CN101506287A - Compositions and methods for polymer composites - Google Patents

Compositions and methods for polymer composites Download PDF

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CN101506287A
CN101506287A CNA2007800310078A CN200780031007A CN101506287A CN 101506287 A CN101506287 A CN 101506287A CN A2007800310078 A CNA2007800310078 A CN A2007800310078A CN 200780031007 A CN200780031007 A CN 200780031007A CN 101506287 A CN101506287 A CN 101506287A
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group
composition
organic
aromatic group
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陈国邦
埃里克·哈格伯格
塔拉·J·马伦
罗伊·R·奥德尔
詹姆斯·M·怀特
山口则光
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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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 method of making a polymer-organoclay composite composition, said method comprising melt mixing a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polyetherimide composition; said melt mixing being carried out at a temperature in a range between about 300 DEG C and about 450 DEG C to provide a polymer-organoclay composite composition, said polymer-organoclay composite composition being characterized by a percent exfoliation of at least 10 percent.

Description

The composition and the method that are used for polymer complex
Related application and priority request
The right of priority of U.S. Provisional Patent Application 60/805821 that the application requires to submit on June 21st, 2007 U.S.'s non-provisional application was submitted at June 26 in 11/766423,2006 and the U.S. Provisional Patent Application of submitting on June 20th, 2,007 60/945150; All these U. S. applications all are incorporated herein by reference.
Background technology
The present invention relates to be used to prepare the organic salt composition of organic clay composition, the polymer-organoclay composite composition reaches the method for preparing polymer nanocomposites.
Organic clay serves as the benefit-additives in the polymer composition preparation, and this polymer composition has enhanced physical character with respect to unfilled polymeric material and the polymer composite compositions that comprises inorganic clay.Organic clay is preparation usually so, promptly replaces the inorganic cation that exists in the passage between the silicate layer of conventional inorganic clay with organic cation.The major advantage of organic clay composition is, when it is mixed in the polymer composition, find that organic clay peels off and with the situation of the interactional degree of polymeric matrix greater than the composition that comprises pure inorganic clay accordingly.The organic moiety that is present between the inorganic silicic acid salt deposit of organic clay not only makes organic clay expand, promptly increase the d-spacing of organic clay, and strengthen the tendency that organic clay peels off during the shearing force in standing polymeric matrix with respect to the d-spacing of corresponding inorganic clay.In some cases, peel off and take place so fully, the result produces the polymer composition that comprises the high silicate layer of dispersity, and this polymer composition that contains organic clay is called nano composite material.
Although this field progress in 10 years in the past makes us with deep impression, people are still exploring improved organic clay composition energetically, and prize this organic clay composition very highly when finding.One of shortcoming of a lot of organic claies is the organic cations thermolability that exists, making them be unsuitable for the polymer-organoclay composition needs the application of processing at high temperature, and the situation that comprises the polymer composition that contains organic clay of " heat-stable " polymkeric substance such as polyetherimide is exactly like this.Another shortcoming of a lot of known organic clay compositions is, can disadvantageous interaction take place with polymeric matrix when organic clay composition is scattered in the polymeric matrix, and the result can make the edge of performanceization of the polymer composition that contains organic clay.For example, when organic positively charged ion was uncle's ammonium cation and polymer-based carbon confrontation amine groups sensitivity, the result can be in the molten degraded of sneaking out generation polymeric matrix in the journey of for example polymeric matrix and organic clay composition.
Thereby, strongly need the such organic clay composition of exploitation, promptly be not only heat-staple and favourable interactional organic clay composition take place with polymeric matrix in the polymer composition that contains organic clay.The invention solves these and other technological challenge.
Summary of the invention
In each embodiment, the invention provides and can be used for preparing the new Ji Youji phosphonium salt of organic clay composition and new season pyridinium salt.Thereby, in one embodiment, the invention provides the organic clay composition that utilizes new organic salt provided by the present invention to prepare.Another aspect the invention provides the new polymer-organoclay composite composition that comprises organic clay composition disclosed herein.Again on the one hand, the invention provides the novel method of preparation polymer-organoclay composite composition.These and other aspect of the present invention is at length disclosed herein.
Description of drawings
Fig. 1 shows the film of the present invention that obtains, and it has 7% nano silicate loading level, 33.0ppm/ ℃ machine direction CTE, and 255 ℃ Tg.
Embodiment
To mention a large amount of terms in specification sheets below and the appended claims, these term definitions are for having following meanings.
Unless spell out in addition in the context, otherwise singulative (corresponding to " a " in the English, " an " and " the ") comprises plural number discussion object.
" optional " or " randomly " means incident or the item described thereafter and can take place or not take place, and this description comprises the situation that situation that incident takes place and incident do not take place.
As used herein, term " solvent " can refer to single solvent, also can refer to the mixture of multiple solvent.
As employed in whole specification sheets and claims, can use approximate language and modify and allow that any amount that change does not but cause associated basic function to change represents.Therefore, the numerical value with word is modified as " pact " is not limited to accurate regulation numerical value.In some cases, described approximate language can be equivalent to measure the precision of the instrument of this numerical value.
As used herein, term " aromatic group " be meant comprise at least one aryl, valency is at least the univalent atomic arrangement.This comprises at least one aryl, valency is at least the univalent atomic arrangement and can comprises heteroatoms such as nitrogen, sulphur, selenium, silicon and oxygen, also can only be made up of carbon and hydrogen.As used herein, term " aromatic group " includes but not limited to phenyl, pyridyl, furyl, thienyl, naphthyl, phenylene, and xenyl.Should be noted that aromatic group comprises at least one aryl.Aryl always has the ring texture of 4n+2 " delocalization " electronics, and wherein " n " is 1 or bigger integer, phenyl (n=1) for example, thienyl (n=1), furyl (n=1), naphthyl (n=2), Azulene base (n=2), anthryl (n=3) etc.Aromatic group also can comprise non-aromaticity integral part.For example, benzyl is the aromatic group that comprises benzyl ring (aryl) and methylene radical (non-aromaticity integral part).Similarly, tetralyl is to comprise to be fused to non-aromaticity integral part-(CH 2) 4-on aryl (C 6H 3) aromatic group.For convenience, prescribed term " aromatic group " comprises functional group miscellaneous such as alkyl, alkenyl in this article; alkynyl, haloalkyl, halogenated aryl; conjugated diene, alcohol radical, ether; aldehyde radical, ketone group, carboxylic acid group; acyl group (for example carboxylic acid derivative is such as ester and acid amides); amido, nitro, or the like.For example, the 4-aminomethyl phenyl is the C that comprises methyl 7Aromatic group, this methyl are alkyl functional group.Similarly, the 2-nitrophenyl is the C that comprises nitro 6Aromatic group, this nitro are functional group.Aromatic group comprises halogenated aromatic group, as the 4-trifluoromethyl, hexafluoroisopropyli,ene two (4-benzene-1-base oxygen base) (promptly-OPhC (CF 3) 2PhO-), 4-chloromethylbenzene-1-base, 3-trifluoro vinyl-2-thienyl, 3-benzenyl trichloride-1-base (is 3-CCl 3Ph-), 4-(3-bromine third-1-yl) benzene-1-base (is 4-BrCH 2CH 2CH 2Ph-), or the like.The further example of aromatic group comprises 4-allyloxy benzene-1-oxygen base, and 4-amino-benzene-1-base (is 4-H 2NPh-), 3-aminocarboxyl benzene-1-base (is NH 2COPh-), 4-Benzoylbenzene-1-base, dicyano methylene radical two (4-benzene-1-base oxygen base) (promptly-OPhC (CN) 2PhO-), 3-methylbenzene-1-base, methylene radical two (4-benzene-1-base oxygen base) (promptly-OPhCH 2PhO-), 2-ethylbenzene-1-base, phenyl vinyl, 3-formyl radical-2-thienyl, 2-hexyl-5-furyl, hexa-methylene-1,6-two (4-benzene-1-base oxygen base) (promptly-OPh (CH 2) 6PhO-), 4--methylol benzene-1-base (is 4-HOCH 2Ph-), 4-thiopurine methyltransferase benzene-1-base (is 4-HSCH 2Ph-), 4-methylthio phenyl-1-base (is 4-CH 3SPh-), 3-anisole-1-base, 2-methoxycarbonyl benzene-1-base oxygen base (as methyl salicyl), 2-nitro methylbenzene-1-base (is 2-NO 2CH 2Ph), 3-trimethyl silyl benzene-1-base, 4-t-butyldimethylsilyl benzene-1-base, 4-vinyl benzene-1-base, vinylidene two (phenyl), or the like.Term " C 3-C 10Aromatic group " comprise the aromatic group that contains at least 3 but be not more than 10 carbon atoms.Aromatic group 1-imidazolyl (C 3H 2N 2-) represent C 3Aromatic group.Benzyl (C 7H 7-) represent C 7Aromatic group.
Term used herein " alicyclic group " is meant and comprises ring-type but non-aromaticity atomic arrangement, valency are at least the univalent group.Regulation " alicyclic group " does not comprise aryl in this article." alicyclic group " can comprise one or more non-annularity integral part.For example, cyclohexyl methyl (C 6H 11CH 2-) for comprising the alicyclic group of cyclohexyl ring (ring-type but non-aromaticity atomic arrangement) and methylene radical (non-annularity integral part).Alicyclic group can comprise heteroatoms such as nitrogen, sulphur, selenium, silicon and oxygen, also can only be made up of carbon and hydrogen.For convenience, prescribed term " alicyclic group " comprises many functional groups such as alkyl, alkenyl, alkynyl, haloalkyl in this article; conjugated diene, alcohol radical, ether, aldehyde radical, ketone group; the carboxylic acid group, acyl group (for example carboxylic acid derivative is such as ester and acid amides), amido, nitro, or the like.For example, 4-methyl ring penta-1-base is for comprising the C of methyl 6Alicyclic group, this methyl are alkyl functional group.Similarly, 2-nitro ring fourth-1-base is for comprising the C of nitro 4Alicyclic group, this nitro are functional group.Alicyclic group can comprise one or more identical or different halogen atom.Halogen atom comprises for example fluorine, chlorine, bromine and iodine.The alicyclic group that comprises one or more halogen atom comprises 2-trifluoromethyl hexamethylene-1-base, 4-bromine difluoro methyl ring suffering-1-base, and 2-chlorodifluoramethyl-hexamethylene-1-base, hexafluoroisopropyli,ene-2,2-two (hexamethylene-4-yl) (promptly-C 6H 10C (CF 3) 2C 6H 10-), 2-chloromethyl hexamethylene-1-base, 3-difluoro methylene hexamethylene-1-base, 4-trichloromethyl hexamethylene-1-base oxygen base, 4-bromine dichloromethyl hexamethylene-1-base sulfenyl, 2-bromotrifluoromethane ring penta-1-base, 2-bromopropyl hexamethylene-1-base oxygen base is (as CH 3CHBrCH 2C 6H 10O-), or the like.The further example of alicyclic group comprises 4-allyloxy hexamethylene-1-base, and 4-is amino, and hexamethylene-the 1-base (is H 2NC 6H 10-), 4-aminocarboxyl ring penta-1-base (is NH 2COC 5H 8-), 4-acetoxyl group hexamethylene-1-base, 2,2-dicyano isopropylidene two (hexamethylene-4-base oxygen base) (promptly-OC 6H 10C (CN) 2C 6H 10O-), 3-methyl cyclohexane-1-base, methylene radical two (hexamethylene-4-base oxygen base) (promptly-OC 6H 10CH 2C 6H 10O-), 1-ethyl ring fourth-1-base, the cyclopropyl vinyl, 3-formyl radical-2-tetrahydrofuran base, 2-hexyl-5-tetrahydrofuran base, hexa-methylene-1,6-two (hexamethylene-4-base oxygen base) (promptly-OC 6H 10(CH 2) 6C 6H 10O-), 4--methylol hexamethylene-1-base (is 4-HOCH 2C 6H 10-), 4-thiopurine methyltransferase hexamethylene-1-base (is 4-HSCH 2C 6H 10-), 4-methylthio group hexamethylene-1-base (is 4-CH 3SC 6H 10-), 4-methoxyl group hexamethylene-1-base, 2-methoxycarbonyl hexamethylene-1-base oxygen base (2-CH 3OCOC 6H 10O-), 4-nitro methyl cyclohexane-1-base (is NO 2CH 2C 6H 10-), 3-trimethyl silyl hexamethylene-1-base, 2-t-butyldimethylsilyl ring penta-1-base, 4-trimethoxysilylethylgroup group hexamethylene-1-base is (as (CH 3O) 3SiCH 2CH 2C 6H 10-), 4 vinyl cyclohexene-1-base, vinylidene two (cyclohexyl), or the like.Term " C 3-C 10Alicyclic group " comprise at least 3 but be not more than the alicyclic group of 10 carbon atoms.Alicyclic group 2-tetrahydrofuran base (C 4H 7O-) represent C 4Alicyclic group.Cyclohexyl methyl (C 6H 11CH 2-) represent C 7Alicyclic group.
Term used herein " aliphatic group " be meant by acyclic straight or branched atomic arrangement form, valency is at least the univalent organic group.The regulation aliphatic group comprises at least one carbon atom.The atomic arrangement that comprises aliphatic group can comprise heteroatoms such as nitrogen, sulphur, silicon, selenium and oxygen, also can only be made up of carbon and hydrogen.For convenience, as the part of " acyclic straight or branched atomic arrangement ", prescribed term " aliphatic group " comprises a lot of functional groups such as alkyl herein; alkenyl, alkynyl, haloalkyl; conjugated diene, alcohol radical, ether; aldehyde radical, ketone group, carboxylic acid group; acyl group (for example carboxylic acid derivative is such as ester and acid amides); amido, nitro, or the like.For example, 4-methylpent-1-base is for comprising the C of methyl 6Aliphatic group, this methyl are alkyl functional group.Similarly, 4-nitro fourth-1-base is for comprising the C of nitro 4Aliphatic group, this nitro are functional group.Aliphatic group can be the haloalkyl that comprises one or more identical or different halogen atom.Halogen atom comprises for example fluorine, chlorine, bromine and iodine.The aliphatic group that comprises one or more halogen atom comprises haloalkyl such as trifluoromethyl, bromine difluoro methyl, and chlorodifluoramethyl-, hexafluoroisopropyli,ene, chloromethyl, the difluoroethylene fork, trichloromethyl, the bromine dichloromethyl, bromotrifluoromethane, 2-bromine trimethylene (as-CH 2CHBrCH 2-), or the like.The further example of aliphatic group comprises allyl group, and aminocarboxyl (promptly-CONH 2), carbonyl, 2,2-dicyano isopropylidene (promptly-CH 2C (CN) 2CH 2-), methyl (promptly-CH 3), methylene radical (promptly-CH 2-), ethyl, ethylidene, formyl radical (promptly-CHO), hexyl, hexa-methylene, methylol (promptly-CH 2OH) ,-and thiopurine methyltransferase (promptly-CH 2SH), methylthio group (promptly-SCH 3), methylthiomethyl (promptly-CH 2SCH 3), methoxyl group, methoxycarbonyl (is CH 3OCO-), the nitro methyl (promptly-CH 2NO 2), thiocarbonyl, trimethyl silyl (i.e. (CH 3) 3Si-), t-butyldimethylsilyl, 3-trimethoxy-silylpropyl (i.e. (CH 3O) 3SiCH 2CH 2CH 2-), vinyl, vinylidene, or the like.As further example, C 1-C 10Aliphatic group comprises at least 1 but be not more than 10 carbon atoms.Methyl (is CH 3-) be C 1The example of aliphatic group.Decyl (is CH 3(CH 2) 9-) be C 10The example of aliphatic group.
In one embodiment, the invention provides You Ji phosphonium salt with structure I:
Figure A200780031007D00101
Ar wherein 1, Ar 2And Ar 3Be C independently 2-C 50Aromatic group; Ar 4Be chemical bond or C 2-C 50Aromatic group; " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain; And X -Be the charge balance gegenion.
The included representational You Ji phosphonium salt of general formula I is illustrated in the Table I.Those of ordinary skill in the art knows the relation between the discrete structure of clauses and subclauses 1a～1j of general formula I and Table I.For example, the structure of clauses and subclauses 1a is represented the included material of general formula I, wherein Ar 1-Ar 3Phenyl (C respectively does for oneself 6H 5-), Ar 4Be metaphenylene, variable " c " is 0, and variable " a " is 2, X -Be iodide ion, and radicals R 2C for divalence 15Aromatic group-OC 6H 4C 3H 6C 6H 4O-.
Table I You Ji phosphonium salt
Figure A200780031007D00111
As further example, the clauses and subclauses 1f of Table I illustrates such You Ji phosphonium salt, wherein Ar 1-Ar 3Be phenyl, Ar 4Be metaphenylene, " a "=1, " c "=0, R 2Be C 4Aliphatic group C 4F 9O-, and X -Be chlorion.
The clauses and subclauses 1g of Table I illustrates such You Ji phosphonium salt, wherein Ar 1-Ar 3Be phenyl, Ar 4For to phenylene, " a "=1, " c "=0, R 2Be C 6Aromatic group C 6H 5O-(phenoxy group), and X -Be bromide anion.
The clauses and subclauses 1h of Table I illustrates such You Ji phosphonium salt, wherein Ar 1-Ar 3Be phenyl, Ar 4For to phenylene oxygen base, " a "=1, " c "=0, R 2Be C 6Aromatic group C 6H 5-(phenyl), and X -Be tetrafluoroborate ion BF 4 -
The clauses and subclauses 1i of Table I illustrates such You Ji phosphonium salt, wherein Ar 1-Ar 3Be phenyl; Ar 4For to phenylene oxygen base; " a "=2; " c "=0; R 2Be the polyetherimide chain, it is represented together with the metaphenylene between right parenthesis and group Q by the structure that is added with bracket that subscript " n " limits, for this exemplary You Ji phosphonium salt, subscript " n "=50.In many other embodiments, " n " is 1 to about 500 number.Gegenion X -Be sulfate radical (SO 4 2-).
In one embodiment, R in the structure I 2Shown group is the polyetherimide polymer chain clauses and subclauses 1i of Table I (for example referring to).In another embodiment, R in the structure I 2Shown group is the polyetherketone polymer chain.In yet another embodiment, R in the structure I 2Shown group is the polyether sulfone polymer chain.
R therein 2In the embodiment for polymer chain, this polymer chain can be high molecular or low-molecular-weight polymer chain.The high-molecular weight polymer chain is number-average molecular weight (M n) greater than the polymer chain of 8000 gram/moles, adopt polystyrene molecular weight standard specimen to measure according to gel permeation chromatography.The low-molecular weight polymer chain is number-average molecular weight (M n) be 8000 gram/moles or littler polymer chain, adopt polystyrene molecular weight standard specimen to measure according to gel permeation chromatography.In one embodiment, the invention provides You Ji phosphonium salt, wherein R with structure I 2Be number-average molecular weight M nFor about 1000 polymer chains, measure according to gel permeation chromatography to about 50000 gram/moles.In another embodiment, R 2Be number-average molecular weight M nFor about 1000 polymer chains, measure according to gel permeation chromatography to about 20000 gram/moles.In yet another embodiment, R 2Be number-average molecular weight M nFor about 1000 polymer chains, measure according to gel permeation chromatography to about 5000 gram/moles.
In one embodiment, the invention provides You Ji phosphonium salt with structure I I:
Figure A200780031007D00131
X wherein -Be the charge balance gegenion.
In another embodiment, the invention provides You Ji phosphonium salt with structure III:
X wherein -Be the charge balance gegenion.
In yet another embodiment, the invention provides You Ji phosphonium salt with structure I V:
X wherein -Be the charge balance gegenion, m is about 10 to about 1000 number, and Ar 5Be C 2-C 50Aromatic group or polymer chain.
In one embodiment, the invention provides You Ji phosphonium salt, wherein group Ar with structure I V 5Have structure V:
Figure A200780031007D00142
X wherein -Be the charge balance gegenion.
In structure I of the present disclosure and other place, radicals X -Represent the charge balance gegenion.What those having ordinary skill in the art will appreciate that is that many charge balance gegenions are available.Usually, X -Represent the anionic charge balance gegenion of monovalence, divalence or trivalent.For example, in one embodiment, X -Be selected from: fluorion, chlorion, bromide anion, iodide ion, sulfate radical, inferior sulfate radical, carbonate, bicarbonate radical, acetate moiety, oxalate, and combination.The inorganic anion fluorion, chlorion, bromide anion, iodide ion, and bicarbonate radical is the example of univalent anion.Inorganic anion carbonate and sulfate radical and organic anion oxalate are the examples of dianion.The trianion of Kemp triprotic acid is the anionic example of trivalent.
New You Ji phosphonium salt provided by the invention can make by several different methods.Experimental section of the present disclosure provides the concrete grammar and the condition of the You Ji phosphonium salt that many preparations have structure I.In one embodiment, You Ji phosphonium salt can make by making the reaction of aryl halide and triaryl phosphine, and this reaction is chosen wantonly in the presence of catalyzer such as acid chloride (II) and carried out.In alternate embodiment, amine replaces De phosphonium salt and anhydride reaction, obtains Bao Kuo phosphonium salt part at the interior imido product that contains.
In one embodiment, the invention provides the method for preparing You Ji phosphonium salt, comprise that (a) makes the amine with structure VI replace the De phosphonium salt and contact with the anhydride compound with structure VII,
Figure A200780031007D00151
Ar wherein 1, Ar 2, Ar 3And Ar 4Be C independently 2-C 50Aromatic group, and X -Be the charge balance gegenion;
Figure A200780031007D00152
Wherein " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain; And (b) separated product You Ji phosphonium salt.
In one embodiment, compound VI is amino (NH 2) between bit strip the aniline of triphenyl phosphonium part is arranged, and wherein the charge balance gegenion is an iodide ion.In another embodiment, compound VI is amino (NH 2) contraposition has the aniline of triphenyl phosphonium part, and wherein the charge balance gegenion is a chlorion.
In one embodiment, anhydride compound VII is selected from: dihydroxyphenyl propane dianhydride (BPADA), 4,4 '-biphenyl dianhydride, and 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (4,4 '-ODPA).In one embodiment, anhydride compound VII is the dihydroxyphenyl propane dianhydride.In another embodiment, anhydride compound VII is the polymer dianhydride that comprises the acid anhydride end group, and this polymer dianhydride is the polyetherimide that comes from BPADA and mphenylenediamine, and has the number-average molecular weight M of about 10000 gram/moles n
Usually, the amine with structure VI replaces the De phosphonium salt and betides in the solvent with reaction (" contact ") between the anhydride compound with structure VII, and temperature of reaction is removed the water that forms as the condensation reaction by product simultaneously above 100 ℃.In one embodiment, this is reflected in the organic solvent in about 120 ℃ and carries out to about 160 ℃ temperature.In another embodiment, this reaction is carried out with melt form.
In some cases, it is favourable carrying out this reaction in the presence of catalyzer, for example catalyzer that uses in the imidization reaction such as sodium phenylphosphinate (SPP).
The suitable solvent comprises oDCB (orthodichlorobenzene), toluene, dimethylbenzene, chlorobenzene, phenylmethylether, veratrole, and combination.
In one embodiment, the invention provides the method for preparing You Ji phosphonium salt, comprise that (a) makes the amine with structure I X replace the De phosphonium salt and contact with the anhydride compound with structure VII,
Figure A200780031007D00161
X wherein -Be the charge balance gegenion,
Figure A200780031007D00162
Wherein " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain; And (b) separated product You Ji phosphonium salt.
In one embodiment, the anhydride compound with structure VII is selected from: 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride), 3,4 '-oxygen di-(Tetra hydro Phthalic anhydride), 3,3 '-oxygen di-(Tetra hydro Phthalic anhydride), the dihydroxyphenyl propane dianhydride, 6F-dianhydride, 3,4 '-biphenyl dianhydride, 4,4 '-biphenyl dianhydride, and combination.
In yet another embodiment, the invention provides the method for preparing You Ji phosphonium salt, comprise that (a) makes aromatic amine contact with halogenated acid anhydrides, obtains halogenated imide; (b) make the reaction of described halogenated imide and triaryl phosphine, to realize the nucleophilic substitution of triaryl phosphine to halogen; Reach (c) separated product You Ji phosphonium salt.
In one embodiment, halogenated acid anhydrides is selected from: 3-chloro-phthalic anhydride (3-ClPA), 4-chloro-phthalic anhydride (4-ClPA), 3-difluorophthalic anhydride, and 4-difluorophthalic anhydride.In another embodiment, halogenated acid anhydrides comprises the 4-chloro-phthalic anhydride.In yet another embodiment, halogenated acid anhydrides comprises the mixture of 3-chloro-phthalic anhydride and 4-chloro-phthalic anhydride.
Aromatic amine can be monoamine or polyamines.In one embodiment, aromatic amine is the polymkeric substance that comprises amido.The example of monoamine has aniline, the 1-amino naphthalenes, and the 3-chloroaniline, the 4-chloroaniline, 2,4 dichloro aniline, 4-chloro-4 '-phenylaniline, or the like.
Suitable triaryl phosphine comprises triphenylphosphine, tolylphosphine, and three (xylyl) phosphine, three (4-tert.-butoxy phenyl) phosphine, or the like.
The reaction of preparation halogenated polyimide and with the suitable reaction condition of the follow-up reaction of triaryl phosphine, referring to experimental section of the present disclosure.
In one embodiment, the invention provides new pyridinium salt with structure XV:
Figure A200780031007D00171
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; " d " is 0～4 number; R 3And R 4Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Z is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; Ar 9Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl; And X -Be the charge balance gegenion.
As confirming that herein the pyridinium salt that structure XV is contained can be used for preparing organic clay composition and polymer-organoclay composite composition.The representational pyridinium salt that general formula X V is contained is illustrated in the Table II.
The pyridinium salt XV that Table II is exemplary
Figure A200780031007D00172
Figure A200780031007D00181
Those of ordinary skill in the art understands, the such pyridinium salt with structure XV of pyridinium salt representative of the clauses and subclauses 2a of Table II, wherein Ar 6, Ar 7And Ar 8The phenyl of respectively doing for oneself; " b " is 0; " d " is 2; R 4Be methyl; Z is the oxygen linking group; Ar 9Be C 12Aromatic group; And X -Be chlorion.Similarly, the pyridinium salt that the representative of the pyridinium salt of the clauses and subclauses 2b of Table II is such, wherein Ar with structure XV 6, Ar 7And Ar 8Be phenyl; " b " is 0; " d " is 0; Z is the oxygen linking group; Ar 9Be C 12Aromatic group; And X -Be acetate ion.
In one embodiment, the invention provides wherein Ar 9Pyridinium salt for the polyetherimide polymer chain with structure XV.In another embodiment, the invention provides wherein Ar 9Pyridinium salt for the polyetherketone polymer chain with structure XV.In one embodiment, Ar 9Be number-average molecular weight M nAbout 1000 polymer chains to about 50000 gram/moles.In another embodiment, Ar9 is number-average molecular weight M nAbout 1000 polymer chains to about 20000 gram/moles.In yet another embodiment, Ar 9Be number-average molecular weight M nAbout 1000 polymer chains to about 5000 gram/moles.In another embodiment, Ar 9Be number-average molecular weight M nAbout 1000 polyetherimide polymer chains to about 20000 gram/moles.
In specific embodiment, Ar 9Be number-average molecular weight M nAbout 1000 polyetherimide polymer chains to about 50000 gram/moles.
In one embodiment, the invention provides pyridinium salt with the general formula X V shown in structure XVI:
Figure A200780031007D00191
X wherein -Be the charge balance gegenion when occurring independently at every turn.In specific embodiment, X -Be BF 4 -
In one embodiment, the invention provides pyridinium salt with structure XVII:
Figure A200780031007D00192
X wherein -Be the charge balance gegenion when occurring independently at every turn.In specific embodiment, X -Be acetate moiety.
In yet another embodiment, the invention provides pyridinium salt with structure XVIII:
Figure A200780031007D00193
X wherein -Be the charge balance gegenion; " e " is about 10 to about 1000 number; And Ar 10Be C 2-C 50Aromatic group, perhaps polymer chain.In specific embodiment, X -Be tetrafluoroborate negatively charged ion (BF 4 -), variable " e " is about 100, and Ar 10Be C 25-aromatic group 2,4,6-triphenyl pyridinium tetrafluoroborate salt.Those of ordinary skill in the art understands, and aromatic group can comprise relevant gegenion, is BF here 4 -, and still fall into the definition of defined term aromatic group herein.Similarly, aliphatic group can comprise relevant gegenion equally with alicyclic group.If group comprises a plurality of electric charges that need have the charge balance gegenion, then in group, can comprise a plurality of charge balance gegenions.Those of ordinary skill in the art also knows, can comprise the charge balance gegenion of fractional part in the group equally.For example at single positive charge by dianion such as sulfate radical (SO 4 2-) in the equilibrated synthetics, single sulfate anion can be associated with two molecules or group.Thereby, in one embodiment, Ar 10For comprising 1/2 (SO 4 2-) aromatic group.In one embodiment, Ar 10For having the aromatic group of structure XIX:
Figure A200780031007D00201
X wherein -Be the charge balance gegenion.In specific embodiment, X -Be the divalent ion of fractional part, this divalent ion is selected from sulfate radical, carbonate and oxalate.In one embodiment, X -Be 1/2 (CO 3 2-), i.e. the carbonate anion of fractional part.
Can be present in the charge balance gegenion among the pyridinium salt structure XV, comprise the charge balance gegenion that is used for structure I disclosed herein.In one embodiment, the charge balance gegenion is selected from: fluorion, chlorion, bromide anion, iodide ion, sulfate radical, inferior sulfate radical, carbonate, bicarbonate radical, acetate moiety, oxalate, and combination.
In one embodiment, the invention provides the method that preparation has the pyridinium salt of structure XV, it comprises that (a) makes aromatic amine with structure XX and pyrans (pyrilium) reactant salt with structure XXI,
Figure A200780031007D00202
Wherein " d " is 0～4 number; R 4Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Z is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; Ar 9Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl; And X -Be the charge balance gegenion;
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And X -Be the charge balance gegenion; And (b) separated product has the pyridinium salt of structure XV.
Aromatic amine XX contact with pyranium salt XXI the reaction that causes generally include make these reactants approximately-20 ℃ to about 150 ℃ temperature contact.Although adopt solvent usually, the form that this reaction also can melt is carried out.
In one embodiment, the invention provides polymer pyridinium salt and preparation method thereof.The polymer pyridinium salt can prepare through the following steps: (a) make the polymer aromatic diamine and have the pyranium salt reaction (contact) of structure XXI, reach (b) separated product polymer pyridinium salt.
In one embodiment, described polymer aromatic diamine comprises the structural unit that comes from least a on-macromolecular aromatic diamine and at least a dianhydride.For example, the diamines that can make molar excess as 4,4 '-oxydiphenyl amine (4,4 '-ODA) with 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (4,4 '-ODPA) in orthodichlorobenzene (oDCB), react down in refluxing, obtain amine terminated polyether imide.Amine terminated polyether imide and the pyranium salt reaction with structure XXI obtain product polymer pyridinium salt, and it can separate by for example anti-solvent precipitation.
In one embodiment, the on-macromolecular aromatic diamine is a mphenylenediamine.In one embodiment, the on-macromolecular aromatic diamine is a mphenylenediamine, and dianhydride is BPADA.In one embodiment, the dianhydride that is adopted is the mixture of BPADA and 4,4 '-ODPA.
In one embodiment, the invention provides polymer pyridinium salt with structure XXII:
Wherein " f " is 10 to about 1000 number, and X -Be the charge balance gegenion.
Thereby, in one embodiment, the invention provides a kind of method, this method comprises that (a) makes the polymer aromatic diamine with structure XXIII contact with the pyranium salt with structure XXIV,
Wherein variable " f " is 10 to about 1000 number;
Figure A200780031007D00222
X wherein -Be the charge balance gegenion; And
(b) separate product polymer pyridinium salt with structure XXII.
As described herein, polymer diamines such as XXIII can react down in polycondensation condition (oDCB for example refluxes) by excessive aromatic diamine and dianhydride and make.Those of ordinary skill in the art understands, diamines XXIII can by excessive mphenylenediamine and 4,4 '-ODPA reacts under the polycondensation condition and makes.Pyranium salt such as XXIV can obtain from commercial, also can make according to method well known in the art.In one embodiment, the invention provides the polymer pyridinium salt with structure XXII, wherein variable " f " is 10 to about 100 number.
Except new You Ji phosphonium salt I and pyridinium salt XV was provided, the present invention also provided other organic salt that can be used for the polymer-organoclay composite composition for preparing organic clay composition and come from this organic clay composition.
Thereby, in one embodiment, the invention provides the pyridinium salt that comprises positively charged ion XXV:
Figure A200780031007D00223
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
The pyridinium salt that comprises positively charged ion XXV is illustrated in the Table III.This pyridinium salt that comprises positively charged ion XXV can utilize method preparation disclosed herein and be mixed in organic clay composition and the polymer-organoclay composite composition.For example, the method that those are suitable for preparing and using the pyridinium salt with structure XV can be applicable to prepare and use the pyridinium salt that comprises positively charged ion XXV.
The pyridinium salt that comprises positively charged ion XXV that Table III is exemplary
Figure A200780031007D00231
Ph: phenyl
On the other hand, the invention provides the organic salt that contains phenyl ketone that can be used for preparing organic clay composition and come from the polymer-organoclay composite composition of this organic clay composition.Thereby, in one embodiment, the invention provides and comprise the cationic salt that contains phenyl ketone of structure XXXIII De quaternary phosphine:
Figure A200780031007D00232
Ar wherein 12, Ar 13, Ar 14And Ar 15Be C independently 2-C 50Aromatic group; And Ar 16Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
Comprising the cationic salt that contains phenyl ketone of structure XXXIII De quaternary phosphine is illustrated in the Table IV.The salt that contains phenyl ketone that comprises quaternary phosphine positively charged ion XXXIII can openly prepare like that by this paper.The salt that contains phenyl ketone that comprises quaternary phosphine positively charged ion XXXIII can utilize disclosed herein and shows the method that is suitable for You Ji phosphonium salt I and pyridinium salt XV, is blended in organic clay composition and the polymer-organoclay composite composition.For example, those are suitable for the mixed method in organic clay composition of the cationic components of You Ji phosphonium salt I be can be applicable to prepare organic clay composition with the salt that contains phenyl ketone that comprises quaternary phosphine positively charged ion XXXIII.
The salt that contains phenyl ketone that comprises positively charged ion XXXIII that Table IV is exemplary
Figure A200780031007D00241
Ph: phenyl
In one embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises wherein Ar 16Be polyetherketone polymer chain De quaternary phosphine positively charged ion XXXIII.This salt can so prepare, and for example, chooses wantonly in solvent in the presence of catalyzer, and the polyetherketone that comprises one or more end chlorobenzene formacyls and triaryl phosphine such as triphenylphosphine are reacted.
In one embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIII, wherein Ar 16Be number-average molecular weight M nBe about 1000 polymer chains to about 50000 gram/moles.In another embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIII, wherein Ar 16Be number-average molecular weight M nBe about 1000 polymer chains to about 20000 gram/moles.In yet another embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIII, wherein Ar 16Be number-average molecular weight M nBe about 1000 polymer chains to about 5000 gram/moles.
In one embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIII, wherein Ar 16Be number-average molecular weight M nBe about 1000 polyetherimide polymer chains to about 50000 gram/moles.In another embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIII, wherein Ar 16Be number-average molecular weight M nAbout 1000 polyetherimide polymer chains to about 20000 gram/moles.
One concrete aspect, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXIV.Those of ordinary skill in the art knows that this positively charged ion falls in the defined upperseat concept scope of structure XXXIII.Thereby structure XXXIV represents the wherein Ar of structure XXXIII 15Be adjacent phenylene oxygen base and Ar 16Situation for 4-(2-triphenyl phosphonium phenylene oxygen base) phenyl.
Figure A200780031007D00251
In another embodiment, the invention provides the salt that contains phenyl ketone, this salt that contains phenyl ketone comprises quaternary phosphine positively charged ion XXXV.
In one embodiment, the invention provides the high molecular salt that contains phenyl ketone, it comprises the macromolecule quaternary phosphine positively charged ion with structure XXXVII:
Figure A200780031007D00253
Wherein " g " and " h " is 0～4 number independently; W is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; R 5And R 6Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; " i " is about 10 to about 1000 number; And Ar 17Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
The high molecular salt that contains phenyl ketone is illustrated in the following Table V, and this salt comprises the macromolecule quaternary phosphine positively charged ion with structure XXXVII.
Table V
Figure A200780031007D00261
Clauses and subclauses 5a and 5b illustrate in the Table V, in one embodiment Ar 17For comprising the aromatic group of structure XXXVIII.
Figure A200780031007D00262
The high molecular salt that contains phenyl ketone, as those salt that exemplified in the Table V, can be by described herein like that by making by corresponding halogenated polyether ketone with the triaryl phosphine reaction.Halogenated polyether ketone can obtain by the known method of those of ordinary skill in the art, and dihalo benzophenone that can be by the disodium salt of bis-phenol (as the disodium salt of dihydroxyphenyl propane) for example and molar excess (as 5% molar excess) is (as 4,4 '-difluoro benzophenone) reaction makes, and this is reflected at phase-transfer catalyst (as the hexaethylguanidiniumchloride chloride guanidinesalt) and exists down and carry out in inert solvent (as orthodichlorobenzene) and under the high temperature (as 130～180 ℃).
In one embodiment, the invention provides and comprise season organic cations organic clay composition.Season, organic cation can Shi quaternary phosphine positively charged ion, quaternary ammonium cation, perhaps its combination.Season, organic cation was the cationic components of various organic quaternary salts disclosed herein.Thereby You Ji phosphonium salt I is the organic quaternary salt that comprises season organic cation X:
Figure A200780031007D00271
Ar wherein 1, Ar 2And Ar 3Be C independently 2-C 50Aromatic group; Ar 4Be chemical bond or C 2-C 50Aromatic group; " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain.
Similarly, pyridinium salt XV is the organic quaternary salt that comprises season organic cation XXVI:
Figure A200780031007D00272
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; " d " is 0～4 number; R 3And R 4Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Z is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; And Ar 9Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
Equally, pyridinium salt XXXI
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl; And X -Be the charge balance gegenion;
For comprising organic quaternary salt of season organic cation XXV:
Figure A200780031007D00281
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
Similarly, the You Ji phosphonium salt XXXVI that contains phenyl ketone
Figure A200780031007D00282
Ar wherein 12, Ar 13, Ar 14And Ar 15Be C independently 2-C 50Aromatic group; Ar 16Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl; And X -Be the charge balance gegenion;
For comprising the organic quaternary salt of season organic cations with following structure:
Figure A200780031007D00283
Ar wherein 12, Ar 13, Ar 14And Ar 15Be C independently 2-C 50Aromatic group; And Ar 16Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
By above-mentioned discussion and those of ordinary skills' understanding as can be known, the constitutional features that exists in various organic quaternary salts disclosed herein is reproduced in corresponding season organic cation.For example, the aromatic group Ar that in You Ji phosphonium salt I, defines 1With the aromatic group Ar among the You Ji phosphonium cation X 1Has identical implication.Thereby, if Ar 1In You Ji phosphonium salt I is phenyl, and then it is similarly phenyl in You Ji phosphonium cation X.
Organic clay composition of the present invention comprises alternative inorganic silicic acid salt deposit and organic layer.The inorganic silicic acid salt deposit can come from any suitable source, for example natural clay.In one embodiment, the inorganic silicic acid salt deposit comes from synthesis of clay.Suitable clay comprises kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica (tetrasilylic mica), sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.In specific embodiment, the inorganic silicic acid salt deposit comes from montmorillonitic clay (montmorillomite clay).
Organic clay composition provided by the present invention is characterised in that the interlamellar spacing between each inorganic silicic acid salt deposit is 5 to approximately In one embodiment, organic clay composition provided by the present invention is characterised in that the interlamellar spacing between each inorganic silicic acid salt deposit is 10 to approximately
Figure A200780031007D00292
And be about 20 to approximately in another embodiment
Figure A200780031007D00293
In one embodiment, organic clay composition provided by the present invention prepares through the following steps: organic quaternary salt is contacted in the presence of solvent with layered silicate, reach (b) separated product organic clay composition.In one embodiment, organic quaternary salt is the You Ji phosphonium salt with structure I.In another embodiment, organic quaternary salt is the pyridinium salt with structure XV.In yet another embodiment, organic quaternary salt is the pyridinium salt with structure XXXI.In an embodiment again, organic quaternary salt is the You Ji phosphonium salt that contains phenyl ketone with structure XXXVI.
As already mentioned, organic clay composition provided by the present invention can contact with layered silicate in the presence of solvent by organic quaternary salt and make.In one embodiment, layered silicate is a natural clay.In another embodiment, layered silicate is a synthesis of clay.In one embodiment, layered silicate comprises and is selected from following inorganic clay: kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica, sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.In another embodiment, layered silicate comprises montmorillonitic clay.
As already mentioned, organic clay composition provided by the present invention can contact with layered silicate in the presence of solvent by organic quaternary salt and make.In one embodiment, the solvent that is adopted comprises organic solvent, for example acetone.In another embodiment, the solvent that is adopted comprises water.In yet another embodiment, the solvent that is adopted comprises water and organic solvent simultaneously, for example contains the methanol aqueous solution of about 10% weight water and about 90% weight methyl alcohol.
Organic clay composition can utilize such as ordinary methods such as filtration, centrifugal, anti-solvent deposition, decants and separate.Be suitable for separating the whole bag of tricks of organic clay composition provided by the present invention referring to experimental section of the present disclosure.
In one embodiment, the invention provides the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure X:
Figure A200780031007D00301
Ar wherein 1, Ar 2And Ar 3Be C independently 2-C 50Aromatic group; Ar 4Be chemical bond or C 2-C 50Aromatic group; " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain.
The example of You Ji phosphonium cation X is referring to the cationic components of disclosed You Ji phosphonium salt in the Table I.
， quaternary phosphine positively charged ion has structure XI in one embodiment.
Figure A200780031007D00302
， quaternary phosphine positively charged ion has structure XII in another embodiment.
Figure A200780031007D00303
In one embodiment, the invention provides and comprise the cationic organic clay composition of macromolecule quaternary phosphine.In one embodiment, the invention provides and comprise the cationic organic clay composition of macromolecule quaternary phosphine with structure XIII:
Figure A200780031007D00311
Wherein m is about 10 to about 1000 number; And Ar 5Be C 2-C 50Aromatic group, perhaps polymer chain.In one embodiment, Ar 5For having the aromatic group of structure XIV.
In one embodiment, the invention provides the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXV:
Figure A200780031007D00313
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
The example of pyridylium with structure XXV is referring to the cationic components of the disclosed pyridinium salt of this paper Table III.
In one embodiment, the invention provides the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXVI:
Figure A200780031007D00314
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; " d " is 0～4 number; R 3And R 4Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Z is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; And Ar 9Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
The example of pyridylium with structure XXVI is referring to the cationic components of the disclosed pyridinium salt of this paper Table II.
In one embodiment, the invention provides the organic clay composition that comprises pyridylium, this pyridylium has structure XXVII.
Figure A200780031007D00321
In another embodiment, the invention provides the organic clay composition that comprises pyridylium, this pyridylium has structure XXVIII.
Figure A200780031007D00322
In one embodiment, organic clay composition provided by the present invention comprises polymer season organic cation, and it is the polymer pyridylium.In one embodiment, the polymer pyridylium comprises structure XXIX:
Figure A200780031007D00331
Wherein variable " e " is about 10 to about 1000 number; And Ar 10Be C 2-C 50Aromatic group, perhaps polymer chain.In one embodiment, Ar 10For having the C of structure XXX 23Aromatic group.
Figure A200780031007D00332
In another embodiment, the invention provides organic clay composition, it comprises the polymer pyridylium with structure XXXII:
Figure A200780031007D00333
Wherein " f " is about 10 to about 1000 number.In specific embodiment, the numerical value of " f " is about 10.In another embodiment, the numerical value of " f " is about 30.
In one embodiment, the invention provides the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XXXIII:
Figure A200780031007D00334
Ar wherein 12, Ar 13, Ar 14And Ar 15Be C independently 2-C 50Aromatic group; And Ar 16Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
Have structure XXXIII De quaternary phosphine positively charged ion and be called " the You Ji phosphonium cation that contains phenyl ketone " in this article sometimes.Have the cationic components of the cationic example of structure XXXIII De quaternary phosphine referring to disclosed You Ji phosphonium salt in this paper Table IV.
In one embodiment, the invention provides and comprise the cationic organic clay composition of quaternary phosphine, Gai has structure XXXIV by quaternary phosphine positively charged ion.
Figure A200780031007D00341
In another embodiment, the invention provides and comprise the cationic organic clay composition of quaternary phosphine, Gai has structure XXXV by quaternary phosphine positively charged ion.
Figure A200780031007D00342
In yet another embodiment, the invention provides and comprise the cationic organic clay composition of macromolecule quaternary phosphine, this macromolecule quaternary phosphine positively charged ion has structure XXXVII.
Figure A200780031007D00343
Wherein " g " and " h " is 0～4 number independently; W is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; R 5And R 6Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; " i " is about 10 to about 1000 number; And Ar 17Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.In one embodiment, Ar 17For having the aromatic group of structure XXXVIII:
Figure A200780031007D00351
Have the cationic components of the cationic example of macromolecule quaternary phosphine of structure XXXVII referring to the disclosed Gao of this paper Table V Fen You Ji phosphonium salt.
In one embodiment, the invention provides the polymer-organoclay composite composition, the organic clay composition that it comprises (a) fluoropolymer resin and (b) comprises alternative inorganic silicic acid salt deposit and organic layer, wherein said organic layer comprises the season organic cation.
In one embodiment, fluoropolymer resin comprises amorphous thermoplastic polymer.In another embodiment, fluoropolymer resin comprises the crystalline state thermoplastic polymer.In another embodiment, fluoropolymer resin comprises amorphous thermoplastic polymer and crystalline state thermoplastic polymer.The example of amorphous thermoplastic polymer has PPSU (Polyphenylene Sulfone), PEI (polyetherimide), PES (polyethersulfone), PC (polycarbonate), PPO (polyphenylene oxide), PMMA (polymethylmethacrylate), ABS (polyacrylonitrile-butadiene-styrene), and PS (polystyrene).The example of crystalline state thermoplastic resin has PFA (PFA polymkeric substance), MFA (multipolymer of tetrafluoroethylene and fluorinated vinyl ether), FEP (fluorizated ethylene propylene polymerization thing), PPS (polyphenylene sulfide), PEK (polyetherketone), PEEK (polyether-ether-ketone), ECTFE (ethylene-chlorotrifluoro-ethylene copolymer), PVDF (poly(vinylidene fluoride)), PTFE (tetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polymeric amide), UHMW-PE (ultrahigh molecular weight polyethylene(UHMWPE)), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene(HDPE)), LDPE (new LDPE (film grade)), and high-performance engineering resin such as PBI (polybenzimidazole) and PAI (polyamide-imide), polyphenyl, polybenzoxazole, polybenzothiozole, and their blend and multipolymer.
In one embodiment, fluoropolymer resin is selected from: polyetherimide, and polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl, polycarbonate, and comprise the combination of at least a aforementioned polymer.In specific embodiment, fluoropolymer resin comprises polyetherimide resin, the GE Plastics that for example derives from, the ULTEM of Inc..In another embodiment, fluoropolymer resin comprises polyphenylene resin, for example derives from Solvay, the PRIMOSPIRE of Inc..In another specific embodiments, fluoropolymer resin comprises polyethersulfone, for example derives from Solvay, the RADELA of Inc..In a specific embodiments again, fluoropolymer resin comprises polyetherketone.
Be present in organic clay composition in the polymer-organoclay composite composition and be preferably highly exfoliately, the distance that means each inorganic silicate interlayer is greater than same organic clay composition distance between corresponding each silicate layer before it sneaks in the polymeric matrix of polymer-organoclay composite composition.Design organic clay composition provided by the present invention,, promote that silicate layer more easily separates so that when in the presence of fluoropolymer resin or solvent, making organic clay composition stand shearing force.Thereby, in one embodiment, polymer-organoclay composite composition provided by the invention comprises organic clay composition, this organic clay composition comprises alternative inorganic silicic acid salt deposit and organic layer, and wherein alternative inorganic silicic acid salt deposit is a high dispersing with respect to the organic clay composition of the silicate layer that is used to obtain the polymer-organoclay composite composition.
In one embodiment, polymer-organoclay composite composition provided by the invention comprises the inorganic silicic acid salt deposit that comes from inorganic clay, and described inorganic clay is selected from: kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica, sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.In one embodiment, this inorganic clay at first changes into organic clay composition, uses this intermediary organic clay composition to prepare the polymer-organoclay composite composition then.In one embodiment, the organic clay composition that is adopted in the preparation of polymer-organoclay composite composition is characterised in that about 5 to about
Figure A200780031007D00361
Interlamellar spacing.Although a large amount of used organic clay compositions can polymer-organoclay composite composition camber peel off, keep 5 to approximately to the used organic clay composition of small part
Figure A200780031007D00362
Interlamellar spacing.
In one embodiment, the invention provides the goods that comprise polymer-organoclay composite composition provided by the present invention.In one embodiment, these goods are film.In specific embodiment, these goods are cast film.In another embodiment, these goods are the solvent cast film.Cast film can utilize method preparation as herein described.The solvent cast film that comprises polymer-organoclay composite composition of the present invention can be according to method preparation well known in the prior art.
In specific embodiment, the invention provides the solvent cast film that comprises polyetherimide, this polyetherimide has dianhydride component and diamine components and about 180～450 ℃ second-order transition temperature (Tg), and wherein this film has: a) less than 70ppm/ ℃ CTE; B) thickness of about 0.1 μ m to 250 μ m; And c) comprises residual solvent less than 5% weight.
In one embodiment, the invention provides the polymer-organoclay composite composition that comprises fluoropolymer resin, described fluoropolymer resin is the polyetherimide with dianhydride component and diamine components.This means that polyetherimide comprises the structural unit that comes from least a dianhydride and at least a diamines.Polyetherimide with dianhydride component and diamine components and required Tg, can make by making one or more diamines and one or more two anhydride reactants (for example in the presence of catalyzer sodium phenylphosphinate (SPP) backflow orthodichlorobenzene in the reactor that the reaction water removal device is housed) under the polycondensation condition.
Suitable dianhydride comprises:
2,2-two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
2,2-two [4-(2, the 3-di carboxyl phenyloxy) phenyl] propane dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dianhydride;
4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) biphenyl-2,2-propane dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dianhydride;
4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
1,3-two (2, the 3-di carboxyl phenyloxy) benzene dianhydride;
1,4-two (2, the 3-di carboxyl phenyloxy) benzene dianhydride;
1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride;
1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride;
The tetramethylene tetracarboxylic dianhydride;
The pentamethylene tetracarboxylic dianhydride;
Hexanaphthene-1,2,5, the 6-tetracarboxylic dianhydride;
2,3,5-tricarboxylic basic ring amyl group acetate dianhydride;
5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride;
1,3,3a, 5-dioxo-3-furyl)-naphtho-[1,2 ,-c]-furans-1, the 3-diketone;
3,5,6-three carboxyls norbornane-2-acetate dianhydride;
2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride;
3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride;
The dianhydride of naphthalene is as (2,3,6,7-naphthalene dianhydride etc.);
3,3 ', 4,4 '-biphenyl sulfonic acid tetracarboxylic dianhydride (3,3 ', 4,4 '-biphenylsulphonictetracarboxylicdianhydride);
3,3 ', 4,4 '-the phenyl ether tetracarboxylic dianhydride;
3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride;
4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride;
3,3 ', 4,4 '-perfluor Phenazopyridine (pyridene) two O-phthalic acid dianhydrides;
3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
Two (O-phthalic acidic group) phenyl hydroxide sulphur dianhydride (bis (phthalic) phenylsulphineoxidedianhydride);
To phenylene-two (triphenyl phthalic acid) dianhydride;
Metaphenylene-two (triphenyl phthalic acid) dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the phenyl ether dianhydride;
Two (triphenyl phthalic acids)-4,4 '-the ditan dianhydride;
2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride;
4,4 '-oxygen di-(Tetra hydro Phthalic anhydride);
Pyromellitic dianhydride;
3,3 ', 4,4 '-diphenylsulfone acid's dianhydride;
4 ', 4 '-the dihydroxyphenyl propane dianhydride;
The quinhydrones diphthalic anhydrides;
Ethylene glycol bisthioglycolate (trimellitic acid 1,2-anhydride);
6,6 '-two (3, the 4-di carboxyl phenyloxy)-2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two [1h-indenes] dianhydride;
7,7 '-two (3, the 4-di carboxyl phenyloxy)-3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-spiral shell two [2h-1-chromene] dianhydride;
1,1 '-two [1-(3, the 4-di carboxyl phenyloxy)-2-methyl-4-phenyl] hexanaphthene dianhydride;
3,3 ', 4,4 '-diphenylsulfone acid's dianhydride;
3,3 ', 4,4 '-the diphenyl sulfide tetracarboxylic dianhydride;
3,3 ', 4,4 '-the thionyl benzene tetracarboxylic dianhydride;
3,4 '-oxygen di-(Tetra hydro Phthalic anhydride);
3,3 '-oxygen di-(Tetra hydro Phthalic anhydride);
3,3 '-benzophenone tetracarboxylic dianhydride;
4,4 '-the carbonyl diurethane Tetra hydro Phthalic anhydride;
3,3 ', 4,4 '-the ditan tetracarboxylic dianhydride;
2,2-two (4-(3,3-dicarboxyl phenyl) propane dianhydride;
2,2-two (4-(3,3-dicarboxyl phenyl) hexafluoropropane dianhydride;
(3,3 ', 4,4 '-phenylbenzene) the Phenylphosphine tetracarboxylic dianhydride;
(3,3 ', 4,4 '-phenylbenzene) the phenyl phosphine oxide tetracarboxylic dianhydride;
2,2 '-two chloro-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-dimethyl-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-dicyano-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two bromo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two iodo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (trifluoromethyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-methyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-2-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-3-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-trifluoromethyls-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
2,2 '-two (1-phenyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
4,4 '-the dihydroxyphenyl propane dianhydride;
5,5 '-[1,4-phenylene two (oxygen base)] two [1, the 3-isobenzofurandione];
3,3 ', 4,4 '-the thionyl benzene tetracarboxylic dianhydride;
4,4 '-the carbonyl diurethane Tetra hydro Phthalic anhydride;
3,3 ', 4,4 '-the ditan tetracarboxylic dianhydride;
2,2 '-two (1,3-trifluoromethyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride;
Their isomer; And
Their combination.
Suitable diamines comprises: quadrol; Inferior propylene diamine (propylenediamine); The trimethylene diamines; Diethylenetriamine; Triethylenetetramine (TETA); Hexamethylene-diamine; The heptamethylene diamines; Eight methylene diamine; Nine methylene diamine; Decamethylene diamine; 1,12-dodecane diamines; 1, the 18-octadecamethylene diamine; 3-methyl heptamethylene diamines; 4,4-dimethyl heptamethylene diamines; 4-methyl nine methylene diamine; 5-methyl nine methylene diamine; 2,5-dimethyl hexamethylene-diamine; 2,5-dimethyl heptamethylene diamines; 2, the 2-dimethylated propyl diethylenetriamine; N-methyl-two (3-aminopropyl) amine; 3-methoxyl group hexamethylene-diamine; 1,2-two (the amino propoxy-of 3-) ethane; Two (3-aminopropyl) sulfoxide; 1, the 4-cyclohexane diamine; Two (4-aminocyclohexyl) methane; Mphenylenediamine; Ursol D; 2,4 di amino toluene; 2, the 6-diaminotoluene; M-xylene diamine; The p-Xylol diamines; 2-methyl-4,6-diethyl-1,3-phenylenediamine; 5-methyl-4,6-diethyl-1,3-phenylenediamine; P-diaminodiphenyl; 3,3 '-tolidine; 3,3 '-dimethoxy benzidine; 1, the 5-diaminonaphthalene; Two (4-aminophenyl) methane; Two (2-chloro-4-amino-3,5-diethyl phenyl) methane; Two (4-aminophenyl) propane; 2,4-two (b-amino-tertiary butyl) toluene; Two (p-b-amino-tert-butyl-phenyl) ether; Two (p-b-methyl-o-amino-phenyl-) benzene, two (p-b-methyl-neighbour-amino amyl group) benzene, 1,3-diamino-4-isopropyl benzene, two (4-aminophenyl) thioether, two (4-aminophenyl) sulfone, two (4-aminophenyl) ether; 1,3-two (3-aminopropyl) tetramethyl disiloxane; 4,4 '-diamino-diphenyl propane; 4,4 '-diaminodiphenyl-methane; (4,4 '-methylene dianiline (MDA)); 4,4 '-diaminodiphenyl sulfide; 4,4; 3,3 '-diaminodiphenylsulfone(DDS); 4,4 '-diaminodiphenyl sulfide; 3,3 '-diaminodiphenyl sulfide; 4 (4,4 '-oxydiphenyl amine); 1, the 5-diaminonaphthalene; 3,3 ' tolidine; 3-methyl heptamethylene diamines; 4,4-dimethyl heptamethylene diamines; 2,11-dodecane diamines; Eight methylene diamine; Two (3-aminopropyl) tetramethyl disiloxane; Two (the amino butyl of 4-) tetramethyl disiloxane; Two (p-amino-tert-butyl-phenyl) ether; Two (p-methyl-o-amino-phenyl-) benzene; Two (p-methyl-neighbour-amino amyl group) benzene; 2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two [1H-indenes]-6,6 '-diamines; 3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-spiral shell two [2H-1-chromene]-7,7 '-diamines; 1,1 '-two [1-amino-2-methyl-4-phenyl] hexanaphthene; Their isomer; And their combination.
Polymer-organoclay composite composition provided by the invention comprises organic clay composition.In one embodiment, the organic clay composition that is adopted is an organic clay composition provided by the present invention.Thereby, in one embodiment, the polymer-organoclay composite composition comprises at least a organic clay composition, this organic clay composition comprises the season organic cation, this, organic cation was selected from season: the You Ji phosphonium cation with structure X, pyridylium with structure XXV has the pyridylium of structure XXVI; And has the You Ji phosphonium cation that contains phenyl ketone of structure XXXIII.
Thereby, in one embodiment, the invention provides the polymer-organoclay composite composition, comprise (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure X.In another embodiment, the invention provides the polymer-organoclay composite composition, comprise (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XI.In yet another embodiment, the invention provides the polymer-organoclay composite composition, comprise (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XII.
In one embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, described composition comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure X.
In another embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, described method is included in fluoropolymer resin is contacted with the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, and described organic layer comprises the quaternary phosphine positively charged ion with structure X.
In one embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXV.In another embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXVI.In yet another embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXVII.In an embodiment again, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXVIII.
In one embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, described composition comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXV.In another embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, described composite composition comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the pyridylium with structure XXVI.
In another embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method is included in fluoropolymer resin is contacted with the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, and described organic layer comprises the pyridylium with structure XXV.In another embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method is included in fluoropolymer resin is contacted with the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, and described organic layer comprises the pyridylium with structure XXVI.
Thereby, in one embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XXXIII.In another embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XXXIV.In yet another embodiment, the invention provides the polymer-organoclay composite composition, it comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XXXV.
In one embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, described composite composition comprises (a) fluoropolymer resin; Reach the organic clay composition that (b) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the quaternary phosphine positively charged ion with structure XXXIII.
In another embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method is included in fluoropolymer resin is contacted with the organic clay composition that comprises alternative inorganic silicic acid salt deposit and organic layer, and described organic layer comprises the quaternary phosphine positively charged ion with structure XXXIII.
Form the melting mixing approach of polymer-organoclay composite composition
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method comprises that melting mixing comprises the season organic clay composition and fluoropolymer resin of alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, the temperature of described melting mixing is about 300 ℃ to about 450 ℃, to obtain the polymer-organoclay composite composition, described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.Season, organic clay composition was to comprise the season organic cation as the organic clay composition of You Ji phosphonium cation with structure X.
The season organic cation that is adopted is not had special restriction, and just it must be enough stable in the melting mixing step, so that organic clay composition can carry out peeling off of enough levels in polymeric matrix.If still keep about season organic cation more than 90% after the melting mixing step, and intensity is enough to realize at least 10% the percentage ratio that peels off, and thinks that then the season organic cation is stable.In one embodiment, organic cation has structure XXXIX season:
Figure A200780031007D00431
Wherein Q is nitrogen or phosphorus; And R 7, R 8, R 9And R 10Be C independently 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 20Aromatic group, perhaps polymer chain.In one embodiment, has the season organic cation Wei quaternary phosphine positively charged ion of structure XXXIX, for example tetraphenylphosphoniphenolate positively charged ion TPP.In another embodiment, the season organic cation with structure XXXIX is to have structure X De quaternary phosphine positively charged ion.In yet another embodiment, the season organic cation with structure XXXIX is to have structure XXXIII De quaternary phosphine positively charged ion.
In one embodiment, the season organic cation with structure XXXIX is a quaternary ammonium cation, for example tetraphenyl ammonium cation TPA.
In one embodiment, organic cation is the pyridylium with structure XXV season.In another embodiment, organic cation is the pyridylium with structure XXVI season.
In one embodiment, the inorganic silicic acid salt deposit comes from and is selected from following inorganic clay: kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica, sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.Usually, elder generation changes into inorganic clay and comprises season organic cations organic clay composition.In certain embodiments, organic clay composition can prepare in the presence of fluoropolymer resin.Suitable organic clay composition comprises those organic clay compositions disclosed herein.In one embodiment, the organic clay composition that is adopted is characterised in that about 5 to about Interlamellar spacing.In this case, the product polymer-organoclay composite composition to small part has interlamellar spacing about 5 equally to about
Figure A200780031007D00433
Feature.
In one embodiment, by about 300 ℃ to about 450 ℃ temperature melting mixing comprise organic cations season in season organic clay composition and the polymer-organoclay composite composition that makes of fluoropolymer resin comprise poly (arylene sulfide), polyphenylene sulfide (PPS) for example.In another embodiment, by about 300 ℃ to about 450 ℃ temperature melting mixing comprise organic cations season in season organic clay composition and the polymer-organoclay composite composition that makes of fluoropolymer resin comprise polyethersulfone, for example comprise the multipolymer of the structural unit that comes from dihydroxyphenyl propane and two (4-chloro-phenyl-) sulfone.In yet another embodiment, by about 300 ℃ to about 450 ℃ temperature melting mixing comprise organic cations season in season organic clay composition and the polymer-organoclay composite composition that makes of fluoropolymer resin comprise polyetherketone, for example comprise come from dihydroxyphenyl propane and 4,4 '-multipolymer of the structural unit of dichloro benzophenone.
Described melting mixing can adopt any melting mixing technology to carry out, this melting mixing technology have concurrently enough shearing forces and about 300 ℃ to about 450 ℃ of temperature heating organic clay composition and fluoropolymer resin be at least 10% ability to realize the percentage ratio that peels off of organic clay composition in fluoropolymer resin.Usually, can utilize forcing machine to implement melting mixing.In one embodiment, forcing machine is the twin screw extruder that has evacuation port.In another embodiment, forcing machine is the single screw rod Reciprocatory forcing machine that has evacuation port.In one embodiment, melting mixing is carried out in kneader.In one embodiment, the lasting time and intensity of melting mixing is enough to realize that the peel off percentage ratio of organic clay composition in fluoropolymer resin is at least 20%.In yet another embodiment, the lasting time and intensity of melting mixing is enough to realize that the peel off percentage ratio of organic clay composition in fluoropolymer resin is at least 30%.
In one embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, this polymer-organoclay composite composition is to prepare with (b) fluoropolymer resin by the season organic clay composition that melting mixing (a) comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, described melting mixing about 300 ℃ to about 450 ℃ temperature and be enough to realize carry out under the shearing force of peeling off percentage ratio at least 10% of organic clay composition in fluoropolymer resin.
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method comprises that melting mixing comprises the season organic clay composition and fluoropolymer resin of alternative inorganic silicic acid salt deposit and organic layer; Described organic layer comprises the season organic cation; Described fluoropolymer resin comprises at least a following polymkeric substance that is selected from: polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl, and polycarbonate; Described fluoropolymer resin does not contain polyetherimide substantially; Described melting mixing is carried out to about 450 ℃ temperature at about 300 ℃, and to obtain the polymer-organoclay composite composition, described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.When the gross weight according to fluoropolymer resin, when it comprised less than the polyetherimide of 5 weight %, then fluoropolymer resin did not contain polyetherimide substantially.When it comprised the polyetherimide of 0 weight %, same said polymer resin was substantially free of polyetherimide.
In another embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, this polymer-organoclay composite composition comprises the season organic clay composition that (a) comprises alternative inorganic silicic acid salt deposit and organic layer, and described organic layer comprises the season organic cation; Reach (b) fluoropolymer resin, this fluoropolymer resin comprises at least a following polymkeric substance that is selected from: polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl, and polycarbonate; This fluoropolymer resin does not contain polyetherimide substantially; Wherein said polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.In one embodiment, these goods are film.In another embodiment, these goods are the solvent cast film, and it comprises the polyetherimide with dianhydride component and diamine components and has about 180～450 ℃ Tg, and wherein this film has: a) less than 70ppm/ ℃ CTE; B) thickness of about 0.1 μ m to 250 μ m; And c) comprises residual solvent less than 5% weight.
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method is included in the season organic clay composition and fluoropolymer resin that melting mixing in the forcing machine comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, described fluoropolymer resin comprises polyethersulfone, described fluoropolymer resin does not contain polyetherimide substantially, described melting mixing is carried out so that the polymer-organoclay composite composition to be provided to about 450 ℃ temperature at about 300 ℃, and described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.In one embodiment, organic cation has structure X season.In another embodiment, organic cation has structure XXV season.In another embodiment, organic cation has structure XXVI season.In yet another embodiment, organic cation has structure XXXIII season.
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method comprises that melting mixing comprises the season organic clay composition and polyetherimide amine component of alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, described melting mixing is carried out so that the polymer-organoclay composite composition to be provided to about 450 ℃ temperature at about 300 ℃, and described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.In one embodiment, organic cation has structure X season.In another embodiment, organic cation has structure XXV season.In another embodiment, organic cation has structure XXVI season.In yet another embodiment, organic cation has structure XXXIII season.In one embodiment, the polyetherimide amine component also comprises at least a following polymkeric substance that is selected from: polyvinyl chloride, polyolefine, polyester, polymeric amide, polysulfones, polyethersulfone, polyphenylene sulfide, polyetherketone, polyether-ether-ketone, ABS, polystyrene, polyhutadiene, poly-(acrylate), poly-(alkyl acrylate), polyacrylonitrile, polyacetal, polycarbonate, polyphenylene oxide, ethylene-vinyl acetate copolymer, polyvinyl acetate, liquid crystalline polymers, aromatic polyester, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene, poly(vinylidene fluoride), polyvinylidene dichloride, tetrafluoroethylene, and comprise the combination of at least a aforementioned polymer.In one embodiment, the polyetherimide amine component comprises polyethersulfone.In another embodiment, the polyetherimide amine component comprises polyetherketone.
In one embodiment, the invention provides the goods that comprise the polymer-organoclay composite composition, this polymer-organoclay composite composition comprises the season organic clay composition that (a) comprises alternative inorganic silicic acid salt deposit and organic layer, and this organic layer comprises the season organic cation; Reach (b) polyetherimide amine component, wherein the polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.Suitable polyetherimide amine component comprises the ULTEM polyetherimide that derives from GE Plastics.
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method is included in the season organic clay composition and polyetherimide amine component that melting mixing in the forcing machine comprises alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, described polyetherimide amine component comprises at least a polyetherimide and at least aly is selected from other following polymkeric substance: polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl, and polycarbonate; Described melting mixing is carried out to obtain the polymer-organoclay composite composition to about 450 ℃ temperature at about 300 ℃, and described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.In one embodiment, organic cation has structure X season.In another embodiment, organic cation has structure XXV season.In another embodiment, organic cation has structure XXVI season.In yet another embodiment, organic cation has structure XXXIII season.
Form the in-situ polymerization approach of polymer-organoclay composite composition
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method adopts in-situ polymerization technology, produces fluoropolymer resin in the presence of organic clay composition.The method of being developed has lot of advantages, contacts with the tight of nascent fluoropolymer resin comprising organic clay composition.
Thereby, on the one hand, the invention provides the method for preparing the polymer-organoclay composite composition, this method comprises that (a) makes first monomer, second monomer, solvent contact with organic clay composition under the polycondensation condition, obtain first polymerization reaction mixture, wherein said organic clay composition comprises alternative inorganic silicic acid salt deposit and organic layer, and one of described first monomer and second monomer are diamines, and another is a dianhydride; (b) first polymerization reaction mixture is implemented the stoichiometry checking procedure; (c) optional other reactant that adds in first polymerization reaction mixture is to obtain second polymerization reaction mixture; Reach (d) to remove from first polymerization reaction mixture or second polymerization reaction mixture and desolvate, obtain comprising the first polymer-organoclay composite composition of polymeric constituent and organic clay component, wherein organic clay component at least 10% scales off.In one embodiment, described polymeric constituent is a polyetherimide.
In one embodiment, being aggregated in catalyzer for example carries out under sodium phenylphosphinate (SPP) existence.
In one embodiment, first monomer is a dianhydride, and second monomer is a diamines.Suitable diamines and dianhydride comprise disclosed herein those, for example BPADA and mphenylenediamine.
The suitable solvent comprises aromatic solvent such as orthodichlorobenzene, toluene, dimethylbenzene, chlorobenzene, and the combination of aforementioned solvents.
Organic clay composition can be any organic clay composition disclosed herein.
The stoichiometry checking procedure can be utilized and be suitable for accurately measuring in first reaction mixture any analytical technology of first monomer and second monomer ratio and carry out.For example, the infrared analysis of the film that can make by the aliquots containig of taking from first reaction mixture is measured first monomer and the second monomeric ratio in first reaction mixture, as described in experimental section of the present disclosure.As selection, first monomer and the second monomeric ratio in first reaction mixture can be measured by methods such as technology commonly known in the art such as high speed liquid chromatography (HPLC), nucleus magnetic resonance (NMR) and end group titrations.The stoichiometry checking procedure is important, because have only the stoichiometry of careful control reaction, could realize one or more target property of product polymer-organoclay composite composition.In one embodiment, the stoichiometry checking procedure comprises the ratio of measuring amine and acid anhydride.
If detect a kind of monomer deficiency after the stoichiometry checking procedure, then can replenish the interpolation monomer.As selection, the stoichiometry checking procedure can be sent the signal that needs to add other reactant such as chain terminator.When other reactant is added into first polymerization reaction mixture, be considered as having constituted second polymerization reaction mixture, this second polymerization reaction mixture can the further reaction by for example heating.
Finish after the polyreaction, remove and desolvate, obtain comprising the first polymer-organoclay composite composition of polymeric constituent and organic clay component, wherein organic clay component at least 10% scales off.The removal of solvent can be carried out as technology such as distillation, filtration, anti-solvent deposition-subsequent filtrations by known in the art.In one embodiment, the removal of solvents from first polymerization reaction mixture or second polymerization reaction mixture utilizes devolatilization hair style forcing machine, scrapes the wall type thin-film evaporator or its combination is carried out.
In one embodiment, the first polymer-organoclay composite composition further stands in about 300 ℃ of melting mixing steps to about 450 ℃ of temperature.In certain embodiments, this melting mixing further strengthens the degree of peeling off of organic clay component in the polymer-organoclay composite composition.
In one embodiment, the temperature that the contact under the polycondensation condition is included in greater than 100 ℃ heats.In alternate embodiment, the temperature that the contact under the polycondensation condition is included in less than 100 ℃ heats.In another embodiment, the contact under the polycondensation condition is included in solvent and the catalyzer existence is heated in the temperature greater than 100 ℃ down.In alternate embodiment, the contact under the polycondensation condition is included in solvent and the catalyzer existence is heated in the temperature less than 100 ℃ down.
In one embodiment, first monomer is the dianhydride with structure XL:
Figure A200780031007D00481
Wherein " j " and " k " is 0～3 number independently; R 11And R 12Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Reaching W is chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group.
In one embodiment, dianhydride XL is selected from: dihydroxyphenyl propane dianhydride (BPADA), 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (4,4 '-ODPA), 3,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (3,4 '-ODPA), 3,3 '-oxygen di-(Tetra hydro Phthalic anhydride) (3,3 '-ODPA), 4,4 '-biphenyl dianhydride, 3,4 '-biphenyl dianhydride, and combination.
In another embodiment, the dianhydride that is adopted is any dianhydride disclosed herein.
In one embodiment, second monomer is for being selected from any diamines disclosed herein, for example mphenylenediamine.In one embodiment, second monomer is an aromatic diamine.In one embodiment, aromatic diamine is selected from: mphenylenediamine, and Ursol D, 4,4, and 4,4 '-oxydiphenyl amine.
In one embodiment, organic clay composition comprises the season organic cation.In one embodiment, organic cation has structure XXXIX season:
Figure A200780031007D00482
Wherein Q is nitrogen or phosphorus; And R 7, R 8, R 9And R 10Be C independently 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 20Aromatic group, perhaps polymer chain.In some cases, the organic clay composition that comprises season organic cation XXXIX can obtain from commercial.As selection, the organic clay composition that comprises season organic cation XXXIX can utilize method preparation disclosed herein.
In one embodiment, season organic cation be selected from: decyl trimethyl ammonium positively charged ion, the dodecyl trimethyl ammonium positively charged ion, tetradecyl trimethyl ammonium positively charged ion, the cetyltrimethyl ammonium positively charged ion, octadecyl trimethyl ammonium positively charged ion, and the combination.
In one embodiment, organic clay composition comprises non--Ji organic cation, for example protonated aromatic amine.
As already mentioned, the organic clay composition that is adopted comprises alternative inorganic silicic acid salt deposit and organic layer.The inorganic silicic acid salt deposit as teaching herein, can come from the inorganic clay material.In one embodiment, the inorganic silicic acid salt deposit comes from and is selected from following inorganic clay: kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica, sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.
In one embodiment, the invention provides the method for preparing the polymer-organoclay composite composition, this method comprises that (a) makes dianhydride contact to about 250 ℃ temperature with about 105 ℃ in solvent with diamines in the presence of the organic clay composition, to obtain first polymerization reaction mixture, described organic clay composition comprises alternative inorganic silicic acid salt deposit and organic layer; (b) ratio of amine and acid anhydride in mensuration first polymerization reaction mixture; (c) optional replenishing in first polymerization reaction mixture added dianhydride or diamines, obtains second polymerization reaction mixture; Reach and (d) utilize devolatilization hair style forcing machine, in first polymerization reaction mixture or second polymerization reaction mixture, remove and desolvate, obtain comprising the first polymer-organoclay composite composition of polymeric constituent and organic clay component, wherein organic clay component at least 10% scales off.In one embodiment, this method also is included in about 300 ℃ of steps to about 450 ℃ temperature melting mixing first polymer-organoclay composition.
In one embodiment, the invention provides the method for preparing polyetherimide-organic clay composite composition, this method comprises that (a) is in the presence of organic clay composition, dihydroxyphenyl propane dianhydride (BPADA) is contacted to about 250 ℃ temperature with about 125 ℃ in orthodichlorobenzene with diamines, obtain first polymerization reaction mixture, described organic clay composition comprises alternative inorganic silicic acid salt deposit and organic layer; (b) ratio of amine and acid anhydride in mensuration first polymerization reaction mixture; (c) optional replenishing in first polymerization reaction mixture added dianhydride or diamines, obtains second polymerization reaction mixture; Reach and (d) utilize devolatilization hair style forcing machine, in first polymerization reaction mixture or second polymerization reaction mixture, remove orthodichlorobenzene, obtain comprising the first polymer-organoclay composite composition of polymeric constituent and organic clay component, wherein organic clay component at least 10% scales off.In one embodiment, this organic clay composition has structure X.
In one embodiment, the invention provides the method for preparing polyetherimide-organic clay composite composition, this method comprises that (a) is in the presence of organic clay composition, make 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (4,4 '-ODPA) in orthodichlorobenzene, to about 250 ℃ temperature, contact with about 125 ℃ with diamines, obtain first polymerization reaction mixture, wherein said organic clay composition comprises alternative inorganic silicic acid salt deposit and organic layer; (b) ratio of amine and acid anhydride in mensuration first polymerization reaction mixture; (c) optional replenishing in first polymerization reaction mixture added dianhydride or diamines, obtains second polymerization reaction mixture; Reach and (d) utilize devolatilization hair style forcing machine, in first polymerization reaction mixture or second polymerization reaction mixture, remove orthodichlorobenzene, obtain comprising the first polymer-organoclay composite composition of polymeric constituent and organic clay component, wherein organic clay component at least 10% scales off.
Embodiment
The following examples only are used to method of the present invention and embodiment are described, thereby to should not be construed as be restriction to claims.
Dihydroxyphenyl propane dianhydride (BPADA, CAS No.38103-06-9) (97.7% purity) derives from GEPlastics.4,4 '-oxygen di-Tetra hydro Phthalic anhydride (ODPA, CAS No.1823-59-2) (99% purity) derives from Chriskev Company, Lenexa, Kansas, USA.
2,4,6-triphenyl-pyrans a tetrafluoro borate, aniline, the 4-phenoxybenzamine, the 4-cumyl phenol, salt of wormwood, 1-fluoro-4-nitro-benzene, carbon carries palladium, and ammonium formiate derives from Aldrich.
Unless otherwise noted, otherwise, organic clay composition (organo-clay) Kunipia F montmorillonite preparation.For example, those organic clay compositions of being made by Nanocor PGN.Kunipia F montmorillonite are available from Kunimine Industries Co..The manufacturer reports that cation exchange capacity (CEC) is 115meq/100g.Undried Kunipia F comprises the moisture of 8wt% in room temperature, and the sodium analysis of undried KunipiaF sample provides the sodium content of 23850 (± 500) ppm, and this shows that the CEC of undried sample is 103.7meq/100g.
For the disclosure, the cation exchange capacity value of 100meq/100g is all adopted in all calculating and material preparation.The aspect ratio of Kunipia F montmorillonite is 320 (averages), 80 (minimum value), 1120 (maximum values).Can derive from Nanocor product P GV and PGN for montmorillonite relatively, it has the aspect ratio of 150～200nm and 300～500nm respectively.The cation exchange capacity of PGV and PGN clay is respectively 145 (± 10%) and 120 (± 10%) meq/100g.
Adopt the 450W type to have diameter 0.5 " Branson Sonifier 450 processor for ultrasonic wave of solid probe, the organically-modified montmorillonite of supersound process in solvent.For large-scale supersound process (〉 100g clay), use Sonics ﹠amp; The 1500W type Autotune Series High IntensityUltrsonic Processor of Materials inc..
TGA measures and adopts Pyris software to carry out on Perkin Elmer TGA 7.All samples that at the uniform velocity heat up (ramped sample) all adopt the at the uniform velocity intensification (temperature ramp) of crossing over 25～900 ℃ with 20 ℃/minute speed.Isothermal operation is carried out at 400 ℃, with the thermostability of check at target processing/extrusion temperature.Thermostability keeps percentage ratio to represent with the beginning temperature and the weight of isothermal operation in the time of 30 minutes of mass loss.
Utilize the CTE of thermo-mechanical analysis (TMA) MEASUREMENTS OF THIN sample.2 blades cutting film sample in the anchor clamps (custom jig) of customization with interval 4mm.Analyze on TMA Q400 thermomechanical analyzer and carry out, its sequence number is 0400-0007, derives from TA Instruments.Experiment parameter is so set: the power of 0.050N, and the 5.000g static weight, nitrogen purges speed 50.0mL/min, and the 0.5sec/pt sampling interval.The CTE calibration proceeds to 200 ℃ with aluminium standard specimen at the uniform velocity heat-up rate with 5 ℃/min under nitrogen purges by 0 ℃.Temperature correction is to adopt indium standard specimen at the uniform velocity heat-up rate with 5 ℃/min under nitrogen purges to carry out.After the calibration, check CTE is aligned in the 1ppm/ ℃ of scope, and the check temperature correction is in 0.5 ℃ desired value scope.
Carry out transmission electron microscope (TEM) and measure embedding film sample in the epoxy matrix material, then in room temperature with Reichert Ultracut E thin slice slicing machine, section is to the thickness of～100nm.Sliced section is accumulated on the copper grid (grid), utilize the imaging of Philps CM100-(100KV) transmission electron microscope then.
Utilize
Figure A200780031007D0051091203QIETU
Geometry carries out X-ray diffraction (XRD) (little angle XRD) at the senior diffractometer of Bruker D8 and measures.Use Ni-filtering Cu K α radioactive rays and M-Braun PSD-50m position photosensitive detector, and entrance slit is 0.6mm.Sweep limit is a 1.4-25 degree 2
Figure A200780031007D0051091212QIETU
Sodium content analysis and utilization solution spray inductively coupled plasma emmission spectrum (ICP-AES, VarianLiberty II) carries out.The combustion analysis of organic clay composition (modified clay) (C-H analysis) LECOCorporation (Web: Www.leco.com) carry out.The small-scale melting mixing experiment of polymkeric substance and modified clay is carried out on Haake Rheomix 600 instruments.
Peeling off percentage ratio is defined as follows.Mineral filler has the volume influence to thermal expansivity (CTE).For each percent by volume of sneaking into the filler in the polymeric matrix, exist corresponding C TE to reduce percentage ratio.Therefore, when organic clay composition is added in the fluoropolymer resin, any CTE on the volume influence reduce all with polymeric matrix in organic clay composition peel off directly related.The ratio of the CTE that peeling off percentage ratio can standardized CTE (CTE that fills owing to volumetric) records with experiment calculates.CTE for normalized, can utilize the density (is 2.86g/cc according to manufacturer's technical data sheet) of silicate and the density (is 1.27g/cc according to manufacturer's technical data sheet) of standard polyetherimide, the weight percentage of the silicate that adds is changed into percent by volume.Therefore, can be by multiply by 0.00444, each weight percentage of silicate is changed into percent by volume.Like this,
The unfilled CTE-of standardized CTE=(weight percentage of 0.00444 * unfilled CTE * silicate),
And peeling off percentage ratio is provided by following formula:
The CTE that % peels off=fills (experiment measuring value)/standardized CTE.
The preparation of quaternary alkylphosphonium salt
The preparation of embodiment 1 iodate (3-aminophenyl) triphenyl phosphonium 1
Figure A200780031007D00521
Be equipped with in the three neck round-bottomed flasks of condenser, mechanical stirrer and gas inlet to 3000mL, add the triphenylphosphine (PPh of about 329.33g (1.25mol) 3), Pd (CH 3COO) 2(2.82g, 0.0126mol) and the dimethylbenzene of the 1600mL degassing.This mixture is stirred until PPh under argon gas 3Dissolving.(about 275.00g's Iodoaniline between adding 1.25mol), and refluxes this yellowish-orange solution about 80 minutes.Separate from solution and produce thing phosphonium compounds (iodate (3-aminophenyl) triphenyl phosphonium), it is the yellowish-orange solid.Avoid excessive backward flow, to prevent to produce the variable color of thing phosphonium compounds.Reaction process utilizes thin-layer chromatography (TLC) monitoring, and this thin-layer chromatography adopts 50/50 hexane/ethyl acetate developping solution.After the backflow, filtration product.With product 1 usefulness hot toluene pulp once more, and stirred 15 minutes.Filter this solution then, and wash with other toluene/dimethylbenzene.After dry 20 hours, obtain the canescence product of 585.01g in 150 ℃ of vacuum ovens, yield is 96%.Fusing point is consistent with the structure of product 1 with the NMR data.MP：316.0℃。1HNMR (δ, D 6-DMSO): 8-6.6 (m, 19H, aromatic substance), 5.88 (s, 2H).
The preparation of embodiment 2 4-(4-cumyl)-phenoxy group-phthalonitrile 2
Figure A200780031007D00522
In 3 liters of flasks, add 4-cumyl phenol (170.9g, 0.80 mole), 4-nitrophthalonitrile (150g, 0.87 mole), salt of wormwood (155.8g, 1.13 moles), and dimethyl formamide (1.4L).This solution is heated to about 90 ℃ and kept about 100 minutes at nitrogen with under stirring.With thin-layer chromatography monitoring reaction process.With umbrinaceous reaction mixture cooling, and under agitation add 2M HCl solution (600mL).(3 * 300mL) extract organic layer with chloroform.Tell chloroform layer, water (3 * 100mL) washings, and dry (MgSO 4).This mixture is filtered, and temperature greater than about 100 ℃ hot oil bath on evaporating solvent, obtain crude product nitrile 2, it is the green oily matter (278g, 84% yield) of viscosity. 1H?NMR(δ，D 6-DMSO)：8.09(d，1H)，7.78(d，1H)，7.40-7.15(m，8H)，7.10(d，2H)，1.66(s，6H，Me)。
The preparation of embodiment 3 4-(4-cumyl) phenoxy group-Tetra hydro Phthalic anhydride 3
The three neck round-bottomed flasks of 3L are loaded onto condenser, mechanical stirrer, and feed hopper.In flask, add 4-(4-cumyl phenoxy group)-phthalonitrile (278g, 0.82 mole) and acetate (1.6L).The sulfuric acid (670mL) of adding 70% in feed hopper.Solution is heated to 120 ℃, in 2 hours, in reaction mixture, drips sulfuric acid then.With gained mixture spend the night (12 hours) of refluxing.Reaction mixture is cooled to room temperature, and pour into mixture of ice and water (～1kg) in.(3 * 300mL) extract product with ethyl acetate.The separating ethyl acetate layer, and use anhydrous MgSO 4Dry.Filter this solution to remove MgSO 4, and on rotatory evaporator, remove and desolvate.The gained brown liquid is dried overnight in 160 ℃ vacuum oven.Obtain needed acid anhydrides thus, it is the brown oil (276g, 94% yield) of viscosity. 1H-NMR(δ，D 6-DMSO)：7.96(d，1H)，7.50-7.20(m，9H)，7.03(d，2H)，1.76(s，6H，Me)。
Embodiment 4 cumyl PA-mATPP-I4's is synthetic
Figure A200780031007D00532
In being equipped with the glass reaction container of mechanical stirrer, nitrogen inlet and pneumatic outlet, 500mL adds 4-(4-cumyl) phenoxy group-Tetra hydro Phthalic anhydride 3 of 66.27g (0.1848mol) and iodate (3-aminophenyl) triphenyl phosphonium (mATPP iodide) 1 of 88.97g (0.1848mol).Then this container is placed heating jacket and be heated to about 300 ℃, to produce the fused reaction mixture.After the stir about 3 minutes, apply vacuum, to remove the water that generates as by product.After about 15 minutes total reaction time, pour in the Teflon tray reaction mixture and cooling, obtain compound 4 (145.19g, 95.6%), it is level and smooth brown glass shape thing.1H NMR (δ, D 6-DMSO): 8.07-7.08 (31H, aromatic substance), 1.68 (s, 6H).
Cumyl PA-mATPP-I's is alternative synthetic
Weigh up amino tetraphenylphosphoniphenolate 22.14g (0.046mol) of reactant iodate m-and 4-chloro-phthalic anhydride 8.40g (0.046mol), it is added in the 250ml round-bottomed flask that the Dean-Stark condenser is housed, and makes it to be dissolved in the orthodichlorobenzene of 150mL.Content is heated to backflow, and removes by component distillation and nitrogen purging and to anhydrate.After refluxing 4 hours, add the cumyl phenol sodium (0.046mol) of 10.78g, and with content restir and heating 4 hours.Be cooled to after the room temperature, this solution poured in the ether of 400mL, and collect the solid that is produced by vacuum filtration.This solid is dissolved in again in the chloroform of 100mL, and gained solution is poured in the ether of 300mL.Collect the gained solid by vacuum filtration, and make it dried overnight under vacuum. 13C-NMR is consistent with structure.Total recovery: about 60%.
Embodiment 5 BPADAPA-mATPP-I5's is synthetic
Dihydroxyphenyl propane dianhydride (BPADA) that will about 58.0g (0.1114mol) and iodate (3-aminophenyl) triphenyl phosphonium (mATPP-I) 1 of 107.27g (0.2229mol) shake together.Utilize long paper hopper that this dry mixture is added in the glass reaction flask then, be bonded at the internal upper part of flask to prevent reactant.Reaction flask is found time and twice of backfill nitrogen.Connect outer well heater then and set about 300 ℃.Along with the reactant fusing, form brown solution.After the question response thing has melted 3～5 minutes, reaction flask is found time to anhydrate to remove.Pressure is initially set 600 millibars (mb), and one after the other is reduced to 10mb.When reaction is finished, make pressure return 1000mb and close agitator.With 5 coolings of product Er Phosphonium imide, obtain the brown glass shape thing of 158.48g (98.28%).1H NMR (δ, D 6-DMSO): 8.1-7.1 (m, 52H, aromatic substance), 1.73 (s, 6H).
Synthesizing of two (chlorophthalimide) 6 of embodiment 6 AMS dimer diamines
Figure A200780031007D00542
Agitator, nitrogen inlet being housed and having installed in the three neck round-bottomed flasks of Dean-Stark device of condenser, in the AMS dimer diamines of 29g (0.1mol), add the 4-chloro-Tetra hydro Phthalic anhydride (4-ClPA) of 38.34g (0.22mol) and the orthodichlorobenzene of 300ml.This mixture is heated to 190～200 ℃ and kept 4 hours under nitrogen gas stream, removes simultaneously and anhydrate.Reaction mixture is cooled to envrionment temperature, and is settled out product two (chlorophthalimide) 6 by adding methyl alcohol (1500ml).Filtration product, and in 100 ℃ of baking ovens, be dried to constant weight.Output 40g (91%).
Embodiment 7 two (Phosphonium phthalic imidines) 7 synthesize
Figure A200780031007D00551
In the three-necked flask that agitator, nitrogen inlet and condenser are housed, in two (chlorophthalimide) 6 of 20g (0.05mol), add the triphenylphosphine of 24.5g (0.09mol) and the anhydrous chlorides of rase nickel of 6.05g.Then this mixture is heated to 300 ℃ and kept 4 hours under nitrogen gas stream.In this process, the main body of reactant becomes glaucous liquid.Reaction mass is cooled to envrionment temperature and is solidified into glass blue-greenish colour solids, to wherein adding methylene dichloride (250ml).Heat this mixture to dissolve most of solid and to add water (200ml).Separate organic layer and repetitive scrubbing till the water layer maintenance is colourless (200ml * 4 time washing).Under reduced pressure remove and desolvate, obtain product buttery two phosphonium salts.Add toluene (100ml) so that solid to be provided.Under reduced pressure remove toluene.Repetition toluene adds and removes 4 times, to guarantee the removal of water.At last, add last part toluene (100ml), obtain the slurries of Er phosphonium salt 7.Cross filter solid, and in 100 ℃ of baking ovens, be dried to constant weight.Output 30.3g (60%).
Embodiment 8 two (Phosphonium naphthalimides) 8 synthesize
Figure A200780031007D00552
Agitator, nitrogen inlet being housed and having installed in the reaction flask of Dean-Stark device of condenser, in the naphthalene bromide formic anhydride of 28g (0.1mol), add the 4-chloro-aniline of 13.54g (0.11mol) and the orthodichlorobenzene of 300ml.This mixture is heated to 190～200 ℃ and kept 4 hours under nitrogen gas stream, removes simultaneously and anhydrate.Reaction mixture is cooled to envrionment temperature, the product methanol extraction of 1500ml.Filtration product, and in 100 ℃ of baking ovens, be dried to constant weight.Output 35g (89%).In the flask that agitator, nitrogen inlet and condenser are housed, in the above-mentioned product imide of 15g (0.04mol), add the triphenylphosphine of 20.5g (0.08mol) and the anhydrous chlorides of rase nickel of 5g.This mixture is heated to 220 ℃ and kept 4 hours under nitrogen gas stream, obtains blue-greenish colour liquid.Reaction mixture is cooled to room temperature, obtains solid matter.It is such to press embodiment 7, and purifying and separated product Er phosphonium salt obtain Er phosphonium salt 8.Output 30.5g (75%).
Embodiment 9-10 amine replaces the synthetic of De phosphonium salt 9 and 10
Figure A200780031007D00561
Diamines (4,4 (DDS) or alpha-methyl styrene dimer diamines (AMSDDA) are (0.3mol)) is added in the round-bottomed flask that agitator, nitrogen inlet, Dean-Stark device and condenser are housed.The 4-chloro-phthalic anhydride of about 0.1 mole (18.26g) orthodichlorobenzene together with about 300ml is added in the described diamines.Round-bottomed flask is heated to about 190～200 ℃ and kept 4 hours under nitrogen atmosphere, removes simultaneously and anhydrate.Then reaction mixture is cooled to room temperature, and under agitation is added in the hexane of about 1500ml.Collect product one chlorophthalimide, and dry in 100 ℃ baking oven.
This chloro imide (0.1mol) is added in the flask that agitator, nitrogen inlet and condenser are housed.(26.2g 0.1mol) and nickelous chloride (II) 0.05mol (6.5gm), and is heated to temperature required this mixture under nitrogen atmosphere and kept 6 hours to add triphenylphosphine (TPP).Then reaction mixture is cooled to room temperature, and stirs in the methylene dichloride and water (1000ml) of about 1000ml.Layering, the washing organic layer does not have the color of nickelous chloride until it.Under vacuum, remove and desolvate, and in the residuum of viscosity, add toluene, next under reduced pressure remove toluene.Repeat the adding and the removal of toluene, till obtaining solid product.Then with final product vacuum-drying.Product 9 and 10 structure obtain 1H-NMR confirms.
Embodiment 11 2 (Phosphonium imides) 11 synthesize
With dianhydride (oxygen di-Tetra hydro Phthalic anhydride (0.1mol)), (26.77g, 0.21mol), and orthodichlorobenzene (300ml) is added to the reaction flask that agitator, nitrogen inlet, Dean-Stark device and condenser are housed to the 3-chloroaniline.Reaction mixture is heated to about 190～200 ℃ and kept 4 hours under nitrogen atmosphere, removes simultaneously and anhydrate.Then reaction mixture is cooled to room temperature, and is added in the methyl alcohol of about 1500ml.Filter intermediate two (chloro-imide) then, and in 100 ℃ baking oven, be dried to constant weight.It is such to press embodiment 9 and 10, and two (chloro-imides) are changed into two (Phosphonium imides) 11.
Synthesizing of embodiment 12 imide-Yi phosphonium salts 12
With diamines (three cyclo-dodecyl diamines (0.3mol)), Tetra hydro Phthalic anhydride (0.1mol), and orthodichlorobenzene (300ml) is added in the reaction flask that agitator, nitrogen inlet, Dean-Stark and condenser are housed.This mixture is heated to about 190～200 ℃ and kept 4 hours under nitrogen atmosphere, removes simultaneously and anhydrate.Then reaction mixture is cooled to room temperature, and is stirred in the hexane/methanol of about 1500ml, obtain intermediate one phthalic imidine, it is a mixture of isomers, and is dried to constant weight in 100 ℃.
With a phthalic imidine (0.1mol), 4-chloro-phthalic anhydride (0.1mol), and orthodichlorobenzene (300ml) is added in the equipment flask as above.This mixture is heated to about 190～200 ℃ and kept 4 hours under nitrogen atmosphere, removes simultaneously and anhydrate.Then reaction mixture is cooled to room temperature, and stirs in the hexane/methanol of about 1500ml, obtain intermediate one phthalic imidine-a chlorophthalimide, it is a mixture of isomers, and is dried to constant weight in 100 ℃.
It is such to press embodiment 8, and a phthalic imidine-chlorophthalimide intermediate is reacted with triphenylphosphine in the presence of nickelous chloride (II), obtains product imide-Yi phosphonium salts 12, and it is a mixture of isomers.
Comprise the preparation of the cationic organic clay composition of quaternary phosphine
The organic clay composition of embodiment 13 Bao Han phosphonium cations 13
Figure A200780031007D00572
To 1-rise Jia Ru phosphonium salt 1 in the beaker (embodiment 1,17.36g, 0.036mol) and methyl alcohol (900ml) and be heated to about 64 ℃.In independent flask, with the deionized water and stirring of sodium smectite clay (Na-MMT/Kunipia F clay, 30.00g, 0.030mol equivalent) with about 2.1L.When clay dispersion, these slurries are heated to about 65 ℃ and be added in the stirrer of big preheating.The methanol solution that adds salt in the clay slurry in stirrer lentamente stirs simultaneously tempestuously.The thick foam of initial formation, and scatter subsequently.With about 10 minutes of the violent mixing of this mixture, slowly mixed 20 minutes in addition then.Temperature is about 65 ℃.After mixing about 30 minutes, utilize big thin sinter funnel to filter this mixture.Solid clay is slurried once more in hot water (80 ℃), stirred 15 minutes and filtered.Then that solid clay is slurried in hot methanol (64 ℃), subsequent filtration.The clay of purifying is dry under room temperature and vacuum, till it can be pulverized.About 12 hours of vacuum and 150 ℃ of dryings, and regrinding obtained about 30g exsiccant organic clay composition, yield 76% with the powder of humidity.
The organic clay composition of embodiment 14 Bao Han phosphonium cations 14
Figure A200780031007D00581
In the 5000mL round-bottomed flask, add 2000mL deionization (DI) water and stir with mechanical stirrer.Then, add the Kunipia F clay of about 25.00g (0.025 equivalent) lentamente, stir till clay disperses fully.The dispersive clayish solution is heated to about 80 ℃ then.Individually, the BPADA-mATPP iodide 5 with 20.80g (0.01437mol, 15% is excessive) are dissolved in the 410mL acetonitrile and are heated to about 80 ℃.Then BPADA-mATPP iodide salt solution is added in the clay dispersion, this mixture was stirred 1 hour at about 80 ℃ thereupon.Filter clay then, it is used the pulp once more of 2500mL deionized water, and stirred 15 minutes in 80 ℃.Filter after the clay, carry out the acetonitrile washing equally, then carry out final filtration.With the clay of modification in 25 ℃ vacuum dry 24 hours, can be mixed into powder until it.With the clay of modification in 150 ℃ vacuum further dry 12 hours, with clay blending once more, obtain comprising the organic clay composition of positively charged ion 14, it is a fine powder, yield about 84%.
Embodiment 15-16 Bao Han phosphonium cation 15 or 16 organic clay composition
Figure A200780031007D00591
According to embodiment 14, preparation comprises organic phosphonium cation 15, and (embodiment 15, Cumyl-MMT) or other organic clay composition of 16 (embodiment 16).
The data that comprise the organic clay composition of organic phosphonium cation are listed in the table 1." CE-1 " refers to Comparative Examples 1, and " CE-2 " refers to Comparative Examples 2 etc." Ex-14 " refers to " embodiment 14 ", and " Ex-15 " refers to " embodiment 15 " etc.
Table 1: the organic clay composition that comprises organic phosphonium cation
Embodiment Cation modifier D-spacing (A) At N 2With 400 ℃ of following weight loss of 30 minutes (%)
CE-1 Tetraphenylphosphoniphenolate 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
Embodiment 17-26 prepares the general method of organic clay composition
(sodium montmorillonite, " Na-MMT " derive from Southern Clay with inorganic clay, Inc.) pulp is in the deionized water (" MilliQ water ") of 75 times (volume), with respect to the weight of clay, and, stirred 1 hour at 90～95 ℃ then room temperature (22～25 ℃) stirring 1 hour.In these inorganic clay slurries, drip the solution of You Ji phosphonium salt in methyl alcohol or acetonitrile, and this reaction mass was stirred 18～20 hours at 65～95 ℃.After the cooling, should be thick organic clay composition filter and washing, not till the halide, be dried to constant weight at 125～150 ℃ until washing lotion then.
The organic clay composition that comprises Yi Phosphonium imide You Ji phosphonium cation collects in the table 2 together with the d-spacing data of measuring by X-ray diffraction (XRD).
Table 2: comprise the cationic organic clay composition of Yi Phosphonium imide
Figure A200780031007D00592
Figure A200780031007D00601
The organic clay composition that comprises Er Phosphonium imide You Ji phosphonium cation collects in the table 3 together with the d-spacing data of measuring by X-ray diffraction (XRD).
Table 3: comprise the cationic organic clay composition of Er Phosphonium imide
Figure A200780031007D00602
The organic clay composition that comprises An Ji Phosphonium one imide You Ji phosphonium cation collects in the table 4 together with the d-spacing data of measuring by X-ray diffraction (XRD).
Table 4: comprise the cationic organic clay composition of An Ji Phosphonium one imide
Figure A200780031007D00611
Comprise the preparation of the cationic polymer-organoclay composite composition of quaternary phosphine
Embodiment 27 comprises the polymer-organoclay composite composition of positively charged ion 14
Rise to the 1-that 150mL exsiccant orthodichlorobenzene is housed and add the BPADA-mATPP-MMT that 7.96g (4.77g silicate) prepares in the three neck round-bottomed flasks in embodiment 14.It is 1/2 that employing has diameter " the 400W Branson Sonificator 450 of solid probe, with 20% output rating, with this nanoclay-orthodichlorobenzene dispersion liquid ultrasonication 1 hour.After the ultrasonication, add the Ursol D (pPD) of 16.17g (0.150mol) and the orthodichlorobenzene of 50mL, and stirring under the heating till the pPD dissolving.Then, add the BPADA of 75.31 (0.145mol), the Tetra hydro Phthalic anhydride of 1.43g (0.0096mol), and the extra orthodichlorobenzene of 225mL.This mixture is refluxed, and As time goes on remove orthodichlorobenzene and the water of 225mL.Stir then with this solution cooling, and with the heptane of 300mL.The gained solid polymer filtered and in 150 ℃ vacuum oven dry 15 hours, obtain the polymer-organoclay composite composition of 89.17g (93.4% yield).The design polymerization degree of fluoropolymer resin is 30.The design weight % of silicate is 3%.
Embodiment 28 comprises the polymer-organoclay composite composition of positively charged ion 15
Rise to the 3-that the dry veratrole of 850mL is housed and to add 210.0 grams (g) BPADA and the cumyl PA-mATPP-MMT that in embodiment 15, prepares of 40.1g (23.6g silicate) (0.395mol) in the three neck round-bottomed flasks.It is 1/2 that employing has diameter " the 400W Branson Sonificator450 of solid probe, the output rating with 40% was with this mixture ultrasonication 3 hours.After the ultrasonication, add the 4,4 (DDS) of 100.7g (0.406mol), 2.0g (0.013mol)) Tetra hydro Phthalic anhydride (PA), and the veratrole of 350mL.This mixture heating up is refluxed, and in 12 hours, remove veratrole-water mixture of 200ml.In 3 hours, from reaction vessel, distill out the veratrole of other 400mL then.Then reaction mixture is cooled to 80 ℃ and pour in the homogenizer that 2L methyl alcohol is housed.The gained solid polymer is filtered, and in 250 ℃ vacuum oven dry 15 hours.Obtain product polymer-organoclay composite composition (253g), yield is 75%.The design polymerization degree is 35.The design weight % of silicate is 7%.
Embodiment 29 comprises the polymer-organoclay composite composition of positively charged ion 14
Rise to the 2-that the dry oDCB of 150mL is housed and add the BPADA-mATPP-MMT that 7.51g (4.51g silicate) prepares in the three neck round-bottomed flasks in embodiment 14.With having diameter is 1/2 " the 400W Branson Sonificator 450 of solid probe, the output rating with 20% was with this nanoclay-oDCB dispersion liquid ultrasonication 1 hour.After the ultrasonication, add 4 of 34.90g (0.174mol), 4 '-oxydiphenyl amine (4,4 '-ODA), 52.00g (0.168mol) 4,4 '-oxygen di-(Tetra hydro Phthalic anhydride) (ODPA), the Tetra hydro Phthalic anhydride of 1.987g (0.0134mol), the dimethylbenzene of 20mL, and the oDCB of 300mL.This mixture is refluxed, and As time goes on, remove solvent-water of 225mL.Stir then with this solution cooling, and with the heptane of 300mL.The gained solid polymer is filtered, and in 150 ℃ vacuum oven dry 15 hours, obtaining the polymer-organoclay composite composition that 88.52g comprises positively charged ion 14, yield is 98.22%.The design polymerization degree is 25.The design weight % of silicate is 5%.
Embodiment 30-37 polymer-organoclay composite composition, the fusion preparation
General method below in embodiment 30-37, adopting.Will
Figure A200780031007D00621
1010 polyetherimides (58.2gm) are weighed and are divided into two equal portions.The organic clay composition (Na-MMT of modification) and the thorough mixing that in portion, add 1.8 grams.In about 9 minutes, two parts of polyetherimides are added in the Haake mixing tank that remains on 350 ℃ simultaneously then, mixed about 30 minutes at 350 ℃ then, and periodically sampling.Then from the Haake mixing tank, remove product.Analyze this polymer-organoclay composite composition by gel permeation chromatography (GPC).The data of prepared various polymer-organoclay composite compositions collect in the table 5 together with molecular weight data.Also, examine and determine product polymer-organoclay composite composition by X-ray diffraction (XRD) and transmission electron microscope.In addition, measure thermal expansivity (CTE).In order to reference, (Na-MMT, SouthernClays USA) have to be used to prepare the inorganic clay of the organic clay composition that is adopted
Figure A200780031007D00622
The d-spacing.The polyetherimide that is adopted has the initial weight-average molecular weight (Mw) of 44965 gram/moles and the initial number average molecular weight of 19200 gram/moles, and has the CTE of about 62.1 (ppm).
Table 5: the polymer-organoclay composite composition that comprises polyetherimide
Embodiment Cation modifier The d-spacing ＊ Mw Mn CTE
30 21 >30 4778547785 2317523175 28.7
31 23 --- 50458 25079 ---
32 24 --- 43295 19641 40
33 14 --- 51729 25094 ---
34 22 --- 49518 23753 ---
35 17 --- 51628 24362 ---
36 18 --- 51246 25286 ---
37 19 --- 50449 26621 ---
*D-spacing in the polymer-organoclay composite composition
The data of the embodiment 30-37 that is compiled show, almost do not observe the degraded of polyetherimide matrix in prepared polymer-organoclay composite composition.And when detecting, the d-spacing that is observed is significantly greater than the d-spacing that observes in corresponding organic clay composition.
The polymer-organoclay composite composition that comprises the fluoropolymer resin that contains the structural unit that comes from DDS and BPADA or ODPA that embodiment 38-51 makes by in-situ polymerization
Polymer-organoclay composite composition 38-43 and 46-51 make described in the following examples (embodiment 43).The oxygen di-(Tetra hydro Phthalic anhydride) that 9.05g is comprised the organic clay composition of positively charged ion 14 (BPADA-mATPP-MMT) and 59.85g (ODPA) is added in the veratrole of the orthodichlorobenzene (oDCB) of 219ml and 146mL.This mixture is mixed 2 hours with dissolving ODPA with mechanical stirrer.Then container is immersed in and carries out ultrasonication in the ultrasonic bath, till the fine dispersion liquid that obtains clay.Then flask is loaded onto top agitator and Dean-Stark water trap, and added the 4,4 (DDS) of 46.33g and the aniline of 0.08913g.With the oDCB of 60mL and the veratrole of 40mL DDS is flushed in the container.Stir this mixture, and reflux 3 hours lentamente, and remove by component distillation and to anhydrate.After the reflux 18 hours, obtain the dispersion liquid of fine powder.This dispersion liquid is added in the relatively large methyl alcohol, filters and in 180 ℃ of vacuum-dryings.Then gained dry powder is transferred in the Haake melt mixer and and mixed 60 minutes with 50rpm at 390 ℃.Time sampling with 5 minutes.At 760 ℉, between two tinsels that have a teflon lining, 15 minutes samples are pressed into film.By thermo-mechanical analysis the film sample of being suppressed is analyzed then, and measured the CTE of 30～200 ℃ of scopes.
Polymer-organoclay composite composition 44-45 is prepared as follows.Use SILVERSON mixing tank (laboratory on-line mixing apparatus L4R-PA type, square hole high-shear sieve, rate of pumping～600mL/min), mix organic clay and solvent.By the SILVERSON mixing tank, the orthodichlorobenzene of pumping 450mL (oDCB).The organic clay composition that 13.1g is comprised positively charged ion 14 (BPADA-mATPP-MMT) is added among the round-robin oDCB lentamente.Make this mixture pass through the SILVERSON high-shear mixer 45 minutes with circulation pattern at 6000rpm.Then this mixture is transferred in the three-necked flask of 1L.Then flask is loaded onto top agitator and Dean-Stark water trap.Add the dihydroxyphenyl propane dianhydride (BPADA) of 74.2g and flask is heated to 100 ℃, with the dissolving dianhydride.The 4,4 (DDS) that then adds 33.90g, and with the oDCB of 20mL DDS is flushed in the container.Stir this mixture and it slowly is heated to backflow, and remove water byproduct by component distillation.After the reflux 3.5 hours, remove heating, and make reaction mixture be cooled to room temperature.The gained viscous mixt is transferred to the Haake melt mixer, and mixed 60 minutes with 50rpm in 390 ℃.Time sampling with 5 minutes.At 760 ℉, between two tinsels that have a teflon lining, 15 minutes samples are pressed into film.By thermo-mechanical analysis the film sample of being suppressed is analyzed and is measured the CTE of 30～200 ℃ of scopes then.
Provided the result of the polymer-organoclay composite composition of embodiment 38-51 in the table 6.
The CTE result of the compression molded samples of table 6:DDS and ODPA and BPADA in-situ polymerization
Figure A200780031007D0064091643QIETU
1" DP "=positively charged ion 14, " CUMYL "=positively charged ion 15, the TPP=tetraphenylphosphoniphenolate,
Figure A200780031007D0064091734QIETU
Mixing step utilizes the SILVERSON high-shear mixer to carry out in embodiment 45-46.
Figure A200780031007D0064091740QIETU
Organic clay component in " %Ex " polymer-organoclay composite composition peel off percentage ratio. *" V "=veratrole. *" O/V *The mixture of "=oDCB and veratrole.
By solution mixing and the embodiment 52-53 of the preparation of melt extrusion subsequently and the polymer-organoclay composite composition of contrast
Usually the method preparation comprises the film sample of polymer-organoclay composite composition of the present invention below adopting.
Embodiment 52
The organic clay composition that will comprise positively charged ion 15 carries out ultrasonication in veratrole.This mixture through ultrasonication comprises about 2.7% organic clay composition in the veratrole of 500mL.Carrying out ultrasonication in the 1000mL round-bottomed flask in being submerged in water-bath, utilize to be equipped with 1/2 " the Branson 450W Sonifier of sound wave probe carried out～16 hours with the output of～40% power.To amount to 5 essentially identical organic clay composition-solvent batch of materials and carry out ultrasonication, merge it then.To in the merging batch of material of the organic clay composition of ultrasonication, add the solution of the 20 weight %s of BPADA-DDS polyetherimide in veratrole, and this mixture is mixed fully.Then this mixture is added in the stirrer that methyl alcohol is housed.Filter the gained pressed powder, and with it 220 ℃ of vacuum-dryings, with second polyetherimide, the ODPA-DDS polyetherimide thorough mixing of some amount, the ratio of obtaining is BPADA-DDS polyetherimide and the ODPA-DDS polyetherimide of 69:31 then.With the gained mixture through 3 " sheeting die be extruded into film.The gained film has 7% nano silicate loading level, 33.0ppm/ ℃ machine direction CTE, and 255 ℃ Tg (referring to the TEM image of Fig. 1).
Contrast
Comprise same ratio BPADA-DDS polyetherimide and ODPA-DDS polyetherimide but contrast film not argillaceous and have 48.5ppm/ ℃ machine direction CTE and 262 ℃ T g
Embodiment 53
BPADA-DDS polyetherimide with 60:40: ODPA-DDS polyetherimide and 7% nano silicate loading level, similarly cast film.This film has 28.7ppm/ ℃ machine direction CTE and 266 ℃ T g
Season pyridinium salt preparation
Embodiment 54 1, and 2,4, the preparation of 6-tetraphenyl pyridinium tetrafluoroborate salt 27
Figure A200780031007D00651
In the 500mL round-bottomed flask that condenser is housed, add 2,4,6-triphenyl-pyrans a tetrafluoro borate (22.4g, 0.056 mole), aniline (5.8g, 0.060 mole), and ethanol (200mL).Gained solution is stirred and refluxed 6 hours at the nitrogen atmosphere lower magnetic force.This solution is cooled to room temperature, is settled out product 27, it is yellowish green crystalline solid.Filter collection product, and in 100 ℃ vacuum oven dry (23g, 87% yield).Mp＝253℃
Embodiment 55 1-(4-Phenoxyphenyl)-2,4, the preparation of 6-triphenyl pyridinium tetrafluoroborate salt 28
Figure A200780031007D00661
In the 1L round-bottomed flask that condenser is housed, add 2,4,6-triphenyl-pyrans a tetrafluoro borate (50.0g, 0.126 mole), 4-phenoxybenzamine (25.7g, 0.138 mole), and ethanol (400mL).Gained solution is stirred and refluxed 6 hours at the nitrogen atmosphere lower magnetic force.This solution is cooled to room temperature, and condensation product comes out with the lacteous crystalline deposit.Filter collects this crystallization and is dry in vacuum oven (100 ℃), obtains required product (68g, 95% yield).Mp＝201.7℃
The preparation of embodiment 56 4-(4-(1-methyl isophthalic acid-phenyl-ethyl)-phenoxy group) aniline 29
Figure A200780031007D00662
In the 5L round-bottomed flask that Dean Stark water trap, condenser and mechanical stirrer are housed, add 1-fluoro-4-nitro-benzene (159g, 1.128 mole), 4-cumyl phenol (239g, 1.128 mole), Anhydrous potassium carbonate (103g, 0.744 mole), N, dinethylformamide (1.5L), and toluene (150mL).The gained mixture stirred under nitrogen atmosphere and reflux 2 hours (solution temperature～160 ℃).During this period water is collected in the water trap.
Reaction mixture is cooled back room temperature.In reaction mixture, add carbon and carry palladium (10wt%Pd, 25g, 0.025 mole), add ammonium formiate (350g, 5.463 moles) then.Between the reaction period, utilize cold water to keep the internal temperature of reaction mixture solution to be lower than 55 ℃.
After 2 hours, will react filtration, and collect the settled solution of filtrate.Add water (2L) in filtrate, required product is to be precipitated out from solution as white powder.Filter collect sedimentary powder and in vacuum oven in 100 ℃ of dryings 12 hours, obtain required product (303g, 88% yield).
Embodiment 57 1-(4-(4-(1-methyl isophthalic acid-phenyl-ethyl)-phenoxy group)-phenyl)-2,4,6-triphenyl pyridinium tetrafluoroborate salt 30 synthetic
In the 5L round-bottomed flask that condenser and mechanical stirrer are housed, add 2,4,6-triphenyl-pyrans a tetrafluoro borate (206g, 0.519 mole), 4-[(1-methyl isophthalic acid-phenyl-ethyl)-phenoxy group]-aniline (174g, 0.574 mole), and ethanol (2L).Gained solution is stirred under nitrogen atmosphere and refluxed 3 hours.This solution is cooled to room temperature, and condensation product comes out with the yellow-green colour crystalline deposit.Filter is assembled brilliant and is dry in vacuum oven (100 ℃), obtains required product (333g, 94% yield).Mp＝283.7℃
Embodiment 58 BAPP-TPPy-BF4,31 synthetic
Figure A200780031007D00672
BAPP (4,4 '-(4,4 '-the basic dioxy base of isopropylidene phenylbenzene-1,1 '-two) pentanoic) (220.0g, 0.049 mole), triphenyl pyrans a tetrafluoro borate (40.5g, 0.102 mole) and ethanol (400mL) were mixed and reflux 5 hour.Reaction mixture is cooled to room temperature and filtration, obtains product two pyridinium salts 31 (BAPP-TPPy-BF4).Output 54g (95%).Mp＝354℃。
Table 7 has provided the yield and the characteristic data of pyridinium salt 27,28,30 and 31.
The yield of table 7 pyridinium salt and characteristic data
Figure A200780031007D00673
The data presentation of table 7 has the thermostability of very high and unexpected level according to thermogravimetric analysis (TGA) pyridinium salt.5% weight loss temperature of all pyridinium salts that observe all is higher than 400 ℃.On the contrary, raw material pyranium salt 2,4,6-triphenyl-pyrans a tetrafluoro borate then has very low stability, and has 340 ℃ 5% weight loss temperature under the testing regulation that is adopted.
Comprise the preparation of the organic clay composition of season pyridylium
The general method of embodiment 59 preparation organic clay compositions
For how explanation prevailingly prepares the organic clay composition that comprises pyridylium, provided the synthetic of cumyl phenoxy group-TPPy-MMT here.In the 5L round-bottomed flask that mechanical stirrer is housed, add sodium montmorillonite (40g, 0.041 molar equivalent) and deionized water (3L).With this solution stirring and be heated to 85 ℃, sodium montmorillonite is fully disperseed.In 10 minutes, in sodium montmorillonite suspension, add the 60 ℃ solution of cumyl phenoxy group-TPPy-BF430 (31.4g, 0.046 mole) in acetonitrile (625mL).Add after the salts solution, with reaction mixture 85 ℃ of restir 3 hours.
The montmorillonite of filter collection modification, and with hot water (2L, 80 ℃) washing, to remove inorganic salt by-product NaBF 4The clay (organic clay composition) of modification is further purified: promptly, it is scattered in 60 ℃ the acetonitrile (2L), then filters, to remove any excessive pyridinium salt.The clay of purifying 150 ℃ of vacuum-dryings 24 hours and grind, is obtained fine powder (50.3g, 80% yield).
Embodiment 60 modified montmorillonite used synthesizing on a large scale
In 50 gallons of stainless steel vessels (container 1) of Pfaudler company,, sodium montmorillonite (Na-MMT) clay of 470g is added in the deionized water of 47 liters of stirrings in room temperature.When clay dispersion, with this mixture heating up to 80 ℃.In 10 gallons of stainless steel vessels (container 2) of Brighton, be prepared as follows the solution of organic modifiers: the cumyl phenoxy group-TPPy-BF430 properties-correcting agent that stirs 352g and is heated to 80 ℃ in 7 liters of acetonitriles, till whole organic salts dissolvings.When two kinds of fluid balances to 80 ℃ initial temperature, this salts solution is added in the main reactor in 80 ℃ in about 10 minutes and under the condition of constant agitation montmorillonite.Reaction mixture was stirred 60～90 minutes at 80 ℃.Mixing is efficiently, forecloses without any reaction mixture.After the mixing, with the clay mixture gravity transfer of modification to the filtering centrifuge that 1 micron bag filter is housed.This whizzer turns round at low speed with at a high speed, obtains solid modified clay filter cake.The clay of following this modification of washing: this clay is put back in the container 1, adopted 47 premium on currency, and stirred 15 minutes at 80 ℃.Filter the clay mixture of modification once more.Then, the clay of following once more washing modification: clay is put back in the container 1, adopted 15 liters of acetonitriles, and stirred 15 minutes in 80 ℃.Filter clay once more, to remove the not organic modifiers of exchange.Wash clay in the whizzer basket briefly with methyl alcohol, this helps the exsiccant homogeneity.Clay dried overnight in cryogenic vacuum stove (100 ℃) or whizzer with modification at nitrogen purging.This clay is ground in the Merlin mixing tank, obtain powder.Further dry in 150 ℃ of vacuum ovens, then further mix, obtain the superfine powder of moisture content low (＜2%), yield about 70%.
The characteristic data of a series of organic clay compositions is provided in the table 8.Title " Exp wt% of C " representative " weight percentage of the carbon that exists in the organic clay composition of measuring ".Title " Exp wt%of H " representative " weight percentage of the hydrogen that exists in the organic clay composition of measuring " etc.Similarly, title " Calc wt%C " representative " weight percentage of the carbon that exists in the organic clay composition that calculates " etc.
The ultimate analysis of the montmorillonite of table 8 pyridine modification
Figure A200780031007D00691
Adopt carbon burning analytical data, hydrogen burning analytical data and Na ion concentration data, further characterized this organic clay composition by " the exchange percentage ratio " that organic ion exchanges with " d-spacing " and mineral ion.Data are in table 9, although the exchange degree that is presented slightly changes according to calculating employed analytical procedure, all three kinds of methods show that all sodium ion is exchanged by pyridylium widely.
Table 9 organic clay composition d-spacing and ion-exchange percentage ratio
Figure A200780031007D00692
Comprise the preparation of the cationic polymer-organoclay composite composition of quaternary phosphine
Embodiment 61 adopts the melting mixing experiment of ODPA-DDS polyetherimide polymer
In order to check the polyetherimide that comprises the structural unit that comes from ODPA and DDS, on the HaakeRheomix instrument, carry out the melting mixing experiment in the chainpropagation behavior that comprises in the presence of the cationic organic clay composition of N-aryl-pyridine.With the low-molecular weight polymer that constitutes by the structural unit that comes from ODPA and DDS basically in 390 ℃ and 40rpm silicate level and TPPy-MMT melting mixing with 5wt%.The variation of 60 minutes internal torques of monitoring.With the identical low-molecular weight polymer that does not add organic clay, and, carry out identical experiment with wrapping the organic clay composition cumyl PA-mATPP-MMT that contains phosphonium cation 15.In each experiment of three experiments, in different timed interval samplings and measurement molecular weight.Determine that from molecular weight and moment of torsion data the molecular weight of low-molecular weight polymer is comprising in the presence of the organic clay composition of pyridylium, and has increased under the situation that does not have organic clay.On the contrary, comprise in existence under the situation of Phosphonium nanoclay (cumyl PA-mATPP-MMT) of organic phosphonium cation 15, polymkeric substance is slower to the conversion of high-molecular weight polymer more, with respect to composition that comprises pyridylium and the behavior that do not contain the composition of organic clay.
Embodiment 62 has the BPADA-DDS-aniline polyetherimide of 7wt% layered silicate TPPy-MMT
Figure A200780031007D00701
BPADA-DDS-aniline polyetherimide
In the 3L round-bottomed flask, add DDS (54.28g, 0.2186 mole), cumyl phenoxy group-TPPy-MMT (43.8g) and veratrole (700g).It is 0.5 that utilization has diameter " the 450WBranson Sonifier 450 type ultrasonoscopes of solid probe, the output rating setting with 40% was with gained mixture ultrasonication 3 hours.After the ultrasonication, this mixture very thick being difficult to that become stirs.At this moment, add DDS (61.12g, 0.2461 mole), BPADA (250g, 0.469 mole), aniline (1.825g, 0.0196 mole), and veratrole (700g).With the reaction mixture mechanical stirring and in 2 hours internal heating to 200 ℃, kept 3 hours in this temperature again, and in the Dean-Stark water trap, collect the water that component distillation is removed.When removing the water of theoretical amount, the veratrole of about 500g is removed, and the gained mixture is cooled to room temperature, and pours in the methyl alcohol (8L) in the homogenizer.By filtering separation product polymer-organoclay composite composition, and with filter cake with the washed with methanol of 500mL, in vacuum oven in 150 ℃ of dryings 24 hours, then at 200 ℃ of dry again 24 hours (350g, 88% yields).
Embodiment 63 has the ODPA-DDS-aniline of 7wt% layered silicate TPPy-MMT
The preparation of ODPA-DDS-aniline polyetherimide: the typical synthetic method of ODPA-DDS polyetherimide is as follows.ODPA (15.18kg) is added in the glass lined reactor of stirring with 123.65 kilograms of (kg) oDCB and 0.35kg aniline.Utilize oil heating that reactor is heated to 180 ℃ and remove the oDCB of 8kg.With extremely about 120 ℃ of reactor cooling, and under agitation add 11.215kg DDS.The oil temperature was increased to 155 ℃ in 210 minutes, and slurry temperature reaches about 146 ℃.Water begins to occur; Utilizing nitrogen purging to help to remove from reactor anhydrates.Kept 115 minutes with oily temperature rise to 171 ℃ and at this.Temperature of reaction is increased to about 166 ℃ along with the appearance of water.Slurries still are easy to stir.In subsequently 25 minutes, oily temperature rise to 186 ℃, temperature of reaction is increased to about 177 ℃.Judge that DDS adds,, make that the reacting slurry temperature is 179 ℃ to be enough to further to raise the oil temperature to 195 ℃.In ensuing 1 hour, remove the condensation product of 45kg.Reduce heating, make reaction be cooled to 50 ℃.Do not observe the viscosity of polymkeric substance.Utilize 5 microns centrifugal bags,, from solution, remove sedimentary polyetherimide by carrying out centrifuging at about 12 ℃.With polymkeric substance in double-cone dryer in 150 ℃ of dryings.The gained powder sieve of 2mm.
In the 3L round-bottomed flask, add DDS (41.14g, 0.1657 mole), cumyl phenoxy group-TPPy-MMT (19.9g) and veratrole (350g).Utilizing 450W to have diameter is 0.5 " the Branson Sonifier 450 type ultrasonoscopes of solid probe, the output rating setting with 40% was with gained mixture ultrasonication 3 hours.After the ultrasonication, it is very thick that this mixture becomes, and is difficult to stir.At this moment, add DDS (31.71g, 0.1277 mole), ODPA (95g, 0.303 mole), aniline (0.714g, 0.0077 mole) and veratrole (300g).With the reaction mixture mechanical stirring and in 2 hours internal heating to 200 ℃, kept 3 hours in this temperature again, and in the Dean-Stark water trap, collect the water that component distillation is removed.When removing the water of theoretical amount, the veratrole of about 250mL is removed, and the gained mixture is cooled to ambient temperature overnight.Under agitation add methyl alcohol (300mL) then.By filtering separation resulting polymers-organic clay composite composition powder, with the washed with methanol of 500mL, in vacuum oven in 150 ℃ of dryings 24 hours, then in 200 ℃ of dry again 24 hours (158g, 88% yields).
Embodiment 64 comprises the film that contains the cationic polymer-organoclay composite composition of N-aryl-pyridine
With the thick film of 3 inches wide of resin combination extrusion moldings and 4 Mills (mil), the polymer-organoclay composite composition (the BPADA-DDS polyetherimide that contains 7wt% layered silicate TPPy-MMT) that polymer-organoclay composite composition that this resin combination is prepared in embodiment 63 by 31% weight (the ODPA-DDS polyetherimide that contains 7wt% layered silicate TPPy-MMT) and 69% weight prepare in embodiment 62 is formed.Use 16mm PRISM forcing machine, this forcing machine is equipped with exhaust/arrangement screw rod and 3-inch sheeting die.Resin combination is with about 0.5lb speed charging hourly.The setting screw speed is 200rpm, and barrel zone temperature is 370 ℃, and the sheeting die temperature is 380 ℃.In the film extrusion process, die pressure is about 1500psi.For relatively organic clay is to the influence of die pressure, extrusion molding does not contain the contrast film of the analogous composition of organic clay in identical extrusion system, and measures die pressure, finds that it only is about 900psi.The gpc analysis of cast film shows that polymkeric substance increases molecular weight in the film extrusion process.Although cast film is foldable (creasable), the TEM image of film shows that the dispersion of TPPy-MMT organic clay in polyimide substrate is relatively poor.Relatively poor organic clay disperses to be reflected among the CTE result, wherein with respect to unfilled control sample, only observes 18% CTE and reduces.This silicate that is equivalent to every 1wt% has 2.6% more modest CTE to reduce.
The GPC of table 10 cast film and CTE analyze
Sample Mp *(Kg/mol) Mw(Kg/mol) Mn(Kg/mol) CTE?0-200℃(ppm/℃)
Raw material 28.8 36.9 15.6 N.A.
Cast film 50.5 52.2 20.7 50
*" peak molecular weight "
The data acknowledgement that is compiled in the table 10, the molecular weight of polymer organic clay composition can increase significantly by being extruded into film.
Embodiment 65-72 comprises the polymer-organoclay composite composition of resin compound and the film of making thus, and described resin compound is made up of the BPADA-DDS polyetherimide of 31wt% and the ODPA-DDS polyetherimide of 69wt%
Prepare and a series ofly comprise polyetherimide (ODPA-DDS polyetherimide or BPADA-DDS polyetherimide) and organic clay composition (the polymer-organoclay composite composition of cumyl phenoxy group-TPPy-MMT) is as shown in following table 11.In each embodiment of embodiment 65-68, diamines is DDS, and end-capping reagent is an aniline.In each embodiment of embodiment 65-68, adjust the consumption of end-capping reagent according to " target " molecular weight.For every kind of resin, prepare two molecular weight targets, 25Kg/mol (" Lo ") and 30Kg/mol (" Hi ").
Table 11 comprises the polyimide compositions of cumyl phenoxy group-TPPy-MMT
Embodiment Polymkeric substance Acid anhydride Target Mw Target Mn (Kg/mol) Acid anhydride/amine ratio Wt% silicate Mw(Kg/mol) Mn(Kg/mol)
65 ODPA-DDS polyetherimide-Hi ODPA 30 15.6 1.02 7 30.6 14.8
66 ODPA-DDS polyetherimide-Lo ODPA 25 13.1 1.02 7 26.0 13.0
67 BPADA-DDS polyetherimide-Hi BPADA 30 22.0 1.00 7 78.9 30.4
68 BPADA-DDS polyetherimide-Lo BPADA 25 18.3 1.00 7 58.0 24.6
Next, by the mixture of the ODPA-DDS polyetherimide polyimide resin of the BPADA-DDS polyetherimide of the resins 31wt% of embodiment 65-68 and 69wt%, and extrude four kinds of films (table 11) with different molecular weight combination.Utilize these combination research under the silicate heap(ed) capacity of 7wt% molecular weight to the influence of film ductility.
Employing has exhaust/arrangement screw rod and the 16mm Prism forcing machine of 3-inch sheeting die is housed.With mixture with 0.5lb speed charging hourly.The setting screw rod is 200rpm, and barrel zone temperature is 380 ℃, and the sheeting die temperature is 390 ℃.Die pressure is about 1200psi.The data acquisition of cast film is in table 12.
Table 12 comprises the cast film of polyetherimide combination as the polymer-organoclay composite composition of polymer resin components
*Nd=" undetermined "
The data of cast film show that in the polymer-organoclay composite composition that comprises organic clay composition cumyl phenoxy group-TPPy-MMT, the molecular weight of ODPA-DDS polyetherimide resin increases functional.Thereby, in embodiment 69, the film that the polymer-organoclay composite composition formulation of lower molecular weight ODPA-DDS polyetherimide resin and lower molecular weight BPADA-DDS polyetherimide resin makes has molecular weight behind the extrusion molding suitable with not containing the control mixture of organic clay.Yet the contrast film is ductile, and the film sample of embodiment 69 is crisp.In the middle of four film samples that comprise the polymer-organoclay composite composition of table 12, only find that the film (" Hi "-" Hi ") of embodiment 72 is foldable film, fold is reliably and through being commonly used for the index of ductility.The result shows, needs the fluoropolymer resin of higher molecular weight, the reduction of the ductility that causes because have relatively large (7 weight %) silicate in the film to offset.TEM image with film of cumyl phenoxy group-TPPy-MMT shows that organic clay is scattered in the polymeric matrix well.Tem analysis is consistent with the CTE measuring result, in the CTE measuring result, compares with unfilled control sample, observes total CTE and is reduced to 28%.This is equivalent to per 1% silicate heap(ed) capacity and reduces by 4% CTE.The film (example as shown in embodiment 69-72) that comprises the polymer-organoclay composite composition is called " nanocomposite films " sometimes, because the polymer-organoclay composite composition that is adopted in this film preparation comprises the organic clay composition of very high level of exfoliation.
Contain the preparation of phenyl ketone De quaternary alkylphosphonium salt
The preparation of embodiment 73 4-iodo-phenoxy group-benzophenone
In the 1000mL three neck round-bottomed flasks that Dean-Stark water trap, condenser, splash bar and nitrogen joint are housed, add 4-iodophenol (19.0g, 0.086mol), 4-fluorine benzophenone (15.72g, 0.079mol), salt of wormwood (7.16g, 0.0518mol), DMF (157mL), and toluene (16mL).The gained mixture stirred under nitrogen atmosphere and reflux 2 hours (solution temperature～160 ℃).Water is collected in the water trap around here.After 2 hours, reaction is cooled to room temperature, adds water (400mL) in reaction mixture, required product is precipitated out from solution with Off-white solid.By Virahol (400mL) recrystallization, product is further purified, obtain required product, it is crystalline solid (25g, 87% yield).
Synthesizing of embodiment 74 4-(4-benzoyl-phenoxy group)-phenyl triphenyl phosphonium iodide 32
Figure A200780031007D00741
Adding 4-iodo-phenoxy group-benzophenone in the 250mL three neck round-bottomed flasks that condenser and nitrogen inlet are housed (25.00g, 0.0624mol), triphenylphosphine (16.38g, 0.0624mol), acid chloride (0.14g, 0.624mmol), and the dimethylbenzene (125mL) of the degassing.Make this solution of argon gas bubbling process 1 hour, to eliminate oxygen.This mixture was refluxed 2 hours, generate dark orange solution thereupon.Reaction mixture is cooled to room temperature, and from dimethylbenzene Fen Chu phosphonium salt phase, it is dark orange solid.Utilize TLC monitoring reaction process, the methylene chloride of employing 90/10 is as developping solution.Product is further purified by flash chromatography, and described flash chromatography adopts silica gel 60 (500g), and with the methylene dichloride that contains 5% methyl alcohol as solvent.Elder generation's wash-out be red impurity, then be the phosphonium salt 32 (40g, 82% yield) that is needed, the latter is except that coming out with the lacteous powder separation after desolvating.
The preparation of two-4-(triphenyl phosphonium) benzophenone dichloride
The capped tube of 20mL is loaded onto nitrogen purging, and add the reactant dichloro benzophenone (1.0g, 0.00398mol) and triphenylphosphine (2.1g, 0.00769mol).Utilize the aluminothermy block that reaction is heated to 270 ℃ and kept 2 hours.Be cooled to after the room temperature, solid is dissolved in chloroform and is added drop-wise in the hexane.The water-soluble purple solid of gained is dissolved in the chloroform again, and separates again: earlier chloroformic solution is added in the 20mL ether, collects by vacuum filtration then.GC-MS analyzes and demonstrates two peaks, and a peak is corresponding to Yi Phosphonium product, and second peak is corresponding to Er Phosphonium product.Last isolate output is 1.1g.
Comprise the preparation that contains the cationic polymer-organoclay composite composition of phenyl ketone De quaternary phosphine
Embodiment 75 PhEK-MMT promptly come from organic clay composition synthetic of 4-(4-benzoyl-phenoxy group)-phenyl-triphenyl phosphonium iodide and sodium montmorillonite
In the 5L round-bottomed flask that mechanical stirrer is housed, add sodium montmorillonite (30g, 0.03 mole) and deionized water (2.5L).This solution is heated and stirs at 85 ℃, till sodium montmorillonite disperses well.The solution of phosphonium salt 32 (22.8g, 0.034 mole) in acetonitrile (600mL) is warming up to about 60 ℃, in 10 minutes, adds the suspension of sodium montmorillonite then.Add after the salts solution, with reaction mixture 85 ℃ of stir abouts 3 hours.
By filter collecting organic clay composition (be called equally sometimes modified montmorillonite used, perhaps abbreviate " modified clay " as), and wash, to remove the inorganic salt impurity and the sodium iodide of byproduct of reaction in return with hot water (2L, 80 ℃).The following modified clay that is further purified: it is scattered in the acetonitrile (2L) again at 60 ℃, then filters to remove any excessive De phosphonium salt.The clay of purifying 150 ℃ of vacuum-dryings 24 hours and grind, is obtained PhEK-MMT fine powder (40g, 72% yield).
Two-4-(triphenyl phosphonium) benzophenone-MMT's is synthetic
Two-4-(triphenyl phosphonium) benzophenone dichloride that in the 500mL beaker, adds 200mL water and 0.7183g.This mixture heating up was refluxed 2 hours.To be cooled to room temperature, separate organic clay by centrifuging, with two parts of 200mL deionized water wash, and collect again by centrifuging.
Comprise the preparation that contains the cationic polymer-organoclay composite composition of phenyl ketone De quaternary phosphine
Embodiment 76-78 comprises the polymer-organoclay composite composition of PEEK 450G
With 3mm sieve cryogrinding PEEK 450G resin.The gained material has blended fine powder and bigger particle.Abrasive substance is sieved with the 1mm sieve, and collect fine particle.Need grind, so that the charging of material process minor diameter 16mm forcing machine, and guarantee to grind clay and mix well.
The resin that grinds is mixed with atomizing PhEK-MMT (seeing the preparation of embodiment 75), and the latter's amount is equivalent to 5% inorganic silicate heap(ed) capacity.For organic cations chemical structure relatively to the influence of the character of polymer-organoclay composite composition, also prepare two kinds of other organo-clay (embodiment 77 and 78).So, also use organic clay composition cumyl-MMT (embodiment 77) and TPP-MMT (embodiment 78) to prepare the mixture of the PEEK 450G resin that grinds.Cumyl-MMT promptly comprises the preparation of organic clay composition of organic phosphonium cation 15 referring to embodiment 15 of the present disclosure.TPP-MMT comprises the organic clay composition that comes from sodium smectite clay and the halid silicate layer of tetraphenylphosphoniphenolate, and can be by method preparation disclosed herein.The organic clay composition that uses in embodiment 76-78 and the amount of fluoropolymer resin are referring to table 13.By being placed on two components in the plastics bag and shaking several minutes, mix each formulation.
Table 13
*Embodiment 15 is seen in the preparation of organic clay composition cumyl-MMT.
*TPP-MMT is the organic clay composition that comes from sodium smectite clay and tetraphenylphosphoniphenolate halide salts.
After shaking, on the 16mm twin screw extruder (L/D=25) that has in the same way rotation and engagement screws, with the mixture of organic clay composition and fluoropolymer resin with per hour 0.5 pound extrude, and extrudate is granulated.Utilize thermocompressor, the pellet of every kind of material will collecting with poor throughput (0.5lb/hr) is molded into thin discs.Disk is through tem analysis, to determine degree of scatter.The result collects in the table 14.
Table 14 tem analysis result
Embodiment Organic clay composition Fluoropolymer resin The TEM classification
76 PhEK-MMT PEEK450G Scattered
77 Cumyl-MMT PEEK450G Poor dispersion
78 TPP-MMT PEEK450G Poor dispersion
The analysis of the transmission electron microscope (TEM) of the polymer-organoclay composite composition of the clay of extruding that comprises the PhEK-MMT modification in PEEK (embodiment 76) shows that organic clay composition is dispersed in the polymeric matrix well.The gained dispersiveness is better than in embodiment 77 and 78 viewed.Do not observe big clay colloid (tactoid), most of clay is the form of silicate layer rickle, shows that organic clay composition peels off in polymeric matrix to heavens.The dispersiveness that it is believed that the polymer-organoclay composite composition that observes embodiment 76 strengthens, and is because the structural similarity between used fluoropolymer resin PEEK450G and the used organic clay composition PhEK-MMT.PEEK 450G resin and organic clay composition PhEK-MMT all comprise the benzophenone part that the 4-aryloxy replaces.Do not comprise the benzophenone part that the 4-aryloxy replaces in two organic clay compositions that adopted among the embodiment 77 and 78.
The analysis of the transmission electron microscope (TEM) of the polymer-organoclay composite composition of extruding of embodiment 78 (cumyl in PEEK-MMT modified clay) shows relatively poor dispersion.Observe big organic clay composition colloid in the transmission electron microscopy figure that is produced, this shows, does not flake off into fully in the PEEK polymeric matrix to the organic clay composition of small part.
The TEM result of the TPP-MMT modified clay in PEEK (embodiment 78) shows that equally organic clay composition is dispersed in the fluoropolymer resin relatively poorly.Observe big clay colloid in the transmission electron microscopy figure that is produced, this shows, does not flake off into fully in the PEEK polymeric matrix to the organic clay composition of small part.
In the composition that does not contain polyetherimide substantially, adopt the preparation of the polymer-organoclay composite composition of melting mixing method
Embodiment 79-81
The following examples are for example understood the use for preparing the method for polymer-organoclay composite composition provided by the present invention, and the degree of peeling off that described polymer-organoclay composite composition does not contain polyetherimide and its component organic clay composition substantially is at least 10%.Thereby, 70 gram fluoropolymer resins (table 15 of face as follows) are mixed with 4.98 gram organic clay composition BAPP-TPPy-MMT.By in encloses container, shaking 2 minutes, with powder mixes.The gained mixture is heated in 50rpm in HAAKE mixing roller.This mixture is remained on temperature according to table 15.Per 5 minutes, the molten mixture in the HAAKE mixing roller is taken a sample.15 minutes samples are pressed into film between the tinsel that has the teflon lining of two 760 ℉.By thermo-mechanical analysis the film sample of being suppressed is analyzed then, and measured the CTE of 30～200 ℃ of scopes.The film of being suppressed has CTE value listed in the table 15.
Table 15 is by the polymer-organoclay composite composition of melting mixing preparation
Embodiment Fluoropolymer resin Organic clay composition Mixing temperature The CTE of film (30-230 ℃)
79 PEEK150P BAPP-TPPy-MMT 380℃ 67ppm/℃
80 PPSU * BAPP-TPPy-MMT 340℃ 61ppm/℃
81 PES **(ULTRASON?E2010) BAPP-TPPy-MMT 330℃ 54ppm/℃
*PPSU=RADEL R, *The PES=polyethersulfone
Data acknowledgement in the table 15 does not contain the polymer-organoclay composite composition of polyetherimide substantially, but the method according to this invention, by making to about 450 ℃ temperature melting mixing season organic clay composition and fluoropolymer resin at about 300 ℃.This data presentation is in order to realize high-caliberly peeling off (〉 10% and peel off), fluoropolymer resin and organic clay composition should be under the situation of the shearing force that shearing force is provided greater than low shear mixer such as Haake mixing tank melting mixing.It is believed that if melting mixing in high shear force environment more as to the twin screw extruder of about 450 ℃ temperature work, carrying out in about 300 ℃, then the percentage ratio that peels off of the composition of embodiment 79-81 can be greater than 10%.
Adopt the melting mixing technology in comprising the composition of polyetherimide, to prepare the polymer-organoclay composite composition
Embodiment 82 comprises the preparation of the polymer-organoclay composite composition of polyetherimide
By vigorous stirring, with sodium montmorillonite (cloisite) clay (SouthernClay, the Inc.0.000926 cation equivalent/g) be dispersed in the 200mL water of 2.0g.In this dispersion liquid, add the 0.692g methylenum coeruleum, and this mixture heating up was refluxed 60 minutes.Then this mixture is cooled to room temperature, by centrifuging separated product organic clay composition (modified clay).With wet clay wass twice, way is to be dispersed in the neutralization of 200ml deionized water again to separate once more by centrifuging.Washed wet clay 120 ℃ of dryings 2 hours, is ground then, obtain meticulous pewter solid.
Organic clay composition (clay of methylenum coeruleum modification) (4wt% silica) that 5.19g is as above prepared and the oxygen di-(Tetra hydro Phthalic anhydride) of 59.85g are added among the oDCB of 365mL, be immersed in the ultrasonic bath container and heating, till the fine dispersion liquid that obtains non-settling clay.Then flask is loaded onto top agitator and Dean-Stark water trap, and added the DDS of 46.35g and the aniline of 0.08978g.ODCB with 100mL is flushed to DDS in the container.Stir this mixture and in 3 hours, slowly be heated to backflow, and remove by component distillation and to anhydrate.After under refluxing, heating 18 hours, obtain the dispersion liquid of fine powder.Then this dispersion liquid is transferred to the Haake melt mixer, and desolvates by removing in 60 minutes in 390 ℃ and 50rpm volatilization.In volatilization process, with 5 minutes timed interval sampling.At 760 ℉, between two tinsels that have a teflon lining, 15 minutes samples are pressed into film.By thermo-mechanical analysis the film sample of being suppressed is analyzed then, and measured the CTE of 30～200 ℃ of scopes.The film of being suppressed has 41ppm/ ℃ CTE, and 14.8% peels off.
Embodiment 83-93
Utilize one of melting mixing as herein described, in-situ polymerization or solvent method earlier, prepare a series of polymer-organoclay composite compositions (referring to the embodiment 27-29 that in-situ polymerization for example is described) that comprise polyetherimide.The material that is obtained by polymerization process is the big solid block of dry cake.Filter cake is broken into several about 1 inch fragments, and utilizes Retsch mill and 3mm mesh screen, these fragments are worn into fine powder.Then with the independent extrusion molding of polymer-organoclay composite composition of fine-powdered, perhaps mix and extrusion molding with other efflorescence polymer-organoclay composite composition.The forcing machine that is adopted is 16mm twin screw extruder (L/D=25), and it disposes the screw rod that rotates in the same way and mesh, and makes the polymer-organoclay composite composition can directly be extruded into film, perhaps granulates earlier and then film forming in the second extrusion molding step.Screw design permits melting, mixing, remove volatile component and atomizing polymer-organoclay composite composition is passed to forcing machine film forming die head exit from opening for feed.Use 3 in the routine " (3 inches) or 6 " (6 inches) die head, the polymer-organoclay composite composition that will contain the fusion polyetherimide changes into film.
In contrast and embodiment 83-85, utilize 16mm Prism forcing machine earlier with exhaust/arrangement screw rod and 3mm granulation die head, atomizing polymer-organoclay composite composition is granulated.With organic clay composition-fluoropolymer resin mixture (polymer powder mixture) with 1lb/ hour speed " hungry charging ".The setting screw speed is 250rpm, and barrel zone temperature is 385 ℃, and die head temperature is 385 ℃.With derive from the pellet extruded at last in vacuum oven in 150 ℃ of dried overnight, and utilize have 6 " the Welex 1-1/4 of wide sheeting die and Flapper type (barrier-type) screw rod " single screw extrusion machine is extruded into film with it.Extruder screw was with 4lb/ hour speed " hungry charging ", and screw speed is 25rpm.Die gap is about 8mil, and the film of extrusion molding with different speed drawings, obtains having the film of a lot of different thickness with the film take-up gear.
Usually, when breaking away from die head with Gap Flow, molten resin can be adjusted roller speed by one group of roller drawing, so that, thereby make thinning of product film and orientation with speed drawing film faster than molten polymer-organic clay composite composition disengaging die head.The turning oil of roller inside of flowing through is allowed the temperature that keeps regulation.Usually, film adopts roller to be the chill casting process extrusion molding of " winding of S shape " configuration usually, and wherein film twines around middle and bottom roller, carries out Cooling Heat Transfer so that time enough to be arranged.Be that mip rolls carries out drawing to film by another group roller then,, make film and preliminary roller keep closely contacting in film, to add tension force.Make film through mip rolls and being collected on the coiler then.Also can use other conventional film handling equipment.
Preparation comprises the exemplary film of the polymer-organoclay composite composition that contains polyetherimide, and measures selected film sample at machine direction and horizontal thermal expansivity (CTE).Test-results comes together in the table 16.
Table 16 comprises the CTE and the second-order transition temperature (Tg) of the cast film of polymer-organoclay composite composition, and described polymer-organoclay composite composition comprises 100% BPADA-DDS polymkeric substance as polymeric constituent
Figure A200780031007D0080092307QIETU
*Use melting mixing technology (seeing embodiment 76-78) preparation polymer-organoclay composite composition. *Use solvent technology (seeing embodiment 52-53) preparation polymer-organoclay composite composition.
Figure A200780031007D0080092336QIETU
Use in-situ polymerization technology (seeing embodiment 27-29 and 38-51) preparation polymer-organoclay composite composition.
Add stoichiometry checking preparation polymer-organoclay composite composition by in-situ polymerization
Embodiment 94 comprises 1, the preparation of the organic clay composition of 2-dimethyl-3-hexadecyl glyoxaline cation
In the 2L three neck round-bottomed flasks that the top mechanical stirrer is housed, add 1-chlorine n-Hexadecane (260g, 1.00 moles), 1,2 dimethylimidazole (91.0g, 0.95 mole), and CH 3CN (500mL), and with the stirring tempestuously in 80 ℃ oil bath of this two-phase reaction mixture.After 72 hours, reaction mixture is cooled to room temperature, and the product crystallization is spent the night.The solid of filtering for crystallizing is with cold CH 3The CN thorough washing, and, obtain 1 70 ℃ of vacuum-dryings 3 days, 2-dimethyl-3-hexadecyl imidazolium chloride, it is light gray-white solid (220g, 62% yield).
(30g, SouthemClay USA) and deionized water (1L), and stir this clay 2 hours at room temperature mechanical to add sodium montmorillonite in the 2L three neck round-bottomed flasks that the top agitator is housed.In this clay dispersion, add 1 by transfer pipet, the aqueous solution of 2-dimethyl-3-hexadecyl imidazolium chloride (16g is in 200mL), and reaction mixture is heated to 80 ℃ rapidly kept 2 hours, and in stirred overnight at room temperature.Filtering precipitate is used the cold water thorough washing, uses CH at last 3The OH washing, and, obtain the product organic clay composition in 70 ℃ of vacuum-dryings 3 days, it is pale solid (33g, 94% yield).
Embodiment 95 in-situ polymerizations add the stoichiometry check to obtain comprising the polymer-organoclay composite composition of BPADA-DDS polyetherimide and imidazole modified clay (7% silicate heap(ed) capacity)
In the SILVERSON high-shear mixer, add imidazole modified clay (14g) and oDCB (450mL) and, keep violent the mixing simultaneously this mixture heating up to 120 ℃ maintenance 2 hours.The mixing system that comprises the SILVERSON high-shear mixer is equipped with storage tank and the thermostat that has heat tape.The content of storage tank is added to the bottom of SILVERSON mixing tank.Recirculation line with SILVERSON mixing tank tieback to storage tank.Be cooled to after the room temperature, reaction mixture is transferred in the 2L three neck round-bottomed flasks that top mechanical stirrer, dean-stark water trap and condenser are housed.In this flask, add BPADA (74.2g) and with this mixture 150 ℃ of stirrings.After 2 hours, add DDS (29.4g) and oil bath temperature progressively is increased to 210 ℃, will react and carry out again 3 hours.Between polymerization period, analyze the primary first-order equation mixture at least, and add diamines or dianhydride as required, with the preliminary election stoichiometry that obtains to want.Proceed polymerization then.After the polymerization,, be deposited in CH with the reaction mixture cooling 3Among the OH, filter, and vacuum-drying, obtaining product polymer-organoclay composite composition, it is a brown solid, has about 37ppm/ ℃ CTE.
The in-situ polymerization of the BPADA-DDS polyetherimide under embodiment 96 7wt% cumyl phenoxy groups-Tppy-MMT layered silicate exists and stoichiometry check
Targeted degree of polymerization is 30.Use aniline as end-capping reagent.In the 12L round-bottomed flask, add DDS (280g, 1.128 moles), cumyl phenoxy group-TPPy-MMT (280g) and veratrole (5.5kg).Utilization has the Fisher Scientific PowerGen rotor-stator homogenizer (OmniInternational manufacturing) at 32mm sawtooth tip, with this mixture 9000rmp homogenizing 45 minutes.The 1500W type Autotune series high-strength ultrasonic treater of 1 inch solid probe of diameter is equipped with in utilization, with 70% ultrasonication gained mixture 2 hours is set.After the ultrasonication, it is very thick that this mixture becomes, and is difficult to stir.
In 10 gal reactor, add the dispersive clay mixture, DDS (458.8g, 1.848 moles), BPADA (1600g, 3.004 moles), aniline (11.68g, 0.125 mole), and veratrole (4kg).With the reaction mixture mechanical stirring and at 2 hours internal heating to 200 ℃, kept 2 hours in this temperature again, collect the water that from reaction mixture, distills out.
Get the reaction mixture sample of 10g, and under nitrogen atmosphere and 350 ℃ remove and to desolvate.Remaining polymer samples is pressed into film, infrared (IR) spectrum of MEASUREMENTS OF THIN, and the ratio of definite amine end groups and acid anhydride end group.Find that from IR spectrum polymer samples comprises 0.4 mole of amine that % is excessive.Utilize this information, adjust the reactive chemistry metering, excessive amine content is proofreaied and correct by adding BPADA (6.4g).And then reaction mixture kept 1 hour at 200 ℃.
When not observing when further having water to generate, distill out the 3L veratrole in the autoreactor, and make the gained mixture be cooled to ambient temperature overnight.The reaction mixture of envrionment temperature is poured in the methyl alcohol (50L) in the homogenizer, and with the gained powder transfer to the filtering centrifuge that 1 micron bag filter is housed.Product polymer-organoclay composite composition is with other 10L washed with methanol.Collect powder and with its in vacuum oven in 150 ℃ of dryings 24 hours, and then, obtain the polymer-organoclay composite composition (2175g, 86% yield) of purifying in 200 ℃ of dryings 24 hours.
The in-situ polymerization of embodiment 97 BPADA-DDS polyetherimide in the presence of CLOISITE 30B layered silicate and stoichiometry check
Utilize SILVERSON mixing tank (square hole high-shear sieve carries out pumping, installs like that by embodiment 95 with～600mL/min for laboratory on-line mixing device, L4R-PA type) to mix organic clay and solvent.270mL orthodichlorobenzene (oDCB) and 180mL veratrole are heated to 80 ℃ and carry out pumping by the SILVERSON mixing tank.In the recirculation solvent, slowly add the organic clay composition (13.56g) that comprises CLOISITE 30B and dihydroxyphenyl propane dianhydride (BPADA) (74.51g).This mixture is moved 45 minute in 6000rpm with circulation pattern in the SILVERSON high-shear mixer.The temperature of this solution is increased to 79 ℃ by 56 ℃.Gained solution is transparent, and expression organic clay mixture peels off.This mixture is transferred in the three-necked flask of 1L.Then flask is loaded onto top agitator and Dean-Stark water trap and placed the oil bath that is heated to 100 ℃.The 4,4 (DDS) that adds 33.88g.Stir this mixture and be heated backflow.Remove by component distillation and to anhydrate.Add Tetra hydro Phthalic anhydride (0.86g), and reacted 2 hours.Get the reaction mixture sample of 10g then and under nitrogen, remove and desolvate in 350 ℃.Remaining polymer samples is pressed into film, infrared (IR) spectrum of MEASUREMENTS OF THIN, and the ratio of definite amine end groups and acid anhydride end group.Find that from IR spectrum polymer samples comprises 0.5 mole of acid anhydride that % is excessive.Utilize this information,, adjust the reactive chemistry metering, to proofread and correct excessive acid anhydride content by adding DDS (0.182g).Then reaction mixture was kept 1 hour at 200 ℃ again.By second 10g sample of above-mentioned processing or reaction mixture.By IR spectrum as can be seen, polymer samples comprises 0.5 mole of acid anhydride that % is excessive.In reaction mixture, add the DDS of other 0.189g, and make it to react 1 hour.At this moment, remove the heating and make reactant be cooled to room temperature.The gained viscous mixt is transferred to the Haake melt mixer and mixed 60 minutes at 390 ℃ and 50rpm.The timed interval with 5 minutes is taken sample away.At 760 ℉, between two tinsels that have a teflon lining, 15 minutes samples are pressed into film.By thermo-mechanical analysis the film sample of being suppressed is analyzed then, and on 30～200 ℃ of scopes, measured CTE.
The in-situ polymerization of embodiment 98 BPADA-DDS polyetherimide in the presence of CLOISITE 15A layered silicate and stoichiometry check
Utilize SILVERSON mixing tank (square hole high-shear sieve carries out pumping with～600mL/min for laboratory on-line mixing device, L4R-PA type) to mix organic clay and solvent.270mL orthodichlorobenzene (oDCB) and 180mL veratrole are heated to 60 ℃, and by the pumping of SILVERSON mixing tank.Slowly add the organic clay composition (13.51g) that comprises CLOISITE 15A in the recirculation solvent, 4,4 (DDS) (33.90g) reaches 1mL acetate.This mixture is moved 45 minutes by the SILVERSON high-shear mixer with 6000rpm and recirculation mode.Make the temperature of this solution be increased to 86 ℃ by 60 ℃.Gained solution is viscosity, shows that organic clay peels off.This mixture is transferred in the three-necked flask of 1L, utilizes the oDCB of 50mL to finish transfer.Then flask is loaded onto top agitator and Dean-Stark water trap and placed the oil bath that is heated to 140 ℃.In 15 minutes, divide two parts of dihydroxyphenyl propane dianhydrides (BPADA) that add 70.02g.This mixture stirred and reflux 2 hours.Remove by component distillation and to anhydrate.Add Tetra hydro Phthalic anhydride (0.86g), and reacted 3 hours.Take out the sample 10g of reaction mixture, and under nitrogen and 350 ℃ remove and desolvate.Remaining polymer samples is pressed into film, measures infrared (IR) spectrum of this film, and the ratio of definite amine end groups and acid anhydride end group.Find that by IR spectrum polymer samples comprises 4.7 moles of acid anhydrides that % is excessive.Utilize this information, adjust the reactive chemistry metering by adding DDS (1.55g), to proofread and correct excessive acid anhydride content.Then reaction mixture was kept 3 hours at 200 ℃.Add the DDS of other 0.6g, and make it to react 1 hour.By second 10g sample of above-mentioned processing or reaction mixture.Find that by IR spectrum polymer samples comprises 0.8 mole of acid anhydride that % is excessive.In reaction mixture, add the DDS of other 0.31g, and make it to react 1 hour.At this moment, remove heating, and make reaction be cooled to room temperature.The gained viscous mixt is transferred to the Haake melt mixer, and mixed 60 minutes with 50rpm in 390 ℃.The timed interval with 5 minutes is taken sample away.At 760 ℉, between two tinsels that have a teflon lining, 15 minutes samples are pressed into film.By thermo-mechanical analysis the film sample of being suppressed is analyzed then, and the CTE that records in 30～200 ℃ of scopes is 40.1ppm/ ℃ (28.6% peels off).
Previous embodiment is illustrative, only is used to illustrate some feature of the present invention.Appended claims requires invention wide in range as being susceptible to, and the embodiment that this paper presented is the explanation of the embodiment chosen from all may the numerous species of embodiment.Therefore, the applicant is intended that, and described claims are not benefited from the restriction of the selection of the embodiment of explanation feature of the present invention.When being used for claims, word ＂ comprises (comprise) ＂ and grammatical variants thereof and logically points to equally and comprise that scope changes and different phrases, for example (but being not limited to) ＂ basically by ... form ＂ and ＂ by ... composition ＂.If need, already provided scope comprises subrange therebetween.The expection those of ordinary skill in the art can expect these variants, and if do not offer the public as yet, these variants should be interpreted as being covered by appended claims under possible situation.What can expect equally is, because the imprecision of language, the progress of science and technology can make the equivalence of not considering at present and substitute becomes possibility, and these variants should be construed to by appended claims under possible situation and cover.

Claims (23)

1. the method for preparing the polymer-organoclay composite composition, this method comprises:
Melting mixing comprises the season organic clay composition and fluoropolymer resin of alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation, described fluoropolymer resin comprises at least a polymkeric substance that is selected from polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl and the polycarbonate, and described fluoropolymer resin does not contain polyetherimide substantially;
Described melting mixing is carried out to about 450 ℃ temperature at about 300 ℃, obtains the polymer-organoclay composite composition, and described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.
2. according to the process of claim 1 wherein that described season organic cation has structure XXXIX:
Figure A200780031007C00021
Wherein Q is nitrogen or phosphorus; And R 7, R 8, R 9And R 10Be C independently 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 20Aromatic group, perhaps polymer chain.
3. according to the method for claim 2, wherein said season organic cation Shi quaternary phosphine positively charged ion.
4. according to the method for claim 3, wherein said quaternary phosphine positively charged ion has structure X:
Figure A200780031007C00022
Ar wherein 1, Ar 2And Ar 3Be C independently 2-C 50Aromatic group; Ar 4Be chemical bond or C 2-C 50Aromatic group; " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain; And X -Be the charge balance gegenion.
5. according to the method for claim 3, wherein said quaternary phosphine positively charged ion has structure XXXIII:
Figure A200780031007C00031
Ar wherein 12, Ar 13, Ar 14And Ar 15Be C independently 2-C 50Aromatic group; And Ar 16Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
6. according to the process of claim 1 wherein that described season organic cation is a quaternary ammonium cation.
7. according to the method for claim 6, wherein said quaternary ammonium cation is the pyridylium with structure XXV:
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
8. according to the method for claim 6, wherein said quaternary ammonium cation is the pyridylium with structure XXVI:
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; " d " is 0～4 number; R 3And R 4Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; Z is a chemical bond, the C of divalence 1-C 20Aliphatic group, the C of divalence 5-C 20Alicyclic group, the C of divalence 2-C 20Aromatic group, oxygen linking group, sulphur linking group, SO 2Linking group, perhaps Se linking group; And Ar 9Be C 10-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
9. according to the process of claim 1 wherein that described inorganic silicic acid salt deposit comes from inorganic clay, described inorganic clay is selected from kaolinite, dickite, nakrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, rich magnesium montmorillonite, hectorite, tetramethyl silanization mica, sodium taincolite, white mica, margarite, talcum, vermiculite, phlogopite, xanthophyllite, chlorite, and combination.
10. according to the process of claim 1 wherein that described inorganic silicic acid salt deposit is derived from the inorganic clay that comprises synthesis of clay.
11. according to the process of claim 1 wherein that described polymer-organoclay composite composition is characterised in that interlamellar spacing is about 5 to approximately
Figure A200780031007C00041
12. according to the process of claim 1 wherein that described fluoropolymer resin comprises poly (arylene sulfide).
13. according to the process of claim 1 wherein that described fluoropolymer resin comprises polyethersulfone.
14. according to the process of claim 1 wherein that described fluoropolymer resin comprises polyetherketone.
15. according to the process of claim 1 wherein that described melting mixing carries out in forcing machine.
16. according to the process of claim 1 wherein that described melting mixing carries out in kneader.
17. according to the process of claim 1 wherein that described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is 20%.
18. comprise the goods of polymer-organoclay composite composition, this polymer-organoclay composite composition comprises:
(a) comprise the season organic clay composition of alternative inorganic silicic acid salt deposit and organic layer, described organic layer comprises the season organic cation; And
(b) fluoropolymer resin, this fluoropolymer resin comprise at least a following polymkeric substance that is selected from: polymeric amide, polyester, poly (arylene sulfide), poly (arylene ether), polyethersulfone, polyetherketone, polyether-ether-ketone, polyphenyl, and polycarbonate; This fluoropolymer resin does not contain polyetherimide substantially;
Wherein said polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.
19. according to the goods of claim 18, it is a film.
20. according to the goods of claim 18, it is the solvent cast film, it comprises polyetherimide and this polyetherimide with dianhydride component and diamine components and has about 180～450 ℃ Tg, and wherein this film has: a) less than 70ppm/ ℃ CTE; B) thickness of about 0.1 μ m to 250 μ m; And c) comprises residual solvent less than 5% weight.
21. prepare the method for polymer-organoclay composite composition, this method comprises:
Melting mixing comprises the season organic clay composition and fluoropolymer resin of alternative inorganic silicic acid salt deposit and organic layer in forcing machine, described organic layer comprises the season organic cation, described fluoropolymer resin comprises polyethersulfone, and described fluoropolymer resin does not contain polyetherimide substantially;
Described melting mixing is carried out so that the polymer-organoclay composite composition to be provided to about 450 ℃ temperature at about 300 ℃, and described polymer-organoclay composite composition is characterised in that peeling off percentage ratio is at least 10%.
22. according to the method for claim 21, wherein said season organic cation have structure X,
Figure A200780031007C00051
Ar wherein 1, Ar 2And Ar 3Be C independently 2-C 50Aromatic group; Ar 4Be chemical bond or C 2-C 50Aromatic group; " a " is 1 to about 200 number; " c " is 0～3 number; R 1Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And R 2Be halogen atom, C 1-C 20Aliphatic group, C 5-C 20Alicyclic group, C 2-C 50Aromatic group, perhaps polymer chain.
23. according to the method for claim 21, wherein said season organic cation have structure XXV,
Figure A200780031007C00052
Ar wherein 6, Ar 7And Ar 8Be C independently 2-C 50Aromatic group; " b " is 0～2 number; R 3Be halogen atom, C when occurring independently at every turn 1-C 20Aliphatic group, C 5-C 20Alicyclic group, perhaps C 2-C 20Aromatic group; And Ar 11Be C 2-C 200Aromatic group perhaps comprises the polymer chain of at least one aryl.
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