CN1301278A - Polymer nanocomposite composition - Google Patents

Abstract

A polymer nanocomposite composition of a polyamide and a treated silicate, wherein the treated silicate includes a silicate material treated with at least one ammonium ion of the formula: +NR1 R2R3R4 wherein R1, R2, R3 and R4 are independently selected from a group consisting of a saturated or unsaturated C1 to C2 hydrocarbon, substituted hydrocarbon and branched hydrocarbon, or where R1 and R2 form a N,N-cyclic ether, and optionally, one of R1, R2, R3 and R4 is hydrogen.

Description

Polymer nanocomposite composition

Invention field

The present invention relates to a kind of nano composite material that comprises polyamide matrix and be dispersed in processing silicate wherein.More particularly, the present invention relates to a kind of nano composite material that contains the silicate material that at least a ammonium ion of the usefulness that is dispersed in wherein handled.

Background of invention

International Application No. WO 93/04118 discloses a kind of preparation method of polymer nanocomposites of the plane particle that wherein is scattered here and there.This method relates to carries out melt-processed to polymkeric substance and a kind of swellable and with the stratified material of the mutual embedding of polymer-compatible and it is imposed being enough to make each layer dissociative shearing rate.This stratified material carries out compatible processing with a kind or multiple " effectively swelling/compatilizer " with silane-functional or functionalized cationic.

International Application No. WO 93/04117 discloses a kind of preparation method of polymer nanocomposites of the plane particle that wherein is scattered here and there, wherein to the stratified material melt-processed of polymkeric substance with a kind of swellable, polymkeric substance-compatible mutual embedding.This stratified material carries out compatible processing with a kind or multiple " the effectively swelling/compatilizer " that is selected from uncle's ammonium, secondary ammonium and quaternary phosphonium cations.Swelling/the compatilizer of this selection " ... its surface is become than the organic property of the richer parent in surface that adopts uncle and quaternary ammonium ion title complex to carry out compatible processing ... " impel exfoliate generation, cause the reduction of suffered shearing during the mixed with polymers and the minimizing of decomposition, and the thermostabilization to matrix material is higher than other positively charged ions (for example, quaternary ammonium cation) swelling/compatilizer.

International Patent Application WO 94/22430 discloses a kind of nanocomposite composition, comprising: contain the polymeric matrix of at least a kind of γ phase polymeric amide, and the matrix that is dispersed in a kind of nano level granulated material in the polymeric amide.In nylon 6, add this granulated material and cause improve (7～35%) that modulus in flexure and flexural strength compare with filling nylon 6 not.Then improve considerably lessly (1～3%) with joining to compare in the packless nylon 6,6 adding modulus in flexure that this granulated material produced and flexural strength effect in the nylon 6,6.

International Patent Application WO 93/10098 discloses a kind of polymer composites, stratified material by polymkeric substance and a kind of swellable, polymkeric substance one compatible mutual embedding carries out melt-processed and makes, wherein stratified material has a plurality of layers, and covalent attachment active organosilicon alkane kind on every laminar surface.

International Patent Application WO 95/14733 discloses a kind of production method that does not show the polymer composites of fusing point or second-order transition temperature, comprises that polymkeric substance is with a kind of crystalline silicate melt-processed that contains the stratiform passage.Example comprises: the water glass of embedding and crystallization gather (oxyethane); The montmorillonite and the polystyrene of quaternary ammonium have been embedded; And the montmorillonite and the nylon 6 that have embedded quaternary ammonium.

In the above-mentioned reference, no matter separately or integrate and see do not have one piece to disclose as disclosed the present invention in the claim.

Summary of the invention

The present invention relates to a kind of polymer nanocomposite composition, said composition is applicable to the field of over-all propertieies such as the such ask for something tensile strength of automobile, electronics, film and fiber, tensile modulus and modulus in flexure.In addition, but polymer nanocomposite composition required for protection also has people's appearance, toughness, ductility and dimensional stability.Said composition has good workability and allows in the wide region condition of moulding and process.

This polymer nanocomposite composition comprises the silicate of a kind of polymeric amide and a kind of processing, and wherein the silicate of this processing comprises the silicate material that the following ammonium ion of at least a kind of general formula of a kind of usefulness was handled:

⁺NR ₁R ₂R ₃R ₄Wherein:

R ₁, R ₂, R ₃And R ₄Be independently selected from saturated or unsaturated C ₁～C ₂₂Hydrocarbon, replace hydrocarbon and branched-chain hydrocarbon, perhaps R wherein ₁And R ₂Constitute a N, the N-cyclic ether.Example comprises saturated or unsaturated alkyl, comprises alkylidene group; The alkyl that replaces is as hydroxyalkyl, alkoxyalkyl, alkoxyl group, aminoalkyl, dialkylaminobenzoic acid, haloalkyl, sulfonated alkyl, nitrated alkyl etc.; Branched-chain alkyl; Aryl and substituted aryl are as alkaryl, alkoxy aromatic yl, alkane hydroxyaryl, alkyl alkoxy aryl etc.Randomly, R ₁, R ₂, R ₃And R ₄In one of be hydrogen.The milligramequivalent number (MER) of per 100 gram silicate treatment agents in the silicate of handling, explain in more detail as following, between--from than low about 10 milligramequivalents of cation exchange capacity/100 grams of untreated silicon hydrochlorate～exceed about 30 milligramequivalents/100 grams than the cation exchange capacity of untreated silicon hydrochlorate.This polymer matrix composites shows in test and does not contain the improvement of polymer phase ratio on tensile modulus and modulus in flexure of handling silicate, and tensile strength can obviously not reduce again simultaneously.Here used " obviously reducing " is meant the reduction value of the deviation that surpasses statistics mensuration.

The invention still further relates to a kind of method for preparing above-mentioned polymer nanocomposite composition, but comprise the flowing mixture that forms a kind of polymeric amide and the silicate material of processing, and make at least about 50% but be not whole silicate " disassociation " (about more detailed description will be done below in this term).The silicate of this processing is with at least a kind of silicate material that the following ammonium ion of general formula was handled:

⁺NR ₁R ₂R ₃R ₄Wherein:

R ₁, R ₂, R ₃And R ₄Be independently selected from saturated or unsaturated C ₁～C ₂₂Hydrocarbon, replace hydrocarbon and branched-chain hydrocarbon, perhaps R wherein ₁And R ₂Constitute a N, the N-cyclic ether.Example comprises saturated or unsaturated alkyl, comprises alkylidene group; The alkyl that replaces is as hydroxyalkyl, alkoxyalkyl, alkoxyl group, aminoalkyl, dialkylaminobenzoic acid, haloalkyl, sulfonated alkyl, nitrated alkyl etc.; Branched-chain alkyl; Aryl and substituted aryl are as alkaryl, alkoxy aromatic yl, alkane hydroxyaryl, alkyl alkoxy aryl etc.Randomly, R ₁, R ₂, R ₃And R ₄In one of be hydrogen.The milligramequivalent number (MER) of per 100 gram silicate treatment agents in the silicate of handling, explain in more detail as following, between--from than low about 10 milligramequivalents of cation exchange capacity/100 grams of untreated silicon hydrochlorate～exceed about 30 milligramequivalents/100 grams than the cation exchange capacity of untreated silicon hydrochlorate.This polymer matrix composites shows in test and does not contain the improvement of polymer phase ratio on tensile modulus and modulus in flexure of handling silicate, and tensile strength can obviously not reduce again simultaneously.

Detailed Description Of The Invention

Polymeric amide of the present invention is synthetic line style polycarbonamide, it is characterized in that, exist as the whole part of polymer chain, the repetition carboxamide group of 2 carbon atoms at least at interval each other.This type polymeric amide comprises the technical polymkeric substance that is referred to as nylon usually, and they can be produced by the diamines and the diprotic acid of the repeating unit that comprises following general formula representative:

-NHCOR ₅COHNR ₆-

R wherein ₅Be at least two carbon atoms, the alkylidene group of preferred about 2～about 11 carbon atoms or at least about 6 carbon atoms, the arylidene of preferred about 6～about 17 carbon atoms; R ₆Be selected from R ₅And aromatic yl group.Also comprise copolyamide, terpolyamide and so on, can prepare, for example produce by the condensation between the diprotic acid mixture of hexamethylene-diamine and terephthalic acid and hexanodioic acid composition by currently known methods.Above-mentioned polymeric amide is technically to know, for example comprise: poly-(hexamethylene adipamide) (nylon 6,6), poly-(sebacoyl hexanediamine) (nylon 6,10), poly-(6I hexamethylene isoterephalamide), poly-(hexamethylene terephthalamide), poly-(pimeloyl heptamethylene diamine) (nylon 7,7), poly-(suberoyl octamethylenediamine) (nylon 8,8), poly-(azelaoyl the ninth of the ten Heavenly Stems two by) (nylon 9,9), poly-(sebacoyl the last of the ten Heavenly stems two by) (nylon 10,9), poly-(sebacoyl decamethylene diamine) (nylon 10,10), poly-[two (4-aminocyclohexyl) methane-1,10-decane carboxamide)], poly-(m xylylene adipamide), poly-(sebacoyl p dimethylamine), it is poly-that (paraphenylene terephthalamide 2,2,2-trimethylammonium hexanediamine), poly-(sebacoyl piperazine), poly-(poly P phenylene diamine terephthalamide), the multipolymer and the terpolymer of poly-(mpd-i) and above-mentioned polymkeric substance.Other polymeric amide comprises: nylon 4,6, nylon 6,9, nylon 6,10, nylon 6,12, Ni Long11, nylon 12, amorphous nylon, aromatics nylon and multipolymer thereof.

Other useful polymeric amide be the polymerization by amino acid and derivative such as lactan generate those.The example of these useful polymeric amide is poly-(hexanolactam) (nylon 6), poly-(4-aminobutyric acid) (nylon 4), poly-(7-aminoheptylic acid) (nylon 7), poly-(8-aminocaprylic acid) (nylon 8), poly-(9 aminononanoic acid) (nylon 9), poly-(the amino capric acid of 10-) (nylon 10), poly-(the amino undecanoic acid of 11-) (Ni Long11), poly-(12 amino dodecanoic acid) (nylon 12) etc.

Preferred polymeric amide is Vydyne ^Nylon, promptly a kind of poly-(hexamethylene adipamide) (nylon 6,6), it can make the matrix material (Vydyne that over-all propertieies such as a kind of tensile strength, tensile modulus and modulus in flexure meet this paper desired use ^Be the registered trademark of Solutia company).

The preferred molecular weight of polymeric amide is between 30,000～80,000D (weight average), and more preferably molecular weight is at least 40,000D (weight average).The polymeric amide weight-average molecular weight brings up to 55 from about 35,000, and 000D will cause the unexpected raising of toughness, be reflected on the notched izod Impulse Test Result.Though weight-average molecular weight brings up to 55 from about 35,000,000D causes the toughness of pure polymeric amide to improve seldom, and the amplification of same molecular weight under the situation of nano composite material, but can cause about 2 times of toughness amplification.Therefore, toughness amplification can be improved with respect to the amplification of pure polymeric amide in nano composite material.

In preferred embodiments, the amino end group of polymeric amide/acid end group ratio is greater than 1.More preferably, amino end group content is than the big at least 10mol% of carboxylic end group content.In a further preferred embodiment, the amino end group content of polymeric amide is than the big at least 20mol% of carboxylic end group content, and most preferably, the amino end group content of polymeric amide is than the big at least 30mol% of carboxylic end group content.In another embodiment, amino end group content is substantially equal to carboxylic end group content.

In the middle of embodiment preferred, comprise nylon 6, nylon 6,6 and blend and multipolymer.The scope of the ratio of nylon 6/ nylon 6,6 is between about 1/100～100/1 in the blend.Preferably, this scope is between about 1/10～10/1.In the multipolymer, the scope of the ratio of nylon 6/ nylon 6,6 is between about 1/100～100/1.Preferably, this scope is between about 1/10～10/1.

Randomly, this nanocomposite composition comprises at least a kind of other polymkeric substance.The example of suitable polymers comprises: polyethylene oxide, polycarbonate, polyethylene, polypropylene, poly-(the rare nitrile of vinylbenzene-third), poly-(third rare nitrile-butadiene-styrene), poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(terephthalic acid 1, ammediol ester), poly-(naphthalene dicarboxylic acids glycol ester), poly-(ethylene glycol terephthalate-copolymerization-terephthalic acid cyclohexanedimethanoester ester), polysulfones, poly-(phenylene oxygen base) or poly-(phenylate), poly-(hydroxy-benzoic acid-copolymerization-ethylene glycol terephthalate), poly-(hydroxy-benzoic acid-copolymerization-hydroxyl naphthenic acid), poly-(esteramides), poly-(ether imide), poly-(diphenyl sulfide), poly-(paraphenylene terephthalamide's phenylenediamine).

This mixture can comprise various common optional member as polymeric additive.The examples of such optional composition comprises tensio-active agent, nucleator, coupling agent, filler, impact modifying agent, chain extension agent, softening agent, compatilizer, tinting material, demoulding lubricant, static inhibitor, pigment, fire retardant or the like.

The appropriate filler example comprises carbon fiber, glass fibre, kaolin, wollastonite and talcum powder.The example of appropriate compatilizer comprises the hydrocarbon polymer of sour modification, as maleic anhydride grafted polyethylene (propylethylene), maleic anhydride grafted polypropylene, maleic anhydride grafted ethene-butylene-styrene segmented copolymer.The example of suitable demoulding lubricant comprises alkylamine, stearylamide and two-or three-aluminum stearate.

The example of suitable impact modifying agent comprises ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene, methacrylic ester-butadiene-styrene (having cone-shell type state), through or without carboxy-modified poly-(butyl acrylate), poly-(ethylene-acrylate), poly-(ethylene methacrylate), poly-(ethylene acrylic), poly-(ethylene-acrylate) ionomer, poly-(ethylene-methyl acrylate-vinylformic acid) terpolymer, poly-(styrene butadiene) segmented copolymer, poly-(styrene-butadiene-styrene) ternary block polymer, poly-(styrene-ethylene/butylene-styrene) ternary block polymer and poly-(styrene-ethylene/butylene-styrene carboxylate) ternary block polymer.

Silane coupling agent is technically to know, and can be used for the present invention.The example of suitable coupling agents comprises the octadecyl Trimethoxy silane; γ-An Bingjisanyiyangjiguiwan; γ-An Bingjisanjiayangjiguiwan; γ-aminopropyl phenyl dimethoxy silane; γ-Racemic glycidol oxygen propyl group tripropoxy silane; 3; 3-epoxycyclohexyl ethyl-Trimethoxy silane; γ-propionamido Trimethoxy silane (trithoxysilane); N-trimethoxy-silylpropyl-N (β-aminoethyl) amine; the trimethoxysilyl heptadecyl-amine; trimethoxysilyl-2-chloromethyl phenyl ethane; trimethoxysilylethylgroup group benzenesulfonyl nitrine; chlorination (N-trimethoxy-silylpropyl-N; N; the N-TMA (TriMethylAmine)); chlorination (N-(trimethoxy-silylpropyl)-N-methyl-N, N-diallyl ammonium); trimethoxy-silylpropyl meat silicon ester; 3-sulfydryl propyl group-Trimethoxy silane; 3-isocyanato-propyl group-triethoxyl silane etc.Preferred silane is γ-An Bingjisanyiyangjiguiwan.Optional join dosage of silane coupling agent in the polymer composites between about 0.5～about 5wt% of layered silicate.Preferred silane coupling agent consumption is between about 1～about 3wt% of matrix material laminate silicate.

In another embodiment, nanocomposite composition also comprises a kind of like this composition, and wherein this polymeric amide end group is bonded on the silicate surfaces after the processing by silane coupling agent.

Silicate material of the present invention is selected from layered silicate and fiber-like chain silicate, also comprises lobate silicate.The example of fiber-like chain silicate comprises the chain mineral substance, for example sepiolite and U.S.'s atlapulgite, preferably sepiolite.This type of silicate for example is described among the Japanese patent application Kokoku 6-84435, and 1994-10-26 is open.The example of layered silicate comprises stratiform terre verte ore deposit, if you would take off stone, nontronite, beidellite, volkonskoite, Laponite ^Synthetic hectorite, natural water pyroxene, talcum powder, hot montmorillonite, natural water glass and fibrous morphology crystals; Vermiculite; And the like.Other useful materials comprise the layered illite mineral, as the mixture of illite and illite and a kind or multiple above-mentioned clay pit.Preferred layered silicate is that stone, nontronite, beidellite, volkonskoite, Laponite if you would be taken off in the terre verte ore deposit ^Synthetic hectorite, natural water pyroxene, talcum powder, hot montmorillonite, natural water glass and fibrous morphology crystals.

Be applicable to that layered silicate material of the present invention is technically to know, and is also referred to as " swellable stratified material " sometimes.Further describing of the thin slice that forms during about disclosed layered silicate and with the polymeric amide melt-processed can be referring to International Patent Application WO 93/04117, and be for referencial use in these receipts.Layered silicate material generally has the many plane layers that are arranged in a kind of cohesion coplanar structure, and the binding ratio interlayer of its inside, middle level is in conjunction with more firm, so the increase that shows interfloor distance when handling.

Layered silicate material need be handled to increase interlayer swelling and/or spacing with ammonium ion according to the method that below will describe in more detail, and this will help improving the performance that the present invention handles silicate.Term as used herein " interlayer spacing " is meant the distance that occurs between each laminar surface when they accumulate in the material of processing back, but does not reach the stage that any delamination (scaling off) takes place as yet.Preferred clay material generally comprises interlayer-or commutative-positively charged ion, as Li ⁺, Na ⁺, Ca ²⁺, K ⁺, Mg ²⁺Deng.When being in this state, the interfloor distance that this class material has generally is equal to or less than about 4 dusts and delamination only takes place on not half in host's polymer melt, although stood mixing effect.In disclosed embodiment, the treated cation agent is a kind of ammonium chemical seed, can with such as Li ⁺, Na ⁺, Ca ²⁺, K ⁺, Mg ²⁺And so on interlayer cation exchange, thereby improve the delamination of layered silicate.

Processing silicate of the present invention is a kind of like this silicate material, and as mentioned above, it is handled through at least a kind of following ammonium ion of general formula

⁺NR ₁R ₂R ₃R ₄Wherein:

R ₁, R ₂, R ₃And R ₄Be independently selected from saturated or unsaturated C ₁～C ₂₂Hydrocarbon, replace hydrocarbon and branched-chain hydrocarbon, perhaps R wherein ₁And R ₂Constitute a N, the N-cyclic ether.Example comprises saturated or unsaturated alkyl, comprises alkylidene group; The alkyl that replaces is as hydroxyalkyl, alkoxyalkyl, alkoxyl group, aminoalkyl group, dialkylaminobenzoic acid, haloalkyl, sulfonated alkyl, nitrated alkyl etc.; Branched-chain alkyl; Aryl and substituted aryl are as alkaryl, alkoxy aromatic yl, alkane hydroxyaryl, alkyl alkoxy aryl etc.Randomly, R ₁, R ₂, R ₃And R ₄One of be hydrogen.The mixture of two or more ammonium ions is also at the row of the present invention's consideration.

In one embodiment of the present invention, R ₁Be selected from the hydro carbons of hydrogenated tallow, unsaturated tallow or at least 6 carbon atoms, and R ₂, R ₃And R ₄Contain 1～18 carbon atom independently.Tallow mainly is made up of the octadecyl chain, contains a small amount of homologue, average degree of unsaturation 1～2.It roughly consists of, 70%C ₁₈, 25%C ₁₆, 4%C ₁₄And 1%C ₁₂In another embodiment of the invention, R ₁And R ₂Be independently selected from the hydro carbons of hydrogenated tallow, unsaturated tallow or at least 6 carbon atoms, and R ₃And R ₄Contain 1～12 carbon atom independently.

Suitable R ₁, R ₂, R ₃And R ₄The example of group is an alkyl, as methyl, ethyl, octyl group, nonyl, the tertiary butyl, ethylhexyl, neo-pentyl, sec.-propyl, sec-butyl, dodecyl etc.; Alkenyl is as 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl etc.; Cycloalkyl is as cyclohexyl, cyclopentyl, ring octyl group, suberyl etc.; Alkoxyl group is as oxyethyl group; Hydroxyalkyl; Alkoxyalkyl is as methoxymethyl, ethoxyl methyl, butoxymethyl, propoxy-ethyl, pentyloxy butyl etc.; Aryloxyalkyl group and aryl aryloxycarboxylic are as Phenoxyphenyl, phenoxymethyl, phenoxy group decyl, phenoxy group octyl group etc.; Aralkyl is as benzyl, styroyl, 8-phenyl octyl group, 10-phenyl decyl etc.; Alkaryl such as 3-decyl phenyl, 4-octyl phenyl, nonyl phenyl etc.

The preferred ammonium that is used to handle silicate material comprises following salt, as dimethyl two (hydrogenated tallow) ammonium, dimethyl benzyl hydrogenated tallow ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium, trimethylammonium hydrogenated tallow ammonium, methyl-benzyl two (hydrogenated tallow) ammonium, N, N-2-cyclobutoxy group two (hydrogenated tallow) ammonium, trimethylammonium tallow ammonium, methyl dihydroxy ethyl tallow ammonium, octadecyl methyl dihydroxy ethyl ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium and their mixture.Particularly preferred ammonium comprises quaternary ammonium, as dimethyl two (hydrogenated tallow) ammonium, dimethyl benzyl hydrogenated tallow ammonium, methyl dihydroxy ethyl tallow ammonium, octadecyl methyl dihydroxy ethyl ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium and their mixture.

Processing with ammonium ion carries out also is called " treated cation ", comprises by ion-exchange ion is incorporated in the silicate material.At silicate material is in the embodiment of layered silicate, and the treated cation agent can be incorporated into every layer of stratified material, almost in the gap between every layer or the most of layer, thereby the laminated layer of acquisition is had less than about 20 particulate thickness.Preferred these laminated layers are thick less than about 8 particles, and it is thick to be more preferably less than about 5 particles, and most preferably from about 1 or 2 particle is thick.

The MER content that silicate after the processing has is, from than low about 10 milligramequivalents of cation exchange capacity/100 grams of untreated silicon hydrochlorate～exceed about 30 milligramequivalents/100 grams than the cation exchange capacity of untreated silicon hydrochlorate.Described MER is meant the treatment agent milligramequivalent number in per 100 gram silicate.Every kind of untreated silicon hydrochlorate has certain cation exchange capacity, and just per 100 gram silicate have the positively charged ion milligramequivalent number that can be used for exchanging.For example, it is about 95 that the cation exchange capacity of layered silicate montmorillonite can reach, and the exchange capacity of sepiolite is between about 25～40.When the MER that handles back silicate substantially exceeds cation exchange capacity, will there be excessive treated cation agent, can be for reacting with polymeric amide.This excessive meeting causes the deterioration of polymeric amide performance.

MER is high more, and the silicate mesosilicic acid salts contg of processing is just low more.Therefore, a certain the 1st nano composite material sample may have with the 2nd nano composite material sample compares higher " processing silicate " content, hangs down silicate content but have, and this is because the 1st sample has the cause of the MER higher than the 2nd sample.

Be significantly less than its exchange capacity if handle the MER value of back silicate, for example for preferred montmorillonite, MER is lower than at about 85 o'clock, and then the treated cation agent content is inevitable very few, so that does not reach useful treatment effect.If it is about 125 that MER surpasses, then excessive ammonium ion will diminish the performance of nylon.Preferably, when the exchange capacity of the montmorillonite that is untreated was 95, its cation exchange capacity of handling the back layered silicate should be between about 85～about 125.

The content of composition mesosilicic acid salt is about 0.1～12wt% of this matrix material.Regulate this content, the raising that the composite polymer matrix that can make is provided shows in test tensile modulus and modulus in flexure, tensile strength does not significantly reduce simultaneously.Preferably, tensile modulus and modulus in flexure improve at least about 10%.More preferably, tensile modulus and modulus in flexure improve at least about 20%.Silicate content is very few, and the raising of desired tensile modulus and modulus in flexure can't be provided.Silicate content is too much, and the tensile strength of the polyamide compoiste material that is provided will reduce.Have, the crystallizing field that is preferably polymeric amide in the nanocomposite composition is less than 1.0 μ m again.

The particle size of silicate should be as the criterion to help reaching best contact the between polymkeric substance and the silicate.The scope of particle size can be from about 10 μ m to about 100 μ m.Preferably, particle size is between about 20～80 μ m.Most preferably, particle size is lower than about 30 μ m, for example can pass through those of 450 eye mesh screens, and like this, the polymer nanocomposites that is obtained will have the performance of improvement.

Randomly, this silicate can be handled with a kind or the following ammonium ion of multiple general formula

⁺NR _aR _bR _cR _dR wherein _a, R _bAnd R _cIn at least 1 be hydrogen (H), and R _dBe selected from saturated or unsaturated C ₁～C ₂₂Hydrocarbon, replacement hydrocarbon and branched-chain hydrocarbon.Example comprises saturated or unsaturated alkyl, comprises alkylidene group; The alkyl that replaces is as hydroxyalkyl, alkoxyalkyl, alkoxyl group, aminoalkyl, dialkylaminobenzoic acid, haloalkyl, sulfonated alkyl, nitrated alkyl etc.; Branched-chain alkyl; Aryl and substituted aryl are as alkaryl, alkoxy aromatic yl, alkane hydroxyaryl, alkyl alkoxy aryl etc.Because above-mentioned ammonium ion is a kind of quaternary ammonium in the present embodiment, R _dThe definition of group basically with ammonium ion in R ₄Definition identical, the relevant R that therefore provides above ₄The example of group equally also is R _dThe example of group.Randomly, R _dGroup also can comprise carboxylic moiety, so this ammonium ion

⁺NR _aR _bR _cR _dBe amino acid, 12-aminolauric acid ammonium for example.Especially preferred in this kind embodiment is that the amino end group of polymeric amide/acid end group ratio is greater than 1.

Preferred mixture comprises at least a kind of following compounds: no matter dimethyl two (hydrogenated tallow) ammonium, methyl dihydroxy ethyl tallow ammonium, dimethyl benzyl hydrogenated tallow ammonium and/or dimethyl (ethylhexyl) hydrogenated tallow ammonium are used in combination separately or with 12-aminolauric acid ammonium and all can.

Randomly, this silicate can be further handled with azine cationic dyestuff such as Ni Ge or anthracene dyes.Described cationic dyestuff also can provide fixation and even dyeing effect except the embedding that promotes polymer molecule.

Also wish to have a kind of like this polymer composites, it can provide desired intensity and flexible, and weight is light again simultaneously.This can reach by the content that reduces nano composite material mesosilicic acid salt as far as possible.Preferred nano composite material comprises the about 0.1～about 12.0wt% silicate that accounts for matrix material.Most preferred nano composite material comprises the about 0.5～about 6.0wt% silicate that accounts for matrix material.

In the 1st kind of embodiment of the present invention, nanocomposite composition adopts the three-step approach preparation.But the 1st step comprised the polymeric amide of preparation polymer melt form and the flowing mixture that silicate material is formed.The 2nd step comprised and makes the silicate material of handling at least 50% but be not to dissociate fully.Term as used herein " disassociation " is to instigate the silicate material delamination of handling or be separated into to comprise one by one or the submicron order structure of a plurality of junior units.In the embodiment of using layered silicate, this disassociation step comprises that making the silicate material delamination of handling is to comprise one by one the perhaps submicron order thin slice of many substratums.Under the situation of using the fiber-like chain silicate, this disassociation step comprises to be separated into the silicate material of handling to comprise one by one or the Sub-micro Fibers shape structure of a plurality of junior units.

But the flowing mixture of mentioning in the mixture preparation process is meant that the silicate material that dissociative was handled is dispersed into the mixture of submicron order size.Polymer melt is a kind of like this melt processable polymers or polymeric blends, and it is heated to sufficiently high temperature, is enough to cause submicron order blended degree thereby viscosity is reduced to.This processing temperature should be high at least to the fusing point of used polymeric amide and be lower than polymeric amide and the degradation temperature of silicate organic agent.Actual extruding machine temperature can be lower than the fusing point of used polymeric amide, itself also can generate heat because flow.This processing temperature should be high enough to make polymkeric substance to remain the polymer melt state during process is carried out.Under the situation of crystalline polyamide, this temperature should be higher than the fusing point of polymkeric substance.For example, the fusing point of typical nylon 6 then can be equal to or greater than in temperature and carry out fusion in about 225 ℃ extruding machine, for example between about 225 ℃～about 260 ℃ about 225 ℃.For nylon 6,6, preferably use usually between about 260 ℃～about 320 ℃ temperature.

But can adopt traditional method preparation flowing mixture.For example, but flowing mixture can adopt traditional polymkeric substance-additive blending equipment to prepare, wherein, polymkeric substance is heated to the temperature that is enough to form polymer melt, lump together with the silicate material of the granular or Powdered processing of desired number in suitable mixing machine then, wherein mixing machine for example is extruding machine, Banbury mixer (Banbury ^Type), Brabender ^Type mixing machine, Farrell continuous mixer etc.

In one embodiment, but flowing mixture can contain the silicate masterbatch of handling by polymeric amide and ready-formed is mixed together and prepares.Masterbatch comprises silicate and the polymer support of handling.The selection of the content of the silicate material of handling in the masterbatch and masterbatch consumption should make the silicate that has the processing of requirement content in the final nanocomposite composition.Be fit to do that the examples of polymers of carrier polymer comprises polymeric amide, ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene, ethylene-propylene acetoacetic ester, ethylene methacrylic acid ethyl ester or ethylene methacrylate in the masterbatch.Example comprises Iotek ^Ionomer and Escor ^The ATX acid ter-polymer, the two is supplied by Exxon Corporation.The polyamide polymer that is fit to do carrier polymer comprises nylon, as nylon 6, nylon 6,6, nylon 4,6, nylon 6,9, nylon 6,10, nylon 6,12, Ni Long11, nylon 12, amorphous nylon, aromatics nylon and multipolymer thereof.But the polymkeric substance of carrier can be identical or different with the polymeric amide of flowing mixture.For example, 2 kinds of polymkeric substance can be polymeric amide, and particularly nylon 6,6, but can have identical or different molecular weight.The preferable weight-average molecular weight of masterbatch carrier polymer is between about 5, and 000D～about 60,000D.The most preferably weight-average molecular weight of masterbatch carrier polymer is between about 10, and 000D～about 40,000D.In this embodiment, the disassociation step of the inventive method as following described, can take place at least in part by the forming process of masterbatch, and like this, but the disassociation step just can be carried out before the flowing mixture preparation.Therefore to know, each procedure of processing (for example, preparation and disassociation) though can precedence sequentially, side by side or according to the combination of these 2 kinds of modes carry out.In the 2nd step, but flowing mixture forms the dispersing nanometer composite structure of being made up of disassociation silicate, then cooling through thorough mixing in polymer melt.The disassociation of silicate can realize by it is applied shearing action with effective shearing rate.Term as used herein " effectively shearing rate " is a kind of like this shearing rate, it can effectively promote the silicate disassociation, the composition of formation is comprised: polyamide matrix, silicate basically equably wherein is scattered here and there, but the single cell of silicate (for example, thin slice or fibrous chain) is not destroyed again basically.

Any method that can be used to but flowing mixture or any polymer melt are applied shearing action all can be used.Shearing action can be provided by any proper method, for example by mechanical means, thermal shocking, pressure change or ultrasonic wave.Preferably, the flowable polymer mixture adopts mechanical means to shear, and wherein a part of melt another part with respect to mixture under the forcing of mechanical means flows through, and used mechanical means for example are agitator, Banbury mixer (Banbury ^Type), Brabender ^Type mixing machine, Farrell ^Continuous mixer and extruding machine etc.Most preferably, mixture is accepted repeatedly (multiple tracks or multipass) shearing.Except strengthening the shear effect, also can take to prolong the residence time and improve use properties by repeatedly shearing.Another kind of program adopts thermal shocking, and wherein the principle of shearing action is, by alternately raising or reducing mixture temperature, causes thermal expansion repeatedly, thereby produces the internal stress that causes shearing action.In other programs, shearing action is to adopt voltage-transforming method, realizes by flip-flop pressure; Perhaps adopt ultrasonic technology, rely on cavitation effect or resonance effect to cause the partial confounding compound to vibrate or be subjected to the excitation of out of phase, thereby make it to be subjected to shearing action.These methods that flowable polymer mixture and polymer melt are implemented to shear only are the representative example in the process useful, and any technical method that becomes known for shearing flowable polymer mixture and polymer melt all can be used.

Shearing can be by realizing polymeric aggregate from the introducing of extruding machine (single screw rod or twin screw) end and at the polymkeric substance that the extruding machine the other end is collected after shearing.Preferred Bitruder is to rotate full engagement type in the same way, as ZSK series, is made by Werner and Pfleiderer company.Silicate can join the Bitruder from feed throat or at the downstream row gas port.Preferable methods is that from the adding of downstream row gas port, the composite polymer of producing like this has the performance of improvement with silicate.

Randomly, can increase the additional work step that adds and gather, for example solid state polymerization is wherein kept some hrs through mixing pellet under the high temperature lower than melting point polymer.For example, typical solid phase polymerization conditions is, solid polymer was about 2～5 hours of about 200 ℃～240 ℃ scope internal heating.Described additional processing step can improve molecular weight and improve toughness, ductility and the tensile strength of nano composite material.

Another kind of optional procedure of processing can be a heat treatment step, wherein can improve the nylon molecule and is embedded into process in the silicate sturcture by composition is heated.Described heat treatment step comprises that composition heats about 2～5 hours time in about 200 ℃～240 ℃ temperature.Heat treatment step can randomly combine with the disassociation step and carry out, that is, prolong the residence time of mixture in mixing machine or extruding machine, thereby make it to be subjected to thermal treatment under molten state.

Another kind is preferred, continuous mixer is Farrel continuous mixer (FCM).At composite material by adopting Vydyne ^Under the situation of 21 nylon, preferred melt temperature is between about 275～315 ℃, most preferably from about 275～295 ℃.

The polymer melt that comprises nanometer-dispersive disassociation silicate material also can be extruded preparation by reaction, wherein, silicate material at first is distributed in liquid state or the solid monomer with aggregate form or nanometer size in the equipment of extruding machine and so on, and this monomer carries out polymerization then.Alternatively, polymkeric substance can first granulation and is carried out dry blending with silicate material after handling, and composition can heat until polymer melt in mixing machine then, but forms flowing mixture.

The method for preparing nano composite material is preferably carried out under the secluding air condition, for example in the presence of rare gas element, in argon gas, neon or nitrogen.This method can be implemented by intermittence or discontinuous mode, and for example this method is carried out in encloses container.Alternatively, this method can be implemented in single processing district by continuous mode, for example adopts the extruding machine of basic secluding air, perhaps carries out in this type of reaction zone of a plurality of serial or parallel connections.

In another embodiment of the present invention, but the method for preparing polymer nanocomposite composition comprises and at first prepares the flowing mixture of being made up of polymeric amide, at least a kind of monomer and the silicate material handled; Make at least 50% but be not the silicate material disassociation of all handling; Make this monomer polymerization.Know that polymerization procedure can side by side or sequentially be implemented with one or more other steps in the method for this embodiment.Preferably, at least 1 of the 3rd embodiment kind of monomer comprises such as ε-Ji Neixianan, laurolactam and corresponding lactone thereof.

In another embodiment of the present invention, but the method for preparing polymer nanocomposite composition comprises the flowing mixture of preparation polymeric amide and the silicate material composition of handling; Make at least about 50% but be not the silicate material disassociation of all handling; And add the described polymeric amide of some amount again, most preferably during described disassociation step.

After the embodiment of having implemented each above-mentioned preparation polymer nanocomposite composition method, can further implement additional step or processing, solid state polymerization for example, perhaps by prolong composition in extruding machine the residence time and get rid of condensation product water and realize additional melt polymerization step.

The present composition can be made into but is not limited to: forms such as fiber, film or moulded parts.

Embodiment

Embodiment given below is used for further illustrating the present invention, and limits the scope of claim never in any form.

All used in following example nylon are nylon 6,6.Unless point out in addition, otherwise used nylon is the nylon h that Solutia company makes, its performance is listed in the table of following various nylon types.Unless point out in addition, otherwise all percentage number averages refer to weight.% viscosity is the gross weight of Pristine clay in the final matrix material, can be Pristine or through pretreated.Tensile strength and Young's modulus are pressed ASTM method D638 and are measured, and with kpsi (kip/square inch) and Mpa (MPa) report.Modulus in flexure is pressed ASTM method D790 and is measured, and with kpsi and Mpa report.

Test with " C " numbering is a controlled trial.

Clay type table 1

Below listed all silicate be the polynite that Southern clay product company produces except that other has indicating, its clay exchange capacity is about 95.Below listed processing be that ammonium is handled.Project A-H is in the same old way, and the example of the project I-AA silicate that to be quaternary ammonium of the present invention handle.Project ammonium treatment agent MERA is untreated--the B hectorite, be untreated--C dicyclohexyl 100D 12-aminolauric acid 90E dimethyl two (hydrogenated tallow) 140F methyl-benzyl hydrogenated tallow 140G dimethyl two (hydrogenated tallow) 140H methyl-benzyl two (hydrogenated tallow) 130I trimethylammonium tallow 125J dimethyl two (hydrogenated tallow) 80K dimethyl two (hydrogenated tallow) 85L trimethylammonium hydrogenated tallow 125M dimethyl (ethylhexyl) hydrogenated tallow 90N dimethyl (ethylhexyl) hydrogenated tallow, add wetting agent 90O dimethyl (ethylhexyl) hydrogenated tallow, add wetting agent 90P diethoxymethyl tallow 90Q dimethyl two (hydrogenated tallows), the fine grainding clay has additional 95

Add the poly-R octadecane methyl diethoxy 95S trimethylammonium C of work step ₂₂110T dimethyl two (hydrogenated tallow), better discrete form 95U dimethyl two (hydrogenated tallow), the above-mentioned project U of finished 95V, add 1% tensio-active agent 95W dimethyl two (hydrogenated tallow) 125X dimethyl, two (hydrogenated tallows), fine grainding clay 95Y N, N-2-butoxy two (hydrogenated tallow) 90Z dimethyl two (hydrogenated tallow) 95AA dimethyl benzyl hydrogenated tallow 95

Clay type table 2

Project GG-NN is the example of using more than the polynite of the mixture process of a kind of quaternary ammonium or a kind of quaternary ammonium and ammonium of the present invention otherwise indicated.Project OO-TT is the example of tertiary amine silicate of the present invention.80/20 blend of project ammonium treatment agent MERGG1 sepiolite and terre verte is with methyl benzyl 45

Base two (hydrogenated tallows) and dimethyl two (hydrogenated tallow)

75/25 blend handled HH 2-ethylhexyl dimethyl hydrogenation tallow and dimethyl 2 95

The 50/50 blend II 2-ethylhexyl dimethyl hydrogenation tallow and the dimethyl 2 95 of (hydrogenated tallow)

The 25/75 blend JJ 2-ethylhexyl dimethyl hydrogenation tallow and the dimethyl 2 95 of (hydrogenated tallow)

95 of the 75/25 blend KK 12-aminolauric acid of (hydrogenated tallow) and dimethyl two (hydrogenated tallow)

10.5/89.5 95 of blend LL 12-aminolauric acid and dimethyl two (hydrogenated tallow)

95 of 16/84 blend MM 12-aminolauric acid and dimethyl two (hydrogenated tallow)

5/95 blend NN 12-aminolauric acid and dimethyl (ethylhexyl) hydrogenation 95

16/84 blend OO dimethyl coco group 95PP dimethyl hydrogenation tallow 95QQ dimethyl tallow 95RR 2-ethylhexyl hydrogenated tallow dimethyl 95SS dimethyl hydrogenation tallow 95TT ethoxy octadecyl 125 of tallow

¹The unexamined patent

The nylon type list

Nylon amino end group acid end group ammonia/sour M _w

a 55 60 0.92 35

b 35 60 0.58 42

c 40 40 1.00 50

d 15 50 0.30 62

e 80 50 1.60 31

f 125 70 1.79 21

g 31 60 0.52 44

h 45 70 0.64 35

Amino end group and acid end group are the equivalents of unreacted ammonia functional group and acid functional group in the nylon.M _wThe weight-average molecular weight that records is represented with dalton (D).

Listed the matrix material of 4 kinds of dissimilar processing clays in the table 1.Adopt not reference examples (correlated 2-C, 3-C and 4-C and 1-C when comparing with (promptly correlated) sample not argillaceous of front with the clay of ammonium processing of the present invention, and contrast 6-C, 7-C and 8-C and 5-C), demonstrate the normal reduction of anti-intensity, but reference examples 3-C is an exception, and it and 1-C do not demonstrate the variation of tensile strength when comparing.

Test 1-C～4-C processes with the ZSK Bitruder, and test 5-C～8-C processes with the FCM mixing roll.

Table 1

Controlled trial

Anti-the opening of (the not clay of handling with quaternary ammonium) test number clay resists a deflection fusing point

Type (%) intensity modulus modulus (℃) (MPa) (MPa) 1-C of kpsi kpsi kpsi (MPa)--0 11.6 412 425 286

(80.3) (2860) (2940)2-C A 3.6 11.2 449 463 285

(77.7) (3110) (3210)3-C A 6.5 11.6 466 463 286 (80.7) (3230) (3210)4-C B 7.1 11.3 481 482 286 (78.1) (3330) (3340)5-C -- 0 11.6 445 436 280 (80.7) (3080) (3020)6-C C 2.9 9.65 494 481 291

(66.9) (3420) (3330)7-C C 8.8 8.08 576 568 293

(56.0) (3990) (3940)8-C D 4.8 9.11 580 550 285

(63.1) (4020) (3810)

Listed in the table 2 with 4 kinds of matrix materials different, that MER crosses above 125 quaternary ammonium processing clay treatment.These matrix materials are processed with the ZSK mixing roll.All reference examples all demonstrate the reduction of tensile strength when comparing with the sample of the front that does not add clay (corresponding).

Table 2

Controlled trial

Anti-the opening of (MER surpasses 125 processing clay) test number clay resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)9-C -- 0 11.3 417 432 286

(78.3) (2980) (2990)10-C G 13.3 9.78 610 613 286

(67.8) (4230) (4250)11-C -- 0 11.2 423 416 277

(77.4) (2930) (2880)12-C E 4.2 10.6 520 455 277

(73.4) (3600) (3150)13-C E 4.4 10.6 500 471 279

(73.2) (3460) (3260)14-C E 9.6 9.48 553 501 285

(65.7) (3830) (3470)15-C -- 0 11.3 430 445 286

(78.4) (2980) (3080)16-C H 11.6 7.47 582 573 291

(51.8) (4030) (3970)17-C H 11.8 7.73 561 549 285

(53.6) (3890) (3760)18-C H 6.0 10.6 523 516 288

(73.1) (3620) (3580)19-C H 11.8 5.41 593 571 295

(37.5) (4110) (3960)20-C H 6.0 10.5 510 507 283

(72.6) (3530) (3510)21-C H 8.9 10.3 555 541 289

(71.1) (3850) (3750)22-C -- 0 12.0 424 432 285

(82.9) (2940) (3850)23-C F 7.3 11.2 557 555 287

Listed in the table 3 the clay preparation handled from 13 kinds of different quaternary ammoniums, with the mixing mach matrix material of FCM.When not conforming to the nylon of handling clay and compare, except sample 35,36 and 47, all matrix materials all demonstrate the increase of tensile modulus and modulus in flexure, and tensile strength does not reduce.Yet if consider the standard error of sample 35,36 and 47, these samples might have the tensile strength that is equal to or higher than its control sample.

Table 3

Anti-the opening of the clay experiment clay that quaternary ammonium is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)24-C -- 0 11.6 445 436 280

(80.7) (3080) (3020)25 P 3.0 12.5 580 539 292

(86.3) (4020) (3740)26 P 5.8 11.6 657 633 293

(80.7) (4550) (4390)27 S 3.3 12.1 524 524 291

(84.0) (3630) (3630)28 T 5.4 12.0 596 558 288

(83.2) (4130) (3870)29-C -- 0 11.4 443 425 285

(78.7) (3070) (2940)30 I 1.8 11.6 509 470 286

(80.4) (3530) (3260)31 R 0.6 12.4 482 457 286

(85.9) (3340) (3170)32 M 0.6 11.5 457 438 285

(79.8) (3170) (3040)33 N 1.6 12.1 504 474 286

(83.9) (3490) (3280)34-C -- 0 11.5 463 429 286

(79.5) (3190) (2960)35 J 1.0 10.3 ¹453 448 284

(71.5) (3140) (3100)36 J 3.3 11.3 ²500 496 288

(78.5) (3460) (3440)37 L 2.5 12.0 525 502 284

(83.4) (3640) (3480)38 L 3.3 11.8 535 516 286 ¹+1.44 ²+0.98 (81.6) (3710) (3580)

Table 3, continuous

Anti-the opening of the clay experiment clay that quaternary ammonium is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)39 W 1.7 11.8 462 474 285

(81.8) (3200) (3280)40 W 4.7 11.7 523 507 286

(80.9) (3620) (3510)41 K 0.8 11.7 449 450 285

(80.9) (3110) (3120)42 K 2.3 11.8 474 476 286

(81.8) (3280) (3300)43 Y 2.6 11.7 476 482 285

(81.1) (3300) (3340)44 Y 4.7 12.1 546 525 285

(83.9) (3780) (3640)45-C -- 0 11.5 469 428 281

(79.8) (3250) (2970)46 Q 1.4 12.1 513 478 291

(83.6) (3560) (3310)47 Q 5.7 11.4 ¹614 559 294 ¹+0.4 (79.3) (4260) (3870)

Listed the matrix material of handling from the 8 kinds of different quaternary ammoniums clay preparation, that use the machining of ZSK twin-screw extrusion in the table 4.When not containing the sample of handling clay and compare, all matrix materials all demonstrate the increase of tensile modulus and modulus in flexure, and tensile strength does not reduce.

Table 4

Anti-the opening of the clay experiment clay that quaternary ammonium is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)48-C -- 0 11.5 446 431 285

(79.4) (3090) (2990)49 M 1.7 11.7 480 476 286

(81.1) (3330) (3300)50 M 4.1 12.0 543 532 287

(83.2) (3760) (3690)51 N 2.4 11.6 484 502 287

(80.3) (3350) (3480)52 N 4.1 11.5 508 470 287

(79.7) (3520) (3260)53 O 1.9 11.6 462 470 287

(80.1) (3200) (3260)54 O 4.0 11.5 488 494 287

(79.3) (3380) (3420)55-C -- 0 12.0 424 432 285

(82.9) (2940) (2990)56 U 7.5 12.1 525 520 286

(83.6) (3640) (3600)57 V 7.0 12.1 516 521 285

(84.0) (3580) (3610)

Table 4, continuous

Anti-the opening of the clay experiment clay that quaternary ammonium is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)58-C -- 0 11.5 445 431 287

(80.0) (3080) (2990)59 U 2.1 11.8 475 483 287

(82.1) (3290) (3350)60 U 5.2 11.6 560 540 287

(80.1) (4020) (3740)61 U ¹ 5.3 12.1 575 555 287

(83.4) (3970) (3830)62 U ² 5.3 12.3 564 539 288

(84.8) (3890) (3720)63-C -- 0 11.31 430 445 286

(78.4) (3880) (3080)64 X 4.9 11.76 606 568 288

(81.5) (4200) (3940)65 X 6.4 11.27 573 604 295

(78.1) (3970) (4190)66-C -- 0 11.55 423 424 286

(79.7) (2930) (2930)67 Q 3.0 11.63 487 456 286

(80.6) (3380) (3160)68 Q 6.5 11.61 514 515 288

(80.5) (3560) (3570)69 Q 11.1 11.60 659 579 290

(80.4) (4570) (4010)70 Q 11.4 12.47 782 622 289

(86.4) (5420) (4310) 1. sample 60 the 2nd time by ZSK mixing roll 2. samples 60 the 3rd time by the ZSK mixing roll

Table 4, continuous

Anti-the opening of the clay experiment clay that quaternary ammonium is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)71-C -- 0 11.3 459 446 281

(77.9) (3170) (3080)72 AA 3.8 12.5 552 487 282

(86.2) (3810) (3360)73 AA 6.8 12.2 562 520 282

(84.1) (3880) (3590)74 AA 8.9 11.5 612 553 282

(79.3) (4220) (3810)

Use following 4 kinds of nylon 6,6 products to prepare matrix material in the table 5: the nylon d shown in the nylon type table, nylon c, nylon b, nylon h.Above-mentioned nylon is to list by the order that reduces molecular-weight average.These matrix materials are processed with the ZSK Bitruder.

When not containing the sample of handling clay and compare, all matrix materials all demonstrate the increase of tensile modulus and modulus in flexure, and tensile strength does not reduce.

Table 5

Change anti-the opening of nylon type test number clay and resist a deflection nylon fusing point

Type (%) intensity modulus modulus type (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)75-C -- 0 11.3 427 430 d 291

(78.4) (2960) (2980)76 Q 7.3 12.4 600 559 d 290

(86.0) (4160) (3870)77-C -- 0 11.6 402 435 c 289

(80.4) (2790) (3010)78 Q 7.6 12.6 640 577 c 289

(87.3) (4440) (4000)79-C -- 0 11.6 405 434 b 288

(80.4) (2810) (3010)80 Q 7.3 12.0 569 546 b 289

(83.2) (3940) (3780)81-C -- 0 11.1 435 430 h 288

(76.9) (3010) (2980)82 Q 7.1 11.6 556 528 h 287

(80.4) (3050) (3680)

In the table 6, matrix material is to use the blend polymer of nylon h and nylon b to prepare.A kind of blend, sample 85 prepares as follows: the first masterbatch of the clay of preparation in nylon h, as control sample 83-C, carry out blend with this masterbatch and second kind of polymkeric substance such as nylon b then.Second kind of blend, sample 86 is by preparing the clay masterbatch of nylon b earlier, preparing with nylon h blend then.These matrix materials are processed with the ZSK Bitruder.

Table 6

Change anti-the opening of blend of nylon test number clay and resist a deflection nylon fusing point

Type (%) intensity modulus modulus type (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)83-C Q 20.1 7.77 824 722 h 280

(53.8) (5710) (5000)84 Q 7.1 11.9 612 547 h 281

(82.5) (4240) (3790)85 Q 7.3 12.2 593 549 b/h ¹ 281

(84.5) (4110) (3800)86 Q 5.9 12.3 613 529 h/b ² 281

(85.2) (4250) (3670)87 Q 6.3 12.3 588 540 b 282

(85.2) (4070) (3740) 1. the weight ratio of blend of nylon b/h be 70/30.2. the weight ratio of blend of nylon h/b is 70/30.

The masterbatch of handling clay and non-polyamide polymer in the table 7 reduces or dilution with nylon h.Reference examples is the mixture of straight polymer and nylon h.

Table 7

Resist other fusing point of deflection with anti-the opening of clay/other polymer master batch test number clay of nylon dilution

Type (%) intensity modulus modulus polymkeric substance (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)88-C -- 0 9.49 372 322 12.7 ¹288

(65.7) (2580) (2230)89 Z 6.5 9.96 452 411 12.7 ¹287

(68.9) (3130) (2840)90-C -- 0 10.4 393 370 7.0 ¹ 287

(71.6) (2720) (2560)91 Z 7.1 10.5 472 451 7.0 ¹ 283

(72.8) (3260) (3120)92-C -- 0 8.75 352 319 15.4 ²288

(60.6) (2440) (2210)93 Z 7.4 9.67 436 437 15.4 ²281

(66.9) (3020) (3020)94-C -- 0 9.52 380 354 9.7 ² 287

(65.9) (2630) (2450)95 Z 7.2 10.5 515 471 9.7 ² 281

(72.8) other 1. used polymkeric substance of (3560) (3260) is Iotek 971 ionomers.2. other used polymkeric substance is ATX 320 acid ter-polymers.

In each test of table 8, when processing nylon, clay changes feed points with handling.Clay joins in the ZSK Bitruder in throat or throat downstream.Used nylon is the multipolymer of 80% nylon 6,6 and 20% nylon 6.

Table 8

Change anti-anti-deflection fusing point of opening of feed points test number clay of processing nylon

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)96-C -- 0 10.5 376 286 251

(72.8) (2600) (1980)97 Q 5.4 10.7 468 391 251 ¹

(73.4) (3240) (2710)98 Q 5.5 10.8 489 370 249 ²

(74.5) (3370) (2560)99 Q 2.9 10.5 467 378 250 ³

(72.7) (3230) (2620)100 Q 3.4 10.9 490 377 250 ⁴

(75.2) (3390) (2610)101 Q 4.7 10.6 500 375 250 ⁵

(73.6) (3460) (2600)102 Q 4.8 10.8 521 406 250 ⁶

(75.1) (3620) (2810)103 Q 3.8 10.6 463 350 256 ⁷

(73.4) (3200) (2420)104 Q 4.2 10.8 490 359 250 ⁸

(74.7) (3390) (2480) 1. add nylon in ZSK Bitruder throat.2. testing second time of 97 passes through.3. add nylon in extruding machine throat downstream.4. testing second time of 99 passes through.5. add nylon in extruding machine throat downstream.6. testing second time of 101 passes through.7. add nylon in extruding machine throat.8. testing second time of 103 passes through.

In table 9, matrix material is to prepare with the silicate that 8 kinds of different quaternary ammoniums/ammonium blend is handled.These matrix materials are processed with the ZSK Bitruder.If consider the standard error that tensile strength is measured, then all samples all demonstrates the increase of tensile modulus and modulus in flexure, and tensile strength does not reduce.Sample 125～135 demonstrates the effect that changes the nylon type.

Table 9

Anti-the opening of the clay experiment clay that the ammonium blend is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)105-C ^*?-- 0 11.4 455 450 259

78.6) (3140) (3100)106 ^* GG 5.6 13.7 596 578 263

(94.5) (4110) (3990)107-C -- 0 11.5 463 429 286

(79.3) (3190) (2960)108 HH 1.3 11.8 476 472 285

(81.4) (3280) (3260)109 HH 5.2 11.41552 545 286

(78.7) (3810) (3760)110 II 2.3 12.0 465 429 286

(82.8) (3210) (2960)111 II 5.6 11.8 560 545 285

(81.4) (3860) (3760)112 JJ 2.0 11.9 470 483 285

(82.1) (3240) (3330)113 JJ 4.3 11.5 542 537 286

(79.3) (3740) (3700) *. nylon f is used in test 105 and 106.1. standard error is+0.85.

Table 9, continuous

Anti-the opening of the clay experiment clay that the ammonium blend is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)114-C -- 0 11.2 411 405 287

(77.2) (2830)?(2790)115 KK 2.8 11.5 470 475 287

(79.3) (3240)?(3280)116 KK 6.2 10.9 ¹494 536 288

(75.2) (3410)?(3700)117 LL 3.4 11.6 500 510 288

(80.0) (3450)?(3520)118 LL 6.7 11.0 ²544 542 288

(75.9) (3750)?(3740)119 MM 3.2 11.5 480 497 287

(79.3) (3310)?(3430)120 MM 6.5 11.0 ³529 540 288

(75.9) (3670)?(3720)121-C -- 0 11.6 427 466 282

(80.0) (2940)?(3210)122 NN 3.5 12.6 522 568 282

(86.9) (3600)?(3920)123 NN 6.5 12.6 572 623 282

(86.9) (3940)?(4300)124 NN 8.4 11.3 ⁴650 664 283

(77.9) (4480) (4580) 1. standard error be ± the 1.222. standard error for ± 0.243. standard error for ± the 0.494. standard error is ± 0.60

Table 9 is continuous

Anti-the opening of the clay experiment clay that the ammonium blend is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)125-C ¹ -- 0 11.7 488 481 268

(80.7) (3370) (3320)126 ¹ NN 8.1 11.9 640 598 265

(82.1) (4410) (4120)127-C ² -- 0 11.4 482 454 285

(78.6) (3320) (3130)128 ² NN 8.1 11.7 658 618 315

(80.7) (4540) (4260)129-C ³ -- 0 11.4 434 441 262

(78.6) (2990) (3040)130 ³ NN 1.7 12.1 491 506 270

(83.4) (3390) (3490)131 ³ NN 4.0 12.8 567 557 276

(88.3) (3910) (3840)132-C ⁴ -- 0 11.8 434 439 269

(81.4) (2990) (3030)133 ⁴ NN 2.2 12.1 480 509 276

(83.4) (3310) (3510)134 ⁴ NN 4.3 12.5 580 557 282

(86.2) (4000) (3840)135 ⁴ NN 6.8 12.4 635 643 286

(85.5) (4380) (4430) 1. sample use nylon a2. sample to use nylon c3. sample to use nylon a4. sample to use nylon e

In table 10, matrix material is to prepare with the silicate that 6 kinds of different tertiary amines are handled.These matrix materials are processed with the ZSK Bitruder.If consider the standard error that tensile strength is measured, then all samples all demonstrates the increase of tensile modulus and modulus in flexure, and tensile strength does not reduce.

Table 10

Anti-the opening of the clay experiment clay that tertiary amine is handled resists a deflection fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)136-C -- 0 12.1 443 456 296

(83.4) (3060) (3140)137 OO 5.4 13.0 591 568 297

(89.7) (4080) (3920)138 PP 4.9 12.9 588 545 297

(89.0) (4060) (3760)139 QQ 4.1 12.8 573 549 296

(88.3) (3950) (3790)140 RR 4.4 12.4 533 518 297

(85.5) (3680) (3570)141 SS 3.1 11.9 ¹488 499 296

(82.1) (3370) (3440)142-C -- 0 11.6 445 436 280

(80.0) (3070) (3010)143 TT 2.7 12.2 508 497 283

(84.1) (3500) (3430)144 TT 6.2 12.3 587 571 287

(84.8) (4050) (3940) 1. standard error be ± 1.1

In table 11, sample 147,150,152,154 and 156 has carried out solid state polymerization.Observe the surprising improvement of tensile strength and elongation.

Table 11

Anti-the opening of process reform test number clay resists a deflection % elongation fusing point

Type (%) intensity modulus modulus (℃)

kpsi kpsi kpsi

(MPa) (MPa) (MPa)145-C -- 0 11.7 488 481 29.4 268

(80.7) (3370) (3320)146 NN 8.1 11.9 640 598 2.5 265

(82.1) (4410) (4120)l47 ¹ NN 8.1 14.2 689 630 3.2 265

(97.9) (4750) (4340)148-C -- 0 11.4 482 454 33.8 285

(78.6) (3320) (3130)149 NN 8.1 11.7 658 618 2.1 315

(80.7) (4540) (4260)150 ¹ NN 8.1 13.9 681 663 2.9 315

(95.9) (4700) (4570)151-C -- 0 11.4 421 430 38.8 275

(78.6) (2910) (2980)152 ¹-C?-- 0 11.5 428 446 40.4 275

(79.7) (2970) (3090)153 NN 5.1 13.6 620 569 12.7 --

(94.2) (4300) (3940)154 ¹ NN 5.1 13.7 536 574 10.7 --

(94.9) (3710) (3980)155 ² NN 3.9 12.7 560 538 5.8 280

(88.0) (3880) (3730)156 ^1,2?NN 3.9 12.9 524 513 20.5 280

(89.4) solid polycondensation and about 3～4 hours are 1. carried out at about 200 ℃ in (3630) (3560).2. the 0.25%IrganoxLC21FF stablizer of selling with Ciba-Geigy company is stablized.Sample 145～147 and 151～156 uses nylon a.Sample 148～150 uses nylon c.

Claims (59)

1. polymer nanocomposite composition, said composition comprises:

(1) a kind of polymeric amide;

(2) treated silicate, wherein said silicate material comprises the silicate material of handling with the following ammonium ion of at least a general formula:

⁺NR ₁R ₂R ₃R ₄

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from saturated or unsaturated C ₁-C ₂₂The hydrocarbon of hydrocarbon, replacement and the hydrocarbon of branching, perhaps R wherein ₁And R ₂Form 1 N, the N-cyclic ether; Wherein randomly, R ₁, R ₂, R ₃And R ₄In one of be hydrogen;

Wherein the MER of the silicate of Chu Liing is from than low about 10 milligramequivalents of the cation exchange capacity of untreated silicon hydrochlorate/100 grams～exceed about 30 milligramequivalents/100 grams than the cation exchange capacity of untreated silicon hydrochlorate; And

Wherein this polyamide nano-composite shows in test the improvement of comparing with the polymeric amide that does not contain layered silicate aspect tensile modulus and modulus in flexure, and tensile strength can obviously not reduce again.

2. the composition of claim 1, wherein polymeric amide is selected from nylon 6, nylon 6,6, nylon 4,6, nylon 6,9, nylon 6,1O, nylon 6,12, Ni Long11, nylon 12, amorphous nylon, aromatics nylon and multipolymer thereof.

3. the composition of claim 1, wherein polymeric amide is nylon 6,6 and multipolymer thereof.

4. the composition of claim 1, the silicate of wherein said processing is selected from montmorillonite, nontronite, beidellite, volkonskoite, natural or synthetic hectorite, talcum powder, hot montmorillonite, natural water glass and water hydroxyl water glass.

5. the composition of claim 1, the silicate of wherein said processing is a kind of fibrous, the chain silicate that is selected from chain material, sepiolite and U.S.'s atlapulgite.

6. the composition of claim 1, wherein composition also comprises in the following material at least a kind: tensio-active agent, nucleator, coupling agent, filler, softening agent, impact modifying agent, chain extension agent, compatilizer, tinting material, demoulding lubricant, static inhibitor, pigment or fire retardant.

7. the composition of claim 6, wherein coupling agent is a silane.

8. the composition of claim 7, wherein silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.

9. the composition of claim 8, wherein the content of silane coupling agent in polymer composites is about 0.5wt%～5wt% of layered silicate.

10. the composition of claim 1, wherein R ₁Be selected from hydrogenated tallow, unsaturated tallow or contain the hydrocarbon of at least 6 carbon atoms, and R ₂, R ₃And R ₄Contain 1～12 carbon atom independently.

11. the composition of claim 1, wherein ammonium ion is to be selected from following quaternary ammonium ion: dimethyl two (hydrogenated tallow) ammonium, dimethyl benzyl hydrogenated tallow ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium, trimethylammonium hydrogenated tallow ammonium, methyl-benzyl two (hydrogenated tallow) ammonium, N, N-2-cyclobutoxy group two (hydrogenated tallow) ammonium, trimethylammonium tallow ammonium, methyl dihydroxy ethyl tallow ammonium and octadecyl methyl dihydroxy ethyl ammonium and their mixture.

12. the composition of claim 1, wherein ammonium ion is to be selected from following quaternary ammonium ion: dimethyl two (hydrogenated tallow) ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium, dimethyl benzyl hydrogenated tallow ammonium, methyl dihydroxy ethyl tallow ammonium and their mixture.

13. the composition of claim 1, wherein the content of the layered silicate of handling in the composition is about 0.1wt%～about 12.0wt% of matrix material.

14. the composition of claim 1, wherein the content of the layered silicate of handling in the composition is about 0.5wt%～about 6.0wt% of matrix material.

15. the composition of claim 1, wherein said composition comprise at least a other polymkeric substance.

16. according to the composition of claim 15, wherein said at least a other polymkeric substance comprises polyphenylene oxides or polyphenylene oxide.

17. according to the composition of claim 1, the weight-average molecular weight of wherein said polymeric amide is at least about 40,000D.

18. composition according to claim 15, wherein said other polymkeric substance comprises polyethylene oxide, polycarbonate, polyethylene, polypropylene, poly-(the rare nitrile of vinylbenzene-third), poly-(third rare nitrile-butadiene-styrene), poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(terephthalic acid 1, ammediol ester), poly-(naphthalene dicarboxylic acids glycol ester), poly-(ethylene glycol terephthalate-copolymerization-terephthalic acid cyclohexanedimethanoester ester), polysulfones, poly-(phenylene oxygen base) or poly-(phenylate), poly-(hydroxy-benzoic acid-copolymerization-ethylene glycol terephthalate), poly-(hydroxy-benzoic acid-copolymerization-hydroxyl naphthenic acid), poly-(esteramides), poly-(ether imide), poly-(diphenyl sulfide), poly-(paraphenylene terephthalamide's phenylenediamine).

19. according to the composition of claim 1, the silicate granules of wherein said processing is with the mixture process of the following ammonium ion of one or more quaternary ammonium ions and general formula:

⁺NR _aR _bR _cR _d

R wherein _a, R _bAnd R _cIn at least one is hydrogen (H), and R _dThen be selected from saturated or undersaturated C ₁-C ₂₂Hydrocarbon, the hydrocarbon that replacement is arranged and branched hydrocarbon, perhaps R wherein ₁And R ₂Form a N, the N-cyclic ether.

20. according to the composition of claim 19, wherein R _dComprise carboxylic moiety.

21. according to the composition of claim 19, wherein said mixture comprises the combination of at least a and 12-aminolauric acid ammonium in dimethyl two (hydrogenated tallow) ammonium, dimethyl hydroxyethyl tallow ammonium and/or dimethyl (ethylhexyl) the hydrogenated tallow ammonium.

22. according to the composition of claim 1, wherein layered silicate particle is handled with the azine cationic dyestuff.

23. according to the composition of claim 22, wherein said cationic dyestuff comprises Ni Ge or anthracene dyes.

24. according to the composition of claim 6, wherein said filler comprises carbon fiber, glass fibre, high Cen soil, wollastonite or talcum powder.

25. according to the composition of claim 6, wherein said compatilizer comprises at least a sour modification hydrocarbon polymer.

26. according to the composition of claim 6, wherein said compatilizer comprises maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene or maleic anhydride grafted ethene-butylene-styrene segmented copolymer.

27. according to the composition of claim 6, wherein said lubricant comprises at least a alkylamine, stearylamide, two-aluminum stearate or three-aluminum stearate.

28. composition according to claim 6, wherein said impact modifying agent comprises ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene, methacrylic ester-butadiene-styrene (having cone-shell type state), through or without carboxy-modified poly-(butyl acrylate), poly-(ethylene-acrylate), poly-(ethylene methacrylate), poly-(ethylene acrylic), poly-(ethylene-acrylate) ionomer, poly-(ethylene-methyl acrylate-vinylformic acid) terpolymer, poly-(styrene butadiene) segmented copolymer, poly-(styrene-butadiene-styrene) ternary block polymer, poly-(styrene-ethylene/butylene-styrene) ternary block polymer and poly-(styrene-ethylene/butylene-styrene carboxylate) ternary block polymer.

29. according to the composition of claim 1, wherein said composition comprises matrix material, wherein the crystallizing field of polymeric amide is less than 1.0 μ m.

30. according to the composition of claim 1, wherein said composition is fiber, film or moulded parts form.

31. one kind prepares polymeric amide sodium nano composite material method for compositions, comprises

(1) but form the flowing mixture of a kind of polymeric amide and a kind of treated silicate material;

(2) make at least about 50% but the disassociation of the silicate material of non-whole described processing to form this sodium nano composite material composition;

Wherein the silicate of this processing comprises the silicate material of handling with the following ammonium ion of at least a general formula:

⁺NR ₁R ₂R ₃R ₄

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from saturated or unsaturated C ₁-C ₂₂The hydrocarbon of hydrocarbon, replacement and the hydrocarbon of branching, perhaps R wherein ₁And R ₂Form 1 N, the N-cyclic ether; Wherein randomly, R ₁, R ₂, R ₃And R ₄In one of be hydrogen;

Wherein the MER of the silicate of Chu Liing is from than low about 10 milligramequivalents of the cation exchange capacity of untreated silicon hydrochlorate/100 grams～exceed about 30 milligramequivalents/100 grams than the cation exchange capacity of untreated silicon hydrochlorate; And wherein this polyamide nano-composite shows in test the improvement of comparing with the polymeric amide that does not contain layered silicate aspect tensile modulus and modulus in flexure, but can not reduce tensile strength.

32. the method for claim 31, wherein polymeric amide is selected from nylon 6, nylon 6,6, nylon 4,6, nylon 6,9, nylon 6,10, nylon 6,12, Ni Long11, nylon 12, amorphous nylon, aromatics nylon and multipolymer thereof.

33. the method for claim 31, wherein silicate is selected from montmorillonite, nontronite, beidellite, volkonskoite, natural or synthetic hectorite, sepiolite, talcum powder, hot montmorillonite, natural water glass and water hydroxyl water glass.

34. the method for claim 31, wherein composition also comprises in the following material at least a kind: tensio-active agent, nucleator, coupling agent, filler, softening agent, impact modifying agent, chain extension agent, compatilizer, tinting material, demoulding lubricant, static inhibitor, pigment or fire retardant.

35. the method for claim 34, wherein coupling agent is a silane.

36. the method for claim 35, wherein silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.

37. the method for claim 35, wherein the content of silane coupling agent in polymer composites is about 0.5wt%～5wt% of layered silicate.

38. the method for claim 31, wherein R ₁Be selected from hydrogenated tallow, unsaturated tallow or contain the hydrocarbon of at least 6 carbon atoms, and R ₂, R ₃And R ₄Contain 1～12 carbon atom independently.

39. the method for claim 31, wherein dimethyl two (hydrogenated tallow) ammonium, dimethyl benzyl hydrogenated tallow ammonium, dimethyl (ethylhexyl) hydrogenated tallow ammonium, trimethylammonium hydrogenated tallow ammonium, methyl-benzyl two (hydrogenated tallow) ammonium, methyl dihydroxy ethyl tallow ammonium and N, N-2-cyclobutoxy group two (hydrogenated tallow) ammonium.

40. the method for claim 31, wherein the content of the layered silicate of handling in the composition is about 0.1wt%～about 12.0wt% of matrix material.

41. the method for claim 31, wherein the content of the layered silicate of handling in the composition is about 0.5wt%～about 6.0wt% of matrix material.

42. the method for claim 31, wherein the silicate material of handling adopts and is selected from mechanism, thermal shocking, pressure change or hyperacoustic method realization disassociation.

43. the method for claim 42, wherein mechanism is selected from agitator, Banbury ^Type Banbury mixer, Brabender ^Type mixing machine, Farrel ^Continuous mixer and extruding machine.

44. the method for claim 43, wherein extruding machine is selected from single multiple screw extruder and Bitruder.

45. the method for claim 44, wherein Bitruder is to rotate full meshed double screw extruding machine in the same way.

46. the method for claim 42, but wherein said flowing mixture stands multiple described dissociation methods.

47. the method for claim 31, mix described polymeric amide wherein said poly-comprising in formation step with a kind of silicate that contains the processing of masterbatch, and described masterbatch comprises the silicate and the carrier polymer of described processing.

48. the method for claim 47, wherein said carrier polymer comprise polymeric amide, ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene, ethylene-propylene acetoacetic ester, ethylene-methyl methacrylate ethyl ester or ethylene methacrylate.

49. the method for claim 48, wherein the polymeric amide carrier polymer is selected from nylon 6, nylon 6,6, nylon 4,6, nylon 6,9, nylon 6,10, nylon 6,12, Ni Long11, nylon 12, amorphous nylon, aromatics nylon or their multipolymer.

50. the method for claim 47, but the weight-average molecular weight of wherein said carrier polymer is different from the molecular weight of the polymeric amide in the described flowing mixture.

51. the method for claim 47, wherein said carrier polymer are the polymkeric substance except that polymeric amide.

52. the method for claim 47, the weight-average molecular weight of wherein said carrier polymer be between 10,000～40,000D.

53. the method for claim 31, but wherein said flowing mixture also comprises monomer.

54. the method for claim 53, wherein said monomer comprise ε-Ji Neixianan, laurolactam or its corresponding lactone.

55. the method for claim 53, wherein said method also comprise described monomeric polymerization.

56. the method for claim 31, but also be included in the polymeric amide that in described flowing mixture, adds additional content during the described disassociation step.

57. the method for claim 31 further comprises the solid state polymerization or the additional melt polymerization of described polymeric amide.

58. the method for claim 57, wherein solid state polymerization comprises, polymeric amide is heated about 2～5 hours time in about 200 ℃～240 ℃ temperature.

59. the method for claim 31 further comprises composition is heat-treated about 2～5 hours time in about 200～240 ℃ temperature, wherein such thermal treatment can cause solid state polymerization, or promotes the polymeric amide molecule to embed in the silicate material.