TW200900452A - Compositions and methods for polymer composites - Google Patents

Abstract

This invention relates to organic salt compositions useful in the preparation of organoclay compositions, polymer-organoclay composite compositions, and methods for the preparation of polymer nanocomposites. In one embodiment, the present invention provides a polymer-organoclay composite composition comprising (a) a polymeric resin; and (b) an organoclay composition comprising altemating inorganic silicate layers and organic layers, said organic layers comprising a quatemary phosphonium cation having structure XXXIII wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C50 aromatic radicals; and Ar16 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.

Description

200900452 IX. Description of the invention [Technical field to which the invention pertains] This case is proposed in the form of No. 60/945, 1 50 and 2 007 and Application No. 1 1 / 7 6 6, 3 8 2 in 2007. U.S. Provisional Application for the U.S. Application No. 20, filed on June 21, the U.S. non-temporary priority; both cases are cited as a whole [Prior Art] The present invention relates to a product, a polymer-organic clay compound rice. The method of composite materials. In comparison to the unfilled polymer polymer composite composition, the organic clay is prepared as an inorganic cation effective in replacing the organic cations present in the channels. The degree of interaction of the matrix of the composition within the polymer composition is high. The organic clay is swelled in the organic clay, and even if the d-spacing in the narrow inorganic clay is subjected to a shearing force in the substrate, the peeling proceeds quite completely to form a polymer composition, and the organic machine is formed. The organic salt composition of the organic clay composition contains the material composition and the additive for preparing the polymer naphthalene material and the polymer composition containing the reinforcing physical property of the inorganic clay. The main advantage of organic clay in the organic clay composition of the general inorganic clay is that it is found that the organic clay is peeled off and there is an organic part between the inorganic silicate layer which is concentrated in the corresponding group containing only inorganic clay. The d-spacing in the clay corresponds to, and at the same time increases the tendency of the organic clay to polymerize. In some cases, the polymer composition of the clay that is stripped of the extremely highly dispersed tantalate layer is referred to as the Na-5-200900452 meter composite. Although this area has not made significant progress in the past decade, it is actively seeking improved organic clay compositions that are highly regarded in all discoveries. A disadvantage of many organic clays is the thermal instability of the organic cations present, making them unsuitable for applications where the polymer-organic clay composition must be treated at elevated temperatures, such as polymers containing "high heat" (such as polyethers). The case of a polymer composition containing organic clay of quinone imine. Another disadvantage of many known organic clay compositions is that when the organic clay composition is dispersed in the polymer matrix, the organic clay composition may interact adversely with the polymer matrix, possibly resulting in a polymer composition containing organic clay. The marginal performance of the object. For example, when the organic cation is a primary ammonium cation and the polymeric matrix is sensitive to the amine group, it may cause degradation of the polymer matrix during melt mixing (e.g., of the polymer matrix and the organic clay composition). Therefore, there is a great need to develop an organic clay composition which is thermally stable and which at the same time advantageously interacts with a polymer matrix in a polymer composition containing organic clay. The present invention is directed to these and other technical challenges. SUMMARY OF THE INVENTION In various embodiments, the present invention provides novel quaternary organic scale salts and novel quaternary pyridine salt salts useful in the preparation of organic clay compositions. Thus, in one embodiment, the present invention provides novel organic clay compositions prepared using the novel organic salts provided herein. In another aspect, the present invention provides a novel polymer-organic clay composite composition comprising the organic clay composition disclosed herein. In still another aspect -6 - 200900452, the present invention provides a novel method of preparing a polymer-organic clay composite composition. These and other aspects of the invention are disclosed in detail herein. DETAILED DESCRIPTION A number of terms are used in the following description and claims, which should be defined to have the following meanings. The singular forms "a", "the" and "the" “As appropriate” or “as appropriate” means that the events or circumstances described below may or may not occur, and that the description includes the occurrence and non-occurrence. The term "solvent" as used in the present invention may mean a single solvent or a mixture of solvents. Approximating terms used in the present specification and claims are intended to modify any quantity that is to be construed as a change. Therefore, modifications such as "about" are not limited to the precise ones described. In some cases, the approximation may correspond to the accuracy of the instrument used to measure the chirp. As used herein, the term "aromatic group" means an array of atoms having at least one valence comprising at least one aromatic group. The array of atoms having at least one valence containing at least one aromatic group may include a hetero atom such as nitrogen, sulfur, selenium, tellurium, and oxygen, or may be composed only of carbon and hydrogen. The term "aromatic group" as used in the present invention includes, but is not limited to, phenyl, pyridyl, furyl, thienyl, naphthyl, phenylene and biphenyl. As previously mentioned, the 'aromatic 200900452 group contains at least one aromatic group. The aromatic group is necessarily a cyclic structure having 4n + 2 "delocalized" electrons, wherein "η" is an integer equal to 1 or more, such as phenyl (n = 1), thienyl (n = 1) , furanyl = υ 'naphthyl (η = 2), azulenyl (η = 2), fluorenyl (η = 3) and the like. Aromatic groups can also include non-aromatic components. For example, the benzyl group is an aromatic group containing a benzene ring (aromatic group) and a methylene group (non-aromatic component). Similarly, the tetrahydronaphthyl group is an aromatic group containing an aromatic group (C6H3) fused to the non-aromatic component -(CH2)4-. For convenience, the term "aromatic group" is defined in the present invention to include a wide range of functional groups such as alkyl, alkenyl, alkynyl, haloalkyl, haloaromatic, conjugated dienyl, alcohol Bases, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, sulfhydryl groups (such as carboxylic acid derivatives such as esters and decylamines), amine groups, nitro groups, and the like. For example, the 4-methylphenyl group is a functional group containing a methyl group (: 7 aromatic group and a methyl group is an alkyl group. Similarly, the 2-nitrophenyl group is a c6 containing a nitro group. The nitro group of the aromatic group is a functional group. The aromatic group includes a halogenated aromatic group such as 4-trifluoromethylphenyl, hexafluoroisopropylidene bis(4-phenyl-1-yloxy). (ie, -OPhCCCFshPhO-), 4_chloromethylbenzene-buyl, 3_trifluorovinyl-2-thienyl, 3-trichloromethylbenzene-buyl (ie, 3-CCl3Ph-), 4 -(3-Bromopropan-1-yl)benzene-buyl (ie, 4-BrCH2CH2CH2Ph-) and the like. Other examples of aromatic groups include 4-allyloxyphenyl-1-oxyl, 4-aminophenyl-1-yl (ie, 4-H2NPh-), 3-aminocarbonylphenyl-1-yl (ie, NH2C0Ph-), 4-benzylbenzyl-i-yl, dicyano) Methyl bis(4-phenyl-1-yloxy) (ie, -〇PhC(CN)2PhO-), 3-methylphenyl-1-yl, methylenebis(4-benzene-:!-yl) Oxy) (ie, _OPhCH2PhO-), 2-ethylbenzene-1-200900452, benzyl group, 3-lanyl-2-propenyl, 2-hexyl-5-nonyl, six Methylene-1,6-bis(4-phenyl-1-yloxy) ( That is, -OPh(CH2)6PhO-), 4-hydroxymethylphenyl-1-yl (ie, 4_H〇CH2Ph.), 4-sulfomethylben-1-yl (ie, '4-HSCH2PI1-), 4 -methylthiobenzene-1-yl (ie, 4-CH3SPh-), 3-methoxyphenyl-1-yl, 2-methoxy-phenyl-1-yloxy (eg, methyl water)醯-), 2-nitromethylbenzene_ι_yl (ie '2-N02CH2Ph), 3-trimethyldecylphenyl-1-yl, 4-tert-butyldimethylamylbenzene-1- a group, 4-vinylphenyl-1-yl, phenylidene bis(phenyl), and the like. The term "C3 - C1 () aromatic group" includes at least three but not more than 10 carbons. An aromatic group of an atom. The aromatic group 1-imidazolyl (C3H2N2-) represents a C3 aromatic group. The benzyl (c7h7-) system represents a c7 aromatic group. The term "is used in the present invention" "Cycloaliphatic group" means a group having at least one valence and comprising a cyclic but non-aromatic atomic array. The "cycloaliphatic group" as defined herein does not contain an aromatic group. "Cycloaliphatic group" "Group" may comprise one or more acyclic components. For example, a cyclohexylmethyl (C6H M CH2-) system comprises a cyclohexane ring (cyclic ring but a cycloaliphatic group of an aromatic atomic array) and a methylene group (monocyclic component). The cycloaliphatic group may include a hetero atom such as nitrogen, sulfur, selenium, tellurium, and oxygen, or may be only carbon And hydrogen composition. For convenience, the term "cycloaliphatic group" is defined in the present invention to include a wide range of functional groups such as alkyl, alkenyl, alkynyl, haloalkyl, conjugated dienyl, alcohol groups. And an ether group, an aldehyde group, a ketone group, a carboxylic acid group, a mercapto group (for example, a carboxylic acid derivative such as an ester and a decylamine), an amine group, a nitro group, and the like. For example, the 4-methylcyclopentan-1-yl group is a c6 cycloaliphatic group containing a methyl group, and the methyl group -9-200900452 is a functional group of an alkyl group. Similarly, the 2-nitrocyclobutane-buyl group is a C4 cycloaliphatic group containing a nitro group, and the nitro group is a functional group. The cycloaliphatic group may contain one or more of the same or different halogen atoms. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine. The cycloaliphatic group containing one or more halogen atoms includes 2-trifluoromethylcyclohexyl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1- , hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (ie, -C6H1()C(CF3)2C6H1()-), 2-chloromethylcyclohex-1-yl , 3-difluoromethylenecyclohex-1-yl, 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethyl A cyclopentan-1-yl group, a 2-bromopropylcyclohex-1-yloxy group (for example, CH3CHBrCH2C6H1()0-), and the like. Other examples of cycloaliphatic groups include 4-allyloxycyclohex-1-yl, 4-aminocyclohexyl-buyl (ie, 'H2NC6H1Q-), 4-aminocarbonylcyclopentan-1- Base (ie, NH2COC5H8-), 4-ethyloxycyclohex-1-yl, 2,2-chloro-isopropylidene bis(cyclohex-4-yloxy) (ie '-OC6Hi〇C (CN) 2C6Hi〇0-), 3-methylcyclohex-1-yl, methylene bis(cyclohex-4-yloxy) (ie, -〇C6H丨gCH2C6H1()0-), ethyl ethyl ring Butyl-buyl, cyclopropylvinyl, 3-methylindol-2-tetrahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy) (ie, an OC6Hi〇(CH2)6C6Hi〇0-), 4-methylmethylcyclohex-1-yl (β卩,4-HOCH2C6H10-), 4-carbylmethylcyclohex-1-yl (ie '4-HSCH2C6H10-), 4-methylthiocyclohex-1-yl (ie, 4-CH3SC6H10-), 4-methoxycyclohex-1-yl, 2-methoxycarbonylcyclohexane -1-yloxy (2-CH3OCOC6H10O-), 4-nitromethylcyclohex-1-yl (ie, NO2CH2C6H10-), 3-dimethylsilylcyclohexan-1-yl, 2- Dibutyl-10-200900452 Dimethyldecylcyclopenta-buyl, 4-trimethoxydecane Ethyl-cyclohex-1-yl (e.g. '(CH30) 3SiCH2CH2C6H1 () -), 4- vinylcyclohexene-1-yl, ethenylene bis (cyclohexyl) and the like are. The term "C3-C1() cycloaliphatic group" includes cycloaliphatic groups containing at least three but not more than 10 carbon atoms. The cycloaliphatic group 2-tetrahydrofuranyl (C4H70-) represents a c4 cycloaliphatic group. The cyclohexylmethyl group (C6HWCH2-) represents a C7 cycloaliphatic group. The term "aliphatic group" as used in the present invention means an organic group having at least one valence and consisting of an array of acyclic linear or branched chain atoms. An aliphatic group is defined to contain at least one carbon atom. The array of atoms comprising aliphatic groups may include heteroatoms such as nitrogen, sulfur, sand, selenium and oxygen or may consist solely of carbon and hydrogen. For convenience, the term "aliphatic group" is defined in the present invention as part of "an array of acyclic linear or branched chain atoms" to define a wide range of functional groups such as alkyl, alkenyl, alkynyl groups. , haloalkyl, conjugated dienyl, alcohol, ether, aldehyde, keto, carboxylic acid, sulfhydryl (eg, carboxylic acid derivatives such as esters and decylamines), amines, nitro groups, and the like . For example, the 4-methylpent-1-yl group is a C6 aliphatic group containing a methyl group, and the methyl group is a functional group of an alkyl group. Similarly, the 4-nitrobut-1-yl group is a C4 aliphatic group containing a nitro group, and the nitro group is a functional group. The aliphatic group may be a haloalkyl group containing one or more of the same or different halogen atoms. The halogen atom system includes, for example, fluorine, chlorine, bromine and iodine. The aliphatic group containing one or more halogen atoms includes an alkyl halide trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluoroethylene Base, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (eg, -11 - 200900452 -CHzCHBrCH2-) and the like. Other examples of aliphatic groups include allyl, aminocarbonyl (ie, '-C〇NH2), carbonyl, 2,2-dicyanoisopropylidene (ie, '-CH2C(CN)2CH2-), Methyl (ie, -CH3), methylene (ie, -CH2-), ethyl, ethyl, methyl ketone (ie, _CH〇), hexyl, hexamethylene, hydroxymethyl (ie ' _CH2OH), mercaptomethyl (ie, -CH2SH), methylthio (ie, -SCH3), methylthiomethyl (ie, -CH2SCH3), methoxy, methoxycarbonyl (ie, CH30C0) -), nitromethyl (ie '-CH2N〇2), thiocarbonyl, trimethyldecyl (ie, (CHshSi-), tert-butyldimethylalkyl, 3-trimethyloxy) Alkylpropyl (i.e., (CH30)3SiCH2CH2CH2-), vinyl, vinylidene, and the like. As for other examples, the C?-C! sulfonyl group contains at least one but no more than 10 carbon atoms. The methyl group (ie, CH3-) is an example of a C! aliphatic group. The fluorenyl group (ie, 'CH3(CH2)9-) is an example of a C1Q aliphatic group. In one embodiment, The invention provides an organic rust salt having structure I

Wherein Ar1, Ar2 and Ar3 are independently a c2-C5Q aromatic group; Ar4 is a bond or a C2-C5q aromatic group; "a" is a number from 1 to about 200 -12-200900452; "C " is 0 to 3; R1 is each independently a halogen atom, a C丨-C2Q aliphatic group, a C5_C2Q cycloaliphatic group or a C2-C2G aromatic group; R2 is a halogen atom, a Ci-C2Q aliphatic group, a C5-C2Q cycloaliphatic group, a C2-C5 fluorene aromatic group or a polymer chain; and X- is a relative ion that balances the charge. Representative organic iron salts encompassed by the general structure I are exemplified in Table I. Those skilled in the art will appreciate the relationship between the general structure 1 and the individual structures of the blocks 13 to U in Table 1. For example, the structure of the column 1 a is represented by the general structure I wherein Arl to Ar3 are each a phenyl group (C6H5-), the Ar4 is a meta-phenyl group, and the variable "c" is The zero 'variable number "a" is 2, the X-system is an iodide ion, and the group R2 is a type of a divalent Cl5 aromatic group -OC6H4C3H6C6H4〇-.

200900452

-14- 200900452

As for other examples, the field 1 f of Table 1 indicates that A r 1 - Α Γ 3 is a phenyl group; Ar4 is a meta-phenyl group, "a" = 1, "c" is 0, and R2 is It is a C4 aliphatic group C4F9〇- and X- is an organic money salt of chloride ion. The column 1 g of Table I indicates that Arl_Ar3 is a phenyl group; Ar4 is a p-phenylene group, "a" = l, "c" is 0, and R2 is a C6 group C6H50- (benzene Oxygen) and X- is an organic squama salt of bromide ion. The column lh of Table I indicates that Ar^Ar3 is a phenyl group; Ar4 is a p-phenyleneoxy group, "a" = l' "c" is an O'R2 system is a C6 aromatic group C6H5 - (Phenyl) and X - is an organic phosphonium salt of a tetrafluoroborate ion BF plant. The column π of Table I indicates one of the organic phosphonium salts, Ar1 to Ar3 are phenyl groups; Ar4 is p-phenyleneoxy, "a" = 2, "c" is ruthenium, and R2 is the following The polyether quinone imine chain represented by the structure in parentheses modified by "η", which shows that the "η" of the organic money salt is equal to 5 〇, and has the meta-extension benzene between the right-hand side bracket and the group Q. Base part. In various other embodiments, "η" is a number from 1 to about 5 。. The relative ion XI is sulfate (S04 = ). In one embodiment, the group represented by R2 in structure I is a polyetherimine polymer chain (see, for example, column 1 i of Table I). In another embodiment, the group represented by R2 in Structure I is a polyether -15-200900452 ketone polymer chain. In still another embodiment, the group represented by R2 in Structure I is a polyether oxime polymer chain. In a specific embodiment wherein R2 is a polymer chain, the polymer chain can have a high molecular weight or a low molecular weight. The high molecular weight polymer chain is one which has a number average molecular weight (Mn) of greater than 8,000 g/mole when measured using gel permeation chromatography using a polystyrene molecular weight standard. The low molecular weight polymer chain is one which has a number average molecular weight (Mn) of 8,000 g/mole or less when measured by gel permeation chromatography using a polystyrene molecular weight standard. In a specific embodiment, the present invention provides an organic scale salt having the structure I, wherein the R2 system has a number average molecular weight in the range of from about 1000 to about 50,000 g/mole as determined by gel permeation chromatography. Polymer chain of Mn. In another embodiment, the 'r2 is a polymer chain having a number average molecular weight Mn ranging from about 1000 to about 20,000 grams per mole as determined by gel permeation stratification. In still another embodiment, R2 is a polymer chain having a number average molecular weight Mn ranging from about 1000 to about 5,000 grams per mole as determined by gel permeation chromatography. In one embodiment, the present invention provides an organic phosphonium salt having structure II.

-16- 200900452 where χ_ is the relative ion of the equilibrium charge. In another embodiment, the present invention provides an organic scale salt having structure 111

Where f is the relative ion of the equilibrium charge. In still another specific embodiment, the present invention provides an organic phosphonium salt having the structure IV.

Wherein X is the relative ion of the equilibrium charge, m is a number ranging from about 1 Torr to about 1 000 and the Ar5 is a C2-C5 〇 aromatic group or a polymer chain.

In one embodiment, the present invention provides an organic iron salt having the structure IV, wherein the group Ar5 has the structure V -17-

V 200900452

The χ-system is the relative ion that balances the charge. In Structure I and elsewhere in this disclosure: A counter ion that balances charge. As is familiar to the skilled artisan, a wide variety of opposing ions of equilibrium charge. A relative charge of a relative charge, which is monovalent, divalent or tri-. For example, in a specific embodiment, X-selective scorpion, bromide, iodide, sulfate, sulfite hydrogen, acetic acid Roots, oxalates and combinations thereof. Inorganic anions, bromide ions, iodide ions and hydrogencarbonates are examples of monovalent inorganic anionic carbonates and sulfates and organic anion ions. An example of a tri-anion of Kemp's triacid. The novel organic squama salts provided by the present invention can be provided in several experimental ways to prepare specific methods and conditions for forming the knots. In one embodiment, the aryl halide and the triarylphosphine are optionally prepared as a catalyst (such as the next reaction. In a specific embodiment, the anhydride is reacted to provide a quinone imine containing a portion of the money salt. In a specific embodiment, the present invention provides a method for providing a salt salt, which comprises (a) having a structure VI; a group χ-line representing a cognition, which can be used, and a χ-line representing a pentavalent anion species. Examples of ions, chloride ion, carbonate, carbonate ion fluoride ion, chloride anion. Oxalate is prepared by a bivalent anion ternary anion method. The organic sulfonium salt of the constitutive I, the organic sulfonium salt can be palladium acetate (II) )) The presence of amine substituted money salts and products. Used to prepare organic S amine substituted scale salts -18- VI200900452

Ar3

Ar2—P

Ar1 wherein Ar1, Ar2, Ar3 and Ar4 are independently an aromatic group, and x_ is a relative ion of equilibrium charge; contact with an anhydride compound having structure VII

〇 “a” is a number from 1 to about 200; “c” is a number from 0 to 3; each occurrence of R1 is independently a halogen atom, a Ci-Cu aliphatic group, and a C5-C20 cycloaliphatic group. a group or a C^-Cm aromatic group; and the R2 is (^-(:2() aliphatic group, C5-C2 anthracene aliphatic group, C2-C5Q aromatic group or polymer chain) And (b) the isolated organic salt of the product. In a specific embodiment, the compound VI is an aniline having a triphenyl scale portion in the meta position to the amine (NH 2 ) group, and wherein the equilibrium charge is relative The ion system is iodide ion. In another embodiment, the compound VI is an aniline having a triphenyl scale portion in an aligned position with an amine (NH2) group, and wherein the opposite ion of the equilibrium charge is a chloride ion. In one embodiment, the anhydride compound VII is selected from the group consisting of bisphenol A II-19- 200900452 anhydride (BPADA), 4,4'-biphenyl dianhydride, and 4,4,-oxy dianhydride. (4,4-ODPA). In a specific embodiment, the anhydride compound VII is a biguanide A dianhydride. In another embodiment, the 'anhydride compound VII is a polymeric monoanhydride containing an anhydride terminal group, The polymeric dianhydride is from BPA DA and m-phenyleneamine-derived polyether quinone imine The polymerized dianhydride has a number average molecular weight Μη of about 10, gram/mole. Generally, the amine-substituted sulfonium salt having the structure VI has a structure The reaction between the anhydride compounds of VII ("contact") is carried out in a solvent to remove the by-product water formed in the condensation reaction at a temperature exceeding 100 ° C. In one embodiment, the reaction is based on The organic solvent is carried out at a temperature in the range of about 120 ° C to about 160 ° C. In another embodiment, the reaction is carried out by melting. In certain cases, it is preferably used, for example, for imidization. The reaction is carried out in the presence of a catalytic catalyst such as sodium phenyl phosphonate (SPP). Suitable solvents include ODCB (o-dichlorobenzene), toluene, xylene, chlorobenzene, anisole, cucurbit ether, and combinations thereof. In one embodiment, the present invention provides a process for the preparation of an organic phosphonium salt comprising U) an amine substituted acid salt having the structure IX

-20-

IX 200900452 where X-system is the opposite ion of equilibrium charge and is in contact with an anhydride compound having the structure νπ

Wherein "a" is a number from 1 to about 200; "c" is a number from 0 to 3; each occurrence of R1 is independently a halogen atom, a C^-Cm aliphatic group, and a Cs-Cm cycloaliphatic group. a group or a C2-C2Q aromatic group; and R2 is a halogen atom, an h-Cw aliphatic group, a C5_C2Q cycloaliphatic group, a C2_C5Q aromatic group or a polymer chain; and (b) an isolated product Organic strontium salt. In one embodiment, the anhydride compound having the structure V 系 is selected from the group consisting of 4,4′-oxydiphthalic anhydride, 3,4,-oxydiphthalic anhydride, and 3,3-oxyl. Terephthalic anhydride, bisphenol a dianhydride, 6F-dianhydride, 3,4,-biphenyl dianhydride, 4,4,-biphenyl dianhydride, and combinations thereof. In still another embodiment, the invention provides a method of preparing an organic scale salt comprising: (a) contacting an aromatic amine with a halogen-substituted anhydride to provide a halogen-substituted quinone imine; (b) The halogen-substituted oxime/, cycline reaction is carried out 'to carry out the reaction of nuclear substitution of halogen by diaryl phosphine' and (c) the isolated product organic squama salt.

-21 - 200900452 Dicarboxylic anhydride and 4-fluorophthalic anhydride. In another embodiment, the halogen-substituted anhydride comprises 4-chlorophthalic anhydride. In still another embodiment, the halogen-substituted anhydride comprises a mixture of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. The aromatic amine can be a monoamine or a polyamine. In one embodiment, the aromatic amine is a polymer comprising an amine group. Examples of the monoamine are aniline, 1-aminonaphthalene, 3-chloroaniline, 4-chloroaniline, 2,4-dichloroaniline, 4-chloro-4'-aminobiphenyl and the like. Suitable triarylphosphine systems include triphenylphosphine, tolylphosphine, tris-tolylphosphine, tris(4-tert-butoxyphenyl)phosphine, and the like. Suitable reaction conditions for the preparation of the halogen-substituted quinone imine and its subsequent reaction with the triarylphosphine are provided in the experimental part of the present disclosure. In one embodiment, the present invention provides a novel pyridine key salt having the structure XV

Wherein Ar6, Ar7 and Ar8 are independently c2-C5G aromatic groups; "b" is 〇 to 2; "d" is 〇 to 4; R3 and R4 are each independently a halogen atom, a Ci-Cn aliphatic group, a C5-C2 anthracycline aliphatic group or a Ca-Czo aromatic group; the z system is a bonded, divalent Ci-Cao-22-200900452 aliphatic group, two a C5-C2Q cycloaliphatic group, a divalent C2-C2G aromatic group, an oxygen linkage, a sulfur linkage, a S02 linkage or a Se linkage; the Ar9 is a C]()-C2c)() aromatic a group or a polymer chain comprising at least one aromatic group; and X_ is a relative ion that balances the charge. As exemplified by the present invention, the pyridyl key salt encompassed by structure XV can be used to prepare organic clay compositions and polymer-organic clay composite compositions. Representative pyridinium salts encompassing the general structure XV are shown in Table II °

-23- 200900452

Those skilled in the art should understand that the pyridyl salt of the table π column 2a represents a pyridine key salt having the structure XV, wherein each of Ar6, Ar7 and Ar8 is a phenyl group; "b" is 0; "d" is 2; R4 is a methyl group; Z is an oxygen linkage; Ar9 is a C12 aromatic group; and X- is a chloride ion. Similarly, the pyridinium salt of the surface field 2b represents a pyridine gun salt having the structure XV, wherein Ar6, Ar7 and Ar8 are phenyl groups; "b" is 0; "d" is 0; An oxygen linkage; the Ar9 system is a C12 aromatic group; and the X_ system is an acetate ion. In one embodiment, the invention provides a pyridine key salt having the structure XV, wherein the Ar9 is a polyether quinone polymer chain. In another embodiment, the invention provides a pyridine key salt having the structure XV wherein the Ar9 is a polyether ketone polymer chain. In one embodiment, the Ar9 is a polymer chain having a number average molecular weight Mn in the range of from about 1000 to about 50,000 grams per mole. In another embodiment, the Ar9 is a polymer chain having a number average molecular weight Mn in the range of from about 1,000 to about 20,000 grams per mole. In still another embodiment, the Ar9 is a polymer chain having a number average of -24 to 200900452 having a molecular weight Mn in the range of from about 1,000 to about 5,000 grams per mole. In another embodiment, the 'Ar9 is a polyether quinone imine polymer chain having a number average molecular weight Mr in the range of from about 1,000 to about 20,000 grams per mole. In a particular embodiment, the Ar9 is a polyether quinone imine polymer chain having a number average molecular weight Mr in the range of from about 1,000 to about 50,000 grams per mole. In one embodiment, the present invention provides a pyridine key salt having the structure XVI encompassed by the general structure XV.

Ph XVI where X- appears each time as a counter ion that is independently balanced. In a specific embodiment, the X-system is BF4-. In a specific embodiment, the present invention provides a pyridine key salt having the structure XVII -25- 200900452

Among them, each time X appears as a relative ion of equilibrium charge. In a specific embodiment, X is acetate. In still another specific embodiment, the present invention provides a pyridinium salt having the structure XVIII

Wherein X is a relative ion of equilibrium charge; "e" is a number in the range of from about 10 to about 1000; and Ar1 (3 is a C2-C5. aromatic group or polymer chain. Specific embodiment) In the X-form is a tetrafluoroborate (bf4-) anion, the variable "e" is about 100 and the Ar1() is a C25-aromatic group tetrafluoroborate 2,4,6-triphenylpyridine. It will be understood by those skilled in the art that the aromatic group can include associative relative ions, in this case BP, and still be within the definition of the term aromatic group as defined herein. Similarly, aliphatic groups and The cycloaliphatic group may also include associative ions. When the group contains a plurality of charges and a counter ion having an equilibrium charge is required, the group may contain a plurality of counter ions of equilibrium charges. The general practitioner should also understand Within the group -26- 200900452 may also contain the relative ions of the equilibrium charge of the fractional part. For example, in a composition that balances a single positive charge by a divalent anion such as sulfate (S04 = ), a single sulfate anion may be combined with two Independent molecules or groups are associated. Therefore, in a specific embodiment, A R1() is an aromatic group containing yKSOT). In a specific embodiment, Ar1. Is an aromatic group having the structure XIX

X" is the relative ion that balances the charge. In a specific embodiment, the χ-system is a fractional portion of a divalent ion selected from the group consisting of sulfate, carbonate, and oxalate. In one embodiment, X is a 1/2 (C03 = ), fractional portion of the carbonate anion. The relative ionization of the equilibrium charge which may be present in the pyridine salt salt structure XV includes those disclosed herein for structure I. In one embodiment, the relative ion of the equilibrium charge is selected from the group consisting of fluoride ion, chloride ion, bromide ion, iodide ion, sulfate, sulfite, carbonate, bicarbonate, acetate, oxalate, and combinations thereof. . In one embodiment, the present invention provides a process for the preparation of a pyridinium salt having the structure XV comprising (a) an aromatic amine having structure XX /Ar9 -27-

XX 200900452 where "d" is the number from 〇 to 4; each occurrence of R4 is independently a halogen atom, a Ci-Czo aliphatic group, a C5-C2 anthracycline aliphatic group or a C aromatic group; Bonded, divalent Ci-Cu aliphatic group, di-C20 cycloaliphatic group, divalent C2-C2G aromatic group, oxygen linkage, substituent, S〇2 linkage or Se linkage; Ar9 system Is a Ciq-C2g aryl group or a polymer chain containing at least one aromatic group; and the χ_ is a counter-charged relative ion; in contact with the pyridine iron salt having the structure XXI, it is 2 - C 2 0 f C5-sulfur Lianke base balance (R3)b

Ar6 XXI wherein Ar6, Ar7 and Ar8 are independently a C2-C5Q aromatic group "b" is a number from 0 to 2; each occurrence of R3 is independently a halogenated Ci-C^ aliphatic group, C5- a C2Q cycloaliphatic group or a C2-C2Q aryl group; and X- is a relative ion of an equilibrium charge; and (b) a pyridyl key salt of the isolated product structure XV. The reaction by contacting the aromatic amine XX with the pyridine gun salt XXI generally involves contacting the reactants at a temperature of from about -2 (TC to about 15 (in the range of TC. Although a solvent is generally employed, the reaction may also be melted). In one embodiment, the present invention provides a polymeric pyridine and a process for the preparation thereof. The polymeric pyridinium salt can be reacted (contacted) and (b) with (a) a polymeric aromatic group with a pyridine salt having the structure XXI. a single quaternary -28- group; a sub- and a aryl group having m-temperature 0-key salt diamine complex 200900452 in combination with a pyridine gun salt. In one embodiment, the polymeric aromatic diamine is included from at least A non-polymeric aromatic diamine and at least one dianhydride derived structural unit. For example, a molar excess of a diamine such as 4,4'-oxydiphenylamine (4,4'-ODA) can be combined with 4,4'- Oxydiphthalic anhydride (4,4'-ODPA) is reacted in o-dichlorobenzene (〇DCB) under reflux to provide a polyether quinone imine having an amine terminal. The reaction of an amine with a pyridine salt having the structure XXI produces a product polymeric pyridyl salt which can be precipitated, for example, by an antisolvent. In a specific embodiment, the non-polymeric aromatic diamine is m-benzene dioxane. In one embodiment, the non-polymeric diamine is m-phenylenediamine and dianhydride. The system is BP ADA. In one embodiment, the dianhydride used is a mixture of BPADA and 4,4′-ODPA. In a specific implementation of the Ss sample, the present invention provides a polymeric pyridine gun having a structure ΧΧΠ. salt

XXII wherein "f" is a number from 10 to about 1000 and the X-system is a counter ion of equilibrium charge. Thus, in one embodiment, the invention provides a method comprising (a) polymerizing an aromatic diamine having structure XXIII -29- 200900452 h2n

XXIII wherein the variable "f" is from 10 to about 1000; in contact with the pyridine salt having the structure XXIV

Ph

XXIV wherein X is the opposite ion of the equilibrium charge; and (b) the isolated product has the polymeric pyridine salt of structure XXII. As discussed herein, polymeric diamines such as XXIII can be prepared by reacting an excess of an aromatic diamine with a dianhydride under polycondensation conditions (e.g., refluxed ODCB). Those skilled in the art will recognize that diamine XXIII can be prepared by reacting excess m-phenylenediamine with 4,4'-ODPA under polycondensation conditions. Pyridine salts are commercially available as XXIV or may be prepared by methods known in the art. In one embodiment, the invention provides a polymeric pyridine gun salt having structure XXII wherein the variable "f" is from 10 to about 100. In addition to providing novel organic phosphonium salts I and pyridine gun salts XV, the present invention also provides for obtaining other polymer-organic clay composite compositions useful for preparing organic clay compositions and derived from the organic clay compositions. - 200900452 Method of organic salt. Thus, in one embodiment, the present invention provides a method (R3)b for obtaining a pyridinium salt comprising a cationic ion XXV.

At6 XXV wherein Ar6, Ar7 and Ar8 are independently C2-C5〇 aromatic groups; the number is 〇 to 2; each occurrence of R3 is independently a halogen atom, and the mountain-(:2() aliphatic group a C5-C2 anthracene aliphatic group or a C2-C2〇 aromatic group; and the Ar11 is a C2-C2QG aromatic group or a polymer chain comprising at least one aromatic group. Salts are exemplified in Table III. The pyridine gun salt containing the cation XXV can be prepared and incorporated into the organic clay composition and the polymer-organic clay composite composition using the method disclosed in the present invention. For example, it is suitable for preparation and use of the structure XV. The method of the pyridine key salt can be applied to the preparation and use of a pyridine gun salt containing a cation XXV. -31 - 200900452 Table exemplifies a pyridine salt salt column containing a cationic χχν (R3)b X Ar6 Ar6 Ar7 Ar8 Ar11 R3 "b" Relative ion x- 3a Ph Ph Ph Ph ___ 0 bf4—3b Ph H Ph 4-ClPh MeO 2 c plant 3c Ph Ph Ph 4-CF3Ph ___ 0 bf4—3d Ph Ph Ph 2-port ratio —定—— bf4~ In one aspect, the invention provides for obtaining an organic clay composition and from the organic clay composition The raw polymer - an organic salt of benzene-one organoclay composite composition thus, in a particular aspect of the embodiment, the present invention provides a method for obtaining the benzene-one salt having the structure comprising the four money cation XXXI11

Wherein Ar12, Ar13, Ar14 and Ar15 are independently a C2-C5o aromatic group; and Ar16 is a C2-C2G() aromatic group or a polymer chain comprising at least one aromatic group. The benzophenone-containing salt comprising a quaternary cation having the structure XXXIII is exemplified in Table IV. The benzophenone-containing salt comprising a quaternary iron cation XXXIII can be prepared as disclosed in the present invention as disclosed in -32-200900452. The benzophenone-containing salt comprising a quaternary squamous cation XXXIII can be incorporated into an organic clay composition and a polymer-organic clay composite composition using the method disclosed in the present invention and shown to be suitable for the organic scale salt I and the pyridine key salt XV. For example, a method suitable for the incorporation of the cationic component of the organic phosphonium salt I into the organic clay composition can be applied to the preparation of an organic clay composition using a benzophenone-containing salt comprising a quaternary cation XXXIII. Table IV exemplifies the benzophenone-containing salt column containing cation XXXIII. 0 Ar14 V /^Ar16 Ar13——P--1® χΘ Ar12 Ar12 Ar13 Ar14 Ar15 Ar16 Relative ion X_ 4a Ph Ph Ph 1,4-phenylene Ph cr 4b Ph Ph Ph 1,3-phenylene Ph Cl-4c o-tolyl o-tolyl o-tolyl 1,4-phenylene 2-naphthyl plant 4d 3,4-dimethylphenyl 3,4 -Xylyl 3,4-dimethylphenylpyridine-2,6-diyl Ph CF3SO3 ~ In one embodiment, the present invention provides a method for obtaining a benzophenone-containing salt comprising a quaternary phosphonium XXXIII, wherein Ar16 It is a polyether ketone polymer chain. The salt compositions can be prepared, for example, by reacting a polyether ketone comprising one or more terminal benzylidene groups with a triarylphosphine (e.g., triphenylphosphine) in a solvent and, if appropriate, in the presence of a catalyst. In one embodiment, the present invention provides a method for obtaining a benzophenone-containing salt comprising a quaternary calcium cation XXXIII, wherein the Ar16 is a number average of -33 to 200900452 and the molecular weight Mn is in the range of from about 1,000 to about 50,000 g/mole. The polymer chain. In another embodiment, the invention provides a method for obtaining a benzophenone-containing salt comprising a quaternary iron cation XXXIII, wherein the Ar16 is a polymer chain having a number average molecular weight Mn in the range of from about 1,000 to about 20,000 g/mole. . In still another embodiment, the present invention provides a process for obtaining a benzophenone-containing salt comprising a quaternary phosphonium cation XXXIII, wherein the Ar" is in a range having a number average molecular weight Mn in the range of from about 1,000 to about 5,000 g/mole. Polymer Chains. In one embodiment, the present invention provides a method of obtaining a benzophenone-containing salt comprising a quaternary rust cation XXXIII, wherein Ar is a number average molecular weight Mn in the range of from about 1000 to about 50,000 grams per mole. The polyether quinone imine polymer bond. In another embodiment, the present invention provides a method for obtaining a benzophenone-containing salt comprising a quaternary phosphonium cation XXXIII, wherein the Ar16 is in a range of from about 1 Torr to about 20,000 g/mole. Polyether quinone imine polymer chain. In a particular aspect, the invention provides a method of obtaining a benzophenone-containing salt comprising a quaternary calcium cation XXXIV. Those skilled in the art should recognize that cations are included within the scope of the type defined by structure XXX. Therefore, the structure XXXIV represents a case where the Ar15 system of the structure XXXIII is an o-phenyloxy group and the Ar16 is a 4-(2-triphenylscalinoxyphenyl)phenyl group. -34- 200900452 Ο

Ph Ph XXXIV Ο

Ph - 2ρ ph In another specific embodiment, the invention provides a method of obtaining a benzophenone-containing salt comprising a quaternary cation XXXV.

〇

XXXV In a specific embodiment, the present invention provides a polymeric benzophenone salt comprising a polymeric quaternary cation having structure XXXVII.

Wherein "g" and "h" are independently 0 to 4; W is a bond, a divalent Ci-Cu aliphatic group, a divalent c5-c2 anthracene aliphatic group, and a divalent c2- C2 an aromatic group, an oxygen linkage, a sulfur linkage, a so2 linkage or

Se linking group; each of R5 and R6 is independently a halogen atom, <^-(:20-35-200900452 aliphatic group, c5-c2Q cycloaliphatic group or C2-C2G aromatic group; "i" is a number from about 10 to about 1,000; and Ar17 is a C1G-C2G〇 aromatic group or a polymer chain comprising at least one aromatic group. Polymerization comprising a polymeric quaternary cation having structure XXXVII The benzophenone-containing salts are exemplified in Table V below.

As shown in the columns 5a and 5b in Table V, in one embodiment, Ar17 is an aromatic group comprising structure XXXVIII. -36 - 200900452 ο

The polymerization of the ketone-containing salt, such as those shown in Table V, can be prepared from the corresponding halogen-substituted polyether ketone by reaction with a triarylphosphine as described herein. The halogen-substituted polyether ketone can be prepared by methods known to those skilled in the art and can be, for example, by exposure to an intermediate solvent (e.g., o-dichlorobenzene) at elevated temperatures (e.g., 130 to 18 (TC)). In the presence of a medium (for example, hexaethylguanidinium chloride), the disodium salt of bisphenol (such as the disodium salt of bisphenol A) and the molar excess (for example, a 5 molar percentage excess) dihalodibenzophenone (For example, 4,4'-difluorodiphenyl ketone) is prepared by reacting. In one embodiment, the present invention provides an organic clay composition comprising a quaternary organic cation. The quaternary organic cation may be The fourth-order cation, the quaternary ammonium cation, or a combination thereof. The quaternary organic cation is a cationic component of various quaternary organic salts disclosed in the present invention. Therefore, the 'organic sulfonium salt I contains a quaternary organic cation X Quaternary organic salt

X -37- 200900452 wherein Ar1, Ar2 and Ar3 are independently C2-C5Q aromatic groups; Ar4 is a bonding or C2-C5G aromatic group; "a" is from 1 to about 200; c" is a number from 0 to 3; each occurrence of R1 is independently a halogen atom, a C^-Cm aliphatic group, a C5-C2 anthracycline aliphatic group or a C2-C2G aromatic group: and R2 It is a halogen atom, a C^-Cm aliphatic group, a C5-C2Q cycloaliphatic group, a C2-C5c aromatic group or a polymer chain. Similarly, the pyridine key salt XV is a quaternary organic salt containing a quaternary organic cation XXVI.

Wherein Ar6, Ar7 and Ar8 are independently C2-C5Q aromatic groups; "b" is a number from 0 to 2; "d" is a number from 0 to 4; each occurrence of R3 and R4 is a tooth atom, a C1-C20 aliphatic group, a C5-C2Q cycloaliphatic group or a c2-c2G aromatic group; a Z system is a bonded, divalent Κμ aliphatic group, a divalent c5-c2C) cycloaliphatic a group, a divalent C2-C2G aromatic group, an oxygen linkage, a sulfur linkage, a S02 linkage or a Se linkage; and the Ar9 is a C1G-C2()() aromatic group or comprises at least one aromatic Family-based polymer chains.

Similarly, pyridine key salt XXXI -38- 200900452

Office X

Ar6 XXXI wherein Ar6, Ar7 and Ar8 are independently a C2-C5Q aromatic group; "b" is a number from 0 to 2; each occurrence of R3 is independently a halogen atom, a CkCm aliphatic group, C5- a C2G cycloaliphatic group or a C2-C2Q aromatic fluorene; the Ar11 is a C2-C2G() aromatic group or a polymer chain comprising at least one aromatic group; and X- is a counter ion of equilibrium charge; Is a quaternary organic salt (R3)b containing a four-stage organic cation XXV

N, ©

Ar6 XXV wherein Ar6, Ar7 and Ar8 are independently C2-C5〇 aromatic groups; "b" is a number from 0 to 2; each occurrence of R3 is independently a halogen atom, a CJ-C20 aliphatic group a C5-C2Q cycloaliphatic group or a C2-C2G aromatic group; and the Ar11 is a C2-C2G() aromatic group or a polymer chain comprising at least one aromatic group.

Similarly, the benzophenone-containing organic iron salt XXXVI-39-

XXXVI 200900452

Wherein ArI2, Arl3, Ar14 and Ar15 are independently C2_C5() aromatic groups; Ar16 is a C2-C2D() aromatic group or a polymer chain comprising at least one aromatic group; and x is an equilibrium charge The relative ion, is a quaternary organic salt containing a quaternary organic cation having the following structure

XXXIII wherein Ar12, Ar13, Ar14 and Ar15 are independently a c2-C5〇 aromatic group; and Ar is a C2-C2GG group or a polymer chain comprising at least an aromatic group. As discussed above and as appreciated by those skilled in the art, the structural features present in the various quaternary organic salts disclosed herein are reproduced in the corresponding quaternary organic cations. For example, the aromatic group Ar1 as defined in the organic money salt I has the meaning of the aromatic group Ar1 in the organic money cation X. Therefore, if the Ar1 system in the organic scale salt I is a phenyl group, the organic scale cation X also has a phenyl group. The organic clay composition of the present invention comprises alternating inorganic silicate layers and organic layers. The inorganic citrate layer can be derived from any suitable source, such as natural -40-200900452 clay. In one embodiment, the inorganic silicate layer is derived from synthetic clay. Suitable clays include kaolin, dickite, pearlite, halloysite, serpentine, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, smectite, strontium Magnesia, hectorite, tetradecyl mica, sodium band mica, muscovite, pearl mica, talc, pumice, phlogopite, green crisp mica, chlorite and combinations thereof. In a specific embodiment, the inorganic tellurite layer is derived from smectite clay. The organic clay composition of the present invention is characterized in that the interlayer spacing between the inorganic tellurite layers is from 5 to about 1,000 angstroms. In one embodiment, the organic clay composition provided by the present invention is characterized in that the interlayer spacing between the inorganic tantalate layers is from 1 〇 to about 1 〇〇, and in another embodiment, 20 to about 100 angstroms. In one embodiment, the organic clay composition provided by the present invention is prepared by: (a) contacting a quaternary organic salt with a layered citrate in the presence of a solvent in the first reaction mixture and b) The isolated organic clay composition. In a specific embodiment, the quaternary organic salt is an organic money salt having the structure I. In another embodiment, the quaternary organic salt is a pyridine key salt having the structure XV. In still another embodiment, the quaternary organic salt is a pyridine key salt having the structure XXXI. In still another embodiment, the quaternary organic salt is a benzophenone-containing organic iron salt having the structure XXXVI. As described above, the organic clay composition of the present invention can be prepared by contacting a quaternary organic salt with a layered citrate in the presence of a solvent. In a specific embodiment, the layered tantalate is a natural clay. Another -41 - 200900452 In a specific embodiment, the layered citrate is a synthetic clay. In a specific embodiment, the layered citrate comprises a layer selected from the group consisting of kaolin, dickite, pearlite, halloysite, serpentine, chrysotile, pyrophyllite, montmorillonite, beidellite, Berberite, saponite, zinc montmorillonite, strontite, hectorite, tetradecyl mica, sodium band mica, muscovite, pearl mica, talc, vermiculite, phlogopite, green crisp mica, chlorite and Its combination of inorganic clay. In another embodiment, the layered citrate comprises montmorillonite clay. As described above, the organic clay composition of the present invention can be prepared by contacting a quaternary organic salt with a layered citrate in the presence of a solvent. In one embodiment, the solvent employed comprises an organic solvent such as acetone. In another embodiment, the solvent employed comprises water. In still another embodiment, the solvent employed comprises both water and an organic solvent, such as an aqueous methanol solution containing about 1% by weight water and about 90% by weight methanol. The organic clay composition can be isolated using conventional techniques such as filtration, centrifugation, antisolvent precipitation, decantation, and the like. Various techniques suitable for separating the organic clay compositions provided by the present invention are disclosed in the experimental part of the present disclosure. In one embodiment, the present invention provides an organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising a quaternary cation having a structure X - 42 - 200900452

Wherein Ar1, Ar2 and Ar3 are independently C2-C5Q aromatic groups; Ar4 is a bonding or C2-C5G aromatic group; "a" is a number from 1 to about 200; "c" is 0 Up to 3; each occurrence of R1 is independently a halogen atom, an aliphatic group, a C5-C2Q cycloaliphatic group or a C2-C2G aromatic group; and R2 is a halogen atom, an aliphatic group, C5_C2Q cycloaliphatic group, C2-C5 〇 aromatic group or polymer chain. The organic scale cation X is illustrated by the cationic component of the organic iron salt disclosed in Table I. In one embodiment, the quaternary phosphonium cation has the structure XI.

In another embodiment, the quaternary cation has a structure of -43-XII.

XII 200900452

In one embodiment, the present invention provides an organic clay composition comprising a polymeric quaternary cation. In one embodiment, the present invention provides an organic clay composition comprising a polymeric quaternary phosphonium cation having structure XIII.

0

-Ar5

m XIII wherein m is a number in the range of from about 10 to about 1,000; and Ar5 is a C2-C5Q aromatic group or a polymer chain. In one embodiment, the 'Ar5 is an aromatic group having the structure XIV.

In one embodiment, the present invention provides an organic clay composition comprising alternating no-44-200900452 organic sulphate layers and an organic layer comprising a pyridine gun cation having a structure XXV

Wherein Ar6, Ar7 and Ar8 are independently C2-C5〇 aromatic groups; "b" is a number from 0 to 2; each occurrence of R3 is independently a halogen atom, an aliphatic group, a Cs-Cu ring An aliphatic group or a C2_C2 fluorene aromatic group; and the Ar11 is an aromatic group or a polymer chain comprising at least one aromatic group. The pyridinium cation having the structure XXV is illustrated by the cationic component of the pyridyl salt disclosed in the surface of the present invention. In one embodiment, the present invention provides an organic clay composition comprising alternating inorganic silicate layers and an organic layer comprising a pyridinium cation having structure XXVI

-45- 200900452 wherein Ar6, Ar7 and Ar8 are independently C2-C5〇 aromatic groups; "b" is 0 to 2; "d" is 0 to 4; R3 and R4 are each Each of which is independently a halogen atom, an aliphatic group, a C5-C2 anthracycline aliphatic group or a C2-C2G aromatic group; the Z system is a bonded, divalent CrCM aliphatic group, and a divalent c5-c2Q a cycloaliphatic group, a divalent c2-c2G aromatic group, an oxygen linkage, a sulfur linkage, a S02 linkage or a Se linkage; and the Ar9 is a Clc-C2()() aromatic group or comprises at least An aromatic based polymer chain. The pyridyl cation having the structure XXVI is illustrated by the cationic component of the pyridine gun salt of Table II of the present invention. In one embodiment, the invention provides an organoclay composition comprising a pyridine gun cation having structure XXVII.

Ph

In another embodiment of the invention, the invention provides an organoclay composition comprising a pyridine gun cation having structure XXVIII. -46 - 200900452

In one embodiment, the organic clay composition provided by the present invention comprises a polymeric quaternary organic cation.

child. In a specific embodiment, the polymeric pyridyl cation system comprises a structure XXIX

XXIX wherein the variable "e" is from about 1 〇 to about 1000; and Ar10 is a C2-C5 〇 aromatic group or a polymer chain. In one embodiment, the Ar1G system is a C23 aromatic group having the structure XXX.

Ph

Ph

In another specific embodiment of the present invention, the present invention provides an organic clay composition comprising a polymeric pyridyl cation having the structure χχχιι -47- 200900452

XXXII where "f" is a number from about 10 to about 1000. In a specific implementation, "f" has about 1〇. In another specific embodiment, "f" has about 30 miles. In one embodiment, the present invention provides an organic clay composition comprising alternating inorganic silicate layers and an organic layer comprising a quaternary cation having a structure of XXXIII

XXXIII wherein Ar12, Ar13, Ar14 and Ar15 are independently a C2-C50 aromatic group; and Ar16 is a C2-C2Q (3 aromatic group or a polymer chain comprising at least one aromatic group) having the structure XXXIII The fourth-stage rust cation is sometimes referred to as "benzophenone-containing organic squamous cation" in the present invention. The quaternary iron cation having the structure XXXIII is illustrated by the cationic component of the organic squama salt disclosed in Table IV of the present invention. 200900452 In one embodiment, the present invention provides an organic clay composition comprising a quaternary cation having structure XXXIV.

Ph

Ph-^P-Ph

I

Ph

In another specific embodiment of the invention, the present invention provides an organic clay composition comprising a quaternary cation having a structure of XXXV.

Ph

Ο

XXXV In still another embodiment, the present invention provides an organic clay composition comprising a polymeric quaternary phosphonium cation having the structure XXXVII

XXXVII -49 200900452 wherein "g" and "h" are independently 0 to 4; W is a bonded, divalent C^-Cm aliphatic group, and a divalent C5-C2() cycloaliphatic group a group, a divalent C2-C2 anthracene group, an oxygen linkage, a sulfur linkage, a s〇2 linkage or a Se linkage; each of R5 and R6 is independently a halogen atom, a Cl-C2() lipid a group, a C5-C2G cycloaliphatic group or a C2-C2Q aromatic group; "i" is a number from about 10 to about 1000; and the Ar17 is a C1Q-C2()() aromatic group or A polymer chain comprising at least one aromatic group. In a specific embodiment, the 'Ar17 system is an aromatic group having a structure of χχχνίΐΐ. 〇

XXXVIII The polymeric quaternary quaternary cation having structure XXXVII is illustrated by the cationic component of the polymeric organic squara salt disclosed in Table V of the present invention. In one embodiment, the present invention provides a polymer-organic clay composite composition comprising (a) a polymer resin and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer Wherein the organic layer comprises a quaternary organic cation. In one embodiment, the polymer resin comprises an amorphous thermoplastic polymer. In another embodiment, the polymer resin comprises a crystalline thermoplastic polymer. In another embodiment, the polymer resin -50-200900452 comprises an amorphous thermoplastic polymer and a crystalline thermoplastic polymer. Examples of amorphous thermoplastic polymers are PPSU (polyphenylene fluorene), PEI (polyether sulfimine), PES (polyether oxime), PC (polycarbonate), PP oxime (polyphenylene ether), PMMA ( Polymethyl methacrylate), ABS, (acrylonitrile butadiene styrene) and PS (polystyrene). Examples of crystalline thermoplastic resins are PFA (perfluoroalkoxy alkane), MF A (copolymer of tetrafluoroethylene and perfluorinated vinyl ether), FEP (fluorinated ethylene propylene polymer), PPS (polyphenylene sulfide) ), PEK (polyether ketone), PEEK (polyether-ether ketone), ECTFE (ethylene chlorotrifluoroethylene), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PET (polyphenylene terephthalate) Ethylene formate), POM (polyacetal), PA (polyamide), UHMW-PE (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene) , LDPE (Low Density Polyethylene) and advanced engineering resins such as PBI (polybenzimidazole) and PAI (polyamido-quinone imine), polyphenylene, polybenzoxazole, polybenzothiazole and their blends Compounds and copolymers. In one embodiment, the polymer resin is selected from the group consisting of polyetherimine, polyamine, polyester, polyarylene sulfide, polyarylene ether, polyether oxime, polyether ketone, polyether ether ketone, Polyphenylene, polycarbonate, and combinations comprising at least one of the foregoing polymers. In a particular embodiment, the polymeric resin comprises a polyetherimide resin, such as ULTEM, available from GE Plastics' In another specific embodiment, the polymeric resin comprises a polyphenylene resin, such as PRIMOSPIRE, available from Solvay, Inc. In another specific embodiment, the polymeric resin comprises a polyether oxime, such as RA DEL A, available from Solvay, Inc. In still another specific embodiment, the polymer resin comprises a polyether ketone. -51 - 200900452 The organic clay composition present in the polymer-organic clay composite composition is preferably highly exfoliated, indicating that the distance between the inorganic tellurite layers is greater than the same organic clay composition in the intrusion polymer - organic The polymer matrix of the clay composite composition is preceded by the distance between the corresponding silicate layers. The organic clay composition provided by the present invention is designed to promote the relatively smooth separation of the tantalate layer because shear forces are applied to the organic clay composition in the presence of a polymer resin or solvent. Therefore, in one embodiment, the polymer-organic clay composite composition provided by the present invention comprises an organic clay composition comprising alternating inorganic silicate layers and an organic layer, wherein the alternating inorganic cerium salt The layer is highly dispersed relative to the organic clay composition used to derivatize the silicate layer of the polymer-organic clay composite composition. In a specific embodiment, the polymer-organic clay composite composition provided by the present invention comprises an inorganic tantalate layer selected from the group consisting of kaolin, dickite, pearlite, halloysite, and serpentine. , chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, alley stone, montmorillonite, attapulgite, hectorite, tetradecyl mica, sodium band mica, muscovite, pearl mica, Inorganic clay derived from talc, vermiculite, phlogopite, green fragile mica, chlorite and combinations thereof. In one embodiment, the inorganic clay is selectively converted to an organic clay composition and the intermediate organic clay composition is subsequently used to prepare a polymer-organic clay composite composition. In one embodiment, the organic clay composition used to prepare the polymer-organic clay composite composition is characterized by an interlayer distance of from about 5 to about 100 angstroms. Although the organic clay composition used in the actual mass can be highly stripped in the polymer-organic clay composite-52-200900452 material composition, the interlayer distance of at least a portion of the organic clay composition used is maintained at 5 to about 1 〇〇. Within the range of ang. In one embodiment, the invention provides an article comprising a polymer-organic clay composite composition provided by the invention. In a particular embodiment, the article is a film. In a particular embodiment, the article is an extruded film. In another specific embodiment, the article is a solvent cast film. Extruded films can be made using the techniques described herein. Solvent cast films comprising the polymer-organic clay composite compositions of the present invention can be prepared by art recognized methods. In a specific embodiment, the present invention provides a solvent cast film comprising a polyether oxime having a dianhydride component and a diamine component and having a glass transition temperature (Tg) of between about 180 ° C and 450 ° C. An imine, and wherein the film has: a) a CTE of less than 70 ppm/°C; b) a thickness between about ί. ίμιη and 250 μηη; and c) a residual solvent of less than 5% by weight. In one embodiment, the present invention provides a polymer-organic clay composite composition comprising a polymer resin which is a polyether quinone imine having a dianhydride component and a diamine component. This means that the polyether oximine comprises a structural unit derived from at least one dianhydride and at least one diamine. The polyether oxime having a dianhydride component and a diamine component and a desired Tg can be subjected to polycondensation conditions by one or more diamines and one or more dianhydrides (for example, by means of a device to remove reaction water) The refluxing ortho-dichlorobenzene in the vessel is prepared by reacting in the presence of sodium phenylphosphonate (SPP). Suitable dianhydrides include: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; -53- 200900452 4,4'-bis(3,4-dicarboxybenzene Oxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy Diphenyl ketone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylborane dianhydride; 2.2-bis[4-(2,3-dicarboxyphenoxy) Phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl Thioether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ketone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl Terpene anhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3 -dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4^(3,4- Dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ketone dianhydride; -(2,3-dicarboxyphenoxy)-4'-( 3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride; 1.3-bis(2,3-dicarboxyphenoxy)phthalic anhydride; 1,4-bis(2,3-dicarboxyphenoxy) Benzene phthalic anhydride; 1.3-bis(3,4-dicarboxyphenoxy)phthalic anhydride; 1.4-bis(3,4-dicarboxyphenoxy)phthalic anhydride; cyclobutane tetracarboxylic dianhydride; Pentane tetracarboxylic dianhydride; -54 200900452 cyclohexane-1,2,5,6-tetracarboxylic dianhydride; 2.3.5-tricarboxycyclopentyl acetic acid dianhydride; 5-(2,5-dioxygen Tetrahydrofurfural)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride; 1,3,3a,5-dioxy-3-furanyl)-naphtho[1, 2,-c]-furan-1,3-dione; 3.5.6- tricarboxy-norbornane-2-acetic acid dianhydride; 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride; 3,3', 4,4'-diphenyltetracarboxylic dianhydride; 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride; naphthalene dicarboxylic acid dianhydride such as (2,3,6,7-naphthalene Formic acid dianhydride, etc.); 3,3',4,4'-diphenylsulfonic acid tetracarboxylic dianhydride; 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride; 3,3',4 , 4'-dimethyldiphenyldecane tetracarboxylic dianhydride; 4,41-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis (3,4- Carboxyphenoxy)diphenyl phthalic anhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride; 3,3',4,4'-perfluoropyridinediphenyl Dicarboxylic acid dianhydride; 3,3\4,4'-biphenyltetracarboxylic dianhydride; bis(phthalic)phenylsulphine oxide dianhydride; Base-bis(triphenylphthalic acid) dianhydride; m-phenylene-bis(triphenylphthalic acid) dianhydride; bis(triphenylphthalic acid)-4,4'-diphenyl Ether dianhydride; -55- 200900452 bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride; 2,2'-bis-(3,4-dicarboxyphenyl)hexafluoro- Propane dianhydride; 4,4'-oxydiphthalic anhydride; pyromellitic dianhydride; 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride; 4',4'-bisphenol A dianhydride; hydroquinone diphthalic anhydride; ethylene glycol diphenyl trimellitic anhydride; 6,6'-bis(3,4-dicarboxyphenoxy)-2,2',3,3'-four Hydrogen-3,3,3',3'-tetramethyl-1,1'-spiro[lh-indole] dianhydride; 7,7'-bis(3,4-dicarboxyphenoxy)-3 ,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2'-spiro[2h-l-benzophenone Di-anhydride; 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'-diphenyl sulfoxide tetracarboxylic dianhydride; 3,4'-oxygen Diphthalic anhydride; 3,3'-oxydiphthalic anhydride; 3,3'-diphenylmethanone tetracarboxylic 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; -56- 200900452 (3,3',4,4'-diphenyl)phenylphosphine tetracarboxylic dianhydride; (3,3',4,4'-diphenyl)phenyl Phosphonium oxide tetracarboxylic dianhydride; 2,2'-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; 2,2'-dibromo-3,3' , 4,4'-biphenyltetracarboxylic dianhydride; 2,2'-diiodo-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2 di-trifluoromethyl- 3,3 , 4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1-methyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1_trifluoromethyl-2-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1-trifluoromethyl) 3-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1-trifluoromethyl-4;phenyl)-3,3' , 4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1-phenyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 4,4'-bisphenol A dianhydride; 5,5'-[1,4-phenylenebis(oxy)]bis[1,3-isobenzofuranedione]; 3,3',4 , 4'-diphenylarylenetetracarboxylic dianhydride; 4,4'-carbonyldiphthalic anhydride; 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride; 2,2'- Bis(1,3-trifluoromethyl-4-phenyl)-3,3',4,4'-biphenyltetramethyl-57- 200900452 acid dianhydride; isomers thereof; and combinations thereof. Suitable diamines include: ethylidene diamine; propylenediamine; trimethylenediamine; diethyltriamine; triethylamine; hexamethylenediamine; heptamethylenediamine ; octamethylenediamine; nonamethylenediamine; decamethylene diamine; 1,1 2 -dodecanediamine; 1,18-octadecanediamine; 3-methylhepta Methyldiamine; 4,4-dimethyl heptamethylenediamine; 4-methylhexamethylenediamine; 5-methylhexamethylenediamine; 2,5-dimethylhexaa Methyldiamine; 2,5-dimethyl heptamethylenediamine; 2, 2-dimethylexylenediamine; N-methyl-bis(3-aminopropyl)amine; 3-methyl Oxyhexamethylenediamine; 1,2-bis(3-aminopropoxy)ethane; bis(3-aminopropyl) sulfide; 1,4-cyclohexanediamine; (4-Aminocyclohexyl)methane; m-phenylenediamine; p-phenylenediamine; 2,4-diaminotoluene; 2,6-diaminotoluene; m-phenyldimethylamine; Benzene-methylamine; 2-methyl-4,6--_ethyl-1,3-extension-based-monoamine; 5-methyl-4,6-diethyl-1,3-benzene -diamine; benzidine; 3,3'-dimethylbenzidine; 3,3'-dimethoxybenzidine; 1,5-diaminonaphthalene; bis(4-aminophenyl)methane; bis(2-chloro-4-amino-3,5-diethylphenyl)methane; bis(4-aminobenzene) Propane; 2,4-bis(b-amino-t-butyl)toluene; bis(p-b-amino-t-butylphenyl)ether; bis(p-b-methyl-o- -aminophenyl)benzene, bis(p-b-methyl-o-aminopentyl)benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) Thioether, bis(4-aminophenyl) milled, bis(4-aminophenyl)ether and 1,3-bis(3-aminopropyl)tetramethyldioxane; 4,4' -diaminodiphenylpropane; 4,4'-diaminodiphenylmethane (4,4'-methylenediphenylamine); 4,4'-diaminodiphenyl sulfide; 4,4 '-Diaminodiphenyl maple; 3,3'-di-58- 200900452 Aminodiphenylboron; 4,4'-diaminodiphenyl sulfide; 3,3,diaminodiphenylsulfide Ether; 4,4·-diaminodiphenyl ether (4,4'-oxydiphenylamine); 1,5-diaminonaphthalene; 3,3'dimethylbenzidine; 3-methyl-7 Methylene diamine; 4,4-dimethyl heptamethylenediamine; 2,1 1-dodecanediamine; octamethylenediamine; bis(3-aminopropyl)tetramethyl two Oxane; bis(4-aminobutyl)tetramethyldioxane: bis(p-amino-t-butylphenyl)ether; bis(p-methyl-o-aminophenyl) Benzene; bis(p-methyl-o-aminopentyl)benzene; 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethylspiro[1H-茚]-6,6·-diamine; 3,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2,-spiro[2H-l-benzene And piper]-7,7'-diamine; l,l'-bis[l-amino-2-methyl-4-phenyl]cyclohexane; isomers thereof; and combinations thereof. The polymer-organic clay composite composition provided by the present invention comprises an organic clay composition. In one embodiment, the organic clay composition used is the organic clay composition provided by the present invention. Therefore, in a specific embodiment, the polymer-organic clay composite composition comprises at least one organic clay composition comprising an organic iron cation having a structure X, a pyridyl cation having a structure XXV, having a pyridyl cation of structure XXVI and a quaternary organic cation having a benzophenone organophosphonium cation of structure XXXIII. Therefore, in one embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer The organic layer comprises a quaternary cation having a structure X. In another embodiment -59-200900452, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay comprising alternating inorganic silicate layers and an organic layer A composition comprising a quaternary iron cation having structure XI. In still another embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic citrate layers and an organic layer' The organic layer comprises a quaternary cation having structure XII. In one embodiment, the present invention provides an article comprising a polymer-organic clay composite composition comprising (a) a polymer resin; and (b) comprising an alternating inorganic bismuth layer and An organic clay composition of an organic layer comprising a quaternary cation having structure X.

In another embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition comprising melt-mixing conditions to polymerize a resin with an inorganic tantalate layer comprising The organic layer is contacted with an organic clay composition comprising a quaternary scale cation having structure X. In one embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a pyridine gun cation having structure XXV. In another specific embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises pyridine cation-60-200900452 having the structure XXVI. In still another embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a pyridyl cation having structure XXVII. In still another embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a pyridinium iron cation having structure XXVIII. In one embodiment, the present invention provides an article comprising a polymer-organic clay composite composition comprising (a) a polymer resin; and (b) comprising an alternating inorganic bismuth layer and An organic clay composition of an organic layer comprising a pyridine gun cation having structure XXV. In another embodiment, the present invention provides an article comprising a polymer-organic clay composite composition comprising (a) a polymer resin; and (b) comprising an alternating inorganic bismuth layer and An organic clay composition of an organic layer comprising a pyridyl cation having structure XXVI. In another embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition comprising melt-mixing conditions to polymerize a resin with an inorganic tantalate layer comprising The organic layer is contacted with an organic clay composition comprising a pyridyl cation having structure XXV. In another embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition comprising melt-mixing conditions to polymerize a polymer resin with an inorganic hydrazine comprising -61 - 200900452 The acid salt layer is contacted with an organic clay composition of the organic layer comprising a pyridyl cation having structure XXVI. Therefore, in one embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer The organic layer comprises a quaternary cation having the structure XXXIII. In another specific embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a quaternary cation having the structure XXXIV. In still another embodiment, the present invention provides a polymer-organic clay composite composition (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a quaternary scale cation having the structure xxxv. In one embodiment, the present invention provides an article comprising a polymer-organic clay composite composition comprising (a) a polymer resin; and (b) comprising an alternating inorganic bismuth layer and An organic clay composition of an organic layer comprising a quaternary cation having a structure of XXXIII. In another embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition comprising melt-mixing conditions to polymerize a resin with an inorganic tantalate layer comprising The organic layer is contacted with an organic clay composition comprising a quaternary cation having structure XXXIII. -62- 200900452 Preparation of a Melt Mixing Path of a Polymer-Organic Clay Composite Composition In one embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition, which is included Melting and mixing a four-stage organic clay composition comprising an alternating inorganic silicate layer and an organic layer (the organic layer comprising a quaternary organic cation) and a polymer resin at a temperature of about 300 ° C and a temperature in the range of about 450 ° C A polymer-organic clay composite composition is provided, the polymer-organic clay composite composition characterized by a peel percentage of at least 10%. The quaternary organic clay composition is an organic clay composition comprising a quaternary organic cation (e.g., an organic scaly cation having structure X).

The fourth-order organic cation to be used is not particularly limited except that it must have sufficient stability during the melt-mixing step to allow the organic clay composition to achieve an effective peeling level of the polymer matrix. A fourth-order organic cation is considered to be stable if more than about 90 percent of the fourth-order organic cation remains after the process time and strength sufficient to achieve a strip percentage melting mix of at least 1 〇. In one embodiment, the quaternary organic cation has the structure XXXIX R9 R8 - Q R1. Γ

R7 XXXIX wherein Q is nitrogen or phosphorus; and R7, R8 'R9 and R1G are independently H20 aliphatic group, C5-C2G cycloaliphatic group, c2-c2Q aromatic group-63-200900452 group or polymerization Chain of things. In a specific embodiment, the fourth-order organic cation having structure XXXIX is a quaternary scale cation such as tetraphenyl cation, TPP. In another embodiment, the fourth-order organic cation having structure XXXIX is a quaternary rust cation having structure X. In still another embodiment, the quaternary organic cation having structure XXXIX is a quaternary cation having a structure of XXXIII. In one embodiment, the quaternary organic cation having structure XXXIX is a quaternary ammonium cation, such as a tetraphenylammonium cation, TPA. In one embodiment, the quaternary organic cation is a pyridyl cation having a structure XXV. In another embodiment, the quaternary organic cation is a pyridyl cation having the structure XXVI. In one embodiment, the inorganic silicate layer is derived from an inorganic clay selected from the group consisting of kaolin, dickite, pearlite, halloysite, serpentine, chrysotile, pyrophyllite, and montmorillonite. Stone, beide stone, nontronite, saponite, zinc montmorillonite, strontite, hectorite, tetradecyl mica, sodium band mica, muscovite, pearl mica, talc, vermiculite, phlogopite, green fragile Mica chlorite and its combination. Typically, the inorganic clay is selected to be converted to an organic clay composition comprising a quaternary organic cation. In some embodiments, the organic clay composition can be prepared in the presence of a polymeric resin. Suitable organic clay compositions include the organic clay compositions of the present invention. In one embodiment, the organic clay composition used is characterized by a layer distance of from about 5 to about 100 angstroms. In this case, at least a portion of the product polymer-organic clay composite composition also has a feature that the interlayer distance is from about 5 to about 100 angstroms. -64 - 200900452 In one embodiment, the preparation is carried out by melt mixing a quaternary organic clay composition comprising a fourth-order organic cation with a polymer resin at a temperature in the range of about 300 ° C and about 45 ° The polymer-organic clay composite composition comprises a polyarylene sulfide such as polyphenylene sulfide (PPS). In another embodiment, the polymerization prepared by melt mixing a quaternary organic clay composition comprising a fourth-order organic cation with a polymer resin at a temperature ranging between about 300 ° C and about 45 ° ° C The organic-organic clay composite composition comprises a polyether oxime, such as a copolymer comprising structural units derived from bisphenol A and bis(4-chlorophenyl)anthracene. In still another embodiment, the polymerization is prepared by melt mixing a fourth-order organic clay composition comprising a fourth-order organic cation with a polymer resin at a temperature ranging between about 300 ° C and about 450 ° C. The organic-organic clay composite composition comprises a polyether ketone, such as a copolymer comprising bisphenol A and 4,4'-dichlorodiphenyl ketone derived structural units. Melt mixing can be carried out using any of the melt mixing techniques combined with a range of about 300 ° C and about 450 ° C in sufficient shear to achieve at least 10 percent peeling of the organic clay composition in the polymer resin. The ability to heat organic clay compositions and polymer resins at temperatures. Generally, melt mixing can be carried out using an extruder. In one embodiment, the extruder is an exhaust twin-screw extruder. In another embodiment, the extruder is an exhaust single screw reciprocating extruder. In one embodiment, the melt mixing is carried out in a kneader. In one embodiment, the melt blend has sufficient time and strength to achieve a percent peeling of the organic clay composition in the polymer resin of at least 20 percent. Further, in another embodiment, the molten mixed system has a sufficient history time and strength so that the percentage of peeling of the organic clay composition in the polymer resin reaches at least 30%. In one embodiment, the present invention provides an article comprising a polymer-organic clay composite composition having a composition of between about 300 volts and about 45 (TC range) The internal temperature is prepared by melt-mixing the following components under shear for a percentage of peeling of the organic clay composition in the polymer resin to at least 10%: (a) Four layers comprising alternating inorganic citrate layers and organic layers a layered organic clay composition comprising a quaternary organic cation; and (b) a polymer resin. In one embodiment, the invention provides a method of making a polymer-organic clay composite composition, And a polymer resin comprising a quaternary organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising a quaternary organic cation comprising at least one polymer selected from the group consisting of Indoleamine, polyester, polyarylene sulfide, polyarylene ether, polyether mill, polyether ketone, polyetheretherketone, polyphenylene and polycarbonate Free of polyether oximine; the melt mixing is carried out at a temperature in the range of about 300 ° C and about 45 ° C to provide a polymer-organic clay composite composition, the polymer-organic clay composite The material composition is characterized by a percentage of peeling of at least 1%. When the polymer resin contains less than 5 weight percent of polyetherimine based on the total weight of the polymer resin, it is substantially free of polyether quinone The polymer resin containing ruthenium by weight polyether oximine is also referred to as substantially free of polyether 醯-66 - 200900452 imine. In another embodiment, the invention provides a polymer-organic clay composite An article of material composition, the polymer-organic clay composite composition comprising (a) a four-stage organic clay composition comprising alternating inorganic silicate layers and an organic layer, the organic layer comprising a quaternary organic cation; And (b) the polymer resin comprises at least one polymer selected from the group consisting of polyamines, polyesters, polyarylene sulfides, polyarylene ethers, polyether oximes, polyether ketones, polyetheretherketones, polyphenylenes. And polycarbonate; The polymer resin is substantially free of polyetherimine; wherein the polymer-organic clay composite composition is characterized by a percentage of peeling of at least 1%. In one embodiment, the article is a film. In one embodiment, the article is a solvent cast film comprising a polyether quinone having a dianhydride component and a diamine component and between about 180 ° C and 4500 ° C. Τg, and wherein the film has: a) a CTE of less than 70 ppm/°C; b) a thickness between about ί. ίμιη and 205 μm; and 〇 contains less than 5% by weight of residual solvent. In one embodiment, the present invention provides a method of making a polymer-organic clay composite composition comprising melt-mixing a four-stage organic clay comprising alternating inorganic silicate layers and an organic layer in an extruder a composition comprising a polymer resin comprising polyether maple, the organic layer comprising a quaternary organic cation, the polymer resin being substantially free of polyether quinone; the molten mixture being at about 300 ° C and about 45 The temperature in the range of 0 °C is carried out to provide a polymer·organic clay composite composition characterized by a peel percentage of at least 10%. In a specific embodiment, the quaternary organic cation has a structure X. Further -67- 200900452 In a specific embodiment, the quaternary organic cation has a structure XXV. In another embodiment, the quaternary organic cation has a structure XXVI. In still another embodiment, the quaternary organic cation has the structure XXXIII. In one embodiment, the present invention provides a method of making a polymer-organic clay composite composition comprising melt mixing a quaternary organic clay composition comprising an alternating inorganic silicate layer and an organic layer with a polyether a quinone imine composition comprising a quaternary organic cation; the molten mixture is carried out at a temperature between about 300 ° C and about 45 (TC) to provide a polymer-organic clay composite composition, The polymer-organic clay composite composition is characterized by a percentage of peeling of at least 1%. In one embodiment, the quaternary organic cation has a structure X. In another embodiment, the quaternary organic The cation system has the structure XXV. In another embodiment, the quaternary organic cation system has the structure XXVI. In still another embodiment, the quaternary organic cation system has the structure XXXIII. In a specific embodiment The polyether quinone imine composition further comprises at least one polymer selected from the group consisting of polyvinyl chloride, polyolefin, polyester, polyamine, poly maple, poly Maple, polyphenylene sulfide, polyether ketone, polyetheretherketone, ABS, polystyrene, polybutadiene, poly(acrylate), poly(alkyl acrylate), polyacrylonitrile, polyacetal, polycarbonate Ester, polyphenylene ether, ethylene-vinyl acetate copolymer, polyvinyl acetate, liquid crystal polymer, aromatic polyester, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride Ethylene, polytetrafluoroethylene, and a combination comprising at least one of the foregoing polymers. In one embodiment, the polyether-68-200900452 quinone imine composition comprises a polyether oxime. In another embodiment, The polyether quinone imide composition comprises a polyether ketone. In one embodiment, the invention provides an article comprising a polymer-organic clay composite composition (a) comprising alternating inorganic silicate layers and a fourth-order organic clay composition of an organic layer, the organic layer comprising a quaternary organic cation; and (b) a polyether quinone composition, wherein the polymer-organic clay composite composition is characterized by a peel percentage of at least 1 〇 percentage. Appropriate The ether quinone imine composition comprises ULTEM polyether quinone imine available from GE Plastics. In one embodiment, the invention provides a method of making a polymer-organic clay composite composition, which is included in extrusion Melting and mixing a four-stage organic clay composition comprising an alternating inorganic silicate layer and an organic layer with a polyether sulfimine composition, the organic layer comprising a quaternary organic cation, the polyether quinone imine composition comprising At least one polyetherimine and at least one additional polymer selected from the group consisting of polyamines, polyesters, polyarylene sulfides, polyarylene ethers, polyether oximes, polyether ketones, polyetheretherketones, polyphenylenes And a polycarbonate; the molten mixture is carried out at a temperature in the range of about 300 ° C and about 450 ° C to provide a polymer-organic clay composite composition, the polymer-organic clay composite The material composition is characterized by a percentage of peeling of at least 1%. In a specific embodiment, the quaternary organic cation system has a structure X. In another embodiment, the quaternary organic cation system has a structure XXV. In another embodiment, the quaternary organic cation has the structure XXVI. In still another embodiment, the quaternary organic cation has the structure XXXIII. -69- 200900452 Preparation of In-situ Polymerization Path of Polymer-Organic Clay Composite Composition In one embodiment, the present invention provides a method for preparing a polymer-organic clay composite composition, which is organic The in-situ polymerization technique is used to produce a polymer resin in the presence of a clay composition. The developed method presents various advantages, especially the close contact between the organic clay composition and the original polymer resin. Thus in one aspect the invention provides a method of making a polymer-organic clay composite composition comprising (a) subjecting a first monomer, a second monomer, a solvent, and an organic to polycondensation conditions. The clay composition is contacted to provide a first polymerization mixture comprising alternating inorganic silicate layers and an organic layer, wherein one of the first monomer and the second monomer is two An amine and the other is a dianhydride; (b) performing a stoichiometric verification step on the first polymerization mixture; (c) optionally adding additional reactants to the first polymerization mixture to provide a second polymerization mixture And (d) removing the solvent from the first polymerization reaction mixture or the second polymerization reaction mixture to provide a first polymer-organic clay composite composition comprising a polymer component and an organic clay component, wherein the organic component The clay component is at least 1% peeled off. In one embodiment, the polymer component is a polyetherimine. In one embodiment, the polymerization is carried out in the presence of a catalyst such as sodium phenyl phosphonate (SPP). In one embodiment, the first single system is a dianhydride and the two -70-200900452 single system is a diamine. Suitable diamines and dianhydrides include those disclosed herein, such as BPADA and m-phenylenediamine. Suitable solvents include aromatic solvents such as o-dichlorobenzene, toluene, xylene, chlorobenzene and combinations of the foregoing solvents. The organic clay composition can be any of the organic clay compositions disclosed herein. The stoichiometric verification step can use any analytical technique suitable for accurately determining the ratio of the first monomer to the second monomer in the first reaction mixture. For example, the ratio of the first monomer to the second monomer in the first reaction mixture can be determined by infrared analysis of a film prepared from a portion of the sample obtained from the first reaction mixture as described in the experimental section of the present invention. Alternatively, the ratio of the first monomer to the second monomer in the first reaction mixture can be determined by techniques recognized by the art such as high performance liquid chromatography (HPLC), nuclear magnetic resonance spectroscopy (NMR), and terminal titration. The stoichiometric verification step is of importance because the reaction stoichiometry must be carefully controlled to achieve one or more of the target polymer-organic clay composite compositions. In one embodiment, the stoichiometric verification step comprises determining the ratio of amine to anhydride. Additional monomer may be added if a monomer deficiency is detected after the stoichiometric verification step. Alternatively, the stoichiometric verification step can signal the need to add additional reagents, such as chain terminators. When additional reactants are added to the first polymerization mixture, it is considered to constitute a second polymerization mixture which can be further reacted by, for example, heating. After completion of the polymerization reaction, the solvent is removed to provide a first polymer-organic clay composite composition comprising a polymer component and an organic clay group - 71 - 200900452 parts wherein the organic clay component is at least 10% stripped . Solvent removal can be carried out by techniques recognized by the art, such as distillation, filtration, anti-solvent filtration, and the like. In one embodiment, the solvent is removed from the first polymerization mixture or the second polymerization mixture using a devolatilization extruder, a wiped film evaporator, or a combination thereof. In a specific embodiment, the first polymer/organic clay composite composition is further subjected to a step of melt-mixing at a temperature in the range of about 3,000 ° C and about 450 Torr. In particular, the melt mixing further increases the degree of exfoliation of the organic clay component of the polymer-organic clay composite composition. In one embodiment, the contact system is heated at a temperature greater than 100 ° C under polycondensation conditions. In a specific embodiment, the contact system is heated at a temperature below 1 001 under polycondensation conditions. In another embodiment, the contact system is heated at a temperature greater than 100 ° C in the presence of a solvent and a catalyst under polycondensation conditions. In a specific embodiment, the contact system is heated at a temperature lower than 100 ° C in the presence of a solvent and a catalyst under polycondensation conditions. In a specific embodiment, the first single system is a dianhydride having the structure XL.

-72- 200900452 where "j" and rk" are independently 0 to 3; R1 and R12 are each independently a halogen atom, a Ci-C 2 0 aliphatic group, C 5 - C 2 An anthracycline aliphatic group or a C 2 -C 20 aromatic group j and W is a bonded, divalent Ci -C 2 0 aliphatic group '-' fS c 5 -C 2 0 cycloaliphatic group, Divalent c 2 -C 2 〇aromatic group, oxygen linkage, sulfur linkage>S〇2 linkage or se linkage 〇 in a specific embodiment, the dianhydride XL is selected from 1 bisphenol A dianhydride (BPADA), 4,4,-oxydiphthalic anhydride (4,4,_〇DPA), 3,4,-oxydiphthalic anhydride (3,4'-〇DPA) 3,3,-oxydiphthalic anhydride (3,3'-ODPA), 4,4'-biphenyl dianhydride, 3,4'-biphenyl dianhydride, a combination thereof. In another embodiment, the dianhydride used is any dianhydride disclosed in the present invention. In one embodiment, the second single system is a diamine selected from any of the diamines disclosed herein, such as m-phenylenediamine. In a specific embodiment, the second single system is an aromatic diamine. In one embodiment, the aromatic diamine is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylanthracene, and 4,4'-oxydiphenylamine.

In one embodiment, the organoclay composition comprises a quaternary organic cation. In one embodiment, the quaternary organic cation has the structure XXXIX R9 R*—Q-R10 I®

R7 XXXIX -73- 200900452 wherein Q is nitrogen or phosphorus; and R7, R8, R9 and R1Q are independently C^-Czo·aliphatic groups, C5-C2Q cycloaliphatic groups, C2-C2e aromatics a group or a polymer chain. The organic clay composition containing the four-stage organic cation XXXIX is commercially available under specific conditions. Alternatively, an organic clay composition comprising a four-stage organic cation XXXIX can be prepared using the techniques disclosed herein. In one embodiment, the quaternary organic cation is selected from the group consisting of a decyltrimethylammonium cation, a dodecyltrimethylammonium cation, a tetradecyltrimethylammonium cation, and a hexadecacarbyl tertiary Alkyl ammonium cation, octadecyl trimethyl ammonium cation, and combinations thereof. In one embodiment, the organoclay composition comprises a non-quaternary organic cation, such as a protonated aromatic amine. As mentioned above, the organic clay composition employed comprises alternating inorganic silicate layers and organic layers. The inorganic silicate layer, as taught by the present invention, can be derived from inorganic clay materials. In a specific embodiment, the inorganic bismuth layer is selected from the group consisting of kaolin, dickite, pearlite, halloysite, serpentine, chrysotile, pyrophyllite, montmorillonite, beidellite, and green Stone, saponite, zinc montmorillonite, attapulgite, hectorite, Sishayuan mica, sodium band mica, muscovite, pearl mica, talc, vermiculite, phlogopite, green crisp mica, chlorite and Derived from a combination of inorganic clay. In one embodiment, the invention provides a method of making a polymer-organic clay composite composition comprising (a) between about 105 ° C and about 250 in a solvent. (The temperature in the range is such that the dianhydride is contacted with the diamine in the presence of an organic clay composition to provide a first polymerization mixture, -74-200900452. The organic clay composition comprises alternating inorganic silicate layers and organic layers (b) determining the ratio of amine to anhydride in the first polymerization mixture; (c) adding an additional dianhydride or diamine to the first polymerization mixture as appropriate to provide a second polymerization mixture; and (d) using A devolatilizer extruder removes solvent from the first polymerization reaction mixture or the second polymerization reaction mixture to provide a first polymer-organic clay composite composition comprising a polymer component and an organic clay component, wherein The organic clay component is at least 1% exfoliated. In one embodiment, the method further comprises melt mixing the first polymer at a temperature in the range of about 3 ° C and about 45 ° C. - a step of an organic clay composition. In one embodiment, the invention provides a method of making a polyether sulfimine-organic clay composite composition comprising (a) in o-dichlorobenzene The bisphenol A dianhydride (BP ADA) is contacted with a diamine in the presence of an organic clay composition at a temperature in the range of about 125 ° C and about 250 ° C to provide a first polymerization mixture, the organic clay composition Including alternating inorganic citrate layers and organic layers; (b) determining the ratio of amine to anhydride in the first polymerization mixture; (c) optionally adding additional dianhydride or diamine to the first polymerization mixture to provide a second polymerization mixture; and (d) removing o-dichlorobenzene from the first polymerization reaction mixture or the second polymerization reaction mixture using a devolatilizing extruder to provide a first polymer-organic clay composite composition, The composition comprises a polymer component and an organic clay component, wherein the organic clay component is at least 10% exfoliated. In a specific embodiment, the organic clay composition has a structure X. In a specific embodiment, The present invention provides a method of making a polyether oxime-75-200900452 amine-organic clay composite composition comprising (a) a temperature in the range of about 125 Torr and about 250 ° C in o-dichlorobenzene. Organic clay group 4,4'-oxydiphthalic anhydride (4,4'-ODPA) is contacted with a diamine in the presence of a product to provide a first polymerization mixture comprising alternating inorganic tannins a salt layer and an organic layer; (b) determining an amine to anhydride ratio in the first polymerization mixture; (c) optionally adding an additional dianhydride or diamine to the first polymerization mixture to provide a second polymerization mixture; And (d) removing o-dichlorobenzene from the first polymerization reaction mixture or the second polymerization reaction mixture using a devolatilizing extruder to provide a first polymer-organic clay composite composition comprising the polymer component And an organic clay component, wherein the organic clay component is at least 1% exfoliated. Embodiments The following examples are merely for illustrating the method and the specific embodiment of the present invention, and should not limit the scope of the patent application itself. . Biguanide A dianhydride (BPADA, CAS No. 38103-06-9) (97.7 % purity) was obtained from GE Plastics. 4,4'-oxydiphthalic anhydride (ODPA > CAS No. 1823-59-2) (99% purity) was obtained from Chriskev Company, Lenexa, Kansas, USA. 2,4,6-triphenyl-perpenyltetrafluoroborate, aniline, 4-phenoxyaniline, 4-cumylhydrazine, potassium carbonate, 1-fluoro-4-nitro-benzene, carbon on IG and Ammonium formate is taken from Aldrich.

The organic clay composition (organic modified clay) is made with KuniPia F-76-200900452 montmorillonite unless otherwise stated. See, for example, an organic clay composition made with Nano cor PGN. KuniPia F montmorillonite is available from Kunimine Industries Co. The manufacturer's own cationic parental capacity (CEC) is 115 meq/100 g. Unsaturated Kunipia F contains 8 wt% moisture at room temperature. Sodium analysis of undried Kunipia F sample gives a sodium content of 23,850 (±500) ppm. 'The CEC of the undried sample is 103.7 meq. /100 g. In the present disclosure, all calculations and material preparations used a cation exchange capacity of 毫100 meq/100 g. Kunipia F montmorillonite has an aspect ratio of 320 (average 値), 80 (minimum 値), and 1 120 (maximum 値). The equivalent smectite is available from Nanoc or. The cation exchange capacity of individual PGV and PGis^PGV and PGN clays with aspect ratios 150 to 200 and 300 to 500 nm is 145 (± 10%) and 120 (± 10%) milliequivalent / 100 g, respectively. Ultrasonic oscillations of the organically modified montmorillonite in a solvent were carried out using a 450 W type Branson Sonifier 450 having a 0.5 inch diameter solid probe. Large-scale ultrasonic vibration (>1 gram clay) using the Sonics & Materi a 1 s inc 1 500 00 Autotune S eries High Intensity Ultrsonic Processor ° TGA measurement system for use on perkin Elmer TGA 7 Pyris software is carried out. All elevated samples were used from a temperature rise range of 25 to 900 °C. An isothermal experiment was conducted at 40 °C to detect the thermal stability at the target processing/extrusion temperature. Thermal stability was recorded as the starting temperature of the mass loss and the % weight retention at 30 minutes of the isothermal experiment. -77- 200900452 The CTE of the film samples was measured using thermomechanical analysis (TMA). The film samples were cut with a 4 mm doctor blade in a conventional fixture. The analysis was performed on a TMA Q400 Thermo Mechanical Analyzer, number 0400-0007 from TA Instruments. The experimental parameters were set at a force of 0 · 0 5 0 N, 5 · 0 0 g static measurement, nitrogen flushing was 5 0.0 ml / min and 0.5 sec / point sampling interval. The CTE calibration system uses an aluminum standard at 5. (: / minute heating rate was carried out at 0 to 200 ° C under nitrogen flushing. The temperature calibration was performed using an indium standard at a heating rate of 5 ° C / min under nitrogen purge. After calibration, the CTE correction was verified as 1 Within ppm / °C, the temperature correction has been verified to be within ° 5 ° C. Transmission electron microscopy (TEM) measurements are embedded in an epoxy matrix and then used at room temperature with Reichert Ultracut The E section was cut into a film sample of ~100 nm thickness. The section profile was collected on a copper mesh and imaged using a Philps CM1 00 - (1 00 KV) transmission electron microscope. X-ray diffraction (XRD) ( The low-angle XRD) measurement was performed on a Bruker D8 localized diffractometer using the θ-Θ geometry. Ni-filtered Cu Κα radiation and a Μ-Braun PSD-50m sensory detector were used with an entrance slit of 0.6 mm. The scanning range is from 1.4 to 25 degrees 2. The sodium content analysis is carried out using solution spray inductively coupled plasma emission spectrometry (ICP-AES, Varian Liberty II). Combustion analysis of organic clay compositions (modified clay) CH analysis) is attached to LECO Corporation (Web: www.leco.com). The small-scale melt-mixing experiment of polymer and modified clay was carried out on a Haake Rheomix 600 instrument -78- 200900452. The percentage of peeling is defined as follows. (CTE) has a volume effect. Each volume% of the material injected into the polymer matrix has a corresponding % reduction in CTE. Therefore, when the organic clay composition is added to the polymer resin, any CTE lower than the volume effect is reduced. Directly related to the exfoliation of the organic clay composition in the polymer matrix. The percentage of peeling can be calculated by the ratio of c TE (CTE due to volume filling) to the experimentally measured CTE. Calculating the regularized CTE The weight percentage of the added citrate is converted to the density of citrate (2.86 g/ml according to the manufacturer's technical data) and the density of the standard polyether quinone (1-27 g/ml according to the manufacturer's technical data). Vol%. Therefore, each part by weight of citrate can be converted to vol% by multiplying by 0.00444. Therefore, the regularized CTE=CTE is not charged-(〇.〇〇444*CTE not filled* weight % The salt percentage is expressed as % exfoliated CTE charged (experimental measurement 値) / normalized CTE. Preparation of quaternary scale salt Example 1 iodide (3-aminophenyl) triphenyl Preparation of money 1 -79- 200900452

Add about 329.33 g (1.25 mol) of diphenylphosphine (PPh3), Pd (acetate) 2 to a 3 mL 3-neck round bottom flask equipped with a condenser, mechanical stirrer and gas inlet. 2.82 g, 0.0126 mol) and 16 ml of degassed xylene. The mixture was stirred under argon until PPh3 dissolved. Add iodoaniline (about 275.00 g; 1.25 m) and reflux the orange solution for about 80 minutes. The product hydrazine compound (iodinated (3-aminophenyl)triphenyl iron) was separated from the solution to give an orange solid. Avoid excessive reflow to prevent discoloration of the product money compound. The reaction was carried out using thin layer chromatography (TLC) and the solution was spread using 5 〇/5 hexane/ethyl acetate. After refluxing, the product was filtered. The product 1 was slurried with hot toluene and stirred for 15 minutes. The solution was then filtered and rinsed with additional toluene/xylene. After drying in a vacuum oven at 150 ° C for 20 hours, 585.01 g of pale product was obtained with a yield of 96%. The melting point and NMR data are consistent with the structure of product 1. MP: 316. (TC·1H NMR (δ, D6-DMSO): 8-6.6 (m, 19H, aromatic), 5.88 (s, 2H). Example 2 4-(4-cumyl)-phenoxy Preparation of bis-phthalonitrile 2

-80- 2 200900452 3 liter flask was charged with 4-cumylphenol (170.9 g, 0. 80 mol), 4-nitrophthalonitrile (150 g, 0.87 mol), potassium carbonate (155.8 g, 1.13 moles) and dimethylformamide (1.4 liters). The solution was heated to about 90 ° C under stirring for about 1 minute. The reaction is carried out by thin layer analysis. The dark brown reaction mixture was cooled and 2M HCl solution (600 mL) was then stirred. The organic layer was extracted with chloroform (3×300 mL). The chloroform layer was separated and washed with water (3 x 100 mL) and dried (MgS04). The mixture was filtered and the solvent was evaporated on a hot oil bath over EtOAc (EtOAc EtOAc EtOAc EtOAc (EtOAc) (d, 1H), 7.78 (d, 1 Η) > 7.40-7. 1 5 (m, 8H), 7_10 (d, 2H), 1.66 (s, 6H, Me). Example 3 4-(4 Preparation of -cumyl)phenoxy-phthalic anhydride 3

3 liter 3-neck round bottom flask unit condenser, mechanical stirrer and addition funnel. The flask was charged with 4-(4-cumylphenoxy)-phthalonitrile (278 g '0.82 mol) and acetic acid (1.6 liter). The addition funnel was filled with 7% by weight sulfuric acid (670 ml). The solution was heated to 12 (rc and then sulfuric acid was added dropwise to the reaction mixture over 2 hours. The resulting mixture was refluxed overnight (2 hours). The reaction mixture was cooled to room temperature and poured into ice-water mixture (~1 kg). The product was extracted with ethyl acetate (3×3 mL). EtOAc was evaporated from ethyl acetate and dried over anhydrous EtOAc EtOAc EtOAc EtOAc. The brown liquid was dried overnight in a vacuum oven at 160 ° C. This gave a thick brown oil (276 g, 94% yield) of desired desired.j-NMR (δ, D6-DMSO): 7.96 (d, 1H), 7.5 0 - 7.2 0 (m, 9 Η), 7.0 3 (d, 2H), 1.76 (s, 6H, Me). Example 4 Synthesis of cumyl PA-mATPP-I, 4

66.2 7 g (0.1S48 mol) of 4-(4-cumyl)phenoxy-phthalic anhydride 3 and 88.97 were charged in a 500 ml glass reactor equipped with a mechanical stirrer, nitrogen inlet and gas outlet. Gram (0.1848 mol) iodide 3-(aminophenyl)triphenyl rust (iodinated mATPP) l. The vessel was then loaded into a heated hood screen and heated to about 300 ° C to produce a molten reaction mixture. After stirring for about three minutes, a vacuum was applied to remove the by-product water formed. After a total reaction time of about 15 minutes, the reaction mixture was poured into a Teflon tray and cooled to provide a smooth brown glass of Compound 4 (145.19 g, 95.6%). 1H NMR (δ, D6-DMSO): 8.07-7.08 (31 Η, aromatic), 1.68 (s, 6 Η). Alternate synthesis of cumyl PA-mATPP-I, iodide-aminotetraphenyl rust, 22.14 g (0.046 mol) and 4-chlorophthalic anhydride, 8.40 g (0.046) and added Device has

A 250 ml round bottom flask of a Dean-Stark condenser was dissolved in 150 mL of o-dichlorobenzene. The contents were heated to reflux and washed with azeotropic distillation and nitrogen flushing -82- 200900452. After refluxing for 4 hours, 1 ο · 7 8 g of sodium cumylphenol (0.0 4 6 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 solid formed was collected by vacuum filtration. The solid was redissolved in 100 ml of chloroform and the resulting solution was poured into 300 ml of diethyl ether. The solid formed was collected by vacuum filtration and dried under vacuum overnight. 13C-NMR was consistent with the structure. Total yield: about 60%. Example 5 Synthesis of BPADAPA-mATPP-I,5

About 58_0 grams (0.1114 moles) of bisphenol A dianhydride (BPADA) and 107.27 grams (0.2229 moles) of 3-(aminophenyl)triphenylene iodide (mATPP-I) l were shaken together. The dried mixture was then added to the glass reaction flask using a long paper funnel to prevent the reagent from sticking to the inner side of the flask. The reaction flask was evacuated and the nitrogen was returned twice. Turn on external heating and set at approximately 300 °C. When the reagent melts, a brown solution is formed. When the reagent has melted for 3 to 5 minutes, the reaction flask was evacuated to remove water. The pressure is first set at 600 mbar (mb) and continuously reduced to 1 Omb. When the reaction is complete, set the pressure back to 1 〇〇 〇 mb and turn off the stirrer. The product, bisinimide, was cooled to give 1 5 8.48 g (9 8.2 8%) of brown glass. 1H NMR (δ, D6-DMSO): 8. 1-7.1 (m, 52 Η, aryl), 1.73 (s, 6H). -83- 200900452 Example 6 Synthesis of bis(chlorobenzylideneimine)' 6 of AMS dimer diamine

Add 3 8.34 g (0.22 mol) to 29 g (0.1 mol) of AMS dimer diamine in a 3-neck enamel flask equipped with a stirrer, nitrogen inlet and Dean-Stark unit equipped with a condenser. - Chlorophthalic anhydride (4-C1PA) and 30 ml of o-dichlorobenzene. The mixture was dehydrated under nitrogen and heated to 190-200 °C for 4 hours. The reaction mixture was cooled to ambient temperature and the product bis(chlorobenzylidene imine) 6 was precipitated (1500 mL) by the addition of methanol. The product was filtered and dried in an oven at 〇 (dry to constant weight at TC. Yield 40 g (91%) 〇 Example 7 bis(benzidine imine scale), synthesis of 7 Η.Γ. ΠΗ.

Add 24.5 g (0_〇9 mol) of triphenyl to 20 g (0.05 mol) of bis(chlorobenzidine) 6 in a 3-necked flask equipped with a stirrer, nitrogen inlet and condenser. Phosphine and 6.05 grams of anhydrous nickel chloride. The mixture was then heated to 300 ° C under a stream of nitrogen for -4 hours from -84 to 200900452. During this time the overall reactants turned into a greenish blue liquid form. The reaction mass was cooled to ambient temperature and solidified into a glassy greenish blue solid material to which methylene chloride (250 mL). The mixture was heated to a solvent to dissolve most of the solid and water (200 mL) was added. The organic layer was separated and washed repeatedly until the aqueous layer remained colorless (200 mL X 4 washes). The solvent is removed under reduced pressure to give the product a double iron salt oil. Toluene (100 mL) was added to provide a solid. The toluene was removed under reduced pressure. The addition and removal of toluene was repeated 4 times to determine the removal of water. Finally, the last portion of toluene (100 mL) was added to give a slurry of the double iron salt 7. The solid was filtered off and dried in an oven at 1 ° C to a constant weight. The yield was 30.3 g (60%). Example 8: Synthesis of bis(naphthoquinone imine), 8

In the device there is a stirrer, nitrogen inlet and Dean- equipped with a condenser

To the 28 g (0.1 mol) bromine naphthalene anhydride in the reaction flask of the Stark apparatus, 13.54 g (0.11 mol) of 4-chloro-aniline and 300 ml of o-dichlorobenzene were added. The mixture was heated to a temperature of 190-200 by removing water under nitrogen. (: After 4 hours. The reaction mixture was cooled to ambient temperature and the product was precipitated from 1500 mL of methanol. The product was filtered and dried in an oven at 100 ° C to a constant weight. Yield 35 g (8 9%). Stirring in the apparatus 20.5 g (0.08 mol) of triphenylphosphine and 5 g of anhydrous nickel chloride were added to the aforementioned 15 g (0.04 mol) product of the reactor, nitrogen inlet and condenser flask. The mixture was heated under a nitrogen stream - 85- 200900452 to 220 ° C for 4 hours to produce a greenish blue liquid. The reaction mixture was cooled to ambient temperature to give a solid material. The product bismuth salt was purified as in Example 7 and isolated to give a double iron salt 8. Yield 3 0_5 g (75%). Example 9 -1 0 Amine-substituted scale salt 9 and 1 0 synthesis 〇 2

Diamine (4,4'-diaminodiphenyl hydrazine (DDS) or alpha-methyl styrene dimer diamine (AMSDDA) (0.3 mol)) added to the device with a stirrer, nitrogen inlet, Dean - Round bottom flask in a Stark unit and condenser. About 0" mol (18.26 g) of 4-chlorophthalic anhydride together with about 3 ml of o-dichlorobenzene was added to the diamine. The round bottom flask was heated to about 1 9 〇 · 200 ° C under nitrogen for 4 hours. The reaction mixture was then cooled to room temperature and added to about 1500 ml of hexane with stirring. The product monochlorophthalimide was collected and dried in an oven at 100 °C. Monochloroimine (0.1 mol) was added to a flask equipped with a stirrer, a nitrogen inlet and a condenser. Triphenylphosphine (TPP) (26.2 g, 0.1 mol) and nickel chloride (11) 0.05 mol (6.5 g) were added, and the mixture was heated under nitrogen to -86 - 200900452. The reaction mixture was then cooled to room temperature and stirred in ca. 1000 mL dichloromethane and water (1000 mL). The layers were layered and the organic layer was washed to a nickel chloride free color. The solvent was removed under reduced pressure, toluene was added to the residue, and then toluene was removed under reduced pressure. Toluene addition and removal were repeated until a solid product was obtained. The final product is then dried under vacuum. The structures of products 9 and 10 were confirmed by 1H-NMR. Example 1 Synthesis of 1 bis (indenine scale), 1 1

A dianhydride (oxydiphthalic anhydride (0.1 mol)), 3-chloroaniline (26.77 g, 0.21 mol) and pro-dichlorobenzene (300 ml) were charged with a stirrer, nitrogen inlet, Dean - In the reaction flask of the Stark apparatus and condenser. The reaction mixture was heated to about 1 90-200 °C under nitrogen for 4 hours. The reaction mixture was then cooled to room temperature and added to about 1500 ml of methanol. The intermediate bis(chloro-imine) was then filtered off and dried in an oven at 10 ° C to a constant weight. Bis(chloro-indenine) was converted into bis(indenine iron) 11 as in Examples 9 and 10. Example 12 Synthesis of bisinimide-monoterpene salt 12 -87- 200900452

Diamine (tricyclododecaethylenediamine (0.3 mol)) phthalic anhydride (0.1 mol) and o-dichlorobenzene (300 ml) charged with a stirrer, nitrogen inlet, Dean-Stark and condensation In the reaction flask. The mixture was heated to about 1 90-200 ° C under nitrogen for 4 hours. The reaction mixture was then cooled to room temperature and stirred into about 1,500 ml of hexanes/methanol to give an intermediate mixture of the intermediates of <RTI ID=0.0> Monophthalimide (0.1 mol), 4-chlorophthalic anhydride (0.1 mol) and o-dichlorobenzene (300 ml) were placed in a flask as in the previous apparatus. The mixture was heated to about 190 - 00 °C under nitrogen for 4 hours. The reaction mixture was then cooled to room temperature and stirred into about 1,500 ml of hexanes/methanol to give the mixture of the intermediates of the monomethyleneimine-monochlorobenzidine imine, which was dried on a loot. To the weight. The monoxanthene imine-monochlorophthalimide intermediate reacts with triphenylphosphine in the presence of nickel (II) chloride as described in Example 8 to produce the product bis-imine-single A mixture of isomers of squamous salt 12. Preparation of an organic clay composition comprising a quaternary cation cation Example 1 3 an organic clay composition comprising a scaly cation 13 -88- 200900452

Scale 1 (Example 1, 17.36 g, 0.036 mol) and methanol (900 ml) were charged in a 1 liter beaker and heated to about 64. (: In another flask, sodium montmorillonite clay (Na-MMT/Kunipia F clay, 30.00 g, 0.030 mol equivalent) was stirred with about 2.1 liters of deionized water. When the clay was dispersed, the slurry was heated to About 6 5 t and added to the large preheated blender. The methanol solution of the salt was slowly added to the clay slurry in the blender with vigorous stirring. The thick foam was initially formed and then dispersed. The mixture was blended for 1 〇 minutes, then blended slowly for another 20 minutes. The temperature was about 65 ° C. After 30 minutes of blending, the mixture was filtered using a large fine sintered glass funnel. The solid clay was again in hot (80 ° C) water. The slurry was stirred, stirred for 15 minutes and filtered. The solid clay was then slurried in hot (64 ° C) methanol and filtered. The purified clay was dried under vacuum at room temperature until it could be ground into a powder. It was dried at 150 ° C for about 12 hours and honed again to obtain about 30 g of dry organic clay composition clay, 76% yield. Example 14 Organic clay composition containing money cation 14

200900452 A 5,000 ml round bottom flask was charged with 2000 ml of deionized (DI) water and stirred using a mechanical stirrer. Thereafter, about 25.00 g (0.025 equivalent) of Kunipia F clay was slowly added and stirred until the clay was sufficiently dispersed. The dispersed clay solution was then heated to about 80 °C. Separately, 20.80 g (0.0 1 43 7 mol, 15% excess) of iodinated BPADA-mATPP 5 was dissolved in 410 ml of acetonitrile and heated to about 80 °C. The iodinated BPADA-mATPP salt solution was then added to the clay dispersion, and the combined mixture was stirred at about 80 ° C for one hour. The clay was then filtered, reslurried in 2500 ml of deionized water and stirred at 8 °C for 15 minutes. After the clay was filtered, acetonitrile was also added after the final filtration. The modified clay was dried under vacuum at 25 ° C for 24 hours until the synthetic powder was blended. The modified clay was further dried in a vacuum of 15 ° C for 12 hours, and the clay was again blended to produce a fine powder of the organic clay composition containing the cation 14 in an amount of about 84%. Examples 15-16 comprise an organic clay composition of scaly cations 15 or 16.

Other organic clay compositions containing rust cation 15 (Example 15, cumyl-MTT) or 16 (Example 16) were prepared as in Example 14. -90- 200900452 The data for the organic clay composition containing organic money cations is provided in Table 1. "CE-1" indicates Comparative Example i, and "CE_2" indicates Comparative Example 2 and the like. "Ex-14" means "Example 14", and "Ex-15" means "Example 15". Table 1: Organic clay composition containing 彳_money cation Example cation modifier d-spacing (A) at 40 (weight loss (%) of TC at 30 minutes under N2 CE-1 tetraphenyl scale 17.8 3.1 CE -2 13 19 2.3 Ex-14 14 29 7.0 Ex-15 15 25.5 13.0 Ex-16 16 25.5 8.0 Examples 17-26 General method for the preparation of organic clay compositions Inorganic clay (sodium montmorillonite, "Na-MMT , purchased from Southern Clay, Inc., slurried in 75 parts by volume of deionized water ("MilliQ Water") relative to the weight of the clay and stirred at room temperature (22-25 °C) for 1 hour. Stir at 90-95 ° C for 1 hour. The solution of organic iron salt in methanol or acetonitrile is added to the slurry of inorganic clay in batches. The reaction mixture is stirred at 65-95 ° C for 18-20 hours. The organic clay composition is washed until the washing liquid contains no halogen ions, and then dried to a constant weight at 125 - 150 ° C. The organic clay composition containing the bismuthimine monobasic organic cerium cation is accompanied by X-ray diffraction ( The d-spacing data determined by XRD) is collected in Table 2 〇91 - 200900452 Table 2: Containing bis-imine Organic clay composition example cationic modifier d-spacing (A) Ex-17 Ph3p "Ο 0 17 17.5 Ex-18 o' 18 19.57 Ex-19 ο 19 6 15.05 Ex-20 >Njas"aNi ph f Ph7 20 18.3 The organic clay composition containing the bis-imine imine organic cations, together with the d-spacing data determined by X-ray diffraction (XRD), is collected in Table 3: Table 3: Containing bis-imine Scaly cation organic clay composition example cation modifier d-spacing (A) Ex - 2 1 h3c ch3 21 〇 Ph 22.29 -92- 200900452

The composition of the organic clay containing the amino-monomethylene imine organic scaly cations, together with the d-spacing data determined by X-ray diffraction (XRD), is collected in Table 4 〇

-93- 200900452 Preparation of a polymer-organic clay composite composition comprising a quaternary cation cation Example 27 comprises a cation 14 polymer-organic clay composite composition containing 1 liter of 150 ml of anhydrous o-dichlorobenzene To the 3-neck round bottom flask was added 7.96 g (4.77 g of decanoate) of BPADA-mATPP-MMT prepared in Example 14. The nanoclay-o-dichlorobenzene dispersion was ultrasonically shaken for one hour at a 20% output using a 400 W Branson Sonificator 45 0 with a 1/2 inch diameter solid probe. After the ultrasonic wave was shaken, 16.17 g (0.150 mol) of p-phenylenediamine (pPD) and 50 ml of o-dichlorobenzene were added and stirred with heating until the pPD was dissolved. Thereafter, 75.31 (0.145 moles) of BPADA, 1.43 grams (0.0096 moles) of phthalic anhydride, and 225 milliliters of other o-dichlorobenzene were added. The mixture was brought to reflux, at which time 225 mL of o-dichlorobenzene and water were removed over time. The solution was then cooled and stirred with 300 ml of heptane. The solid polymer formed was filtered off and dried in a vacuum oven at 150 ° C for 15 hours to give 8 9 · 17 g (9 3.4 % yield) of polymer·organic clay composite composition. The degree of polymerization of the polymer resin is 30. The weight percentage of the citrate to be formulated is 3%. Example 28 Polymer-Organic Clay Composite Composition Containing Cationic 15 A 3 liter 3-neck round bottom flask containing 850 ml of anhydrous cucurbitone was added with 210.0 g (g) (0.395 mol) of BPADA and 40.1 g (23.6 g of citrate) of the cumyl PA-mATPP-MMT prepared in Example 15. Mixing -94- 200900452 The instrument was ultrasonically shaken for three hours at 40% output using a 400W Branson Sonificator 45 with a 1/2 inch diameter solid probe. After the ultrasonic wave was shaken, 100.7 g (0·406 mol) of 4,4'-diaminodiphenyl maple (DDS), 2.0 g (0.013 mol) of phthalic anhydride (ΡΑ) and 3 50 ml were added. Huluene ether. The mixture was heated to reflux and a 200 mL cucurbit ether-water mixture was removed over a period of 12 hours. An additional 400 ml of verazone was then distilled from the reactor over a period of 3 hours. The reaction mixture was then cooled to 80 t and poured into a high speed blender containing 2 liters of methanol. The formed solid polymer was decanted and dried in a vacuum oven at 250 ° C for 15 hours. The product polymer-organic clay composite composition (25 3 g) was obtained in 75% yield. The degree of polymerization is 3 5 . The weight percentage of the prepared citrate was 7%. Example 29 Polymer-Organic Clay Composite Composition Containing Cation 14 Addition of 7.51 g (4.51 g of decanoate) to a 2 liter 3-neck round bottom flask containing 150 mL of anhydrous hydrazine DCB was prepared as in Example 14. BPADA-mATPP-MMT. The nanoclay-〇DCB dispersion was ultrasonically shaken for one hour at a 20% output using a 400W Branson Sonificator 450 with a 1/2 inch diameter solid probe. After the ultrasonic vibration, add 3 4·90 g (0.1 74 mol) of 4,4'-oxydiphenylamine (4,4'-OD A), 52.00 (〇·168 mol) 4,4'-oxygen Diphthalic anhydride (〇DPA), 1.9 8 7 (0.0134 mol) phthalic anhydride, 20 ml xylene and 300 ml 〇DCB. The mixture was brought to reflux, at which time 225 mL of solvent-water was removed over time. The solution was then cooled and stirred with 300 ml of heptane. The formed solid -95-200900452 polymer was filtered off and dried in a vacuum oven at 150 °C for 15 hours to yield 88.52 g of a polymer-organic clay composite composition comprising cation 14 in 98.22% yield. The degree of polymerization is 25 . The weight percentage of the formulated citrate is 5%. Example 30-37 Polymer-Organic Clay Composite Composition, Melt Preparation Example 3 0-3 7 The following general procedure was employed. U1 tern® 1010 polyether quinone imine (58.2 g) was weighed and divided into two equal portions. 1.8 g of an organic clay composition (modified Na-MMT) was added to one portion and thoroughly mixed. Two portions of the polyether oximine were then added simultaneously to the Haake mixer maintained at 305 ° C for about 9 minutes and then mixed at 350 Torr for about 30 minutes and sampled periodically. The product was then removed from the Haake mixer. The polymer-organic clay composite composition was analyzed by gel permeation chromatography (GPC). The data and molecular weight data of the various polymer-organic clay composite compositions prepared are summarized in Table 5. The product polymer-organic clay composite composition was also characterized by X-ray diffraction (XRD) and transmission electron microscopy. In addition, the coefficient of thermal expansion (CTE) is determined. The reference material, the inorganic clay (Na-MMT, Southern Clays, USA) used to prepare the organic clay composition used, had a d-spacing of 9.7 angstroms. The polyether quinone imine used had a starting weight average molecular weight (Mw) of 44,965 g/mol and an initial number average molecular weight of 9,200 g/mole and a CTE of about 62.1 (ppm). -96- 200900452 Table 5: Polymers containing polyether sulfimine-organic clay composite composition Examples Cationic modifier d-spacing* Mw Μη CTE 30 21 >30 47,785 23,175 28.7 31 23 50,458 25,079 ... 32 24 43,295 19,641 40 33 14 51,729 25,094 34 22 49,518 23,753 35 17 51,628 24,362 _____ 36 18 51,246 25,286 37 19 50,449 26,621 ——- d-spacing* in polymer-organic clay composite composition Example 3 0-3 The data collected 7 showed that the polyether quinone imide in the polymer-organic clay composite composition prepared was found to be almost or completely free of degradation. Moreover, the d-spacing observed is much larger than the d-spacing observed in the corresponding organic clay composition. Example 3 8 - 5 1 Polymer-organic clay composite composition prepared by in-situ polymerization, comprising a polymer resin polymer-organic clay composite composition 3 comprising structural units derived from DDS and BPADA or ODPA 8-43 and 46·51 were prepared as described in the following examples (Example 43). Organic clay composition containing cationic 14 (BPADA-mATPP-MMT), 9.05 g and 59.85 g of oxydiphthalic anhydride (ODPA) added to 219 ml of o-dichlorobenzene-97-200900452 (oDCB) and 146 ml of hydrazine In the ether. The mixture was mixed with a mechanical stirrer for 2 hours to dissolve Ο D P A. The vessel is then immersed in a trough ultrasonic oscillator and ultrasonically oscillated until a fine dispersion of clay is obtained. The flask was then equipped with an overhead stirrer and a Dean-Stark trap, adding 46.33 grams of 4,4'-diaminodiphenylphosphonium (DDS) and 0.08913 grams of aniline. DDS was rinsed into the container using 60 ml of oDCB and 40 ml of verazone. The mixture was stirred and slowly heated to reflux over three hours, and water was removed by azeotropic distillation. After heating under reflux for 18 hours, a fine powder dispersion was obtained. The dispersion was added to a larger volume of methanol, filtered and dried under vacuum at 180 °C. The resulting dry powder was then transferred to a Haake melt mixer and mixed for 60 minutes at 3 90 ° C and 50 rpm. The samples were taken at 5 minute intervals. A 15 minute sample was pressed at 760 °F between two sheets of Teflon-lined film. The pressed film samples were then analyzed by thermomechanical analysis and the CTE was measured at a range of 30 to 20 °C. The polymer-organic clay composite composition 4 4 - 4 5 was prepared as follows. The organic clay and solvent were mixed using a SILVERSON mixer (laboratory combination mixer, model L4R-PA' square hole shearing net 'lime speed ~ 600 ml/min). 450 ml of o-dichlorobenzene (〇dCB) was pumped through the SILVERSON mixer. The organic clay composition (BPADA-mATPP-MMT) '1 3 · 1 gram containing the cation 14 was slowly added to the oDCB in the cycle. The mixture was passed through a SILVERSON high shear mixer in a cycle mode at 6000 rpm for 45 minutes. The mixture was then transferred to a 1 liter three-necked flask. The flask was then equipped with an overhead stirrer and a Dean-Stark dispenser. Add 74.2 grams of bisphenol a dianhydride (BP ADA) and add -98- 200900452 to the flask to heat to 1 °C to dissolve the dianhydride. Thereafter, 3.90 g of 4,4'-diaminodiphenyltrimide (DDS) was added, and 20 ml of hydrazine DCB was used to rinse the DDS into the container. The mixture was stirred and slowly heated to reflux and the water by-product was removed by azeotropic distillation. Heating was carried out under reflux for 3.5 hours, heat was removed and the reaction mixture was cooled to room temperature. The resulting viscous mixture was transferred to a Haake melt mixer and mixed at 3 90 ° C and 50 rpm for 60 minutes. The samples were taken at 5 minute intervals. A 15 minute sample was pressed at 760 °F between two sheets of Teflon-lined film. The pressed film samples were then analyzed by thermomechanical analysis and C T E was measured at a range of 30 to 200 °C. Example 3 The results of the polymer-organic clay composite composition of 8 - 5 1 are shown in Table 6. Table 6: CTE results obtained by in-situ polymerization molded samples of DDS and ODPA and BPADA Example bis anhydride solvent cation modifier 1 Clay filling rate method 1 CTE %Εχι 38 BPADA o-dichlorobenzoquinone 0% 58 0.0 % 39 BPADA o-dichlorobenzene DP 7% Ultrasonic oscillation 37 34.2% 40 BPADA oDCB cum 7% Ultrasonic oscillation 34 39.5% 41 BPADA v* TPP 3.80% Ultrasonic oscillation 48 15.8% 42 BPADA NMP ΤΡΡ 3.80% Ultrasonic Oscillation 47 17.5% 43 BPADA o/v** DP 3.8 Ultrasonic oscillation 44 22.8% 44 BPADA o/v** DP 7.60% Ultrasonic oscillation 36 35.7% 45 BPADA oDCB DP 7% Silverson 50 11.0% 46 BPADA oDCB cumyl 7% Silverson 38 32.4% 47 BPADA v* cumyl 3.8 Ultrasonic oscillation 45 21.0% 48 ODPA oDCB Μ J \ w 0% 49 0.0% 49 ODPA o/v** DP 3.80% Ultrasonic oscillation 34 29.5% 50 ODPA v * TPP 5% Ultrasonic oscillation 39 18.6% 51 ODPA o/v** cumyl 3.8 Ultrasonic oscillation 36 25.3% -99- 200900452 "DP" = cation 14, "cumyl cation 15, TPP = tetraphenyl scale t The mixing steps in Examples 45-46 were carried out using a SILVERSON high shear mixer. ί "%Ex" Polymer - Organic Percentage of peeling of the organic clay component in the soil composite composition. * "V" = cucurbit ether. 混合物 mixture of oDCB and cucurbit ether. Examples 52-53 and comparative polymerization prepared by solution blending followed by melt extrusion molding. Object-Organic Clay Composite Composition The following method is generally applicable to the preparation of a film sample comprising the polymer-organic clay composite composition of the present invention. Example 5 2 An organic clay composition comprising a cation 15 in a veratrol Ultrasonic oscillation. The mixture subjected to ultrasonic oscillation is composed of about 2.7% organic clay composition in 500 ml of cucurbit ether. Ultrasonic oscillation is applied to a 1 000 ml round bottom flask immersed in a water bath. The 1/2 inch sonic probe Branson 4 50W Sonifier was run at ~40% output power for ~1 6 hours. A total of five batches of substantially identical organic clay composition-solvent batches were ultrasonically oscillated and subsequently combined. A solution of 20 weight percent of BPADA-DDS polyether sulfimine in veratrol was added to the combined ultrasonic oscillating organic clay composition batch and the mixture was thoroughly mixed. This mixture was then added to a blender equipped with methanol. The solid powder formed was filtered off and dried under vacuum at 220 ° C, followed by blending a ratio of BPADA-DDS polyether quinone and ODPA-DDS polyether quinone polyether phthalimide which was sufficient to produce 69:31. 100- 200900452 A second amount of polyether oximine, ODPA-DDS polyether quinone. The resulting mixture was extruded into a film by a 3" film molding. The formed film had a 塡 塡 rate of 7%, a machine direction CTE of 33.0 ppm TC and a Tg 2 5 5 ° C (see TEM image of Figure 1). The control group had a machine direction CTE of 48.5 ppm/°C and a Tg of 262 °C for the control film containing the same BPADA-DDS polyether quinone relative to the ODPA-DDS polyether oxime ratio and containing no clay. Example 5 3 The film was also extruded under BPADA-DDS polyether quinone imine: ODPA-DDS polyether yttrium imine at 60:40 and nano strontium sulphate filling rate of 7%. The machine direction of the film (: 丁£ is 28.7卩?111/. (: 丁丁8 266. (:. Preparation of quaternary pyridinium salt Example 54 tetrafluoroboric acid 1,2,4,6-tetraphenyl) Preparation of Pyridine Key 27

A 500 ml round bottom flask equipped with a condenser was charged with 2,4,6-diphenyl-perpenyl tetrafluoroborate (22.4 g, 0.056 mol), aniline (5.8 g '0.060 mol) and ethanol (2). 〇〇 ml). The resulting solution was stirred by magnetic stirring -101 - 200900452 and refluxed for 6 hours under a nitrogen atmosphere. The solution was cooled to room temperature and product 27 precipitated as a greenish yellow crystalline solid. The product was collected by filtration and dried at 100 ° C (23 g, 87% yield) in vacuo. Mp = 25 3 °c Example 55 Preparation of 1_(4-phenoxyphenyl)-tetrafluoroboric acid 2,4,6-triphenylpyridine 2 8

A 1 liter round bottom flask equipped with a condenser was charged with 2,4,6-triphenyl-perpenone tetrafluoroborate (50.0 g, 0.126 mol), 4-phenoxyaniline (25.7 g, 0.138 mol). ) and ethanol (400 ml). The resulting solution was stirred magnetically and refluxed for 6 hours under a nitrogen atmosphere. The solution was cooled to room temperature, and the condensation product was precipitated as a milky yellow crystal. The crystals were collected by filtration and dried in vacuo to give the desired product (68 g, 95% yield). Mp = 201.7C Example 56 Preparation of 4-(4-(l-methyl-1-phenyl-ethyl)-phenoxy)phenylamine 29

A 5 liter round bottom flask equipped with a Dean Stark collector, condenser and mechanical stirrer was charged with 1-fluoro-4-nitro-benzene (159 g, 1.128 -102 - 200900452 Mohr), 4 - dry Phenol (239 g, 1.128 mol), anhydrous potassium carbonate (103 g, 0.744 mol), N,N-dimethylformamide (1.5 liters) and toluene (150 ml). The resulting mixture was stirred under a nitrogen atmosphere and refluxed for 2 hours (solution temperature ~ 160 ° C). During this time water is collected in the liquid trap. The reaction mixture was cooled back to room temperature. Palladium on carbon (1 〇 wt% Pd '25 g, 0.025 mol) was added to the reaction mixture followed by ammonium formate (350 g, 5.463 mol). During the reaction, the internal temperature of the solution of the reaction mixture was kept below 55 ° C using cold water. After 2 hours, the reaction was filtered and a clear filtrate was collected. Water (2 liters) was added to the filtrate, and the desired product precipitated from the solution as a milky white powder. The precipitated powder was collected by filtration and dried in a vacuum oven at <RTI ID=0.0># </RTI> <RTI ID=0.0> Example 57 Synthesis of 2-(4-(4-(1-methyl-1-phenyl-ethyl)-phenoxy)-phenyl)-tetrafluoroboric acid 2,4,6-triphenylpyridine , 30

A 5 liter round bottom flask equipped with a condenser and a mechanical stirrer was charged with 2,4,6-triphenyl-perpenyl tetrafluoroborate (206 g, 0.519 mol), 4-[(1_methyl) 1-phenyl-ethyl)-phenoxy]-phenylamine (174 g, 0.574 mol) and ethanol (2 liter). The resulting solution was stirred under a nitrogen atmosphere and refluxed for 3 hours. The solution was cooled to room temperature and the condensation product precipitated as a greenish yellow -103- 200900452

crystallization. The crystals were collected by filtration and dried in a vacuum oven ((0) to give the desired product (333 g, 94% yield). Mp=283·7C Example 58: Synthesis BAPP-TPPy-BF4,31

BAPP (4,4'-(4,4'-isopropylidenediphenyl-1,1'-diyldioxy)diphenylamine) (220.0 g, 0.049 mol), triphenyltetrafluoroborate A pipe gun (40.5 g, 0.102 mol) and ethanol (400 ml) were combined and refluxed for 5 hours. The reaction mixture was cooled to room temperature and filtered to give the product bipyridine salt 31 (BAPP-TPPy-BF4). Yield 54 g (95%). Mp = 354 °C. Table 7 provides the yield and qualitative data for the pyridine key salts 2 7 ' 2 8, 30 and 31. -104- 200900452 Table 7: Yield of pyridine key salt Qualitative data pyridine gun salt (abbreviation) initial amine yield (%) mp (°C) TGA 5 wt% loss temperature rc ) 27 (TPPy-BF4) aniline 87 253 420 28 (phenoxy-TPPy-BF4) 4-phenoxyaniline 95 202 420 30 (cumylphenoxy-TPPy-BF4) cumylphenoxyaniline 94 284 420 31 (BAPP-TPPy-BF4) BAPP 95 354 400 The data in Table 7 shows that pyridine gun salt has an extremely high and unexpected degree of thermal stability based on thermogravimetric analysis (TGA). The 5% by weight loss temperature observed for all pyridine key salts was above 400 °C. In contrast, the starting piperazine salt tetrafluoroborate 2,4,6-triphenyl-periphaline has a much lower stability and is shown at 34 ° C under the test method used. 5 wt% loss. PREPARATION OF THE ORGANIC CLAY COMPOSITION COMPRISING A FOUR CLASS OF PYROCARBON CATALYSTS The general method for the preparation of organic clay compositions is to illustrate in a holistic manner how to prepare an organic clay composition comprising a pyridinium cation, where cumyl phenoxy is provided. Synthesis of thio-TPPy-MMT. A 5 liter round bottom flask equipped with a mechanical stirrer was charged with sodium montmorillonite -105-200900452 (40 g '0.041 molar equivalent) and deionized water (3 liters). The solution was stirred and heated to 85 ° C and the sodium montmorillonite was sufficiently dispersed. A solution of cumylphenoxy-TPPy-BF4 30 (31.4 g '0.046 mol) in acetonitrile (625 ml) at 60 ° C was added to a suspension of sodium montmorillonite in 1 Torr. After the addition of the salt solution, the reaction mixture was further stirred at 85 ° C for 3 hours. The modified montmorillonite was collected and washed with hot water (2 liters, 80 ° C) to remove the inorganic salt by-product NaBF4. The modified clay (organic clay composition) was further purified by redispersing at acetonitrile (2 liters) at 60 ° C, followed by filtration to remove any excess pyridine salt. The purified clay was dried under vacuum at 150 °C for 24 hours and milled to give a fine powder (50.3 g, 80% yield). Example 6 Large-scale synthesis of modified montmorillonite In a 50 gallon stainless steel container (container 1) of Pfaudler Inc., 470 g of sodium montmorillonite (Na-MMT) clay was added to 47 liters of stirring at room temperature. Deionized water. When the clay was dispersed, the mixture was heated to 80 °C. In Brighton's 10 gallon stainless steel container (container 2), the organic modifier solution was stirred into 7 liters of acetonitrile by heating 352 grams of cumylphenoxy-TPPy-BF4 30 modifier and heated to 80 ° C until all The organic salt is prepared by dissolving. The salt solution was added to the main reactor under fixed-stacking montmorillonite at 80 ° C for about 10 minutes, at which time the two liquids were equilibrated to a starting temperature of 80 °C. The reaction mixture was stirred at 80 ° C for 60-90 minutes. If it is mixed efficiently, neither part of the reaction mixture is excluded. After mixing, the modified clay mixture was gravity moved to a filtration centrifuge equipped with a micron filter bag. Centrifugation -106- 200900452 The machine is operated at both low and high speeds to produce a solid filter residue of the modified clay. The modified clay was washed by placing the clay back to vessel 1 with 47 liters of water and stirring at 80 ° C for 15 minutes. The modified clay mixture is filtered again. Thereafter, the modified clay was again washed by placing the clay back to the vessel 1 with 15 liters of acetonitrile and stirring at 80T for 15 minutes. The clay is then filtered to remove the unexchanged organic modifier. The clay in the centrifuge basket was briefly rinsed with methanol to help dry consistency. The modified clay is dried overnight in a low temperature vacuum furnace (1 〇〇 °C) or flushed with nitrogen in a centrifuge. The clay was milled in a Merlin mixer to produce a powder. Further drying in a vacuum oven at 150 °C followed by further blending resulted in a very fine powder with a low (&lt;2%) water content, about 70% yield. Table 8 provides qualitative data for a range of organic clay compositions. The heading "% experimental weight of C" indicates the weight percentage of carbon which is experimentally determined to be present in the organic clay composition. The title "Experimental weight of Η./." indicates the weight percentage of hydrogen present in the organic clay composition as determined by the experiment. Similarly, the title "calculated weight % of C" means "the calculated weight percentage of carbon present in the organic clay composition" and the like. Table 8: Analysis of quercetin by pyridinium 1 modified montmorillonite Experimental weight % of nano-clay C Experimental weight % of 实验 Experimental weight % Na C Calculated weight % Η Calculated ray amount % Sodium montmorillonite frrr ΜΙΓ y \\\ 2.46 4πχ ~ΓΠΓ TPPy-MMT 21.52 1.95 0.24 28.28 1.80 phenoxy-TPPy-MMT 25.28 2.10 0.17 31.77 1.98 cumylphenoxy-TPPY-MMT 26.41 2.36 0.24 36.74 2.52 BAPP-TPPy- MMT 24.65 2.09 0.17 32.52 2.10 -107- 200900452 The organic clay composition is additionally characterized by carbon combustion analysis data, hydrogen combustion analysis data, and sodium ion concentration data for "d-spacing" and "exchange percentage" of inorganic ions by organic ion exchange. The data is presented in Table 9, and the degree of exchange is shown to vary depending on the analytical method used in the calculations, but all three methods show that the sodium ions are sufficiently exchanged by the pyridyl cation. Table 9: d-spacing and ion exchange percentage of organic clay composition Percentage of organic clay composition exchange (%) Based on C analysis based on Η analysis based on Na analysis XRD measured d spacing (A) sodium montmorillonite... --- 11 TPPy-MMT 76 108 91 19 phenoxy-TPPy-MMT 80 106 94 19 cumylphenoxy-TPPY-MMT 72 94 91 23 BAPP-TPPy-MMT 75 100 94 19 Polymer containing quaternary cations - Preparation of Organic Clay Composite Composition Example 61 Melt Mixing Experiment Using ODPA-DDS Polyether Yttrium Imine Polymer To test the polyether oximine containing structural units derived from ODPA and DDS to contain N-arylpyridine The chain growth properties of the organoclay composition of the key cation were tested by melt mixing on a Haake Rheomix instrument. The low molecular weight polymer consisting essentially of structural units derived from hydrazine DPA and DDS was melt blended with TPPy_MMT at 3 90 ° C and 40 rpm with a citrate concentration of 5% by weight. The torque is detected in the 60-minute time -108- 200900452. The same experiment was carried out using the same low molecular weight polymer containing the organic clay composition cumin PA-mATPP-MMT containing scaly cation 15 without adding organic clay. In each of the three experiments, samples were taken at various time intervals and the molecular weight was measured. From the molecular weight and torque data, it is determined that the molecular weight of the low molecular weight polymer increases in the presence of an organic clay composition comprising a pyridyl cation and in the absence of organic clay. Conversely, when there is a nano-clay clay (cum-based PA-mATPP-MMT) containing an organic scale cation 15, the polymer becomes higher relative to the composition of the composition containing the pyridine gun cation and the composition containing no organic clay. The conversion of molecular weight polymers is relatively slow. Example 62 contains 7 wt% layered sulphate TPPy-MMT BPADA-DDS-aniline polyether quinone

BPADA-DDS-aniline polyetherimide 3 liter round bottom flask was charged with DDS (54.28 g, 0.2186 mol), cumylphenoxy-TPPy-MMT (43.8 g) and veratrol (7 g) ). The resulting mixture was 450W with a 〇·5 inch diameter probe.

The Branson Sonifier 450 oscillates with ultrasound for 3 hours at 40% output setting. After the ultrasonic wave oscillates, the mixture becomes extremely viscous and difficult to stir. At this time, DDS (61.12 g '0.2461 mol), BPADA (250 g, 0.469 mol) aniline (1.825 g, 0.0196 mol) and verazone-109-200900452 (7 00 g) were added. The reaction mixture was mechanically stirred and heated to 200 ° C over two hours, at this temperature for an additional 3 hours, and the azeotropically removed water was collected in a Dean-Stark trap. When the theoretical amount of water has been removed, about 500 grams of veratrol is taken and the resulting mixture is cooled back to room temperature&apos; and poured into methanol in a high speed blender (8 liters). The product polymer-organic clay composite composition was separated by filtration, the filter residue was rinsed with 500 ml of methanol, dried in a vacuum oven at 150 ° C for 24 hours, and then dried at 200 ° C for another 24 hours (3 50 g, 8 8 % yield). Example 63 ODPA-DDS-aniline containing 7 wt% of layered phthalate TPPy-MMT

Preparation of ODPA-DDS-aniline polyether oxime. The general method for synthesizing ODPA-DDS polyether quinone is as follows. 〇DPA (15.18 kg) was charged together with 〇_35 kg of aniline into a stirred glass liner reactor containing 12.63 kg of 〇DCB. The reactor was heated with oil to heat to 180 ° C and remove 8 kg of oDCB. The reactor was cooled to about 120 ° C and 1 1.2 1 5 kg of D D S was added with stirring. The oil temperature rose to 1200 minutes and the slurry temperature reached approximately 146 °C. Water begins to evolve; nitrogen scrubbing is used to assist in the removal of water from the reactor. The oil temperature rose to 171. (: and maintained for 115 minutes. As the water is released, the reaction temperature is increased to about 166 ° C. The slurry can still be easily stirred. The oil temperature rises to 186 ° C for the next 25 minutes and the reaction temperature increases to about 177 ° C. It was judged that the DDS intrusion was sufficient to further increase the oil temperature to 195 ° C, and the reaction slurry temperature was 179 ° C. 45 kg of the condensate was taken out in the subsequent hour. The heating was reduced and the reaction was cooled to 5 (TC. No polymer adhesive was found. The precipitated polyether oximine was removed from the solution by centrifugation at about 1 2 ° C using a 5 micro-110-200900452 m centrifuge bag. The polymer was dried at 150 ° C in a double cone dryer. Pass through a 2 mm screen. A 3 liter round bottom flask was charged with DDS (41.14 g, 0.1 6 5 7 m), cumylphenoxy-TPPy-MMT (19.9 g) and veratrol (350 g) The resulting mixture was ultrasonically oscillated for 3 hours at 40% output setting using a 450W Branson Sonifier 450 with a 0.5 inch diameter probe. After the ultrasonic wave was shaken, the mixture became extremely viscous and difficult to stir. Add DDS (31.71 grams, 0.1 277 moles), ODPA (95 grams, 0.303 moles), benzene Amine (0.714 g, 0.0077 mol) and veratrol (300 g). The reaction mixture was mechanically stirred and heated to 200 ° C over two hours at this temperature for an additional 3 hours to remove azeotrope The water was collected in a Dean-Stark trap. When the theoretical amount of water was removed, about 250 ml of veratrol was taken out and the resulting polymer mixture was cooled back to room temperature overnight. After that, methanol was added under agitation (300). ML). The formed polymer-organic clay composite composition powder is filtered by filtration, rinsed with 500 ml of methanol, dried in a vacuum oven at 150 ° C for 24 hours, then at 2 0 0 Dry at ° C for an additional 24 hours (1 58 g, 8 8 % yield). Example 64 contains a polymer containing an N-aryl pyridyl cation as an organic clay composite composition free of 31% by weight The polymer-organic clay composite composition prepared in Example 63 (containing 7 wt% of the layered niobate TPPy-MMT, DPA-DDS polyetherimine) and 69 wt% of the polymer prepared in Example 62 -111 - 200900452 Compound-organic clay composite composition (containing 7 wt% layer The resin composition consisting of the sulphate TPPy-MMT BPADA-DDS polyether quinone imine extrudes a 3 inch wide and 4 mil thick film. The device has an exhaust/refining screw and a 3 inch film mold. A 16 mm PRISM extruder. The resin composition was fed at a rate of about 5 lb./hr. The screw speed was set at 200 rpm, the barrel temperature was 370 Ϊ: and the film molding temperature was 380 °C. The molding pressure during film extrusion is about 1 500 psi. In order to compare the effect of organic clay on the mold pressure, a control film having a similar composition but no organic clay was extruded on the same extruder system, and the mold pressure was measured to find only about 90 psi. GPC analysis of the extruded film showed that the polymer established molecular weight during film extrusion. Although the extruded film is malleable, the TEM image of the film shows that the dispersibility of TPPy-MMT organic clay in the polyimide matrix is relatively poor. Relatively poor dispersibility of organic clay was reflected in the CTE results, with only a decrease of 18.8% CTE observed relative to the unfilled control sample. This is equivalent to a fairly conservative 2.6 % C TE reduction/% by weight citrate. Table 1〇: GPC and CTE analysis samples of extruded film Mp* (kg/mole) Mw (kg/mole) Μη (kg/mole) CTE 0-200 °C (PPm/°C) Substance 28.8 36.9 15.6 and extruded film 50.5 52.2 20.7 50 * "The peak molecular weight data collected in Table 10 demonstrates that the molecular weight of the polymer organic clay composition may increase significantly during extrusion film formation. -112- 200900452 Example 65 -72 A polymer-organic clay composite composition comprising 31% by weight of BPADA-DDS polyether quinone and 69% by weight of ODPA-DDS polyether phthalimide resin blend and a film prepared therefrom A series of polymer-organic clay composites containing polyetherimine (ODPA-DDS polyether phthalimide or BPADA-DDS polyether quinone) and organic clay composition (cumylphenoxy-TPPy-MMT) The composition is shown in Table 1 1 below. In each of the Examples 6 - 68, the diamine is DDS and the blocking agent is aniline. In each of Examples 65-6-8, the blocking agent is The amount is adjusted according to the "target" molecular weight. Two molecular targets were prepared for each resin, 25 kg/mole ("Lo") and 30 kg/mole ("Hi"). Table 11: Polyimine composition comprising cumylphenoxy-TPPy-MMT Example Polymeric anhydride Target Mw Target Μη (kg/mole) Anhydride/amine ratio Weight% citrate Mw (kg/mole Μη (kg/mole) 65 ODPA-DDS polyether quinone imine-Hi ODPA 30 15.6 1.02 7 30.6 14.8 66 ODPA-DDS polyether quinone imine-Lo ODPA 25 13.1 1.02 7 26.0 13.0 67 BPADA-DDS polyether醯iamine·Ηί BPADA 30 22.0 1.00 7 78.9 30.4 68 BPADA-DDS polyetherimine-Lo BPADA 25 18.3 1.00 7 58.0 24.6 -113- 200900452 Next, each resin preparation from Example 65_68 3 1% by weight A blend of BPADA-DDS polyether quinone and 69% by weight of hydrazine dpa_DDs polyimine polyimide resin, extruding four films with different molecules (Table 11). These combinations were used to evaluate the effect of molecular weight on film ductility at 7% citrate filling. A 6 mm PRISM extruder with a 3 inch diaphragm mold with an exhaust/refining screw unit was used. The combination was fed at a rate of 0.5 pounds per hour. The screw was set at 200 RPM, the barrel temperature was 380 ° C and the film molding temperature was 3 90 °C. The molding pressure is about 120 Opsi. The data for the extruded film is collected in Table 12. 200900452 Table 1 2: Extrusion film comprising a combination of polyether quinones as a polymer resin component of a polymer-organic clay composite composition Example of a polyimine blend composed of a resin extruded film Mw (kg / Moer) Μη (kg / Moule) Mw (kg / Moule) Μη (kg / Mohr) CTEMD Ist Heating, 0-200〇c (ppm/°C) 69 31% by weight ODPA-DDS Polyether 醯Imine-Lo 69% by weight BPADA-DDS Polyether quinone imine-Lo 46.9 18.9 49.5 20.2 nd* 70 31% by weight ODPA-DDS Polyether quinone imine-Hi 69% by weight BPADA-DDS Polyether quinone imine-Lo 65.9 22.8 56.9 21.9 nd 71 31% by weight ODPA-DDS Polyether quinone-Lo 69% by weight BPADA-DDS Polyether sulfimine-Hi 46.3 19.1 51.8 21.2 nd 72 3 1% by weight ODPA-DDS Polyether sulfimine -Hi 69 weight ° / 〇 BPADA-DDS polyether phthalimide - Hi 57.8 20.8 61.0 23.6 44 眧 group 31% by weight PDFS48 ODPA- DDS polyether phthalimide 69% by weight com. BPADA-DDS polyether phthalimide 40.1 15.3 50.5 21.7 61 nd=“Undetermined” Data from extruded films show that ODPA-DDS polyether oxime resin contains organic clay composition The phenoxy polymer -TPPy-MMT - organoclay composite material sufficiently exhibit its molecular weight was established. Therefore, in Example 69, the film prepared from the low molecular weight ODPA-DDS polyether oxime resin and the low molecular weight BPADA-DDS polyether oxime resin polymer-organic clay composite composition formulation has the same The molecular weight after extrusion of the control blend of organic-115-200900452 clay was not included. However, although the control group was malleable, the film sample of Example 69 was brittle. In the four film samples of the composition 2 comprising the polymer-organic clay composite composition, it was found that only the film of Example 72 ("out" - "then") was a wrinkle film, wrinkle-reducing A malleable indicator that is credible and often used. The results show that a higher molecular weight polymer resin is required to compensate for the reduced ductility due to the relatively large amount (7 weight percent) of the silicate salt present in the film. TEM images of films containing cumylphenoxy-TPPy-MMT show that the organic clay is well dispersed in the polymer matrix. TEM analysis was consistent with CTE measurements, where an overall CTE reduction of 28.8% was observed relative to the unfilled control group. Equivalent to 4〇/〇CTE reduction/percentage citrate filling rate. A film comprising a polymer-organic clay composite composition, such as those described in Examples 69-72, sometimes referred to as a "nano composite film" because of the polymer-organic clay composite composition used to prepare the film The organic clay composition contained in the composition is highly exfoliated. Preparation Example Benzene-Containing Iron-Containing Iron Salt 73 Preparation apparatus of 4-iodo-phenoxy-diphenyl ketone 1000 ml 3-neck of Dean-Stark liquid trap, condenser, stirring rod and nitrogen joint The round bottom flask was charged with 4-iodophenol (19·0 g, 〇_〇86 mol), 4-fluorodiphenyl ketone (15.72 g, 〇·〇79 mol), and potassium carbonate (7.16 g, 0.0518 mol), DMF (157 ml) and toluene (16 pens). The resulting mixture was stirred under a nitrogen atmosphere and refluxed for 2 hours (solution temperature ~ 1 60 ° C). During this time water is collected in the liquid trap. After 2 hours, 'anti-116-200900452 should be cooled to room temperature, and water (400 ml) was added to the reaction mixture, and the product was precipitated from the solution as a milky white solid. The product was re-crystallized from isopropyl alcohol (400 mL) to give the desired product as a white solid (25 g, 87% yield). Example 74 Synthesis of 4-(4-mercapto-phenoxy)-phenyldiyl rust 32

Add 4-iodo-phenoxy-diphenyl ketone (2, gram '0.0624 mol), triphenylphosphine (16.38) to a 250 ml 3-neck round bottom flask equipped with a condenser and a nitrogen gas inlet. Gram, 0.0624 moles of 'palladium acetate (0.14 g, 0.624 mmol) and degassed xylene (125 ml). Argon was bubbled through the solution for 1 hour to eliminate oxygen. The mixture was refluxed for 2 hours at which time a dark orange solution formed. The reaction mixture was cooled to room temperature and the squamous salt phase was separated from xylene as a dark orange solid. The reaction was carried out using TLC detection using a 90/1 0 dichloromethane/methanol distribution solution. The product was further purified by flash chromatography using silica gel 60 (500 g) and methylene chloride containing 5% methanol as solvent. The red impurity was first eluted' followed by the desired squamous salt 3 2 (40 g, 82% yield), which was isolated as a creamy powder after solvent removal. Preparation of dichlorobis-4-(triphenyl)diphenyl ketone 20 ml capped test tube device nitrogen flushing, adding reagent dichlorodiphenyl-117- 200900452 methyl ketone 1_ gram (0.003 98 mol) And 2.1 g of triphenylphosphine (0.00769 mol). The reaction was heated to 27 with an aluminum hot plate (TC for 2 hours. After cooling to room temperature, the solid was dissolved in chloroform and added dropwise to hexane. The water-soluble purple solid formed was redissolved in chloroform by adding the chloroform solution first. It was again isolated in 20 ml of diethyl ether and collected by vacuum filtration. Analysis by GC-MS showed two peaks, one corresponding to a single scale product and the second corresponding to a two-scale product. The final isolated yield was 1.1 g. Preparation of a polymer-organic clay composite composition containing benzophenone quaternary cations. Example 75 PhEK-MMT, self-iodinated 4-(4-benzylindenyl-phenoxy)-phenyl-triphenyl Sodium and sodium montmorillonite derived organic clay composition The synthesis apparatus was equipped with a mechanical stirrer in a 5 liter round bottom flask containing sodium montmorillonite (30 g, 0.03 mol) and deionized water (2.5 liter). The solution was stirred and heated at 851 until the sodium montmorillonite was fully dispersed. The solution of the money salt 32 (22.8 g, 0.034 mol) in acetonitrile (600 mL) was warmed to about 60 ° C then added to sodium over 1 min. a suspension of montmorillonite. After the salt solution is added, the reaction mixture is stirred at 85 ° C. Mix for about 3 hours. Collect organic clay composition (sometimes called modified montmorillonite or simply "modified clay") by filtration and wash with hot water (2 liters, 80 ° C) to remove inorganic salts. Impurities and exchange reaction sodium iodide by-product. The modified clay is further purified by redispersing in acetonitrile (2 liters) at 60 ° C, followed by filtration to remove any excess cerium salt. Drying at 150 ° C for 24 hours under vacuum and milling to produce a fine powder of PhEK-MMT (40 -118 - 200900452 g, 72% yield). Bi-4-(triphenylscale)diphenylmethanone - MMT synthesis 500 ml beaker was charged with 200 ml of water and 0.7183 g of dichlorobis 4-(triphenylscale) diphenyl ketone. The mixture was heated to reflux for 2 hours. After cooling to room temperature, centrifuged to separate organic The clay was washed in two portions of 200 ml of deionized water and collected by centrifugation. Preparation of a polymer-organic clay composite composition comprising a benzophenone quaternary cation containing examples 76-78 comprising a polymer of PEEK 450G - Organic clay composite composition PEEK 450G resin uses 3 mm screen low temperature Grinding. The formed material has a mixture of fine powder and larger particles. The milled material passes through a 1 mm screen to collect fine powder particles. The milling system feeds the material through a small diameter 16 mm extruder and Determine the need to thoroughly mix the milled clay. The milled resin is powdered with PhEK-MMT (prepared see Example 75) corresponding to an inorganic strontium filling rate of 5%. For comparison of the structure of organic cations Two other organically modified clays (Examples 77 and 78) were also prepared for the effect of the properties of the polymer-organic clay composite composition. Thus, a blend of milled PEEK 45 0G resin with the organic clay composition cumyl-MMT (Example 77) and TPP-MMT (Example 78) was also prepared. The preparation of cumyl-MMT, an organic clay composition comprising iron cations 15, is shown in Example 15 of the present invention. The TPP-MMT system is an organic clay composition comprising a citrate layer derived from -119-200900452 sodium montmorillonite clay and a halogenated tetraphenyl scale and can be prepared by the method disclosed in the present invention. The amounts of the organic clay composition and the polymer resin in Examples 76-7 are shown in Table 13. The formulation was mixed by placing the two components in a plastic bag and shaking for a few minutes. Table 13 Example Control group 76 77 78 Polymer resin PEEK 450G PEEK 450G PEEK 450G PEEK 450G Calcium carbonate filling rate 0% 5% 5% 5% Organic clay composition Μ J 1 w PhEK-MMT cumyl-MMT* TPP -MMT** Weight % of citrate in clay 0% 65% 58% 75% Organic clay composition weight f gram 16.92 gram 18.97 gram 14.67 gram PEEK 450G weight 220.00 gram 203.08 gram 201.3 gram 205.33 gram total weight of compound 220.00 g 220.00 g 220.00 g 220.00 g * organic clay composition cumyl-MMT preparation is shown in Example 15. ** TPP-MMT is a mixture of organic clay composition and polymer resin after co-rotation at 0.5 lb/hr after mixing with organic clay composition derived from sodium montmorillonite clay and halogenated tetraphenyl scale salt. The extruder was granulated by extrusion on a 16 mm twin-screw extruder (L/D = 25) of the intermeshing screw. The pellets collected from each material at low throughput (0.5 lbs/hr) were molded into thin discs using a hot press. Thin plates were subjected to TEM analysis to determine the degree of dispersion. The results are collected in Table-120-14 ° 200900452. Table 14: TEM analysis results Example Organic clay composition Polymer resin TE Μ Rating 76 PhEK-MMT PEEK 450G Good dispersion 77 cum-MMT PEEK 450G Poor dispersion 78 TPP-MMT PEEK Transmission electron microscopy (TEM) analysis of a 450G poorly dispersed extruded polymer-organic clay composite composition comprising a PhEK-MMT modified clay in PEEK (Example 76) showing organic clay composition Well dispersed in the polymer matrix. The resulting dispersibility was superior to those observed in Examples 77 and 78. No large clay agglomerates were found, and most of the clay was apparently in the form of a small laminate of tantalate layers, indicating that the organic clay composition was highly exfoliated into the polymer matrix. It is believed that the preferred dispersibility observed for the polymer-organic clay composite composition of Example 76 is due to the structural similarity between the polymer resin PEEK 45000 used and the organic clay composition PhEK-MMT used. Caused. PEEK 45 0G resin and organic clay composition PhEK-MMT system contains a diphenyl methyl ketone moiety substituted with a 4-aryloxy group. The organic clay compositions used in Examples 77 and 78 did not contain a 4-phenyloxy substituted diphenyl ketone moiety. Example 7 The transmission electron microscopy (T E Μ) analysis of the extruded polymer-organic clay composite composition (the clay modified with cumyl-MMT in PEEK) showed no relatively poor dispersibility. The resulting transmission electron micrograph shows that the large mass of the organic clay composition 'shows that at least a portion of the organic clay composition is not completely stripped into the PEEK polymer matrix." TPP-MMT modified clay in PEEK (Example 78) -121 - 200900452 TEM results also show the relatively poor dispersion of organic clay compositions in polymer resins. The resulting transmission electron micrograph shows a large agglomerate of the organic clay composition, showing that at least a portion of the organic clay composition has not been completely stripped into the PEEK polymer matrix. Preparation of a polymer-organic clay composite composition using melt mixing techniques, the composition is substantially free of polyether oximine. Examples 79-81 The following examples illustrate the methods provided herein for preparing polymers - The use of an organic clay composite composition which is substantially free of polyetherimine and which is at least 10 percent exfoliated to form an organoclay composition. Thus, 70 grams of polymer resin (see Table 15 below) was combined with 4.98 grams of the organic clay composition BAPP-TPPy-MMT. The powder was blended by shaking in a closed container for 2 minutes. The resulting mixture was heated in a HAAKE mixing crucible at 50 rpm. The mixture was maintained at the temperature shown in Table 15. The molten mixture in the H A AKE mixing crucible was sampled every five minutes. A 15 minute shovel sample was pressed at 760 °F between two sheets of Teflon-lined film. The pressed film samples were then analyzed by thermomechanical analysis and the CTE was measured in the range of 30 to 200 tons. The pressed film had the CTE(R) listed in Table 15. -122- 200900452 Table 15: Polymer-Organic Clay Composite Compositions Prepared by Melt Mixing

EXAMPLES Polymeric Resin Organic Clay Composition CTE (30-230 ° C) Mixed Temperature Film 79 PEEK 150P BAPP-TPPy- MMT 380 ° C 67 ppm / ° C 80 PPSU* BAPP-TPPy- MMT 340 ° C 61 ppm / ° C 81 PES** (ULTRASON E2010) BAPP-TPPy- MMT 330°C 54 ppm/°C * PPSU=RADEL R,** PES = Polyether 数据 The data in Table 15 demonstrates the substantial absence of polyether quinone The polymer-organic clay composite composition can be melt-mixed with a fourth-order organic clay composition and a polymer resin at a temperature ranging from about 300 ° C and about 450 ° C according to the method of the present invention. And prepared. The data shows that in order to achieve high peel levels (&gt; 10% peel), the polymer resin and organic clay composition should be melt mixed under the shear forces higher than those provided by conventional low shear mixers such as the Haake mixer. . It is believed that the composition of 79-8 1 has been achieved when it is melt mixed in a high shear environment such as a twin screw extruder operating at temperatures between about 300 ° C and about 450 ° C. 10% of the % peeled off. Preparation of a polymer-organic clay composite composition using a melt mixing technique, the composition comprising a polyether quinone imine Example 82 comprising a polyether quinone polymer-organic clay composite composition preparation 2.0 克纳cloisite Clay (Southern Clay, Inc. 0.000926 -123- 200900452 cation equivalent/g) was dispersed in 200 ml of water with vigorous stirring. 0.692 g of methylene blue was added to the dispersion and the mixture was heated under reflux for 60 minutes. The mixture was then cooled to room temperature by centrifugation of the product organic clay composition (modified clay). The moist clay was washed twice by redispersing in 200 deionized water and centrifuging again. The washed moist clay was dried at 1 20 ° C for 2 hours and then ground to give a fine blue-grey solid. 5.19 g of the organic clay composition (methylene blue modified clay) (4 wt% ceria) and 59.8 5 g of oxydiphthalic anhydride were added to 3 65 ml of 〇DCB as previously prepared, and the container was immersed In the trough type ultrasonic oscillator, it is heated until a fine dispersion of the anti-settling clay is obtained. The flask was then equipped with an overhead stirrer and a Dean-Stark dispenser, adding 46.3 5 grams of DDS and 0.0897 8 grams of aniline. DDS is rinsed into the container using 100 ml oDCB. The mixture was stirred and slowly heated to reflux over three hours, and water was removed by azeotropic distillation. After heating under reflux for 18 hours, a fine powder dispersion was obtained. The dispersion was then transferred to a Haake melt mixer and devolatilized at 3 90 ° C and 5 O rpm for 60 minutes to remove the solvent. Samples were taken every 5 minutes during devolatilization. A sample of 1 minute was pressed into a film between two sheets of Teflon-lined sheet at 760 °F. The pressed film samples were then analyzed by thermomechanical analysis and the CTE was measured at a range of 30 to 200 °C. The pressed film had a C T E of 4 1 p p / °C and a peel of 1 4 -8 %. Example 8 3 - 9 3 A series of polymers containing polyether quinones were prepared using one of the techniques of melt mixing, in situ polymerization or solvent mixing according to the present invention - -124- 200900452 Organic clay composite composition Things. (See, for example, Examples 27-29 illustrate in situ polymerization techniques). The material obtained by the polymerization method is a solid large agglomerate of dry filter residue. The filter residue was broken into pieces of about 1 inch, and the pieces were ground to a fine powder using a retsch mill and a 3 mm sieve. The finely divided polymer-organic clay composite composition is then separately extruded or mixed with another powdered polymer-organic clay composite composition and extruded. The extruder used is a 16 mm twin-screw extruder (L/D = 25) with a co-rotating and intermeshing screw. The structure allows the polymer-organic clay composite composition to be directly extruded into a film or The granules are first formed and then formed into a film in a second extrusion step. The screw design is used to melt, mix, devolatilize and transport the powdered polymer-organic clay composite composition from the feed inlet to the film of the extruder to form a mold exit. The molten polyether quinone-containing polymer-organic clay composite composition is often converted into a film using a 3" (3 inch) or 6" (6 inch) mold. In Comparative Examples and Examples 8 3 - 8 5, the powdery polymer-organic clay composite composition was first granulated using a 16 mm PRISM extruder with an exhaust/refining screw and a 3 mm granulation die. The organic clay composition·polymerized resin mixture (polymer powder blend) was "high-speed feed" at a rate of 1 lb / hr. The screw speed was set at 250 RPM, the barrel temperature was 3 8 5 ° C and the mold temperature was 3 8 5 °C. The pellets obtained by the final extrusion were dried overnight in a vacuum oven at 150 ° C, and extruded into films using a Welex 1-1/4" single screw extruder having a 6 inch wide film mold and a barrier type screw. The extruder screw was "high speed feed" at a 4 lb/hr speed and 25 RPM screw speed. The mold gap is about 8 mils and the extruded film is pulled out at various speeds of the film take-up unit to obtain a film of many different thicknesses from -125 to 200900452. Typically, when the slit flows away from the mold, the molten resin is pulled out of the film at a rate that is faster than the rate at which the molten polymer-organic clay composite exits the mold to thin the film. And oriented. The circulating oil passing through the inside of the drum can be kept in a specific manner. The film is extruded by a cold casting method in which the drum is arranged in a "wound" configuration, and the film is wound around the middle and bottom drums to obtain a charge for cooling heat transfer. . The film is then applied to another set of rollers (the tension is applied to the film, the film is held in close contact with the front roller and then passed through the gripping drum and collected on the winder. The film can also be used. Operating Apparatus An exemplary film comprising a polymer-organic clay composition containing polyether sulfimine was prepared, and the coefficient of thermal expansion (CTE) of the specific film sample in the machine direction was measured. The test results are collected in Table 16. Pull the material product to a thin temperature. S-type entanglement time I tube) pull. The other conventional composite materials and cross-126-200900452 Table 16 contains the CTE and glass transition temperature of the extruded film of the polymer-organic clay composite composition containing 100% BPADA-DDS polymer as the polymeric component A ( Tg) Example % citrate modifier method CTE1 CTE 2 % delamination MD/TD Tg °c extrusion number control group 0 ___ 58.2 _·_ ___ 2x 83 5 TPP melt mixing * 48.4 ___ 15% / - 2x 84 5 14 Melt mixing 45.0 ___ 20.9%/— 2x 85 10 14 Melt mixing 39.9 __ 28.2%/— 2x 86 5 15 Solvent mixing** 48.7 50.9 14.5°/〇/10.5°/〇233 87 10 15 Solvent mixing 38.4 41.8 30.9%/ 24.9°/〇226 88 5 14 In-situ polymerization t 39.6 42.0 30.5%/26.3% 240 89 10 14 In-situ polymerization 33.7 34.2 39.3%/38.5% 236 90 5 15 In-situ polymerization 39.9 44.6 29.9%/21.6% 241 91 10 15 In-situ polymerization 31.6 33.5 43.1%/39.7% 233 92 5 15 In-situ polymerization 39.2 44.9 31.2%/21.1% 239 93 5 15 In-situ polymerization 43.6 45.2 23.3%/20.6% 238 *Using melt mixing technology (see example 7 6- 7 8) Preparation of a polymer-organic clay composite composition. ** A polymer-organic clay composite composition was prepared using a solvent mixing technique (see Example 5 2-5 3 ). The polymer-organic clay composite composition was prepared using in situ polymerization techniques (see Examples 27-29 and 3 8-51). Preparation Example 94 of a polymer-organic clay composite composition via in-situ polymerization and verification of stoichiometry comprises 1,2-dimethyl-3-hexadecacarbazole imidazole-127-200900452 organic clay The composition was prepared by adding a 1-liter hexadecane (260 g, 1·molar) to a 2 liter three-necked round bottom flask with a top mechanical stirrer, and 1,2 dimethylimidazole (91_0 g). '0.95 moles' and CH3CN (500 ml) and the biphasic reaction mixture was stirred vigorously in an 80 °C oil bath. After 7 h, the reaction mixture was cooled to room temperature and the product crystallised overnight. The crystalline solid was filtered, washed well with cold CH.sub.3CN and dried in vacuo at 70[deg.] C. for 3 days to give a pale, pale, white solid, hexane, hexane rate. In a 2 liter three-necked round bottom flask equipped with a stirrer at the top of the apparatus, sodium cloisite (30 g, Southern Clay, USA) and deionized water (1 liter) were added, and the clay was mechanically stirred at room temperature for 2 hours. An aqueous solution of 1,2-dimethyl-3-hexadecenilazole (16 g in 200 ml) was added to the clay dispersion via a pipette, and the reaction mixture was briefly heated to 80 ° C for 2 times. Hour and stir overnight at room temperature. The precipitate was filtered off, washed well with cold water, and then washed with CH.sub.3OH and vacuum dried at 70[deg.] C. for 3 days to yield a pale solid solid (33 g, 94% yield). Example 95 In-situ polymerization and stoichiometric verification yielded a polymer comprising BPADA-DDS polyether quinone imine and imidazole-modified clay _ organic clay composite composition (7% citrate filling rate) at SILVERSON high The imidazole-modified clay (14 g) and hydrazine DCB (450 ml) were added to the shear mixer, and the mixture was heated to 120 ° C for 2 hours while maintaining vigorous mixing. The mixing system unit comprising the SILVERSON high shear mixer has a vessel with a heating belt and a temperature -128-200900452 degree controller. The contents of the container are introduced into the bottom of the SILVERS ON mixer. The circulation tube then connects the SILVERSON mixer to the container. After cooling to room temperature, the reaction mixture was transferred to a 2 liter three-necked round bottom flask equipped with a top mechanical stirrer, a Dean-Stark trap, and a condenser. BPADA (74.2 g) was added to the flask, and the mixture was stirred at 150 °C. After 2 hours, DDS (29.4 g) was added, the oil bath temperature was gradually increased to 21 (TC, and the reaction was carried out for another 3 hours. The reaction mixture was assayed at least once during the polymerization, and diamine or dianhydride was added as needed to achieve the desired The stoichiometry is predetermined. The polymerization is then continued. After the polymerization, the reaction mixture is cooled, and the precipitate is 'filtered in CH3OH and vacuum dried to give a brown solid of the product polymer-organic clay composite composition having a CTE of about 37 ppm/°C. Example 96 In situ polymerization and stoichiometric verification, the target degree of polymerization of BPADA-DDS polyether quinone in the presence of 7 wt% cumylphenoxy-Tppy-MMT layered citrate was 30. Using aniline as Blocking agent. In a 12 liter round bottom flask was charged DDS (280 g, 1.128 mol), cumylphenoxy-TPPy-MMT (280 g) and veratrol (5.5 kg). The Fisher Scientific PowerGen rotor-stator homogenizer (manufactured by Omni International), which has a 32 mm serrated tip and operated at 9000 RPM, was homogenized for 45 minutes. The resulting mixture was 1500 W with a 1-inch diameter solid probe. The Autotune Series High Intensity Ultrsonic Processor oscillates for 2 hours at 70% setting. After the ultrasonic wave oscillates, the mixture becomes extremely viscous and difficult to stir. -129- 200900452 The dispersed mixture of clay is placed in the ι〇 animal reactor. Dds (45 8.8 g, ι·848 Moh), BPADA (1 600 g, 3.004 mol), aniline (11.68 g '0.125 mol) and veratrol (4 kg). The reaction mixture was mechanically stirred and Two hours was heated 2 〇〇C, this temperature was maintained for another 2 hours and was taken from the water distilled from the reaction mixture. A sample of 1 gram of the reaction mixture was taken out and the solvent was removed under nitrogen at 305 rpm. The polymer sample was pressed into a film, and the infrared (IR) spectrum of the film was measured to determine the ratio of the amine end group to the anhydride end group. The polymer sample was found to contain 0.4 mol% excess amine by IR spectroscopy. Using this data, The reaction stoichiometry was adjusted by adding BP ADA (6.4 g) to correct the excess amine content. The reaction mixture was then maintained at 20 (TC over another hour. It was found that there was no more water released from the reactor. Distill 3 liters of cucurbit ether, and the resulting mixture was cooled to room temperature overnight. The reaction mixture was poured into methanol (50 liters) in a high-speed blender at ambient temperature, and the resulting powder was transferred to a filter with a micron filter bag. Centrifuge. The product polymer-organic clay composite composition was rinsed with an additional 1 liter of methanol. The powder was collected and dried in a vacuum oven at 15 ° t for 24 hours and then dried at 200 ° C for an additional 24 hours to produce a purified polymer-organic clay composite composition (2 1 7 5 g, 8 6 % yield) rate). Example 97 In-situ Polymerization and Stoichiometric Validation, BPADA-DDS Polyether Yenimine in the Presence of CLOISITE 3 0B Layered Citrate Using SILVERSON Mixer (Laboratory Wire Combination Mixer, Model L4R-PA , square hole high shear net, pump speed ~ 600 ml / min 'device - 130 - 200900452 as in Example 95) mixed organic clay and solvent. 270 ml of o-dichlorobenzene (oDCB) and 180 ml of veratry ether were heated to 80 t and pumped through the SILVERS ON mixer. An organic clay composition comprising CLOISITE 30B (13.56 grams) and bisphenol A dianhydride (B PAD A) (74.51 grams), a solvent that is slowly added to the cycle. The mixture was run in a cycle mode at 6000 rpm through a SIL V E R S ON high shear mixer for 45 minutes. The solution temperature is from 5 6 ° C to 79 ° C. The resulting solution is clear and shows the organic clay mixture peeled off. The mixture was transferred to a 1 liter three-necked flask. The flask was then equipped with an overhead stirrer and a Dean-Stark dispenser and placed in an oil bath heated to 10 °C. 33.8 8 g of 4,4'-diaminodiphenylphosphonium (DDS) was added. The mixture was stirred and heated to reflux. The water was removed by azeotropic distillation. Phthalic anhydride (0.86 g) was added and allowed to react for 2 hours. A 10 g sample of the reaction mixture was taken out and the solvent was removed at 305 ° C under nitrogen. The residual polymer sample was pressed into a film, and the infrared (IR) spectrum of the film was measured to determine the ratio of the amine end group to the anhydride end group. The polymer sample was found to contain 0.5 mol% excess of anhydride by IR spectroscopy. Using this data, the reaction stoichiometry was adjusted by adding DDS (0.182 g) to correct for excess anhydride content. The reaction mixture was then kept at 200 ° C for another hour. The second 1 gram sample or reaction mixture is pretreated. The polymer sample was found to contain 0.5 mol% excess of anhydride by IR spectroscopy. An additional 0-189 grams of DDS was added to the reaction mixture and allowed to react for 1 hour. At this point, the heat was removed and the reaction was allowed to cool to room temperature. The resulting viscous mixture was transferred to a Haake melt mixer and mixed at 390 ° C and 50 rpm for 60 minutes. The samples were taken at 5 minute intervals. A 15 minute sample was pressed at 760 °F between two sheets of Teflon-lined film. The pressed film samples were then analyzed by thermal mechanical -131 - 200900452 analysis and CTE was measured in the range of 30 to 20 °C. Example 98 In-situ Polymerization and Stoichiometric Validation 'BPADA-DDS Polyether oxime in the presence of CLOISITE 15A layered citrate using SILVERS ON mixer (Laboratory Wire Combination Mixer, Model L4R-PA , square hole high shear net, pump speed ~ 600 ml / min) mixed with organic clay and solvent. 270 ml of o-dichlorobenzene (〇DCB) and 180 ml of ruthenium ether were heated to 60 C and pumped through the SILVERS ON mixer. The organic clay composition (containing CLOISITE 15A (13.51 g), 4,4'-diaminodiphenyl hydrazine (DDS) (33.90 g) and ml of acetic acid) was slowly added to the solvent in the cycle. The mixture was passed through a SILVERSON high shear mixer in a cycle mode at 6000 rpm for 45 minutes. The solution temperature was increased from 60 °C to 8 6 °C. The resulting solution is viscous and shows the peeling of the organic clay. The mixture was transferred to a 1 liter three-necked flask. The transfer was completed using 50 ml of oDCB. The flask was then fitted with a top stirrer and a Dean-Stark trap and placed in an oil bath heated to 14 Torr. 70.02 g of diterpene A diterpenoid (BPADA) was added in two portions over 15 minutes. The mixture was stirred and heated to reflux for 2 hours. The water was removed by azeotropic distillation. Phthalic anhydride (0.86 g) was added and allowed to react for 3 hours. A 10 gram sample of the reaction mixture was taken and the solvent was removed at 305 Torr under nitrogen. The remaining polymer sample was pressed into a film, and the infrared (IR) spectrum of the film was measured to determine the ratio of the amine end group to the anhydride end group. The polymer sample was found to contain 4-7 mol% excess anhydride by IR spectroscopy. Using this data, the reaction stoichiometry was adjusted by adding DDS (1.55 grams) to correct for excess anhydride content. The reaction mixture was then maintained at 2001 for 3 hours. An additional 0 6 -132 - 200900452 grams of DDS was added and allowed to react for 1 hour. The second 1 gram sample or reaction mixture is pretreated. The polymer sample was found to contain 0.8 mol% excess of anhydride by IR spectroscopy. An additional 0.31 g of DDS was added to the reaction mixture and allowed to react for 1 hour. At this point, heat was removed and the reaction was allowed to cool to room temperature. The resulting viscous mixture was transferred to a Haake melt mixer and mixed for 60 minutes at 3 90 ° C and 50 rpm. The samples were taken at 5 minute intervals. A sample of 1 minute was pressed into a film between two sheets of Teflon-lined sheet at 760 T. The pressed film samples were then analyzed by thermomechanical analysis and CTE was measured at a temperature ranging from 30 to 200 ° C to produce 40.1 ppm/C (28.6% peel). The foregoing embodiments are illustrative only and are merely illustrative of certain features of the invention. The invention is claimed by the scope of the invention, and the embodiments of the invention are intended to exemplify the specific embodiments of all possible embodiments. The Applicant intends that the scope of the appended claims is not limited by the description of the embodiments of the invention. The word "comprise" and its grammatical variations used in the scope of the patent application also logically include various degrees of terms, such as, for example, (for example, not limited to) "consisting essentially of" and "consisting of" . When a range is required, these ranges cover all sub-ranges in between. It is expected that variations of such ranges will be desirable per se for those skilled in the art, and such changes should be covered by the scope of the appended claims when they are not disclosed. It should also be understood that advances in science and technology will make it possible to present equivalents and substitutes that are currently not covered by language rigor, and such changes may also be covered by the scope of the appended claims. -133- 200900452 [Schematic description of the drawings] Fig. 1 shows the formed film of the present invention having a nano ceric acid filling rate of 7%, a machine direction CTE of 33.0 ppm/°C and a Tg 25 5 °C. -134-

Claims (1)

200900452 X. Patent application scope 1. A polymer-organic clay composite composition comprising: (a) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer, The organic layer comprises a quaternary cation having the structure XXXIII XXXIII wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C5. An aromatic group; and the Ar16 is a C2-C2Q() aromatic group or a polymer chain comprising at least one aromatic group. 2. The polymer-organic clay composite composition of claim 1, wherein the Ar 16 system is a phenyl group. 3. The polymer-organic clay composite composition of claim 1, wherein the polymer resin comprises at least one polymer selected from the group consisting of amorphous thermoplastic polymers, crystalline thermoplastic polymers, and copolymers thereof. . 4. The polymer-organic clay composite composition as claimed in claim 1 wherein the polymer resin is selected from the group consisting of polyetherimine, polyamine, polyester, polyarylene sulfide, polyarylene ether, Polyether mill, polyether ketone, polyetheretherketone, polyphenylene phenyl, polycarbonate, and a group comprising at least one of the foregoing polymers - 135-200900452. 5. The polymer-organic clay composite composition of claim 1, wherein the polymer resin is selected from the group consisting of polyetherimine, polyamine, polyester, polyarylene sulfide, polyarylene ether, Polyether oxime, polyether ketone, polyetheretherketone, polyphenylene phenyl, polycarbonate, and combinations comprising at least one of the foregoing polymers. 6. The polymer/organic clay composite composition of claim 1, wherein the polymer resin comprises polyetherimine. 7. The polymer-organic clay composite composition of claim 1, wherein the polymer resin comprises polyether oxime. 8. The polymer-organic clay composite composition of claim 1, wherein the polymer resin comprises polyetherketone. 9. The polymer/organic clay composite composition of claim 1, wherein the Ar 16 system is a polymer chain. 10. The polymer-organic clay composite composition of claim 1, wherein the Ar 16 system is a polyether quinone polymer chain. The polymer-organic clay composite composition of claim 1, wherein the Ar16 is a polyetherketone polymer chain. 12. The polymer-organic clay composite composition of claim 1 wherein the Ar16 is a polymer chain having a number average molecular weight Mn in the range of from about 1000 to about 50,000 grams per mole. A polymer-organic clay composite composition according to claim 1, wherein the Ar16 is a polymer chain having a number average molecular weight Mn in the range of from about 1,000 to about 20,000 g/mole. -136- 200900452. 14. The polymer-organic clay composite composition of claim </RTI> wherein the Ar 16 system has a number average molecular weight Mn in the range of from about 1 Torr to about 5,000 gram per ohm. The polymer chain. 15. The polymer-organic clay composite composition of claim 1, wherein the Ar system 6 is a polyether quinone imine polymer having a number average molecular weight Mn in the range of from about 1000 to about 50,000 g/mole. chain. 1 6 · The polymer-organic clay composite composition as claimed in claim 1 wherein the Ar16 system has a number average molecular weight Μη in the range of about 1 〇〇 0 to about 2 〇, 〇〇〇 / mol Polyether quinone imine polymer chain. The polymer-organic clay composite composition of claim 1, wherein the quaternary cation system has the structure XXXIV Ph-^p——ph I Ph XXXIV. 18. The polymer-organic clay composite composition of claim 1, wherein the quaternary cation has a structure of XXXV - 137 - XXXV. 200900452 Ο Ph 19. The polymer-organic clay composite composition of claim 1, wherein the inorganic bismuth layer is derived from an inorganic clay selected from the group consisting of kaolin, dickite, pearlite, and Elo Stone, leaf serpentine, chrysotile, yeji stone, montmorillonite, beide stone, green stone, road stone 'zinc montmorillonite, strontite, hectorite, tetradecyl mica, sodium band mica, muscovite, Pearl mica, talc, pumice, phlogopite, green crisp mica, chlorite and combinations thereof. 20. The polymer-organic clay composite composition of claim 1, wherein the inorganic tellurite layer is derived from an inorganic clay comprising synthetic clay. 21. The polymer-organic clay composite composition of claim 1, wherein the organic clay composition is characterized by an interlayer distance of from about 5 to about 1 angstrom. 2 2 . An article comprising a polymer-organic clay composite composition, the composition comprising: U) a polymer resin; and (b) an organic clay composition comprising alternating inorganic silicate layers and an organic layer 'The organic layer comprises a quaternary cation having structure XXXIII - 138- XXXIII XXXIII200900452 Wherein Ar12, Ar13, Ar14 and Ar15 are independently a C2-C5〇 aromatic group; and Ar16 is a C2-C2〇q aromatic group or a polymer chain comprising at least one aromatic group. 2 3. The object of claim 22, which is a film. 2 4. The article of claim 2, which is a solvent cast film comprising a polyether quinone having a dianhydride component and a diamine component and intercalating at about 180. (: Tg ' with 4500 ° C and wherein the film has: a) a CTE below 70 ppm/°C; b) a thickness between about ί. ίμιη and 25 0 μιη; and c) Contains less than 5% by weight of residual solvent. 25. A method for preparing a polymer-organic clay composite composition, the method comprising contacting a polymer resin with an organic clay composition comprising alternating inorganic silicate layers and an organic layer under melt mixing conditions, The organic layer comprises a quaternary cation having a structure of XXXIII XXXIII wherein Ar12, Ar13, Ar14 and Ar15 are independently a c2-C5Q aromatic group; and Ar16 is a CkCmo aromatic group or a polymer chain comprising at least one aromatic group. -139- 200900452 Seven designated representatives: (1) The representative representative of the case is: (1) (2), the representative symbol of the representative figure is a simple description: no eight, if there is a chemical formula in this case, please reveal the most Chemical formula that can show the characteristics of the invention: No 200900452 (here is received by this Council) Text Sticker 852975 Invention Patent Description Amendment of the Republic of China on August 1, 1997 (This application wipes the word 'winning and succession' 1SM 壬 pasta' ※言雕_1^» ※Application number·· 96127605 ※Application date: July 27, 1996. IPC classification: I. Name of the invention: (middle) Composition and method for polymer composites (English) Compositions and methods for polymer composites 2. Applicant: (1 in total) 1. Name: (中) Sabic Innovation Plastic Co., Ltd. (English) SABIC INNOVATIVE PLASTICS IP BV Representative: (middle) 1. Catherinek Laihan (English) l.CLAPHAM, KATHERINE Address: (middle) Platinslaan, No.1 Plastic Lane, Bergen, Netherlands (English) Plasticsport, The Netherlands Nationality: (Chinese-English) Netherlands NETHERLANDS III. hair Mingren: (6 in total) 1. Name: (Chinese) Chen Guobang (English) CHAN, KWOK PONG Nationality: (中) US (English) USA 2. Name: (middle) John McKesson (English) MAXAM, JOHN LESTER Nationality: (middle) US (English) USA 3. Name: (middle) Loy Odo (English) ODLE, ROY RAY Nationality: (middle) US (English) USA · 4. Name: (middle) Taram Lan (51) MULLEN, TARA J. Nationality: (middle) US 200900452 852975 (English) USA 5 · Name: (middle) James Whitt (English) WHITE, JAMES MITCHELL Nationality: (middle) US (English) USA 6. Name: (中) Eric Hagbo (English) HAGBERG, ERIK C. Nationality: (中) US (English) USA IV. Declaration: ◎ Before applying for this case, you have applied for patents from the following countries (regions). Priority: [Format please: Accepting country (region); application date; order number of application number] 1. United States; 2007/06/20; 60/945, 150 d claim priority 2. United States; 2007/06/ 21 ; 11/766,382 0 has a claim priority 200900452 852975 (English) USA 5 · Name: (中) James Whitt (English) WHITE, JAMES MITCHELL Nationality: (中) US (English) USA 6. Name: (中) Eric Hagberg (English) HAGBERG, ERIK C. Nationality: (Chinese) USA (English) USA IV. Declarations: ◎ Before applying for the patent, the following countries (regions) have applied for patents. □ Claim international priority: [Format please: Accepting country (region); application date; application number Sequential Note] 1. United States; 2007/06/20; 60/945, 150 d claim priority 2. United States; 2007/06/21; 11/766,382 0 claim priority