JP2002502913A - Method for producing polymer nanocomposite composition - Google Patents

Abstract

  (57) [Summary] A polymer comprising forming a flowable mixture of a polyamide and a silicate material, dissociating at least about 50%, but not all, of the silicate material and solid phase polymerizing the polyamide in the dissociated mixture to form a nanocomposite. A method for producing a nanocomposite composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for producing a nanocomposite material comprising a polymer matrix containing silicate dispersed therein. More specifically, the present invention relates to a nanocomposite material comprising forming a flowable mixture of a polyamide and a silicate material, dissociating the silicate, and subjecting the dissociated flowable mixture to a solid state polymerization step to produce a nanocomposite material. And a method for producing the same.

BACKGROUND OF THE INVENTION International Patent Application Publication No. WO 93/04118 discloses a method for producing a polymer nanocomposite containing dispersed platelet-shaped particles. The method involves melt treating the polymer with a swellable, polymer-compatible intercalating layered material and subjecting it to a shear rate sufficient to dissociate the layers. The layered material has been compatibilized with one or more "effective swelling / compatibilizing agents" having silane or onium cation functionality.

International Patent Application Publication No. WO 93/04117 discloses a method for producing a polymer nanocomposite containing dispersed platelet-shaped particles, the method comprising a polymer and a swellable / polymer-compatible intercalator. Melt processing of the layered material. The layered material includes a primary ammonium ion, a secondary ammonium ion and
Compatibilized with one or more "effective swelling / compatibilizing agents" selected from secondary phosphonium ions. The selected swelling / compatibilizer "makes the surface more organophilic than that compatibilized by the tertiary and quaternary ammonium ion complexes" promotes surface delamination, thus reducing shear during mixing. Reduces polymer degradation and more thermally stabilizes the composite than other cationic swelling / compatibilizing agents (such as quaternary ammonium cations).

[0004] WO 94/22430 discloses at least one γ
Disclosed is a nanocomposite composition comprising a polymer matrix comprising a phase polyamide, wherein the nanoparticle-sized particulate material matrix is dispersed in the polyamide. The addition of particulate matter to nylon 6 improved the flexural modulus and flexural strength (from 7 to 35%) compared to unfilled nylon 6. The addition of particulate matter to nylon 6,6 increased the flexural modulus and flexural strength only slightly (from 1 to 3%) compared to unfilled nylon 6,6.

[0005] WO 93/10098 discloses melt-treating a polymer with a swellable, polymer-compatible intercalating layered material comprising a layer having a reactive organic-silane moiety covalently bonded to a surface. Discloses a polymer composite produced by the method.

[0006] WO 95/14733 discloses a process for producing a polymer composite that does not exhibit a melting or glass transition by melt-treating a polymer with a layered gallery-containing crystalline silicate. Examples include intercalated sodium silicate and crystalline poly (ethylene oxide)
Montmorillonite and polystyrene intercalated with quaternary ammonium, and montmorillonite and nylon 6 intercalated with quaternary ammonium.

[0007] WO 98/29499 discloses a polyester nanocomposite composition comprising clay particles. The clay particles are preferably synthesized or chemically modified.

US Pat. No. 4,889,885, issued Dec. 26, 1989,
A composite of a non-polyamide resin and a dispersed layered silicate is described.
This silicate has been treated by onium salt ion exchange and has been added to the monomer or oligomer.

US Pat. No. 5,514,734 (issued May 7, 1996) describes a polymer composite comprising layered or fibril-like particles derivatized with an organosilane, organotitanate or organozirconate. I have. The composite material is
It is characterized by thickness, diameter and interlayer distance.

[0010] WO 93/11190 describes a polymer composite comprising a delamination material derivatized with a reactive organosilane. The polymer has been added before mixing in the extruder.

International Patent Application Publication No. WO 94/11430 describes a gamma crystalline phase polyamide containing dispersed layered inorganic substances.

EP-A-0 358 415 describes a polyamide resin which contains a dispersed layered silicate pretreated with an organic cation of a lactam as a swelling agent.

JP 62-252426 describes polymerization of a nylon 6 monomer in the presence of a silicate. The cooling rate of the polymer is adjusted to obtain a specific crystal structure in the final composite.

The above references do not disclose the present invention either alone or in combination.

SUMMARY OF THE INVENTION The present invention is directed to a polymer nanocomposite composition suitable for the fields of automobiles, electronics, films and fibers where a combination of tensile strength, tensile modulus and flexural modulus is required. It relates to a manufacturing method. Furthermore, the polymer nanocomposite compositions of the present invention have the desired surface appearance, toughness, ductility and dimensional stability. The compositions of the present invention process well and allow a wide range of molding conditions.

The present invention provides a method for forming a fluid mixture of a polyamide and a silicate material,
Dissociate at least about 50%, but not all, of the sheet (more on this term)
The polyamide in the dissociated fluid mixture is subjected to a solid-state polymerization step.
And a method for producing the polymer nanocomposite composition. Duty
Preferably, said silicate has the formula:⁺NR₁R₂R₃R₄  Silicate material treated with at least one ammonium ion having
You. In the above formula, R₁, R₂, R₃And R₄Is independently saturated or unsaturated C₁ ~ C₂₂Selected from the group consisting of hydrocarbons, substituted hydrocarbons and branched chain hydrocarbons
Or R₁And R₂Forms an N, N-cyclic ether. Examples include (Archire
Substituted or unsubstituted alkyl, including hydroxya
Alkyl, alkoxyalkyl, alkoxy, aminoalkyl, acid alkyl, halo
Alkylated gens, sulfonated alkyls, nitrated alkyls, etc .; branched alkyls;
Aryl and substituted aryl, such as alkylaryl, alkoxyaryl, a
Alkylhydroxyaryl, alkylalkoxyaryl, and the like. In case
Than R₁, R₂, R₃And R₄One is hydrogen. The processing described in detail below
Mg (MER) of the treating agent per 100 g of the silicate of the physical silicate is preferable.
Or about 100 meq / 100g lower than the cation exchange capacity of untreated silicate
~ 30 meq / 100g more than the cation exchange capacity of the untreated silicate
It is.

Another aspect of the present invention relates to a nanocomposite composition comprising a polyamide and a silicate. The polyamide may have an amine end group concentration at least 10 mol% higher than the carboxylic acid end group concentration. Preferably, the polyamide comprises about 30
It has a weight average molecular weight in the range of 000 to about 40,000 D. Alternatively, the polyamide may have a weight average molecular weight of at least 40,000D.

Another aspect is a polyamide, and a compound of the formula:⁺NR_aR_bR_cR_d  (Where R_a, R_bAnd R_cIs hydrogen (H) and R_dContains a carboxylic acid moiety
) Nanocomposite containing silicate treated with ammonium ion having
The composition.

The composition polymer matrix material of the present invention exhibits an increase in tensile and flexural modulus when tested when compared to a polymer without silicate without substantially reducing tensile strength or toughness. .

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings form part of the present specification and are included to further describe certain aspects of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The invention may be better understood with reference to one or more of the accompanying drawings, in conjunction with the detailed description of specific embodiments set forth herein.

DETAILED DESCRIPTION OF THE INVENTION The polyamide of the present invention is a synthetic linear polymer characterized by the presence of repeating carbon amide groups as an integral part of the polymer chain separated by at least two carbon atoms. Carbon amide. The polyamide of this kind, usually a known as nylon in the art, the general formula: -NHCOR ₅ CONHR ₆ - (wherein, _{R 5} is at least 2 carbon atoms, preferably from about 2 to about 11 amino Alkylene groups having carbon atoms or at least about 6 carbon atoms, preferably about 6 to
(Wherein R ₆ is selected from R ₅ and aryl groups), and polymers obtainable from diamines and dibasic acids. Copolyamides and terpolyamides obtained by condensing a known method such as hexamethylenediamine and a mixture of a dibasic acid composed of terephthalic acid and adipic acid are also included. The above-mentioned polyamides are known in the art and include, for example, poly (hexamethylene adipamide) (nylon 6,6), poly (hexamethylene sebacamide) (nylon 6,10), poly (hexamethylene). Isophthalamide), poly (hexamethylene terephthalamide), poly (heptamethylenepimelamide) (nylon 7,7), poly (octamethylenesuberamide) (nylon 8,8)
, Poly (nonamethylene zeramid) (nylon 9,9), poly (decamethylene sebacamide) (nylon 10,9), poly (decamethylene sebacamide) (nylon 10,10), poly [bis (4 -Aminocyclohexyl) methane-1,10-decanecarboxamide], poly (m-xylene adipamide), poly (p-xylene sebacamide), poly (2,2,2-trimethylhexamethylene terephthalamide)
, Poly (piperazine sebacamide), poly (p-phenylene terephthalamide), poly (metaphenylene isophthalamide), and copolymers and terpolymers of the above polymers. Other polyamides include nylon 4,6, nylon 6,9
, Nylon 6,10, nylon 6,12, nylon 11, nylon 12, amorphous nylon, aromatic nylon and copolymers thereof.

[0022] Other useful polyamides are those formed from the polymerization of amino acids and their derivatives (eg, lactams). Examples of useful polyamides include poly (caprolactam) (nylon 6), poly (4-aminobutyric acid) (nylon 4), poly (7-aminoheptanoic acid) (nylon 7), poly (8-aminooctanoic acid) (Nylon 8
), Poly (9-aminononanoic acid) (nylon 9), poly (10-aminodecanoic acid) (nylon 10), poly (11-aminoundecanoic acid) (nylon 11), poly (12-aminodosecanoic acid) (nylon 12) And so on.

A preferred polyamide is Vydyne® nylon, which is poly (hexamethylene adipamide) (nylon 6,6), which has the desired tensile strength, tensile elasticity for the intended use of the present invention. Gives a combination of modulus and flexural modulus. Vydyne is manufactured by Solutia Inc. Is a registered trademark of Microsoft Corporation.

[0024] The preferred molecular weight (weight average) of the polyamide is from about 30,000 to about 80,00.
0D, more preferably in the range of about 30,000 to about 40,000D. The most preferred molecular weight (weight average) of the polyamide is at least about 40,000D. Increasing the weight average molecular weight of the polyamide from about 35,000 D to about 55,000 D unexpectedly improves the toughness shown in the notched Izod impact test.
On the other hand, the weight average molecular weight of the polyamide neat is from about 35,000 D to about 550,000.
Even if it is increased to 0D, the toughness is only slightly improved. If the molecular weight of the nanocomposite is similarly increased, the toughness will increase by almost a factor of two. Therefore, the improvement in toughness is enhanced in the nanocomposite compared to polyamide neat.

In a preferred embodiment, the polyamide has an amine end group / acid end group ratio of 1 or more. More preferably, the amine end group concentration is at least 10 mol% higher than the carboxylic acid end group concentration. In a further preferred embodiment, the polyamide has an amine end group concentration of at least 20 mol% higher than the carboxylic acid end group concentration. In a most preferred embodiment, the polyamide has a carboxylic acid end group concentration of at least 30%.
It has a higher mol% amine end group concentration. In another embodiment, the amine end group concentration is essentially equal to the carboxylic acid end group concentration.

Preferred are nylon 6, nylon 6,6, blends and copolymers thereof. The ratio of nylon 6 / nylon 6,6 in the blend is about 1/100 to 10
It is in the range of 0/1. Preferably, the range is about 1/10 to 10/1. The ratio of nylon 6 / nylon 6,6 in the copolymer ranges from about 1/100 to 100/1. Preferably, the range is about 1/10 to 10/1.

[0027] Optionally, the nanocomposite composition includes at least one additional polymer.
Examples of suitable polymers include polyethylene oxide, polycarbonate, polyethylene, polypropylene, poly (styrene-acrylonitrile), poly (acrylonitrile-butadiene-styrene), poly (ethylene terephthalate), poly (ethylene terephthalate)
(Butylene terephthalate), poly (trimethylene terephthalate), poly (ethylene naphthalate), poly (ethylene terephthalate-co-cyclohexanedimethanol terephthalate), polysulfone, poly (phenylene oxide) or poly (phenylene ether), poly (hydroxybenzoic acid) -Co-ethylene terephthalate), poly (hydroxybenzoic acid-co-hydroxynaphthenic acid), poly (ester amide), poly (ether imide), poly (phenylene sulfide)
, Poly (phenylene terephthalamide).

The mixture can include various optional components, which are additives commonly used with polymers. The optional components include a surfactant, a nucleating agent, a coupling agent, a filler, an impact modifier, a chain extender, a plasticizer, a compatibilizer, a colorant, a release lubricant, an antistatic agent, and a pigment. , Flame retardants and the like.

[0029] Suitable examples of the filler include carbon fiber, glass fiber, kaolin clay, walstonite, mica or talc. Preferred examples of the compatibilizer include acid-modified hydrocarbon polymers, such as maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, and maleic anhydride-grafted ethylene-
Butylene-styrene block copolymers are included. Preferred examples of the release lubricant include:
Includes alkylamines, stearamide, dialium aluminum stearate and trialuminum stearate.

Preferred examples of the impact modifier include ethylene-propylene rubber, ethylene-propylene diene rubber, methacrylate-butadiene (having a core-shell form).
Styrene, poly (butyl acrylate) with or without carboxyl modification,
Poly (ethylene acrylate), poly (ethylene methacrylate), poly (ethylene-acrylic acid), poly (ethylene acrylate) ionomer, poly (ethylene-methacrylate-acrylic acid) terpolymer, poly (styrene-butadiene) block copolymer, A styrene-butadiene-styrene block terpolymer, a poly (styrene-ethylene / butylene-styrene) block terpolymer, or a poly (styrene-ethylene / butylene-styrene carboxylate) block terpolymer is included.

[0031] Suitable coupling agents include silane, titanate and zirconate coupling agents. Silane coupling agents are known in the art and are used in the present invention. Examples of suitable coupling agents include octadecyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylphenyldimethoxysilane, γ-glycidoxypropyltripropoxysilane, 3,3-epoxycyclohexylethyltrimethoxysilane, γ-propionamidotriethoxy Silane, N-trimethoxysilylpropyl-N- (β-aminoethyl) amine, trimethoxysilylundecylamine,
Trimethoxysilyl-2-chloromethylphenylethane, trimethoxysilylethylphenylsulfonyl azide, N-trimethoxysilylpropyl-N, N, N
-Trimethylammonium chloride, N- (trimethoxysilylpropyl) -N
-Methyl-N, N-diallylammonium chloride, trimethoxysilylpropylcinnamate, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like. A preferred silane is gamma-aminopropyltriethoxysilane. The silane coupling agent is optionally added to the polymer composite at a concentration ranging from about 0.5 to about 5% by weight of the layered silicate. A preferred concentration range of the silane coupling agent is from about 1 to about 3% by weight of the layered silicate in the composite.

In one embodiment, the nanocomposite composition further comprises a composition wherein the end groups of the polyamide are attached to the surface of the treated silicate by a silane coupling agent.

The silicate material of the present invention is selected from the group consisting of a layered silicate and a chain silicate, and includes a phyllosilicate. Examples of fibrous silicates include:
Chain minerals such as sepiolite and attapulgite are included, with sepiolite being preferred. The silicate is described in, for example, Japanese Patent Publication No. 6-84435 published on October 26, 1994.

Examples of layered silicates include layered smectite clay minerals (eg, montmorillonite, nontronite, beidellite, horconscoite, Laponite)
(Registered trademark) synthetic hectorite, natural hectorite, saponite, sauconite, magadite and kenyaite), vermiculite and the like. Other useful materials include layered illite minerals (eg, ladykite) and mixtures of illite with one or more of the clay minerals described above. Preferred layered silicates are smectite clay minerals (eg, montmorillonite, nontronite, beidellite, holkonskoite, Laponite® synthetic hectorite, natural hectorite, saponite, sauconite, magadite and kenyaite).

Layered silicate materials suitable for use in the present invention are known in the art and are sometimes referred to as “swellable layered materials”. Platelets formed by melt processing with the layered silicates and polyamides are described in detail in WO 93/04117, which is hereby incorporated by reference. Layered silicate materials usually have planar layers arranged in an agglomerated coplanar structure, wherein the bonds within the layers are stronger than the bonds between the layers so that the material exhibits a higher interlayer space when processed.

The layered silicate material can be treated as detailed below with ammonium ions to enhance interlayer swelling and / or space useful for the performance of the treated silicates of the present invention. As used herein, "interlayer space" refers to the distance between the planes of the layers when they assemble in the treatment material before delamination (or delamination) occurs. Preferred clay materials usually include intercalated or exchangeable cations such as Li ⁺ , Na ⁺ , Ca ²⁺ , K ⁺ , Mg ^{2+ and} the like. In this case, the material usually has an interlayer space of less than about 4 °, and only slightly delaminates into the host polymer melt regardless of the mixing. In embodiments of the present invention, the cation treating agent is an ammonium material that can be exchanged with interlayer cations such as Li ⁺ , Na ⁺ , Ca ²⁺ , K ⁺ , Mg ^2+, etc. to improve delamination of the layered silicate. .

The treated silicate of the present invention has the formula:⁺NR₁R₂R₃R₄  The above silicate material treated with at least one ammonium ion having
It is. In the above formula, R₁, R₂, R₃And R₄Is independently saturated or unsaturated
C₁~ C₂₂Selected from the group consisting of hydrocarbons, substituted hydrocarbons and branched hydrocarbons.
Or R₁And R₂Forms an N, N-cyclic ether. Examples include (Al
Saturated or unsaturated alkyl (including kylene), substituted alkyl (eg, hydro
Xyalkyl, alkoxyalkyl, alkoxy, aminoalkyl, acid alkyl
, Alkyl halides, sulfonated alkyls, nitrated alkyls, etc.)
Alkyl, aryl and substituted aryl (eg, alkylaryl, alkoxya
Reel, alkylhydroxyaryl, alkylalkoxyalkyl, etc.)
It is. In some cases, R₁, R₂, R₃And R₄One is hydrogen. Two or more
Mixtures of ammonium ions are also contemplated herein.

In one embodiment of the present invention, R ₁ is selected from the group consisting of hydrogenated tallow, unsaturated tallow and hydrocarbons having at least 6 carbon atoms, and R ₂ , R ₃ and R ₄ are independently From 1 to 18 carbon atoms. Tallows are mainly composed of octadecyl chains with small amounts of low homologues and have an average of 1-2 unsaturation. Its approximate composition is 70% C ₁₈ , 25% C ₁₆ , 4% C ₁₄ and 1% C ₁₂ . In another preferred embodiment of the invention, R ₁ and R ₂ are independently selected from the group consisting of hydrogenated tallows, unsaturated tallows and hydrocarbons having at least 6 carbon atoms, wherein R ₃ and R ₄ are Independently has 1 to 12 carbon atoms.

Examples of suitable R ₁ , R ₂ , R ₃ and R ₄ groups are alkyl (eg, methyl, ethyl, octyl, nonyl, tert-butyl, ethylhexyl, neopentyl, isopropyl, sec-butyl, dodecyl, etc.) Alkenyl (eg, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-
Octenyl, etc.), cycloalkyl (eg, cyclohexyl, cyclopentyl,
Cyclooctyl, cycloheptyl, etc.), alkoxy (eg, ethoxy), hydroxyalkyl, alkoxyalkyl (eg, methoxymethyl, ethoxymethyl, butoxymethyl, propoxyethyl, pentoxybutyl, etc.), aryloxyalkyl and aryloxyaryl (eg, Phenoxyphenyl, phenoxymethyl, phenoxydecyl, phenoxyoctyl, etc.), arylalkyl (
For example, benzyl, phenylethyl, 8-phenyloctyl, 10-phenyldecyl and the like, and alkylaryl (for example, 3-decylphenyl, 4-octylphenyl, nonylphenyl and the like).

[0040] Suitable ammoniums used in treating silicate materials include oniums such as dimethyldi (hydrogenated tallow) ammonium, dimethylbenzylhydrogenated tallowammonium, dimethyl (ethylhexyl) hydrogenated tallowammonium, trimethylhydrogenated tallow. Ammonium, methylbenzyldi (hydrogenated tallow) ammonium, N, N-2-cyclobutoxydi (hydrogenated tallow) ammonium, trimethyltallowammonium, methyldihydroxyethyltallowammonium, octadecylmethyldihydroxyethylammonium, dimethyl (ethylhexyl)
Tallow ammonium hydride and mixtures thereof. Particularly preferred ammoniums are quaternary ammoniums such as dimethyldi (hydrogenated tallow) ammonium,
Includes dimethylbenzyl tallow ammonium hydride, methyl dihydroxyethyl tallow ammonium, octadecylmethyl dihydroxyethyl ammonium, dimethyl (ethylhexyl) tallow ammonium hydride and mixtures thereof.

The above-mentioned treatment with ammonium ions, also referred to as “cation treatment”, includes:
Including the introduction of ions into the silicate material by ion exchange. In embodiments in which the silicate material is a layered silicate, the cationic treating agent is applied to each layer, substantially each layer, or a majority of the layer of layered material, such that the resulting platelet layer contains less than about 20 particles in its thickness. Can be introduced into the space between The platelet layer is preferably less than about 8 grains thick, more preferably less than about 5 grains thick, most preferably about 1 or 2 grains thick.

The treated silicate can be about 10 meq / 100 g less than the cation exchange capacity of the untreated silicate to about 30 meq / 100 g less than the cation exchange capacity of the untreated silicate.
It has a MER in the range of 100g more. MER is the milliequivalent of the treating agent per 100 g of silicate. Each untreated silicate has a cation exchange capacity that is a milliequivalent of cations available for exchange per 100 g of silicate. For example, the cation exchange capacity of the layered silicate montmorillonite can be about 95, and the exchange capacity of sepiolite ranges from about 10 to about 20. When the MER of the treated silicate substantially exceeds the cation exchange capacity, there is excess cation treating agent available to react with the polyamide. Such excess may result in polymer properties.

The higher the MER, the lower the silicate concentration in the treated silicate. Thus, the first nanocomposite sample has a higher concentration of the treated silicate than the second nanocomposite sample, but has a lower silicate concentration. This is because the first sample has a higher MER than the second sample.

When the MER value of the treated silicate is substantially below its ion exchange capacity (eg, about 85 MER for the preferred montmorillonite), the beneficial effects obtained with the cation treatment are small. When the MER exceeds about 125, the excess ammonium can impair the properties of the nylon. Preferably, if the untreated montmorillonite has an exchange capacity of about 95, the treated layered silicate will have a cation exchange capacity of about 85 to about 125.

The amount of silicate incorporated in the composition ranges from about 0.1 to about 12% by weight of the composition. The concentrations are adjusted to provide a composite polymer matrix material that exhibits increased tensile and flexural modulus when tested without substantially reducing tensile strength. Preferably, the increase in tensile and flexural modulus is at least about 10%. More preferably, the increase in tensile and flexural modulus is at least about 20%. If the silicate is too low, the tensile and flexural modulus cannot be increased as desired. Too much silicate results in a polyamide composite with low tensile strength. Further, it is desirable that the crystalline area of the polyamide in the nanocomposite composition be less than about 1.0 μm.

The particle size of the silicate is such that optimum contact between the polyamide and the silicate is promoted. The size range can vary from about 10 to about 100 μm. Preferably, the particle size ranges from about 20 to about 80 μm. Most preferably, the particle size is
No more than about 30 μm to pass through a 450 mesh sieve, and the resulting polymer nanocomposite has improved performance characteristics.

Optionally, the silicate has the formula:⁺NR_aR_bR_cR_d  Can be treated with one or more ammonium ions having In the above formula, R_a, R_b And R_cAt least one is hydrogen (H);_dIs saturated or unsaturated C₁ ~ C₂₂Selected from the group consisting of hydrocarbons, substituted hydrocarbons and branched chain hydrocarbons
. Examples include saturated or unsaturated alkyl (including alkylene), substituted alky!
Kill (eg, hydroxyalkyl, alkoxyalkyl, alkoxy, amino
Alkyl, acid alkyl, alkyl halide, sulfonated alkyl, nitrated
Alkyl, aryl, and substituted aryl (eg, alkyl
Reel, alkoxyaryl, alkylhydroxyaryl, alkylalkoxy
And the like. R for the above ammonium ion_dThe definition of the group
R of ammonium ion₄Since it is usually the same as the definition of the group,₄Above for the group
Example is R_dIt is also an example of a group.

In another embodiment, R_a, R_bAnd R_cIs hydrogen (H) and R_dIs Ammoni
Um ion⁺NR_aR_bR_cR_d  Carboxyl such that is an amino acid, for example ammonium 12-aminolaurate
Contains an acid moiety. In this embodiment, the polyamide has one or more amine / acid end groups.
Above is particularly preferred.

Optionally, said ammonium ions may be mixed with at least one quaternary ammonium ion, said mixture being used for treating silicates. The quaternary ammonium ion is preferably a hydrocarbon chain. The hydrocarbon chain may be saturated or unsaturated. The hydrocarbon chain may be a natural source (eg, tallow) or a synthetic source (eg, tallow).
For example, it can be derived from synthetic or purified C ₁₂ , C ₁₄ , C ₁₆ or C ₁₈ chains). Preferred mixtures comprise at least one ammonium dimethyldi (tallow) ammonium, methyldihydroxyethyltallowammonium, dimethylbenzyltallowammonium hydride and / or dimethyl (ethylhexyl) tallowammonium hydride, alone or with 12-aminolaurin Include with ammonium acid.

Optionally, the silicate may be further treated with an azine cationic dye (eg, nigrosine or anthracin). The cationic dye provides discoloration resistance and color uniformity in addition to enhancing the intercalation of the polymer molecules.

It is further desirable that the polymer composite has the desired strength and flexibility and is also lightweight. This is achieved by minimizing the concentration of silicate in the nanocomposite. Preferred nanocomposites comprise about 0.1 to about 0.1% of the composite.
It contains silicate at a concentration of about 12.0% by weight. Most preferred nanocomposites comprise silicate at a concentration of about 0.5 to about 6.0% by weight of the composite.

[0052] In a first aspect of the present invention, the nanocomposite composition is made by a three-step method. The first step involves forming a flowable mixture of the polyamide and silicate material as a polymer melt. The second step involves dissociating at least 50%, but not all, of the silicate material. As used herein, the term "dissociating" means that the silicate material delaminates or separates into submicron sized structures composed of individual units or small composite units.
For embodiments using layered silicates, this dissociation step involves delamination of the silicate material into sub-micron sized platelets of each layer or small composite layer. For embodiments using fibrous linear silicates, this dissociation step involves separating the silicate material into submicron sized fibrous structures composed of individual units or small composite units.

The flowable mixture mentioned in the mixture forming step is a mixture capable of dispersing the dissociated silicate material in submicron size. A polymer melt is a mixture of polymers that can be melt processed or preheated to a sufficiently high temperature to provide a viscosity low enough to perform submicron scale mixing. The processing temperature is
The temperature must be at least as high as the melting point of the polyamide used, but lower than the decomposition temperature of the organic treating agent for polyamide and silicate. The actual extruder temperature can be below the melting point of the polyamide used, since heat is generated by the flow. The processing temperature is high enough so that the polymer remains a bolimer melt during the process. In the case of crystalline polyamide, the temperature is above the melting point of the polymer. For example, about 22
A typical nylon 6 having a melting point of 5 ° C. has a temperature above about 225 ° C., for example about 2 ° C.
It can be melted in an extruder at temperatures ranging from 25 to about 260 ° C. Nylon 6,6
In this case, preferably a temperature of about 260 to about 320 ° C. is usually used.

Conventional methods can be used to form the flowable mixture. For example, a flowable mixture can be made using conventional polymer and additive blending techniques, where an extruder, a Banbury® type mixer, a Brabender® mixer, a Farrel® continuous mixer In a suitable mixer such as, for example, the polymer is heated to a temperature sufficient to form a polymer melt and mixed with the desired amount of the granular or powdered silicate material.

In one embodiment, the flowable mixture may be formed by mixing the polyamide with a previously prepared silicate-containing concentrate. The concentrate comprises a silicate and a polymer carrier. The concentration of the silicate material in the concentrate and the amount of the concentrate are selected to provide the desired silicate concentration for the final nanocomposite composition. Examples of suitable polymers for the carrier polymer of the concentrate include polyamide, ethylene-propylene rubber, ethylene-propylene diene rubber, ethylene-ethyl acrylate, ethylene-ethyl methacrylate or ethylene methacrylate. Examples include Iotek®, all available from Exxon
Ionomer and Escor® ATX acid terpolymer are included. Suitable polyamide polymers for the carrier polymer include nylon, such as nylon 6,
Nylon 6,6, nylon 4,6, nylon 6,9, nylon 6,10, nylon 6,12, nylon 11, nylon 12, amorphous nylon, aromatic nylon and copolymers thereof. The carrier polymer can be the same or different from the polyamide of the flowable mixture. For example, both polymers may be polyamides, especially nylon 6,6, but their molecular weights may be the same or different. The preferred weight average molecular weight of the carrier polymer of the concentrate ranges from about 5,000 to about 60,000 D. The most preferred weight average molecular weight of the carrier polymer ranges from about 10,000 to about 40,000D. In this embodiment, at least a portion of the dissociation step of the present invention described below may be performed through the formation of a concentrate such that the dissociation step may precede the flowable mixture formation step. Accordingly, the method steps (eg, forming and dissociating steps) may be performed sequentially, simultaneously, or in any combination, without regard to order. In the second step, the flowable mixture is thoroughly mixed so as to form a nanocomposite structure of dissociated silicate dispersed in the polymer melt, and then cooled. The silicate can be dissociated by shearing at an effective shear rate. As used herein, the term "effective shear rate" refers to a polyamide comprising a substantially homogeneously dispersed silicate that assists in dissociation of the silicate without substantially breaking individual units (eg, platelets or fibrous chains). Shear rate effective to provide a composition consisting of a matrix.

Any method can be used to apply shear to the flowable mixture or polymer melt. The shearing action may be provided by any suitable method, for example, by mechanical means, thermal shock, pressure change or ultrasound. Preferably, the flowable polymer mixture is prepared by mixing a portion of the melt by mechanical means such as a stirrer, Banbury® type mixer, Brabender® type mixer, Farrel® continuous mixer and extruder. It is sheared by a mechanical method flowing into the other part of the mixture. Most preferably, the mixture is subjected to multiple shears. In addition to providing high shear with multiple shears, long residence times are also provided, which improves performance characteristics. Or
The thermal shock is used to achieve the shear by raising or lowering the temperature of the mixture to cause thermal expansion and creating internal stresses that cause shear. In yet another procedure, the shear is achieved by an ultrasonic method that applies cavitation or resonance that causes the portions of the mixture to vibrate or excite in different phases by abruptly changing the pressure in the pressure change method to apply shear. The methods of shearing flowable polymer mixtures and polymer melts described above are only representative of useful methods, and any method known in the art for shearing flowable polymer mixtures and polymer melts may be used. .

Shearing can be performed by introducing polymer pellets at one end of a (single or twin screw) extruder and receiving the sheared polymer at the other end of the extruder. Preferred twin screw extruders are co-rotating, fully intermeshing, for example We
It is a ZSK series manufactured by Rner and Pfleiderer Company. The silicate can be fed to a twin screw extruder at a feed or downstream vent. Preferably, the silicate is provided at a downstream vent, which produces a composite polymer with improved performance characteristics.

Another preferred continuous compounding machine is the Farrel Continuous Mixe
r (FCM). For composites using Vydyne® 21 nylon, the preferred temperature of the melt is in the range of about 275-315 ° C, and the most preferred range is about 275-295 ° C.

A polymer melt containing a nanodispersed dissociated silicate material is prepared by a reactive extrusion method in which the silicate material is first dispersed as an aggregate in a liquid or solid monomer or on a nanoscale, and the monomer is polymerized in an extruder or the like. It may be formed. Alternatively, the polymer may be granulated and dry blended with the treated silicate material, after which the composition may be heated in a mixer until the polymer melts and forms a flowable mixture.

The third step of the method is a solid state polymerization step in which the blended pellets are held at elevated temperatures at least about 20 ° C. below the melting or softening point of the polymer for several hours. For example, in the case of nylon 6 and nylon 6,6, typical solid state polymerization conditions are to heat the solid polymer in a range from about 200 to about 240 ° C. for about 2 to about 5 hours. It is desirable to remove the water formed during the polymerization, for example by a stream of dry nitrogen. This additional step increases the molecular weight and improves the toughness, ductility and tensile strength of the nanocomposite.

The solid state polymerization step can be performed using a catalyst that increases the molecular weight of the polyamide, for example, a phosphorus-containing catalyst (eg, monosodium phosphate). The aforementioned phosphorus-containing catalyst is described in U.S. Pat. No. 4,966,949. In the case of a composite containing a catalyst, mild processing conditions are required to carry out the desired polymerization. For example, the processing temperature can be lower than the temperature used for solid state polymerization in the absence of a catalyst using the same polyamide, ie, 20 ° C. or more below the melting or softening point of the polyamide. Processing time can be reduced to about 0.5 to about 5 hours.

An optional operational step is a heat treatment step to heat the composition to improve the intercalation of the nylon molecules into the silicate structure. The heat treating step is performed by heating the composition at a temperature ranging from about 220 to about 240C for about 2 to about 5 hours. A heat treatment step can optionally be incorporated during the dissociation step by extending the residence time of the mixture in the mixer or extruder and heating under mild conditions.

The method of forming the nanocomposite is preferably performed in the absence of air, for example in the presence of an inert gas such as argon, neon or nitrogen. The method may be performed batch or continuously, for example, in a sealed container. Alternatively, the method can be performed in one working zone (eg, using an extruder that is largely free of air) or continuously in multiple reaction zones arranged in series or in parallel.

In another embodiment of the present invention, a method of making a polymer nanocomposite composition comprises:
Forming a flowable mixture of the polyamide, at least one monomer and the silicate material, dissociating at least 50%, but not all, of the silicate material, polymerizing the monomers, and subjecting the polyamide in the mixture to solid state polymerization. It should be understood that the monomer polymerization step is performed simultaneously or sequentially with one or more additional steps of the method of this embodiment. Preferably, at least one monomer of this embodiment includes monomers such as ε-caprolactam, lauryl lactam and the corresponding lactone.

In yet another embodiment of the present invention, a method of making a polymeric nanocomposite composition comprises forming a flowable mixture of a polyamide and a treated silicate material, wherein at least about 50%, but not all, of the treated silicate material described above. And most preferably during the dissociation step, adding an additional amount of the polyamide and subjecting the polyamide in the mixture to solid state polymerization.

Any of the above embodiments of the method of making the polymer nanocomposite composition may be followed by additional steps or treatments, or addition of the composition by extending the residence time in the mixer while removing water condensation products. May be carried out. Increasing the residence time can also improve the intercalation of the polyamide into the silicate.

The compositions of the present invention can be made without limitation into fibers, films or molded articles.

Solid state polymerization increases the toughness, strength and ductility of the produced polymer, while usually maintaining processability and modulus. Properties such as elongation at yield, tensile elongation at break, flexural modulus, elasticity, notched and unnotched Izod impact strength can be improved by solid state polymerization. Additional catalyst may be added, but need not be. Acid-functional clay treating agents are especially SSP (eg, SCPX 1016 and SCPX 125).
5) may be met. The treating agent can help build a polymer-clay bond by binding the nylon molecule to the adsorbed acid moiety. The stoichiometric balance of amine groups and acid groups can affect the properties of the resulting polymer. A high amine: acid ratio in nylon is desirable, especially for amino acid treated silicates. The use of solid state polymerization to finish the nanocomposite can be a low RV nylon starting material that will enhance intercalation and exfoliate the clay layer more. The inherent brittleness of nanocomposites incorporated in FCM is S
This can be overcome by SP finishing, making FCM a practical low cost method.

The following examples are presented to illustrate preferred embodiments of the present invention. The techniques described in the following examples are techniques which have been found by the present inventor to function well when practicing the present invention, and it is obvious to those skilled in the art to configure preferred modes for carrying out the present invention. Nevertheless, given the description herein, those skilled in the art can make many changes to the specific embodiments disclosed without departing from the spirit and scope of the invention and obtain the same or similar effects. be able to.

(Example)material  Nylon 6,6 polymers of the type described below are used in the nanocomposite described herein.
Used during

[0071]

[Table 1]

The montmorillonite clay used has an exchange capacity of about 95 meq / 100 g of silicate.

[0073]Example 1: Conventional formulation without SSP  Regarding the ductility and toughness of the nanocomposite,
The high molecular weight of Lix has been found to be advantageous over neat nylon polymer.
Clear. Smectite silicate is treated with nylon during compounding operation, especially during the first pass.
Reduces molecular weight, reduces ductility and toughness. For example, the molecular weight of nylon b is
40m by Krup Werner & Pfleiderer Company
m 7% dimethyldi (hydrogenated tallow) ammonium in a ZSK twin screw extruder
Montmorillonite (2M2HT-montmorillonite) treated with cation
Is passed from 36,500 to 31,500D.
Was. In the second pass, the MW dropped further to 21,000D. Instead, dry
The second pass under conditions increases molecular weight and enhances exfoliation and dispersion of nanoplatelets
To improve mechanical performance.

Solid state polymerization (SSP) can be performed on compounded nanocomposites under similar conditions used for neat polymers as a more efficient way to increase molecular weight. Improvements in tensile strength and elongation, as well as notched and unnotched Izod impact strength are obtained. The modulus sometimes drops slightly, probably due to the degradation of the thin delaminated platelets during the flow of the high viscosity nylon matrix.

[0075]Effect of molecular weight  Compounded by a conventional method in a twin screw extruder and manufactured without subsequent SSP
For nanocomposites, the molecular weight of nylon 6,6 or equivalent relative solution
The effect of viscosity (RV) on mechanical properties is shown in FIGS. Nylon RV is
It is the RV of the raw materials charged in the extruder. P1 and P in FIG. 2 are the first to the compounding machine.
1st pass and 2nd pass.

In the case of nanocomposites, including those that are later subjected to SSP, it is preferred that the amine / carboxyl end group ratio on nylon be high. The combination of the intrinsic Lewis acidity of the clay surface and the acidity introduced from the clay treating agent in the form of amino acid cations or polyacrylate peptizers used in some clay grades alters the end group balance of the nylon, thus Some depolymerization occurs. For example, for Na-montmorillonite and 2M2HT-montmorillonite coated with acrylate, the acidity of 40 μeq / g (4.0 mequiv / 100 g-clay) was measured. Amino acid exchanged grades have higher acid levels according to the degree of substitution, as measured by the milliequivalent exchange ratio (MER), expressed in milliequivalents of cation per 100 g of silicate. Therefore, nylons a and c are preferred over nylon b. The high concentration of amine end groups in nylon d is particularly important for silicates treated with amino acid cations that can react with the amine end groups of nylon. The silicate treated in this way reacts strongly to the effect of the SSP, so that the above properties are significantly improved over nanocomposites containing pure silicate or treated with unreacted parts.

Montmorillonite exchanged with 4% of 12-aminolauric acid (ALA-montmorillonite) was blended, and then subjected to solid-phase polymerization. The change in molecular weight to high-amine nylon d was analyzed by GPC.

[0078]

[Table 2] The symbols used in the above table have the following meanings: Mw weight average molecular weight; Mn number average molecular weight; IV intrinsic viscosity measured in formic acid.

[0079]Example 2: Solid state polymerization (SSP)  As shown in the table above, the molecular weight of nylon or its distribution depends on the extrusion process.
It does not change at will. Although the molecular weight of the nanocomposite increased significantly during SSP,
The presence of acid moieties on the layer allows the gelation of the neat resin
descend. In addition, the nylon matrix binds to the clay during the compounding operation
Is evident. During solid state polymerization, the nylon may be branched or
To form an ultrahigh molecular weight material that becomes insoluble.

Solid state polymerization is accomplished by heating the plastic pellets to 200-240 ° C. (typically 220 ° C.) for 2-4 hours (typically 4 hours) while sweeping with dry nitrogen to remove condensation water. Carried out. It was not necessary to add additional catalyst over the catalyst present from the initial melt polymerization, but the mono- or disodium phosphate was added to 100-15%.
0 ppm can be added. In one example, the addition of 1,000 ppm monosodium phosphate increased the compounded molecular weight from 27,400 D to 30,600 D (SSP was not performed).

Normally, the SSP dryer is set at 470 ° F. (243 ° C.) oil temperature and the nylon nanocomposite is heated to 220 ° C. (230 ° C. shell temperature) after a heating period of about 2 hours.
For 4 hours. The time-temperature profile generated for a representative nanocomposite solid state polymerization run is shown below.

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

[0085]

[Table 6]

[0086]

[Table 7]

[0087]

[Table 8]

[0088]

[Table 9]

[0089]Example 3: Introduction of ductility  An example of the introduction of ductility by SSP was 4.0 w / o ALA-Monon in nylon a.
This is shown by the stress-strain curve for morillonite (FIGS. 3 and 4).

[0090]Example 4: Increasing molecular weight  The increase in the molecular weight of the nylon matrix is indicated by the intrinsic viscosity measurements shown in the table below.
It is.

[0091]

[Table 10]

As shown, for example, in the data and graphs below (FIG. 5), the intrinsic viscosity increases linearly with time in the SSP dryer.

[0093]

[Table 11]

[0094]

[Table 12]

As shown by the ALA-montmorillonite data in the graph (FIG. 6), the rate of increase is faster for long residence time acid-terminated ammonium cations in a high amine nylon matrix.

[0096]Example 5: Injection molding of solid state polymerized nanocomposite  Solid-state polymerized nanocomposites containing nylon c and d as the main components
Molds more easily at high set temperatures. Of these two nylons, Niro
The nanocomposite mainly composed of nylon d is the nanocomposite mainly composed of nylon c.
It is more easily formed than a pit. This is probably due to the nylon c matrix
This is because higher viscosity levels than Ron d are reached. Low pack pressure and holding pressure
You can also use force.

In both cases, higher packing and holding pressures than normally used for injection molding nylon 6,6 are preferred for removal of the molding.

[0098]

[Table 13]

[0099] Higher packs and retention times also usually tend to increase tensile modulus and strength. In the absence of SSP, a low molding temperature is preferred for high ductility of the molded part because the polymer is less thermally decomposed. However, in the case of SSP, higher ductility is achieved with higher molecular weights, and higher temperatures known to be advantageous for the rigidity of the molded nanocomposites can be used. In this way, additional processing flexibility is provided by the SSP method, where the injection molding parameters can be adjusted to optimize the overall molding process and characteristic spectrum.

[0100]Example 6: Machine for concentrate route using high amine nylon matrix Characteristic  To enhance the properties introduced by solid state polymerization of the final nanocomposite composition
The use of high amine terminated carrier nylon in concentrates was evaluated. 17% in nylon d
 High amine nylon concentrates containing ALA-montmorillonite can be combined with different molecular weights
And added to three resins having amine / acid end group concentrations and molded. Optionally, molding
Previously, solid state polymerization was performed. A fairly strong screw design, ZSK 40mm
Feed rate of 100 lbs / hr (43.5 kg / hr) in a screw screw extruder
And a screw speed of 250 rpm. The barrel zone temperature is set at 270 ° C.
Specified.

For solid state polymerization, the polymerization dryer is 470 ° F. (243 ° C.) from start to finish.
Oil temperature, 220 ° C resin temperature and 230 ° C shell temperature up to 4
The residence time was the time. The table below shows the specifications and mechanical properties of the sample.

[0102]

[Table 14] ^* Stress at 5% strain The table above shows the beneficial effects of solid state polymerization in improving the ultimate mechanical properties of tensile strength and elongation, as well as the notched or unnotched Izod impact strength. ALA
The strong effect described above on the nanocomposites containing montmorillonite compensates for the molecular weight reduction of nylon that may occur during compounding.

The effect on the parameters can be analyzed more quantitatively using Neurocomputer CAD / Chem software (AIWare, Cleveland, OH). In this approach, nylon is designated by nominal weight average molecular weight and nominal amine / acid end group ratio. The mineral content of the nanocomposite is shown as a correlation variable to account for the smallest difference between the samples. Based on this criterion,
The following linear correlation coefficient is obtained. SSP refers to solid state polymerization time (hours).

[0104]

[Table 15]

The above results show that solid-state polymerization usually increases tensile properties and two types of Izod impact strength, but has a negligible effect on flexibility as a whole. (
A high initial molecular weight of the nylon (before compounding) is somewhat advantageous for notched Izod impact strength, but has no apparent effect on properties. A high amine / acid end group ratio usually helps maintain the nylon molecular weight by offsetting the additional acidity introduced by the clay treatment, and thus is usually a factor for ductility (elongation) and toughness (unnotched and notched strength). Considered to be advantageous.

However, strong parameter interactions not shown in the table above occur and can be seen in the following response surface. For a solid state polymerization time of 4 hours, a nanocomposite containing 4.9% by weight of ALA-montmorillonite clay (3.9% mineral ash) in 40,000 Mw nylon with balanced end groups is 14. 00 Kpi tensile strength, Young's modulus of 612 Kpsi, final elongation of 21.6%, 558 Kp
flexural modulus of si, bending stress of 18.68 Kpsi at 5% stress (breaking stress or less), notched Izod impact strength of 0.91 ft-lb / in, 43.9 ft-
It is expected to have properties of lb / in unnotched Izod impact strength and 9.5 mil / in shrinkage.

FIG. 7 shows that when nanoclay is present but not in neat nylon, the tensile strength is S
It shows that it increases with SP time.

However, the ductility and toughness of the nanocomposites are significantly increased by solid state polymerization, but not significantly by the high amine / acid ratio and the initial molecular weight of nylon (FIGS. 8, 9 and 10). The ALA-montmorillonite concentration in FIGS.
9%.

The stiffness (tensile modulus) increases slightly due to solid-state polymerization. This is probably due to the formation of a network between the high MW nylon and the clay due to the reactive constraint of the nylon polymer molecules on the ammonium ions adsorbed on the clay surface.

[0110]Example 7: List of data  ALA-montmorillonite including solid state polymerization, 2M2HT-montmorillonite
Of 2MBHT-montmorillonite and sepiolite nanocomposite preparation
For all, a comprehensive summary of composition, SSP time and mechanical properties is given in the table below.

[0111]

[Table 16]

[0112]

[Table 17]

It can be seen that amino acid organoclays provide the most favorable combination of nanocomposite properties after SSP. However, without SSP, more embrittlement can occur than with other clay types. It is believed that the acid functionalization competes with the amine end groups on the nylon chain, thus increasing the end group balance during compounding and reducing the nylon molecular weight. Although a high initial molecular weight or amino / acid end group ratio in a particular nylon is useful to offset this effect, it is preferred to perform SSP after compounding to restore or even increase the nylon molecular weight . It is observed that pure sepiolite has less adverse effects on ductility and toughness compared to montmorillonite.

Farr, which gives the nanocomposite a high modulus, but tends to embrittle
The nanocomposite material compounded in a single pass through the ell continuous mixer can be solid state polymerized to restore ductility and toughness and increase tensile strength. The combination of SSP with FCM and SSP is a low cost method for producing ductile, tough, yet rigid nanocomposites.

[0115] All of the compositions, methods and devices described herein can be made and executed without undue experimentation in light of the description herein. Having described preferred embodiments of the compositions and methods of the present invention, the compositions, methods, apparatus, and steps and order of steps described herein may be used without departing from the spirit, spirit and scope of the invention. It will be obvious to those skilled in the art that changes can be made. More specifically, it is self-evident that equivalent or similar effects can be obtained by using other chemically related substances in place of the substances described herein. All such substitutions and modifications apparent to those skilled in the art are deemed to be within the concept, spirit and scope of the invention.

[Brief description of the drawings]

FIG. 1 shows the effect of molecular weight by 7w / o 2M2HT-montmorillonite.

FIG. 2 shows the effect of molecular weight on the nanocomposite stiffness of 7w / o 2M2HT-montmorillonite.

FIG. 3 is a graph of stress versus strain without an SSP.

FIG. 4 is a graph of stress versus strain with SSP.

FIG. 5 is a graph of intrinsic viscosity versus solid state polymerization time.

FIG. 6 is a graph of intrinsic viscosity versus time at 220 ° C.

FIG. 7 is a graph of final tensile strength versus ash (%) versus SSP.

FIG. 8 is a graph of eu vs. SSP vs. ash (%).

FIG. 9 is a graph of notched Izod impact strength versus Mw versus SSP.

FIG. 10 is a graph of unnotched Izod impact strength versus amine / acid versus SSP.

FIG. 11 is a graph of elongation versus SSP versus ash (%).

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] February 14, 2000 (2000.2.14)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C08L 51/06 C08L 51/06 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ) , TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG , MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor Jorda, Saikat S. United States, Missouri 63021, Bowlwin, Keyfar Trails Drive, 946 F-term (reference) 4J002 BB034 BB072 BB124 BB152 BB153 BB213 BG033 BG043 BG104 BF154 CF04 CF04 CF184 CG004 CH004 CH074 CL002 CL011 CL012 CL021 CL022 CL031 CL032 CL061 CL062 CL064 CL084 CM044 CN014 CN034 DJ006 DJ007 DJ037 DJ047 DJ057 DL007 EG047 EL008 EN006 EN017 EN116 EP017 EU018 EU066 EV236 FA047 FB097 FB117 FB127FB 027 FD097 FD107 FD137 FD167 FD203 FD207 FD317

Claims (41)

[Claims] 1. A fluid mixture of a polymer amide and a silicate material is formed,
Dissociating at least about 50%, but not all, of the silicate material to form a dissociation mixture, subjecting the dissociation mixture to solid state polymerization conditions to polymerize a polyamide to form a polymer nanocomposite composition. A method for producing a polymer nanocomposite composition, comprising: 2. The polyamide is nylon 6, nylon 6,6, nylon 4,6.
The nylon according to claim 1, characterized in that it is nylon 6,9, nylon 6,10, nylon 6,12, nylon 11, nylon 12, amorphous nylon, aromatic nylon, or a copolymer thereof. Method. 3. The method according to claim 1, wherein the silicate is montmorillonite, nontronite, beidellite, horconscoite, hectorite, synthetic or natural sepiolite, saponite, sauconite, magadite or kenyaite. Method. 4. The composition further comprises at least one surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, chain extender, compatibilizer, colorant,
The method according to claim 1, further comprising a release lubricant, an antistatic agent, a pigment or a flame retardant. 5. The method according to claim 4, wherein the coupling agent is a silane, titanate or zirconate. 6. The method according to claim 5, wherein the coupling agent is γ-aminopropyltriethoxysilane. 7. The method according to claim 6, wherein the concentration of γ-aminopropyltriethoxysilane in the polymer nanocomposite composition ranges from about 0.5 to about 5% by weight of the silicate material. The described method. 8. The method according to claim 1, wherein the concentration of the silicate material in the polymer nanocomposite composition ranges from about 0.1 to about 12.0% by weight of the polymer nanocomposite composition. The described method. 9. The method according to claim 1, wherein the concentration of the silicate material in the polymer nanocomposite composition ranges from about 0.5% to about 6.0% by weight of the polymer nanocomposite composition. The described method. 10. The method according to claim 1, wherein the silicate material is dissociated by a mechanical unit, thermal shock, pressure change or ultrasonic waves. 11. The mechanical unit is a stirrer, a Banbury® type mixer, a Brabender® type mixer, a Farrel® continuous mixer or an extruder. Item 10. The method according to Item 10. 12. The method according to claim 11, wherein the extruder is a single screw or twin screw extruder. 13. The method according to claim 12, wherein the twin screw extruder is a co-rotating fully intermeshing twin screw extruder. 14. The method according to claim 1, wherein the silicate material is dissociated using two or more dissociation methods selected from the group consisting of a mechanical unit, a thermal shock, a pressure change, and an ultrasonic wave. The method described in. 15. The method according to claim 1, wherein the silicate material is added as a mixture of the silicate material and the carrier polymer. 16. The carrier polymer comprising polyamide, ethylene-propylene rubber,
Ethylene-propylene diene rubber, ethylene-ethyl acrylate, ethylene-
The method according to claim 15, wherein the method comprises ethyl methacrylate or ethylene methacrylate. 17. The polyamide carrier polymer is nylon 6, nylon 6,6,
17. The method according to claim 16, wherein the material is nylon 4, 6, nylon 6, 9, nylon 6, 10, nylon 6, 12, nylon 11, nylon 12, amorphous nylon, aromatic nylon, or a copolymer thereof. The method described in the section. 18. The method according to claim 15, wherein the carrier polymer has a different weight average molecular weight than the polyamide in the flowable mixture. 19. The method according to claim 15, wherein the carrier polymer is a polymer other than polyamide. 20. The method according to claim 15, wherein the carrier polymer has a weight average molecular weight of about 10,000 to 40,000 D. 21. The method of claim 1, wherein the flowable mixture further comprises a monomer. 22. The method according to claim 19, wherein the monomer is ε-caprolactam, lauryl lactam,
The second aspect of the present invention is caprolactone or lauryl lactone.
Item 2. The method according to item 1. 23. The method according to claim 21, further comprising polymerizing the monomer. 24. The method of claim 1, comprising adding additional polyamide to the flowable mixture during the dissociation step. 25. A silicate material of the formula⁺NR_aR_bR_cR_d  (Where R_a, R_bAnd R_cIs hydrogen (H) and R_dContains a carboxylic acid moiety
The method according to claim 1, wherein the treatment is performed with an ammonium ion having the following formula:
The method described. 26. The method according to claim 1, wherein the silicate is treated with an azine cationic dye. 27. The method according to claim 26, wherein the azine cationic dye is nigrosine or anthracin. 28. The method according to claim 4, wherein the filler is carbon fiber, glass fiber, kaolin clay, walstonite, mica or talc. 29. The method according to claim 4, wherein the compatibilizer is an acid-modified hydrocarbon polymer. 30. A polyethylene in which the compatibilizer is grafted with maleic anhydride,
The method according to claim 4, wherein the method is a polypropylene grafted with maleic anhydride or an ethylene-butylene-styrene block copolymer grafted with maleic anhydride. 31. The method according to claim 4, wherein the lubricant is an alkylamine, stearamide, dialium aluminum stearate or trialuminum stearate. 32. An impact modifier comprising ethylene-propylene rubber or ethylene-propylene rubber.
Propylene diene rubber, methacrylate-butadiene-styrene (having a core-shell morphology), poly (butyl acrylate) with or without carboxyl modification, poly (ethylene-acrylate), poly (ethylene-methacrylate),
Poly (ethylene-acrylic acid), poly (ethylene-acrylate) ionomer, poly (ethylene-methacrylate-acrylic acid) terpolymer, poly (styrene-butadiene) block copolymer, poly (styrene-butadiene-styrene) block terpolymer, poly 4. A styrene-ethylene / butylene-styrene block terpolymer or a poly (styrene-ethylene / butylene-styrene carboxylate) block terpolymer.
The method described in the section. 33. The method of claim 1, wherein the nanocomposite composition comprises a polyamide crystalline region of less than about 1.0 μm. 34. The method according to claim 1, wherein the nanocomposite composition has the form of a fiber, a film or a molded article. 35. The method of claim 1, wherein the solid state polymerization comprises heating the dissociation mixture at a temperature ranging from about 200 to about 240 ° C. for about 2 to about 5 hours. . 36. The solid state polymerization comprises adding a catalyst and heating the dissociation mixture to a temperature at least 20 ° C. below the melting or softening point of the polyamide for about 0.5 to about 5 hours in the presence of the catalyst. The method of claim 1, wherein the molecular weight of the formed nanocomposite composition is higher than the molecular weight of the nanocomposite composition formed in the absence of the catalyst. 37. The method according to claim 1, further comprising heat treating the nanocomposite composition to a temperature in the range of about 200 to about 240 ° C. for about 2 to about 5 hours. . 38. A nanocomposite composition comprising a polyamide and a silicate, wherein the concentration of amine end groups in the polyamide is at least 10 mol% higher than the concentration of carboxylic acid end groups. 39. A nanocomposite composition comprising a polyamide and a silicate, wherein the polyamide has a weight average molecular weight in the range of about 30,000 to about 40,000D. 40. A nanocomposite composition comprising a polyamide and a silicate, wherein the polyamide has a weight average molecular weight of at least 40,000D. 41. A nanocomposite composition comprising a polyamide and a silicate
Wherein the silicate is of the formula⁺NR_aR_bR_cR_d  (Where R_a, R_bAnd R_cIs hydrogen (H) and R_dContains a carboxylic acid moiety
) Wherein said nanocomponent is treated with an ammonium ion having
Jit composition.