Polymer Chemical Edition (the Journal of P〇lymer Science, Polymer)

Chemistry Edition, 1 9 85 Manufactured as described in Volume 23 (6), No. 1 759.1 769 苜). DDS is a diamine monomer also known as 4,4'-diaminodiphenylphosphonium, which is commercially available from Chriskev's Leawood Office, Kansas. MPD is a diamine monomer, also known as m-phenylenediamine, which is commercially available from Aldrich Chemical Company, Milwaukee, Wisconsin. PPD is a diamine monomer, also known as p-phenylenediamine, which is commercially available from Aldrich Chemical Company, Milwaukee, Wisconsin. 0DA is a diamine monomer also known as 4,4'-oxydiphenylamine, -54-200900458 which is commercially available from Chriskev Corporation, Leawood, Kansas. 1,3,4—APB is a diamine monomer also known as 1,3-bis(4-aminophenoxy)benzene, which is commercially available from Chriskev, Inc., Leawood, Kan. 1,3,3 _ APB is a diamine monomer also known as 1,3-bis(3-aminophenoxy)benzene, which is commercially available from Chriskev, Inc., Leawood, Kan. TPPBr is a barium salt, also known as tetraphenyl rust, which is commercially available from Fluorochem, Inc., Old Glossop Office, England. Sodium microcrystalline kaolinite is an inorganic layered silicate which is commercially available from Sud-Chemie. Dusseldorf office, Germany. Bisphenol A dianhydride (BPADA) (97.7% purity) was obtained from GE Plastics. 2,4,6-triphenyl-pyrylium tetrafluoroborate, aniline, 4-phenoxyaniline, 4-isopropylphenylphenol, potassium carbonate, 1-fluoro-4-ninitro-benzene, palladium/carbon And ammonium formate were purchased from Aldrich. The examples were carried out in the following terms: DSC: Differential Scanning Thermal Method was performed on a Perkin Elmer DSC 7 at a heating rate of 20 ° C / min and glass transfer measurements on a second heating. This method is based on ASTM D 3 4 18 . DMA: Film samples that are precisely cut to produce known lengths, widths, and thicknesses on a dynamic mechanical analyzer with a tensile mode at a frequency of 1 Hz and a heating rate of 5 t / minute over a temperature range of 40 - 3 50 °C analysis. Dynamic Machine -55- 200900458 Mechanical Analysis (DMA) is performed in accordance with ASTM Test D5 026, with the exception that only one test sample is tested. The glass transition temperature (Tg) is determined by the maximum point of the tan 5 curve. TMA: The CTE tantalum of the cast film was applied to a thermomechanical analyzer at a heating rate of 5 ° C / min from 〇 1 250 on a tensile mechanical mode. (:Measurement. C TE値 is calculated from the slope in the range of 30 to 200 ° C. Balanced moisture: equilibrium moisture content is defined as being placed in the laboratory under ambient conditions for 72 hours (about 2 5 °) The moisture content of the film of C and 70% RH). The moisture content is accurately weighed by 10.2 cm χ1·27 cm χ63·5 μm (about 4 吋χθ.5吋χθ.0025吋) before and after drying. Sample measurement. Weigh the film (to 0.00005 g) at 150 ((: drying in an oven for 4 hours) and then weigh immediately to determine the moisture loss. The equilibrium moisture content is the mass loss during heating divided by the mass of the dried film. 〇 Hygroscopicity: Dry film samples of known quality (bake at 150 ° C for 4 hours) are submerged in water at ambient temperature for 72 hours (25 ° C). After this period of time 'from the water The film was removed and excess moisture was removed by drying with Kimwipe. The hygroscopicity is the percentage of the mass absorbed when immersed in water divided by the weight of the dried film. Solubility: Positive results are indicated at a concentration of 10% solids, obtained from poly(醯Amine acid) solution casting The ruthenium imidized film was dissolved in dimethylacetamide or N-methylpyrrolidone (the solvent indicated in the test) and passed through a 0.45 micron filter. -56- 200900458 Example 1, Part A Preparation of Organic Steps of upgrading clay (organic clay) The organically modified clay is prepared by ion exchange in water or water and alcohol or water. Na + MMT (clay with sodium relative ions) at 1 to 5 wt% In a dispersion/solvent composition, and heated to 80 ° C. The organic cation is liberated to such a degree that the ratio of the positive capacity of the dispersed cation of the organic cation is equal to or excessive when the solution or dispersion of the organic cation is dissolved or dispersed. The above water or solvent combination is then heated to reflux for 1 to 2 hours. Cooled to room temperature and collected by centrifugation. The supernatant is decanted, and the solid modified clay is redispersed in deionized water or deionized water. Collect again. Pour off the wash solution and repeat the washing process after two centrifugation, dry the solid clay in the oven and then Example 1, Part B detailed example: 2.0 g of Na + ΜΜΤ clay (Na + / gram of clay yang The sub-exchange capacity; 0.001852 sum) was dispersed in 200 ml of deionized water and ethanol and refluxed. Tetraphenyl bromine rust (1.4 1 6 7 mol) was added and the dispersion was stirred under reflux for two hours. Transfer to room temperature and transfer to four 50 ml centrifuge tubes. Rotate in a centrifuge at 3 000 rpm for 5 minutes. Pour off the supernatant and mix the fresh mixture of 5 0/5 0 deionized water and ethanol with acetonitrile. The concentration is in water or in water, and tetraphenyl bromide is added to the clay-dispersed ion exchanger. After the mixture, the modified clay is washed and borrowed by the above. At the most honed into a fine powder. 0.000926 Moer molar cation 5 0 / 5 0 mixture gram, 0.0022 1 6 The mixture is cooled until the tube is placed in a centrifuge, the clay is re-treated to wash the residue -57-200900458 solid, and the solid is collected again by centrifugation. Repeat the washing process twice or more. After the final centrifugation and decantation, the remaining solid was dried in an oven at 120 ° C for two hours and then honed to a fine powder. Table 1 shows the properties of organically modified microcrystalline kaolinite organic clay. Table 1 Modifier d-spacing (Angstrom) Modifier MW Weight loss at TGA at 900 °C at N ° (%) TGA 5% loss at N2 rc) at 400 ° C under N2 Weight loss in 30 minutes (%) TPP 9 17.8 339.4 25.0 449.0 3.1 Example 2 Solvent cast film containing polyimine-organic clay composite material The treatment of tetraphenyl squama obtained from Example 1 was carried out by means of sonic vibration treatment. Crystal kaolinite clay (TPP-MMT) is dispersed in NMP. Oxydiphenylamine (ODA) was added to the resulting solution and mechanically stirred at room temperature until the diamine was completely dissolved. Oxydipic dianhydride (ODPA) was then added to the solution and dispersed by mechanical stirring to form a solution of various poly(proline) in 20% by weight solids. The solution was allowed to react at room temperature for 12 hours. At 70. 〇 Cast the solution on a glass substrate and continue heating at 70 ° C for 2 hours, 150 ton: 4 hours, 200 ° C for 1 hour and 300 ° C for 1 hour. Aminated (imidized). The resulting nano-filled polyimide film was peeled off from the glass substrate for testing. The results are shown in Table 2. -58- 200900458 Table 2 Example No. Polymer Nano-Clay Weight % Citrate CTE% (ppm/°C) Second Scan (0-200) %CTE Reduction (Second Scan) Normalized d% CTE Reduction (Second scan) 2A 440DPA- 440DA te j\w 0 44.0 0% 2B 440DPA- 440DA is 3.8 39.4 11% 2.8% 2C 440DPA- 440DA is 7.5 37.2 15% 2.1% 2D 440DPA- 440DA is 15.0 30.9 30% 2.0 % Example 3 Preparation of (3-aminophenyl)triphenyl iodide scale (18)

Approximately 3 29.3 3 grams (1 _25 moles) of triphenylphosphine (PPh3), Pd (acetate) 2 (2.82 grams, 0.0126 moles) and 1600 milliliters of degassed xylene were added to the condenser, A mechanical stirrer and a gas inlet were placed in a 3 000 ml 3-neck round bottom flask. The mixture was stirred under argon until PPh3 dissolved. Meta-iodoaniline (about 27 5.00 g; 1.25 m) was added and the yellow-orange solution was refluxed for about 80 minutes. Separation of the yellow orange solid from the solution -59- 200900458 product scale compound ((3-aminophenyl) phenyl phenyl iodide). Avoid excessive reflux to prevent discoloration of the product scale compounds. The progress of the reaction was monitored using thin layer chromatography (TLC) with 0%...acetic acid 2 vinegar. After refluxing, the product was filtered. Production % 1 5 Re-formed the prize liquid with toluene and disturbed for 15 minutes. The solution was then filtered and rinsed with additional toluene/xylene. After drying for 20 hours in a 150 C vacuum oven, 585.01 g of an off-white product was obtained in 96% yield. The melting point and NMR data are consistent with the structure of the product. MP: 316. (TC.lH NMR (occupies, D6_dms〇) 8 - 6.6 (m, 19H, aromatic), 5.88 (S, 2H). Example 4 4·(4_isopropyl base)_本串| Preparation of base-駄 meal (19)

In a 3 liter flask, feed 4 cumylphenol (170.9 g, 0.80 mol), 4 nitroquinonitrile (150 g, 〇·87 mol), potassium carbonate (155.8 g, 1.13 mol), And dimethylformamide (1.4 liters). The solution was heated to about 90 ° C under nitrogen and stirred for about 1 〇 〇. The progress of the reaction was monitored by thin layer chromatography. The dark brown reaction mixture was cooled and 2M HCl solution (600 mL) was added and stirred. The organic layer was extracted with chloroform (3×300 mL). The chloroform layer was separated, and washed with water (3 &lt;&lt; 100 ml) and dried (MgSCU). The mixture was filtered and the solvent was evaporated on an oil bath at a temperature greater than ca. </ RTI> </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; 1H NMR ((5, D6-DMSO): 8.09 (d, 1H)

5 7.78 ( d &gt; 1Η ) , 7.40 — 7.15 (m, 8H) , 7.10(d, 2H ), 1 · 66 ( s, 6H, Me ). Example 5 Preparation of 4·(4-isopropylphenyl)phenoxy-phthalic anhydride (20)

A 3 liter 3-neck round bottom flask was fitted with a condenser, mechanical stirrer and addition funnel. The flask was charged with 4-(4-isopropylidenephenoxy)-indenenitrile (278 g, 〇82 mol) and acetic acid (1.6 L). The addition funnel was filled with 70% sulfuric acid (670 mL). The solution was heated to 12 (TC, and then sulfuric acid was added dropwise to the reaction mixture over 2 hours. The resulting mixture was refluxed overnight (12 hours). The reaction mixture was cooled to room temperature and poured into ice-water mixture ( About 1 kg). The product was extracted with ethyl acetate (3×300 mL). The ethyl acetate layer was separated and dried over anhydrous MgS04. The solution was filtered to remove MgS〇4 and the solvent was removed on a rotary evaporator. Dry overnight at 1600 ° C. This gave the desired viscous brown oil anhydride (17) (276 g, 94% yield) NMR (5, d6-DMs): 7.96 (d, lH), 7_50 - 7.20 (m, 9H) , 7. 〇 3 (d, 2H) , 1 _ 76 ( s, 6H, Me ). -61 - 200900458 Example 6 Synthesis of cumene PA-mATPP-I ( 21)

66.27 g (0.1848 mol) of 4-(4-isopropylphenyl)phenoxy-phthalic anhydride and 88.97 g (0.1848 m) were charged in a 500 ml glass reaction vessel equipped with a mechanical stirrer, nitrogen inlet and gas outlet. 3-aminophenyl) Triphenyl iodide scale (mATPP iodide). The vessel was then placed in a heating mantle and heated to about 300 °C to produce a molten reaction mixture. After stirring for about three minutes, a vacuum was applied to remove water formed as a by-product, and after about 15 minutes total reaction time, the reaction mixture was poured into a Teflon disk and cooled to provide smoothing of compound (18) (145.19 g, 95.6%). Brown glass. h NMR ((5 ' D6-DMSO): 8.07 - 7.0 8 (3 1H, aromatic)' 1.68 (s '6H).

Example 6A Substituted one-pot method (One Pot) of cumene PA-mATPP-I (18) The reagent, m-aminotetraphenyl iodine rust 22.14 g (0.046 mol) and 4-chloro 8.80 g (0.046) gram of anhydride and added to Dean-

Stark cold condenser 25 liters in a round bottom flask and dissolved in 150 ml -62- 200900458 o-dichlorobenzene. The contents were heated to reflux and the water was removed by azeotropic distillation and nitrogen flushing. After 4 hours under reflux, 10.78 g of sodium cumylphenolate (0.046 mol) was added and the contents were stirred and heated for another 4 hours. After cooling to room temperature, the solution was poured into 400 ml of diethyl ether and the obtained solid was collected by vacuum filtration. The solid was dissolved in 1 mL of chloroform and the resulting solution was poured into 300 ml of diethyl ether. The resulting solid was collected by vacuum filtration and dried under vacuum overnight. 13c-nmr is consistent with the structure. Total yield: about 60%. Example 7 Synthesis of BPADAPA-mATPP-I (22)

About 58.0 g (0.1114 mol) of bisphenol a dianhydride (BPADA) and 107.27 g (0.2229 mol) of 3-aminophenyl)triphenyl iodide scale (m A T P P -1 ) 1 were shaken. The dried mixture was then added to a glass reaction flask using a long paper funnel to prevent the reagent from sticking to the upper interior of the flask. The reaction flask was evacuated and mounted twice with nitrogen. Turn on the external heater and set it at approximately 300 °C. When the reagent melts, a brown solution is formed. After the reagent has been melted for 3-5 minutes, the reaction flask is evacuated to remove water. The pressure was initially set to 600 mbar (mb) and continuously reduced to 1 〇 mb. When the reaction is complete, the pressure will be set back to 1 〇〇〇 mb and the stirrer is turned off. The product diiron bis-63- 200900458 glaze quinone imine (19) was cooled to yield 158.48 g (98.28 %) of brown glass. NMR (5, D6-DMSO): 8. 1 - 7. 1 (m, 52H' aryl), 1.73 (s, 6H). Example 8 Synthesis of 4-(4-Phenylphenoxy)-phthalonitrile

4-nitrophthalonitrile 4-(4-phenylphenoxy)-phthalonitrile The 1 liter 3-neck round bottom flask was charged with 4-phenylphenol (45.7 g 0.27 mol), 4-nitroguanonitrile (50 g, 0.29 mol), carbonic acid (51.9 g, 0.38 mol), and dimethylformamide (470 ml). The resulting solution was heated under nitrogen and stirred to 90 ° C for 1.5 hours (and vice versa) Can be monitored by TLC). The dark brown reaction mixture was then poured into 2M aqueous HCl (3 mL) and stirred. The product was light brown and finally sank. The powder was collected by filtration and dried in a vacuum oven at 15 C to give the desired product (71 g, 94% yield). iH NMR (&gt; D6-DMSO): 8.13 (d'lH) '7_87(d'lH) &gt; 7.80 d'2H) '7.70(d'2H), 7.55 - 7.35 (m'4H), 7· ( d, 2 H ). Synthesis of 4-(4-phenylphenoxy)-phthalic anhydride Potassium 〇 should be powdered dry δ ( -64 - 30 200900458

A 1 liter 3-neck round bottom flask was fitted with a condenser, mechanical stirrer, and addition funnel. The flask was charged with 4-(4-phenylphenoxy)-phthalonitrile (71 g '0.24 mol) and acetic acid (450 ml). The addition funnel was filled with 70% sulfuric acid (200 mL). The solution was heated to 120 ° C ' and then sulfuric acid was added dropwise to the reaction mixture over 2 hours. The resulting mixture was refluxed overnight (12 h). The reaction mixture was cooled to room temperature&apos; and poured into an ice-water mixture (~1 kg). The product precipitated as a light brown powder. The powder was collected by hydrazine and purified by recrystallization using acetic anhydride (25 5 ml). The crystals were collected by filtration and placed under vacuum in a vacuum oven. (: Dry overnight to give the desired product (75.0 g, 99% yield). MP 199 ° C. NMR ( &lt;5, D6-DMSO): 8.11 (d, 1 Η ), 7.82 ( d &gt; 2H ) , 7.71(d,2H) , 7.58(dd,lH) , 7.55 —7.35 ( m,4H ) , 7_30 ( d,2H ). Synthesis of biphenyl PA-mATPP-I modifier

Install a 250 ml glass reaction vessel with a mechanical stirrer 'nitrogen inlet and -65- 200900458 gas outlet. 4-(4-Phenylphenoxy)-phthalic anhydride (15·8 g, 0.050 旲) and mATPP-I (24.0 g, 0.050 mol) were added thereto. The container was then placed in a heating mantle and heated to 3 Torr (rc. When the reagent started to melt/dissolve, the reaction was allowed to stir only. After the molten reagent was stirred for three minutes, 'vacuum was applied to remove water by-products. 1 5 minutes total After the reaction time, the brown liquid product was poured into a teflon (t Η 〇n) tray which was then cooled to form a smooth brown glassy solid. The reaction produced 3 6.3 g of product, yielding 93% yield. 4 NMR ( &lt; 5, D6-DMSO): 8.10 — 7.25 ( m &gt; 3 1 Η ). Example 9-12 General procedure for the preparation of organic clay compositions. Inorganic clay (Nano-Mingjingshan, "Na-MMT", available From Southern Clay, Inc., slurried in 75 volumes of deionized water ("M i 11 i Q water"), relative to the weight of the clay and stirred at room temperature (22 - 25 ° C) Stir for 1 hour and then at 90-95 ° C for 1 hour. The solution of the organic scale salt from Example 36 in methanol or acetonitrile was then added portionwise to a slurry of inorganic clay and stirred at 65-95 °C. The reaction material is 18 to 20 hours. Once cooled, the crude organic clay composition is filtered and washed. The washing liquid was free of halides and then dried to a fixed weight at 125 _ 150 ° C to produce the structure shown in Table 3. -66- 200900458 Table 3 Example No. Structure 9 0 MMT- 10 ΧΧ〇χ(ΧΧΧ}χ) Γν ° ° ΜΜΤ- 11 9 *3 ^ ΜΜΤ- 12 ^ ΜΜΤ- Example 12 Special steps for the synthesis of biphenyl PA-mATPP-MMT

Biphenyl PA-mATPP-I: MW = 779.6 A 3 liter round bottom flask equipped with a mechanical stirrer was charged with sodium microcrystalline kaolinite (20 g, 0.021 mol equivalent) and deionized water (1.6 L). Dissolve -67-200900458 liquid scramble &amp; to 85 ° C, and uniformly disperse sodium microcrystalline kaolinite. A solution of biphenylPA-mATPP-I (1.79 g, 〇_〇 23 mol) in acetonitrile (3 60 ml) at 60 ° C was added to a suspension of sodium microcrystalline kaolinite over 1 min. After the addition of the salt solution, the reaction mixture was stirred at 85 ° C for another 3 hours. The modified microcrystalline kaolinite was collected by filtration, and washed with hot water (2 liters, 80 ° C) to remove inorganic salt impurities. The modified clay was further purified by redispersing it in acetonitrile (1.5 liters) at 60 t: followed by removal of excess pyridinium salt by filtration. The purified clay was dried in a vacuum at 150 ° C for 24 hours and honed to give a fine powder (27.9 g, S8% yield). Example 1 3 - 2 1 Solution Peeling of Modified Organic Clay Examples 1 3 - 2 1 were prepared using the following records. The modified nano citrate sample was suspended in 25 grams of solvent with 4·6 wt% of the sulphate. The sample was homogenized for 1 〇 minutes using a rotor-stator homogenizer with a 1〇111111 serrated tip (UP) at approximately 9, 〇〇〇RPM. After homogenization, the sample showed uniform dispersion. The sonicated sound was then sonicated for 10 minutes using a Sonics VCF 1500 W sonic vibrator equipped with a 1/2" sonic horn. XRD analysis was performed on a sonicated nanocaprate/solvent mixture ( See Table 4) -68- 200900458 Table 4: Increase in d-spacing of nano-clay in solvent Example No. Modifier / Clay system Solvent dry powder d-spacing (Angstrom) d-spacing after homogenization (Angstrom) D-spacing after sonication (10) 13 9 anisole 17.8 18.7 majority/complete stripping 14 9 NMP 17.8 85, 18.5 small peak at 18.5 15 9 DMAc 17.8 18.5 78, 51, at 18.5 small peak 16 9 cucurbit ether 17.8 86,60 peaks&gt;40 17 8 anisole 27 64,40 29 18 8 NMP 27 49 ' 31 ' 27 60,52,45 19 7 cucurbit ether 25.5 83,65,46,32 mostly/completely stripped 20 10 anisole 25 &gt; 50 at 29 small peaks, some Igr peaks 21 10 cucurbit ether 25 many &gt;28 many &gt;28 examples 2 2 - 3 7 PEI nanocomposite formation to form polyether quinone Typical steps for nanocomposites are as follows. Samples from Experiments 1 1 - 19 will be taken. The product was suspended in a polyether oxime solution. The solvent was quickly removed at 400 ° C, the film was pressed from these composites, and subjected to TEM analysis (see Table 2 and Table 3). Various modified nano 矽A clear difference in the degree of exfoliation was observed between the acid salts. No significant differences in TEM images were observed between the different types of PEI or different solvents studied. Example 3 8 - 4 9 Solvent-blended PEI nanocomposites Film Extrusion For the film extrusion of this material, several batches of the cation-69-200900458 sub/clay from Experiment 7 were sonicated in the cucurbit ether. Each batch was contained in 500 ml 藜. 2.7% modified nano citrate in lye. These mixtures were sonicated in a 1000 ml round bottom flask immersed in a water bath using a Branson 450W sonic shredder mounted on a ~40% power output Η sonic probe. Sonicated for about 16 hours. Processed and combined five batches. This material was blended with a 20% by weight solution of BPADA-DDS polyetherimine in veratrol. Then in a blender in the presence of methanol Precipitate this mixture in a vacuum oven at 220 °C Drying to remove the solvent, the ratio of BPADA-DDS polyether quinone imide: ODPA-DDS polyether quinone imide described in Table 4 is blended with ODPA-DDS polyether phthalimide, and is equipped with aeration/processing The screw and the 3-inch film mold were extruded into a film in a 16 mm PRISM extruder. The resin composition was fed at a rate of about 0.5 pounds per hour. The screw speed was set at 2 0 0 r p m 'the barrel temperature was 370 ° C, and the film mold temperature was 380 ° C. In Examples 3-7-46, ODPA-DDS polyetherimine was blended and extruded with precipitated nano-mineralized BPADA-DDS polyetherimine. In Example 36 and Example 47, the &apos;ODPA-DDS polyetherimine was first extruded once prior to blending with the precipitated nano-mineralized BPADA-DDS polyetherimine. Then squeeze the mixture a second time. -70- 200900458 ^ bO mm (N 226 262.8 252 1- :267 260 258 266 CTETD 50.92 41.76 cn uo 36.04 ΓΛ U-) 1- 43.09 39.72 39.52 32.75 CTEMD 58.2 48.68 38.41 48.51 33.02 m 45.95 38.88 38.54 28.7 TEM Μ 蝈s ^ g ^ § 13⁄4 3 ^ 彳尘名尘^ m &lt;m 〇mm K 0:100 0:100 31:69 31:69 60:40 60:40 60:40 60:40 60:40 60 :40 60:40 铤μ Q QQ bubble&lt;mgm 〇 二次 二次 二次 一次 — — — — — 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次Squeeze once extrusion, secondary extrusion, 4n g狴, l; 9 13⁄4 Ϊ Can S _ _ w ^ mh in 〇〇yri in Modification / Clay system, Bub, Bub, final weight % bismuth 〇 〇〇〇m in ο 卜卜卜 00 Os cn 〇1—1 9 CO 5 -71 - 200900458 Figure 3 shows the TEM evidence for the solvent removal method (in non-solvent) as in the direct venting method. The resulting film had a 7% nanocaprate loading, a machine direction CTE of 33.0 ppm/°C, and a Tg of 25 5 °C. A film having the same ratio of BPADA-DDS polyether quinone to the 0DPA-DDS polyether quinone having no clay has a longitudinal C TE of 48.5 ppm/°C and a Tg of 262 °C. The film was also extruded with a 6 0:400 BPADA-DDS polyether quinone imine: ODPA-DDS polyether quinone and a 7% nano citrate loading. The film had a longitudinal CTE of 2 8.7 ppm/°C and a Tg of 26 6 °C. Example 50 Preparation of a PEI Nanocomposite Using a Sonic Vibrator The sonication treatment in a flow cell has also been shown to be effective in the exfoliation of Example 7 nanocaprate in veratroxe. Advanced Sonics DRC-4-DPP-Hastelloy with a SAE-DRC-DPP dual-frequency reaction cell sonic vibrator was used to sonicate a 2.7% solution of the nanosalt from Experiment 7 in 500 ml of cucurbitic acid. ). The nanocaprate/cucurbit ether mixture was pumped through the sonic vibrator at 10 ml/min and passed through one at a time. Twenty-five passes were made, and the total time in the sonic zone of the flow cell reactor was 37.5 minutes. The sonicated nano citrate/cucurbit ether mixture was suspended in 20% BPADA-DDS polyether quinone solution in veratrol, precipitated in methanol, and placed in a vacuum oven at 220 °C. The excess solvent was removed, pressed into a film, and peeled off by TEM analysis. Figure 4 shows a sonicated experiment in a flow cell. 7 nm-72-200900458 A film made of tantalate is applied to a film made in Experiment 7 using a sonicated probe sonicator in batch mode. Comparison. These two methods produce the same result by TEM. Example 51 Detailed Description of Solvent Cast Films with Nano-Condensation for Reducing CTE Dispersion of Southern Clay Cloisite 30B Clay in N, N- by High Shear Mixing Using a Silverson Mixer In dimethylacetamide (DMAc) (13 grams of clay in 5001 ml of solvent). Adding monomer, 4,4'-oxydianic anhydride (0.5640 g), 4,4-diaminodiphenylphosphonium (0.3611 g), and oxydiphenylamine (0.0903 g) to the clay dispersion The mixture was diluted with additional DM Ac to yield a final mixture of 12.5 % solids (polymer to solvent) and 3 % hydrazine (clay versus polymer). The vials were inertized with N2 and shaken overnight to form various polyamine solutions. This solution was then cast on a pre-clean glass slide and imidized using the aforementioned heating profile. The resulting nano-imide-coated polyimide film was peeled off from the glass substrate for testing. The resulting film had a CTE of Tg = 3 04 ° C and 44 ppm / ° C. All of the patents, patent applications, and other publications disclosed herein are hereby incorporated by reference in their entirety in their entirety in their entirety. While the present invention has been described with reference to the preferred embodiments of the present invention, it should be understood that In addition, many modifications may be made to the teachings of the present invention - 73- 200900458 without adapting to particular circumstances or materials without departing from the scope. Therefore, the invention is not intended to be limited to the particular embodiments disclosed herein, and the invention is intended to include all of the embodiments within the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a transmission electron microscope (TEM) image of a modified nanocitrate that is sonicated and suspended in various polyether oximines in verat ether. . Figure 2 shows a TEM image of a modified nanocitrate which is sonicated in various solvents and suspended in various polyether oximines. Figure 3 shows a TEM image of a modified nanocitrate which is sonicated in various solvents and suspended in various polyether oximines. Figure 4 shows an equivalent TEM image illustrating the peeling between the venting and the precipitation single path. Figure 5 shows a TEM comparison of cumene-modified nanocitrate which is sonicated in a flow cell sonic vibrator and a probe-type sonic vibrator. -74-

Claims (1)

200900458 X. Patent application scope 1. A method for preparing a polymer-organic clay composite composition, comprising: combining a solvent and a non-exfoliating organic clay to provide a first mixture, wherein the non-peeling Type of organic clay comprising alternating inorganic citrate layers and organic layers with a preliminary spacing between the citrate layers&gt; exposing the first mixture to sufficient strength and period of excitation to increase the initial between inorganic silicate layers a spacing to provide a second mixture&gt; contacting the second mixture with the polymer composition such that the polymer composition is filled with at least one region between at least one pair of tantalate layers, wherein the polymer The composition is at least partially dissolved in the solvent; and at least a portion of the solvent is removed from the second mixture, wherein the inorganic silicate layer remains separated by the polymer after removal of the solvent. 2. The method of claim 1, wherein the excitation condition is generated by an acoustic energy source. 3. The method of claim 2, wherein the source of the acoustic energy is an ultrasonic liquid processor. 4. The method of claim 1, wherein the excitation condition is produced by a high shear mixer. 5. The method of any one of claims 1 to 4 wherein the energy has sufficient strength and duration to produce a net increase in the initial d-spacing of the organic clay. The method of any one of claims 1 to 4, wherein the first mixture is exposed to an amount sufficient to increase the initial spacing of the inorganic bismuth layer from 5 angstroms to 90 angstroms. Intensity and period of excitation conditions. 7. The method of any one of claims 1 to 4 wherein the increase in the initial spacing of the inorganic sulphate layer results in a random spacing of the inorganic sulphate layer. 8. The method of any one of claims 1 to 4, wherein the net increase in the initial d-spacing of the organic clay is from about 10 to about 500 percent 〇9. As claimed in the first 1-4 The method according to any one of the preceding claims, wherein the organic clay further comprises a fourth-order organic cation of the formula (1): R9 R8—Q—R10 I R7 (1) wherein Q is nitrogen or phosphorus; and R7, R8, R9 and R1 () is independently a Ci-Cw aliphatic hydrocarbon group, a C5-C2Q cycloaliphatic hydrocarbon group, a C2-C2Q aromatic group or a polymer chain. The method of claim 9, wherein the quaternary organic cation is a quaternary cation. 11. The method of claim 9, wherein the quaternary organic cation is a quaternary ammonium cation. 12. The method of any one of claims 1 to 4, wherein the organic clay further comprises a quaternary iron cation of formula (2): -76- 200900458 -R2 wherein Ar1 is independently from 1 to about C2-C20 aryl, c6-c50 13. The organic of which is Ar1 and Ar16 | 14. The organic r3 〇7(2), Ar2, Ar3 and Ar4 are independently a C6-C5 〇 aromatic group; "a" is a number of 00; "c" is a number from 0 to 3; R1 Each occurrence of a halogen atom, a C^-Cm aliphatic hydrocarbon group, a C5-C2 anthracycline or a group; and R2 is a C^-Cu aliphatic hydrocarbon group, a C5-C2 anthracycline aromatic group or a polymer chain . The method of any one of claims 1 to 4, wherein the clay further comprises a quaternary cation of formula (3): j1'4 〇Ar13-P-At15-^-Ai16 Ar12 (3) Human 1&quot;13, 八^4, and 八1'15 are independently a C6-C5G# group; i c6-c2 〇 «3 aromatic group or a polymer containing at least one aromatic group as claimed in claim 1 In one of the four methods, the clay further comprises a pyridinium cation of formula (4): Wherein the number of Ar6 2; the group, C5-C, Ar7 and Ar8 are independently a C6-C5G aromatic group; "b" from 0 to R3 is independently a halogen atom, C^-Cm aliphatic hydrocarbon 2 at each occurrence. An anthracene cycloaliphatic group or a C2-C2Q aromatic group; and Ar11 is a C6-C200-77-200900458 aromatic group, or a polymer chain comprising at least one aromatic group. 15. The method of claim 14, wherein the organic clay further comprises a quaternary pyridinium cation of formula (5): Wherein Ar6, Ar7 and Ar8 are independently C6-C5〇 aromatic groups; "b" is from 0 to 2; "d" is from 〇 to 4; R3 and R4 are independently halogen atoms at each occurrence. , G-Cm aliphatic hydrocarbon group, C5-C2G cycloaliphatic hydrocarbon group or C6-C2 fluorene aromatic group; Z is bonded, divalent Ci-C^ aliphatic hydrocarbon group, divalent C5-C2G cycloaliphatic hydrocarbon group, divalent C6-C2G An aromatic group, an oxygen bond group, a sulfur bond group, an S02 bond group or a Se bond group; and Ar9 is a C1Q-C2()() aromatic group or a polymer chain containing at least one aromatic group. The method of any one of claims 1 to 4, wherein the inorganic silicate layer is derived from a group selected from the group consisting of kaolinite, dickite, perlite, sapphire, serpentine, serpentine , pyrophyllite, microcrystalline kaolinite, aluminum bentonite, iron bentonite, saponite, saponite, strontite, hectorite, tetrasilylic mica, sodium band mica, muscovite, pearl mica, Inorganic clays of talc, vermiculite, phlogopite, green-clay mica, chlorite, synthetic silicates or combinations thereof. The method of any one of claims 1 to 4, wherein the solvent is selected from the group consisting of hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, hydrazine-methyl Pyrrolidone, dimethyl arsenide, cyclobutyl milling, tetrahydrofuran, diphenyl ketone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, -78- 200900458 phenol, acetol , isopropyl phenol, tert-butyl phenol, xylenol, 2,4,6-trimethylphenol, chlorophenol, dichlorophenol, phenylphenol, ethylene having from 1 to about 4 carbon atoms in the alkyl group a monoalkyl ether of an alcohol, a monoalkyl ether having a diethylene glycol of 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, a tetramethyl urea, a phenoxy group Ethanol, propylene glycol phenyl ether, anisole, cucurbit ether, o-dichlorobenzene, chlorobenzene, trichloroethane, dichloromethane, chloroform, pyridine, N-cyclohexylpyrrolidone, ethyl lactate, ionic liquid Or a combination of them. The method of any one of claims 1 to 4, wherein the polymer-organic clay composite comprises a material selected from the group consisting of polyvinyl chloride, polyolefin, polyester, polyamine, poly maple, polyphthalamide Amine, polyether phthalimide, polyether oxime, polyphenylene sulfide, polyether ketone, polyether ether ketone, acrylonitrile-butadiene-styrene, polystyrene, polybutadiene, polyacrylate, polyalkane Acrylate, polyacrylonitrile, polyacetal, polycarbonate, polyphenylene ether, ethylene-vinyl ethyl ester copolymer, polyethylene ethyl ester, liquid crystal polymer, aromatic polyester, ethylene-tetrafluoroethylene copolymer, A polymer of polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, or a combination comprising at least one of the foregoing polymers. The method of claim 18, wherein the polymer-organic clay comprises a polyether oxime. The method of claim 18, wherein the polymer-organic clay composite comprises polyimine. The method of claim 18, wherein the polymer-organic clay composite comprises polyetherimine. -79- 200900458 22. The method of claim 18, wherein the polymer-organic clay composite comprises polyetherketone. The method of any one of claims 1 to 4 wherein the polymer-organic clay composite comprises a polymer having a glass transition temperature of from about 180 ° C to about 450 ° C. . 24. The method of any one of claims 1 to 4 wherein at least a portion of the solvent is removed in a venting extruder. 25. A method of preparing a polymer-organic clay composite composition, the method comprising: combining a solvent and a non-exfoliated organic clay to provide a first mixture, wherein the organic clay comprises alternating inorganic a citrate layer and an organic layer, and a quaternary organic cation of the formula (1) R9 R8—Q^-R10 I R7 (1) wherein Q is phosphorus or nitrogen; and R7, R8, R9 and R1() are independently Heart-(: 20 aliphatic hydrocarbon group, c5-c2G cycloaliphatic hydrocarbon group, c2-c2Q aromatic group or polymer chain, and the organic clay additionally has an initial spacing between the citrate layers; exposing the first mixture to the excitation condition Forming a second mixture, wherein the excitation condition has sufficient strength and a period of time to produce a net increase in the initial spacing between the inorganic silicate layers; the second mixture is separated from the inorganic bismuth layer The polyimide is contacted to form a third mixture, wherein the polyimine is at least partially dissolved in the solvent; and at least a portion of the solvent is removed from the third mixture, wherein after the dissolution of -80-200900458 agent is removed矽The acid salt layer is kept separated by the polymer. 2 6 The method of claim 25, wherein the solvent is removed in a venting extruder. 27 - an object comprising a patent application scope The polymer-organic clay composite prepared by the method of any one of the items 1 to 24. The object of claim 27, which is in the form of a film having a thickness of 0.1 to 1000 μm. The article of any one of claims 2-7 to 28, wherein the film is a solvent cast film. 30. A method for preparing a polymer-organic clay composite comprising a solvent and An unexfoliated organic clay to form a first mixture, wherein the organic clay comprises alternating inorganic silicate layers and an organic layer with an initial spacing between the citrate layers; exposing the first mixture to sufficient Strength and duration of the excitation conditions to increase the initial spacing between the inorganic silicate layers to form a second mixture; contacting the first or second mixture with the polymer precursor; The precursor polymerizes to form a polymer; and at least a portion of the solvent is removed from the second mixture, wherein the inorganic citrate layer remains separated by the polymer after removal of the solvent. 31 - Method of claim 30 Wherein the polymerization occurs at least partially during the exposure. 32. The method of claim 30, wherein the polymerization system -81 - 200900458 occurs at least partially after exposure. 33. The method of claim 30 And wherein the polymerization is carried out at least in part during the removal of the solvent. The method of any one of claims 3 to 3, wherein the polymer precursor is polylysine. The method of any one of the above-mentioned claims, wherein the polymer precursor comprises a dianhydride component and a diamine component. 3 6 · A method for preparing a polymer-organic clay composite comprising: a combined solvent, a non-peeling organic clay, a dianhydride component, and a diamine component to form a first mixture, wherein the organic clay comprises The alternating inorganic sulphate layer and the organic layer have an initial spacing between the silicate layers; exposing the first mixture to a sufficient strength and during the excitation conditions to increase the initial spacing between the inorganic silicate layers, thereby forming a The two mixtures t polymerize the dianhydride component and the diamine component to form poly-proline; and remove at least a portion of the solvent from the polyamid acid mixture to provide a polyimine, wherein the inorganic silicate layer remains after removal of the solvent Separated by the polyimine. -82- 200900458 七无• 明图说) Single 1 Jane C No. ^ For the generation of map elements, the map refers to the table: the representative of the case, the table, the generation /-•'N fixed one two eight, this case When there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: Formula (1) R9 R8—Q—R10 I R7 (1) -4-