CA2315076C - Polyester nanocomposites for high barrier applications - Google Patents
Polyester nanocomposites for high barrier applications Download PDFInfo
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- CA2315076C CA2315076C CA002315076A CA2315076A CA2315076C CA 2315076 C CA2315076 C CA 2315076C CA 002315076 A CA002315076 A CA 002315076A CA 2315076 A CA2315076 A CA 2315076A CA 2315076 C CA2315076 C CA 2315076C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
Abstract
The present invention relates to a composition comprising a polymer having dispersed therein at least one layered clay material which has been cation exchanged with an organic cation salts represented by Formula (I) wherein M represents either nitrogen or phosphorous; X- represents an anion selected from the group consisting of halogen, hydroxide, or acetate anions, preferably chloride and bromide; R1 is selected from the group consisting of straight and branched alkyl groups having at least 8 carbon atoms; R2, R3, and R4 are independently selected from straight or branched alkyl groups having 1 to four carbon atoms; and at least one expanding agent which is compatible with said polymer. Preferred polymers include polyesters. The compositions of the present invention show vastly improved platelet separation as evidenced by higher than previously reported basal spacing.
Description
POLYESTER NANOCOMPOSITES FOR HIGH BARRIER
APPLICATIONS
Background of the Invention Polyesters such as polyethylene terephthalate) (PET) are widely used in bottles and containers which are used for carbonated beverages, fruit juices, and certain foods. Because of the limited barrier properties with regard to oxygen, carbon dioxide and the like, PET containers are not generally used for products requiring long shelf life. It would therefore be desirable to provide improved barrier properties.
This invention relates to polyester composite materials having improved barrier. The polyester composite materials of this invention are useful for forming ~ packages that have improved gas barrier properties. Containers made from these polyester composite materials are ideally suited for protecting consumable products, such as foodstuffs, soft drinks, and medicines.
Prior Art A. Usuki, M. Kato, A. Okada, T. Kurauchi, J. Appl. Polym. Sci. 63, 137(1997) describes a polypropylene composite that is made by melt mixing polypropylene with an organoclay that has been expanded with a polyolefin oligomer.
Y. Kurokawa, H. Yasuda, A. Oya, J. Mater. Sci. Letters. 15, 1481 (1996) describes a polypropylene composite that is made by copolymerizing diacetone acrylamide and malefic acid modified-polypropylene in the presence of an 3 0 organoclay and melt mixing with polypropylene.
T. J. Pinnavaia and Tie Lan, Chem. Mater. 6, 2216 (1994) describes organoclays that have been expanded with epoxy resin monomers.
M. Kawasumi, N. Hasegawa, M. Kato, A. Usuki, and A Okada, Macromolecules, 30, 6333 (1997) describes a polypropylene composite that is 3 5 made by simple melt-mixing of polypropylene, malefic anhydride modified polypropylene oligomers, and clays intercalated with stearylammonium ion.
U. S. Patent 4,739,007 discloses polyamide composite materials containing layered clay mineral intercalated with organic opium salts.
U. S. Patent 5,164,460 discloses polyimide composite materials containing layered clay mineral intercalated with organic opium salts.
l0 WO 93/04118 relates to a process for forming polymeric composites which are comprised of platelet particles containing organic opium salts and dispersed in a polymeric matrix.
U. S. Patent 5,336,647 and 5,429,999 describe the preparation of layered clays containing polyaikoxylated ammonium salts. Use of these clays in polyesters was not recognized.
Among the numerous patents that describe the preparation of layered clays containing ammonium salts are U. S Pat. Nos. 2,531,427; 2,966,506; 4,081,496;
4,105,578; 4,116,866; 4,208,218; 4,391,637; 4,410,364; 4,412,0I8; 4,434,075;
4,434,076; 4,450,095; 4,517,112; 4,677,158; 4,769,078; 5,110,501; and 5,334,241.
Description of the Invention This invention relates to polyester composite materials which are comprised of a polyester polymer and a pre-swelled layered organociay material.
Specifically, the present invention relates to a composition comprising a polymer having dispersed therein at least one pre-swelled organoclay material comprising A layered clay material which has been ration exchanged with an organic ration salts represented by Formula I:
R, 3o I +
RZ-M-R3 x I
3 5 wherein M represents either nitrogen or phosphorous; x represents an anion selected from the group consisting of halogen, hydroxide, or acetate anions, preferably chloride and bromide; Rl is selected from the group consisting of straight and branched alkyl groups having at least 8 carbon atoms; R2, R3, and r a r' f 1 !' ~' a. r t « c! se t . n t f t t t t f f t 1 t f f r n t ,t t t 1 t 1 t r 1 f r 1 ( t ! f - t f t t t ( l a t t t t l f t f f 1, , t s r r r l r ( t f r r a I l are independently selected from hydrogen or a straight or branched alkyl group having 1 to 22 carbon atoms, preferably having 1 to 4 carbon atoms; and at least one expanding agent which is compatible with said polymer.
.A.nother embodiment of the present invention is a polyester composite comprising at IO least one polyester having dispersed therein up to' about 30 weight percent of an expanded organoclay comprising (a) 20 to 80 weight percent of a swellable layered silicate clay such as montmorillonite that has been ion exchanged with an opium salt having one substituent selected from the group consisting of straight and branched alkyl 15 groups having at least 8 carbon atoms and (b) 80 to 20 weight percent of at Ieast one expanding agent.
.A,lthough some enhancement of barrier of a polyester occurs by incorporation of an organoclay itself, it was found unexpectedly that a greater improvement in barrier occurred when the organoclay was pre-swelled with an expanding agent.
20 Without being bound by any particular theory, it is believed that the interlayex spacing of the clay increases due to the expanding agent, and as a result, the interaction of the platelet particle layers are weakened to provide improved dispersion in the polyester.
An organoclay is defined as a swellable layered clay material that has been ion exchanged with an opium ion. An expanding agent is defined here as any material that will 25 increase the basal spacing of an organoclay when introduced into the gallexies~ An expanded organoclay is defined here as an organoclay that has been pre-swelled with an expanding agent.
These novel polyester composites containing the expanded organoclay exhibit lower oxygen permeability than the polyester or the polyester organoclay blend alone. The 30 improvement in oxygen permeability is .clearly apparent in the comparison of film prepared from (I) unmodifiedpoly(ethylene terephthalate) and (2) poly(ethylene.terephthalate)-platelet particle composites containing 2 wt. % of bis(2-hydroXyethyl) methyl tallow ammonium .
montmorillonite and (3) polyethylene terephthalate) platelet particle composite containing 2 wt. % of bis(2-hydroxyethyl) methyl tallow ammonium montmoriilonite and pre-swelled with :15 the A~IEN~ED S~Ft~' s . t.
w0 99132403 PCT/US97/24I03 expanding agent polyethylene oxide) with molecular weight of 3350. The-oxygen permeabilities of(1), (2), and (3) are 12, 11, and 6 cc-mil/I00 in2-24 hours-atm, respectively. These examples and other examples demonstrating this invention are shown in Table 1.
:l.0 raanoclav materials The compositions of the present invention comprise between about 0.01 and t.
about 25 wt%, preferably between 0.5 and 2S wt%,.more preferably between O.S
and 15 wt% and most preferably between 0.5 arid lQ~wt% of at least one certain expanded organoclay which is derived from organic and inorganic clay materials.
The amount of expended organoclays is determined by measuring the amount of ash of the polyester-platelet compositions when.treated in accordance with ASTM
DS630-94 .
The platelet particles of the present invention have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 1000 nm. For the purposes of this invention measurements refer only to the platelet particle and not any dispersing aids or pretreatment compounds which might be used. Suitable platelet particles are derived from clay materials which are free flowing powders having a ration exchange capacity between about 0.3 and about 3 meq/g and pr-efer-ably beturreen about 0.8 and about 1.S meQlg. Examples of suitable clay materials include mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontranite, beidellite, volkonskoite, saponite, sauconite, magadiite, vermiculite; mica, kenyait~, synthetic.
sodium hecotorites, and the like. Clays of this nature are available from various companies including Southern Clay Products and Nanocor, Inc. Generally the clay 3 0~ materials are a dense agglomeration of platelet particles which are closely stacked together like cards.
Preferred swellable layered clay materials are phyllosilicates of the 2:1 type having a ration exchange capacity of 50 to 200 milliequivalents per 100 grams of mineral. The mo$t preferred swellable layered clay materials are smectite clay minerals, specifically montmorillonite.
APPLICATIONS
Background of the Invention Polyesters such as polyethylene terephthalate) (PET) are widely used in bottles and containers which are used for carbonated beverages, fruit juices, and certain foods. Because of the limited barrier properties with regard to oxygen, carbon dioxide and the like, PET containers are not generally used for products requiring long shelf life. It would therefore be desirable to provide improved barrier properties.
This invention relates to polyester composite materials having improved barrier. The polyester composite materials of this invention are useful for forming ~ packages that have improved gas barrier properties. Containers made from these polyester composite materials are ideally suited for protecting consumable products, such as foodstuffs, soft drinks, and medicines.
Prior Art A. Usuki, M. Kato, A. Okada, T. Kurauchi, J. Appl. Polym. Sci. 63, 137(1997) describes a polypropylene composite that is made by melt mixing polypropylene with an organoclay that has been expanded with a polyolefin oligomer.
Y. Kurokawa, H. Yasuda, A. Oya, J. Mater. Sci. Letters. 15, 1481 (1996) describes a polypropylene composite that is made by copolymerizing diacetone acrylamide and malefic acid modified-polypropylene in the presence of an 3 0 organoclay and melt mixing with polypropylene.
T. J. Pinnavaia and Tie Lan, Chem. Mater. 6, 2216 (1994) describes organoclays that have been expanded with epoxy resin monomers.
M. Kawasumi, N. Hasegawa, M. Kato, A. Usuki, and A Okada, Macromolecules, 30, 6333 (1997) describes a polypropylene composite that is 3 5 made by simple melt-mixing of polypropylene, malefic anhydride modified polypropylene oligomers, and clays intercalated with stearylammonium ion.
U. S. Patent 4,739,007 discloses polyamide composite materials containing layered clay mineral intercalated with organic opium salts.
U. S. Patent 5,164,460 discloses polyimide composite materials containing layered clay mineral intercalated with organic opium salts.
l0 WO 93/04118 relates to a process for forming polymeric composites which are comprised of platelet particles containing organic opium salts and dispersed in a polymeric matrix.
U. S. Patent 5,336,647 and 5,429,999 describe the preparation of layered clays containing polyaikoxylated ammonium salts. Use of these clays in polyesters was not recognized.
Among the numerous patents that describe the preparation of layered clays containing ammonium salts are U. S Pat. Nos. 2,531,427; 2,966,506; 4,081,496;
4,105,578; 4,116,866; 4,208,218; 4,391,637; 4,410,364; 4,412,0I8; 4,434,075;
4,434,076; 4,450,095; 4,517,112; 4,677,158; 4,769,078; 5,110,501; and 5,334,241.
Description of the Invention This invention relates to polyester composite materials which are comprised of a polyester polymer and a pre-swelled layered organociay material.
Specifically, the present invention relates to a composition comprising a polymer having dispersed therein at least one pre-swelled organoclay material comprising A layered clay material which has been ration exchanged with an organic ration salts represented by Formula I:
R, 3o I +
RZ-M-R3 x I
3 5 wherein M represents either nitrogen or phosphorous; x represents an anion selected from the group consisting of halogen, hydroxide, or acetate anions, preferably chloride and bromide; Rl is selected from the group consisting of straight and branched alkyl groups having at least 8 carbon atoms; R2, R3, and r a r' f 1 !' ~' a. r t « c! se t . n t f t t t t f f t 1 t f f r n t ,t t t 1 t 1 t r 1 f r 1 ( t ! f - t f t t t ( l a t t t t l f t f f 1, , t s r r r l r ( t f r r a I l are independently selected from hydrogen or a straight or branched alkyl group having 1 to 22 carbon atoms, preferably having 1 to 4 carbon atoms; and at least one expanding agent which is compatible with said polymer.
.A.nother embodiment of the present invention is a polyester composite comprising at IO least one polyester having dispersed therein up to' about 30 weight percent of an expanded organoclay comprising (a) 20 to 80 weight percent of a swellable layered silicate clay such as montmorillonite that has been ion exchanged with an opium salt having one substituent selected from the group consisting of straight and branched alkyl 15 groups having at least 8 carbon atoms and (b) 80 to 20 weight percent of at Ieast one expanding agent.
.A,lthough some enhancement of barrier of a polyester occurs by incorporation of an organoclay itself, it was found unexpectedly that a greater improvement in barrier occurred when the organoclay was pre-swelled with an expanding agent.
20 Without being bound by any particular theory, it is believed that the interlayex spacing of the clay increases due to the expanding agent, and as a result, the interaction of the platelet particle layers are weakened to provide improved dispersion in the polyester.
An organoclay is defined as a swellable layered clay material that has been ion exchanged with an opium ion. An expanding agent is defined here as any material that will 25 increase the basal spacing of an organoclay when introduced into the gallexies~ An expanded organoclay is defined here as an organoclay that has been pre-swelled with an expanding agent.
These novel polyester composites containing the expanded organoclay exhibit lower oxygen permeability than the polyester or the polyester organoclay blend alone. The 30 improvement in oxygen permeability is .clearly apparent in the comparison of film prepared from (I) unmodifiedpoly(ethylene terephthalate) and (2) poly(ethylene.terephthalate)-platelet particle composites containing 2 wt. % of bis(2-hydroXyethyl) methyl tallow ammonium .
montmorillonite and (3) polyethylene terephthalate) platelet particle composite containing 2 wt. % of bis(2-hydroxyethyl) methyl tallow ammonium montmoriilonite and pre-swelled with :15 the A~IEN~ED S~Ft~' s . t.
w0 99132403 PCT/US97/24I03 expanding agent polyethylene oxide) with molecular weight of 3350. The-oxygen permeabilities of(1), (2), and (3) are 12, 11, and 6 cc-mil/I00 in2-24 hours-atm, respectively. These examples and other examples demonstrating this invention are shown in Table 1.
:l.0 raanoclav materials The compositions of the present invention comprise between about 0.01 and t.
about 25 wt%, preferably between 0.5 and 2S wt%,.more preferably between O.S
and 15 wt% and most preferably between 0.5 arid lQ~wt% of at least one certain expanded organoclay which is derived from organic and inorganic clay materials.
The amount of expended organoclays is determined by measuring the amount of ash of the polyester-platelet compositions when.treated in accordance with ASTM
DS630-94 .
The platelet particles of the present invention have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 1000 nm. For the purposes of this invention measurements refer only to the platelet particle and not any dispersing aids or pretreatment compounds which might be used. Suitable platelet particles are derived from clay materials which are free flowing powders having a ration exchange capacity between about 0.3 and about 3 meq/g and pr-efer-ably beturreen about 0.8 and about 1.S meQlg. Examples of suitable clay materials include mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontranite, beidellite, volkonskoite, saponite, sauconite, magadiite, vermiculite; mica, kenyait~, synthetic.
sodium hecotorites, and the like. Clays of this nature are available from various companies including Southern Clay Products and Nanocor, Inc. Generally the clay 3 0~ materials are a dense agglomeration of platelet particles which are closely stacked together like cards.
Preferred swellable layered clay materials are phyllosilicates of the 2:1 type having a ration exchange capacity of 50 to 200 milliequivalents per 100 grams of mineral. The mo$t preferred swellable layered clay materials are smectite clay minerals, specifically montmorillonite.
" " ., .. ..
. ~ , . ' , .
'. ., ,. .,., " ..
Other non-clay materials having the above-described ion exchange capacity and size, such as chalcogens may also be used as the source of platelet particles under the present invention. These materials are known in the art and need not be described in detail here.
Dispersions of platelet particles having large basal spacing (greater than about 3 nm) have not been previously disclosed. Previous patents and applications have claimed to produce polyesters containing intercalated or exfoliated platelet particles, as indicated by large basal spacings or the lack of a detectable basal spacing by X-ray, however, the results could not be reproduced, particularly in polyesters.
Useful organic cation salts for the process of this invention can be represented by Formula I:
RI
Rz-M-R3 X-(I) wherein M represents nitrogen or phosphorous, X- represents an anion selected from the group consisting of halogen, hydroxide, or acetate anions, preferably chloride and bromide;
R, is selected from the group consisting of straight and branched alkyl groups having at least 8 carbon atoms; R2, R3, and R4 are independently selected from organic and oligomeric ligands or may be hydrogen. Examples of useful organic ligands include, but are not limited to, linear or branched alkyl groups having 1 to 22 carbon atoms, aralkyl groups which are benzyl and substituted benzyl moieties including fused ring moieties having linear chains or branches of 1 to 22 carbon atoms in the alkyl portion of the structure, aryl groups such as phenyl and substituted phenyl including fused ring aromatic substituents, beta, gamma unsaturated groups having six or less carbon atoms, and alkyleneoxide groups having 2 to 6 carbon atoms, and alkyleneoxide groups having 2 to 6 carbon atoms. Examples of useful oligomeric ligands include, but are not limited to, poly(alkylene oxide), polystyrene, polyacrylate, polycaprolactone and the like.
AN1~W~~ S;-'rt'C'I
Preferably RZ, R3, and R4 are independently selected from straight or branched alkyl groups having 1 to four carbon atoms. More preferably at least one of R2, R3, and R4 is methyl and preferably all of RZ, I~, and R4 are methyl.
Examples of useful opium ions includes alkyl ammonium ions, such as dodecylammonium, octadecyl ammonium, and bis(2-hydroxyethyl)octadecyl methyl ammonium, and the like, and alkyl phosphonium ions, such as octadecyltriphenyl phosphonium.
According to the process of the present invention, the selected ration exchanged clay material is treated with at least one expanding agent to separate the agglomerates of platelet particles to individual platelet particles and small tactoids prior to introducing the platelet particles to the polyester. Separating the platelet particles also improves the polyester/platelet interface. Any treatment that achieves the above goals may be used. Examples of useful treatments include intercalation with water soluble or water insoluble polymers, organic reagents or monomers, silane compounds, metals or organometallics, organic rations to effect ration 2 0 exchange, and their combinations.
The process for manufacturing the polyester composite material of this invention comprises (1) preparing the organoclay material (2) pre-swelling the organoclay material with an expanding agent and (3) incorporating the expanded organoclay in a polyester.
2 5 The first step of this invention is the preparation of the organoclay material by the reaction of a swellable layered clay with an opium ion. The organoclay materials of this invention may be prepared by dispersing the clay in hot water, most preferably from 50 to 80° C, adding the opium ion with agitation, then blending for a period of time sufficient for the opium compound to exchange most 3 0 of the rations, usually sodium ions, associated with the layers of the clay. It is desirable to use a sufficient amount of the opium ions to exchange most of the rations present in the galleries. The organoclay material is isolated by methods known in the art, such as filtration or centrifugation.
The second step of this invention is to pre-swell the organoclay with an 35 expanding agent. Although several methods are available to incorporate the expanding agent within the organoclay, such as melt mixing of the expanding agent and organoclay, spray drying of a mixture of the expanding agent and organoclay, or preparation of the organoclay in the presence of the expanding agent, the most expedient method for this invention was to dissolve or suspend both the expanding agent and organoclay in a solvent, such as methylene chloride, then evaporate off the solvent to provide the expanded organoclay.
The expanding agents that are useful for this invention encompass a wide range of polymer compositions from oligomers with tow molecular weight to high molecular weight polymers. Preferred polymers are compatible or miscible with the polyester to ensure clarity of the final product.
Suitable expanding agents are polyethylene oxide), poly(caprolactone), and polyesters comprising residues from at least one dibasic acid and one glycol.
In some cases it may be necessary to use more than one glycol to improve miscibility of the expanding agent in organic solvents. The primary dibasic acids are terephthalic, isophthalic, naphthalenedicarboxylic , 1,4-cyclohexanedicarboxylic acid, sodiosulfoisophthalic acid and the like. Typical glycols used in the polyester 2 0 include those containing two to about ten carbon atoms. Preferred glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanedimethanol, and 1,4-cyclohexanedimethanol. Molecular weights of these polymers can range from 250 to 25,000.
The third step of this invention is to incorporate the expanded organoclay 2 5 material into a melt-processible polyester. This process is directed toward preparation of polyester composites wherein the dispersed phase is preferably comprised of individual layers of the layered clay material or tactoids of less than about ten layers having a basal spacing greater than about 30 angstroms. The intercalated clay mineral component of the compound of this invention is present in 3 0 amounts up to 30 weight percent, more preferable up to about 15 weight percent.
The polyester component of the compound of the present invention is present in amounts of at least about 70 weight percent, more preferably at least 85 weight percent.
One method of incorporation of the expanded organoclay into a polyester is 3 5 the polycondensation of monomers to the polyester in the presence of the expanded organoclay material. The polyester in the present invention may be produced using ,8; ; ; , ' ..
well known polycondensation procedures. The polyester composite prepared in this manner may also be treated with solid state polymerization to attain sufficient inherent viscosity to permit melt processing.
Another method of incorporation is by the melt extrusion of a blend of the expanded organoclay and a melt-processible polyester. Conventional polymer and additive blending techniques are used in which the polymer is heated to a temperature sufficient to form a polymer melt and the desired amount of the expanded organoclay is added in a suitable mixer, for example an extruder, a Banbury Mixer, and the like. The process should subject the mixture with sufficient shear to delaminate at least 90% by weight of the intercalated material into individual layers. The polyester composite prepared in this manner may also be treated with solid state polymerization to attain sufficient inherent viscosity to permit melt processing.
In the expansion of organoclays from a solvent, it is preferred that the expanding agent be present in an amount sufficient to provide a fully expanded 2 0 organoclay. Examples of expanded organoclays from a solvent methylene chloride are shown in Table 1.
In the expansion of organoclays in water, a fully expanded organoclay is obtained when the clay content is more than 20% but less than 60% by weight of clay.
Examples of expanded organoclays from water are shown in Table 2.
2 5 The expanding agents that are useful for this invention encompass a wide range of polymer compositions from oligomers with low molecular weight to high molecular weight polymers. In method 2 described above, preferred polymers are P,~'J~cvD~D SHEET
9: , , , ; , ,' ' : .
those that are soluble or will suspend readily in organic solvents, such as methylene chloride or toluene. Preferred organoclays are those that can be swelled by these solvents, thus allowing easy access of the expanding agent to the interlayer spacing of the organoclay. Preferred polymers used as expanding agents should be compatible or miscible with the polyester used to form the final article if clarity is needed in the product.
Suitable expanding agents are poly(caprolactone), poly(dimethylsiloxane), polyepoxides, polystyrene, polyacrylates, polycarbonates, polyurethanes, polysulfones, polyethers, polyketones, polyamides, and polyesters comprising residues from at least one dibasic acid and one glycol. In some cases in the preparation of polyesters it may be necessary to use more than one glycol to improve miscibility of the expanding agent in organic solvents. The primary dibasic acids are terephthalic, isophthalic, octadecyloxyisophthalic acid, naphthalenedicarboxylic, 1,4-cyclohexanedicarboxylic acid, sodiosulfbisophthalic acid and the like. Typical glycols used in the polyester 2 o include those containing two to about ten carbon atoms. Preferred glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanedimethanol, and 1,4-cyclohexanedimethanol. Molecular weights of these polymers can range from 250 to 25,000. Monomeric species may also act as expanding agents. Among these are Zonyl A and vitamin E.
2 5 For convenience in this work, the expanded organoclay was coated on the surface of the polyester pellets prior to extrusion. This was accomplished by blending polyester pellets with the expanded organoclay in methylene chloride followed by evaporation of the methylene chloride.
3 o Pol;~m_e~
The treated organoclay of the present invention may be combined with a wide variety of polymers including thermoplastic polymers and mixtures thereof and vulcanized and thermoplastic resins. Thermoplastic resins include polylactones, polyurethanes, linear long chain diols, polyether diols, polysulfones, polyether ether 3 5 ketones, polyamides, polyesters, polyesteramides, poly(arylene)oxides, polyarylene sulfides, polyetherimides, vinyl polymers and their copolymers, AMENDED SHEET
s.
ethylene acrylic acid copolymers, ethylene vinyl alcohol copolymers, acrylonitrile copolymers, methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers, methacryalted butadiene-styrene compolymers, polyolefins, cellulose ester elastics and the like: Many suitable polymers are disclosed in W4 93/04118 .
Particularly suitable are polyesters 20 J for incorporation of the expanded organoclays which include at least one dibasic acid and at least one glycol. 'The primary dibasic acids are terephthalie, isophthalic, naphthalenedicarboxylic, 1,4-cyclohexanedicarboxy~ic acid and the like. The various isomers of naphthalenedicarboxylic acid or n~i~tures of isomers may be used, but the 1,4-, I,5-, 2,~-, and 2,7-isomers are preferred. The 1,4-cyclohexanedicarboxylic acid may be in the form of cis, trans, or cis/trans mixtures.
In addition to the acid forms, the lower alkyl esters or acid chlorides,may.be alsa be used_ The dica.rboxylic acid component of the polyester may optionally be modified with up to about SO mole percent of one or more different dicarboxylic acids. Such additional dicarboxylic acids include dicarboxylic acids having from 6 to about 40 carbon atoms, and more preferably dicarboxyfic acids selected from aromatic dicarboxyIic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarbaxplic acids preferably having 8 to 12 carbon atoms.. Examples of suitable 2 5 dicacboxyiic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalene- 2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, gtutaric acid, adipic acid, azelaic acid, sebacic acid, diglycolic acid, 1,3-phenylenedioxy diacetic acid and the like_ Polyesters may be prepared from two or more of the above dicarboxylic acids.
The polymer may also contain small amounts of trifunctionat or tetrafunctional comonomers to provide controlled branching in the polymers.
Such comonomers include trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, trimellitic acid, pyromellitic acid and other polyester forming polyacids or polyols generally known in the art:
; ; 11'. .,' , .. ..
Typical glycols used in the polyester include aliphatic glycols containing from two to about ten carbon atoms, aromatic glycols containing from about 6 to about 15 carbon atoms and cycloaliphatic glycols containing from about 7 to about 14 carbon atoms. Preferred glycols include ethylene glycol, 1,4-butanediol, 1,6 hexanediol, 1,4 cyclohexanedimethanol, diethylene glycol and the like. Resorcinol and hydroquinone are preferred aromatic glycols. The glycol component may optionally be modified with up to about 50 mole percent of one or more additional diols. Such additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols include:
diethylene glycol, triethylene glycol, 1,4 cyclohexanedimethanol, propane- 1,3-diol, butane- 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4 trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(2-hydroxyethoxy)-benzene, 1,3-di-(2 hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy 1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2 bis-(4-hydroxypropoxyphenyl)-propane and the like. 1,4-Cyclohexanedimethanol may be used as the cis, trans or cis/trans mixtures.
Polyesters may be prepared from one or more of the above diols.
Bifunctional compounds such as hydroxybenzoic acid may also be included.
2 5 The amount of expanded organoclay incorporated into the polyester may vary widely depending on the intended use of the composite. The amount of material employed, based on the clay content, is preferably from about 2 to 20 % by weight of the mixture.
The polyester containing the homogeneously distributed layered clay can be 3 0 formed into film by suitable filin-forming methods, such as extrusion or pressing, or when the appropriate polyester is used, may be blown into bottles.
All inherent viscosities are determined at 25° C using 0.5 g of polymer per 100 mL of a solvent consisting of 60 parts by weight phenol and 40 parts by weight tetrachloroethane. The melting temperatures are determined by differential scanning 35 calorimetry (DSC) on the second heating cycle at a scanning rate of 20° C per minute AM~NDtD S~'~~ET
: l~ '' , ' .'..
after the sample has been heated to melting and quenched to below the glass transition temperature of the polymer. Oxygen permeability measurements were obtained according to ASTM D-3985 using a MOCON Oxtran-1000 instrument at 30 C and 68% relative humidity with pure oxygen permeant and nitrogen gas carrier. WARS
measurements of the spacings of the <001 > plane were performed on powdered samples using a 2 circle Scintag PAD V diffractometer equipped with a Pettier solid state detector using Cu Ka radiation from a closed tube operated at 20 ma and 45 kV.
Exam~ile 1 This example illustrates the method for preparing the organoclay materials used in this invention. Sodium montmorillonite ( 10 grams, 9.5 milliequivalents, clay supplied by Southern Clay Products and reported to have a cation exchange capacity of 95 milliequivalents/100 grams) was mixed with 490 ml of water at 60°C in a Vitamix blender to form a 2% by weight slurry of clay in water. Bis(2-hydroxyethyl) 2 0 methyl tallow ammonium chloride (4.0 grams, 9.5 milliequivalents) commercially available as a 74% solution as Ethoquad T/12 was added to the Vitamix blender and the mixture blended at high speed for one minute. The solids formed were removed by filtration on a Buchner funnel. The product was reslurned in 250 ml of water in a Vitamix blender, filtered again, and dried in a circulating air oven at 60°C for 16 2 5 hours. The product exhibited a basal spacing by X-ray diffraction of 2.0 nanometers.
le 2 This example illustrates the method used for preparing the expanded organoclay materials used in this invention from an organic solvent. The expanding 3 0 agent polydimethylsiloxane, carbinol terminated (Petrarch Systems, Inc.) (2.26 grams), was dissolved in 60 ml of methylene chloride. The organoclay bis(2 hydroxyethyl) methyl tallow ammonium montmorillonite (2.73 grams) was then added and the mixture blended at high speed in a Vitamix blender. The solvent was then allowed to evaporate to provide a solid material having a basal spacing by X-ray 3 5 diffraction of 4.5 nanometers.
Ar~,~~"D~D S~tEET
Examples 3 -16 -The compositions are prepared according to the procedure set forth in Example 2 and are listed in Table 1. The organoclay used is bis(2-hydroxyethyl) methyl tallow ammonium montmorilionite and the weight percent of clay used in each example based on total weight of expanded organoclay is 40 weight percent.
Ethoquad 18-25 is commercially available from AKZO Chemical Company.
PD7610 is commercially available from Anderson Chemical Company. AQ55 and PETG 6763 are commercial available polyesters made by Eastman Chemical Company. Epon 828 is available from Shell Chemical Company. SCX800 is made by S. C. Johnson V~ax, Co.
Table 1 Example Expanding X-Ray Basal, A ent nm Comparative Exam 1e 1 None 2.0 Polyethylene 3 glycol 4.2 distearate 4 Zon 1 A 3.8 5 Polysar 101 3.7 of st ene 6 Vitamin E 3.6 7 Eth uad 18-25 3.5 8 Polyglycidylacrylate3.4 9 A 55 3.2 10 PETG 6763 3. I
. ~ , . ' , .
'. ., ,. .,., " ..
Other non-clay materials having the above-described ion exchange capacity and size, such as chalcogens may also be used as the source of platelet particles under the present invention. These materials are known in the art and need not be described in detail here.
Dispersions of platelet particles having large basal spacing (greater than about 3 nm) have not been previously disclosed. Previous patents and applications have claimed to produce polyesters containing intercalated or exfoliated platelet particles, as indicated by large basal spacings or the lack of a detectable basal spacing by X-ray, however, the results could not be reproduced, particularly in polyesters.
Useful organic cation salts for the process of this invention can be represented by Formula I:
RI
Rz-M-R3 X-(I) wherein M represents nitrogen or phosphorous, X- represents an anion selected from the group consisting of halogen, hydroxide, or acetate anions, preferably chloride and bromide;
R, is selected from the group consisting of straight and branched alkyl groups having at least 8 carbon atoms; R2, R3, and R4 are independently selected from organic and oligomeric ligands or may be hydrogen. Examples of useful organic ligands include, but are not limited to, linear or branched alkyl groups having 1 to 22 carbon atoms, aralkyl groups which are benzyl and substituted benzyl moieties including fused ring moieties having linear chains or branches of 1 to 22 carbon atoms in the alkyl portion of the structure, aryl groups such as phenyl and substituted phenyl including fused ring aromatic substituents, beta, gamma unsaturated groups having six or less carbon atoms, and alkyleneoxide groups having 2 to 6 carbon atoms, and alkyleneoxide groups having 2 to 6 carbon atoms. Examples of useful oligomeric ligands include, but are not limited to, poly(alkylene oxide), polystyrene, polyacrylate, polycaprolactone and the like.
AN1~W~~ S;-'rt'C'I
Preferably RZ, R3, and R4 are independently selected from straight or branched alkyl groups having 1 to four carbon atoms. More preferably at least one of R2, R3, and R4 is methyl and preferably all of RZ, I~, and R4 are methyl.
Examples of useful opium ions includes alkyl ammonium ions, such as dodecylammonium, octadecyl ammonium, and bis(2-hydroxyethyl)octadecyl methyl ammonium, and the like, and alkyl phosphonium ions, such as octadecyltriphenyl phosphonium.
According to the process of the present invention, the selected ration exchanged clay material is treated with at least one expanding agent to separate the agglomerates of platelet particles to individual platelet particles and small tactoids prior to introducing the platelet particles to the polyester. Separating the platelet particles also improves the polyester/platelet interface. Any treatment that achieves the above goals may be used. Examples of useful treatments include intercalation with water soluble or water insoluble polymers, organic reagents or monomers, silane compounds, metals or organometallics, organic rations to effect ration 2 0 exchange, and their combinations.
The process for manufacturing the polyester composite material of this invention comprises (1) preparing the organoclay material (2) pre-swelling the organoclay material with an expanding agent and (3) incorporating the expanded organoclay in a polyester.
2 5 The first step of this invention is the preparation of the organoclay material by the reaction of a swellable layered clay with an opium ion. The organoclay materials of this invention may be prepared by dispersing the clay in hot water, most preferably from 50 to 80° C, adding the opium ion with agitation, then blending for a period of time sufficient for the opium compound to exchange most 3 0 of the rations, usually sodium ions, associated with the layers of the clay. It is desirable to use a sufficient amount of the opium ions to exchange most of the rations present in the galleries. The organoclay material is isolated by methods known in the art, such as filtration or centrifugation.
The second step of this invention is to pre-swell the organoclay with an 35 expanding agent. Although several methods are available to incorporate the expanding agent within the organoclay, such as melt mixing of the expanding agent and organoclay, spray drying of a mixture of the expanding agent and organoclay, or preparation of the organoclay in the presence of the expanding agent, the most expedient method for this invention was to dissolve or suspend both the expanding agent and organoclay in a solvent, such as methylene chloride, then evaporate off the solvent to provide the expanded organoclay.
The expanding agents that are useful for this invention encompass a wide range of polymer compositions from oligomers with tow molecular weight to high molecular weight polymers. Preferred polymers are compatible or miscible with the polyester to ensure clarity of the final product.
Suitable expanding agents are polyethylene oxide), poly(caprolactone), and polyesters comprising residues from at least one dibasic acid and one glycol.
In some cases it may be necessary to use more than one glycol to improve miscibility of the expanding agent in organic solvents. The primary dibasic acids are terephthalic, isophthalic, naphthalenedicarboxylic , 1,4-cyclohexanedicarboxylic acid, sodiosulfoisophthalic acid and the like. Typical glycols used in the polyester 2 0 include those containing two to about ten carbon atoms. Preferred glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanedimethanol, and 1,4-cyclohexanedimethanol. Molecular weights of these polymers can range from 250 to 25,000.
The third step of this invention is to incorporate the expanded organoclay 2 5 material into a melt-processible polyester. This process is directed toward preparation of polyester composites wherein the dispersed phase is preferably comprised of individual layers of the layered clay material or tactoids of less than about ten layers having a basal spacing greater than about 30 angstroms. The intercalated clay mineral component of the compound of this invention is present in 3 0 amounts up to 30 weight percent, more preferable up to about 15 weight percent.
The polyester component of the compound of the present invention is present in amounts of at least about 70 weight percent, more preferably at least 85 weight percent.
One method of incorporation of the expanded organoclay into a polyester is 3 5 the polycondensation of monomers to the polyester in the presence of the expanded organoclay material. The polyester in the present invention may be produced using ,8; ; ; , ' ..
well known polycondensation procedures. The polyester composite prepared in this manner may also be treated with solid state polymerization to attain sufficient inherent viscosity to permit melt processing.
Another method of incorporation is by the melt extrusion of a blend of the expanded organoclay and a melt-processible polyester. Conventional polymer and additive blending techniques are used in which the polymer is heated to a temperature sufficient to form a polymer melt and the desired amount of the expanded organoclay is added in a suitable mixer, for example an extruder, a Banbury Mixer, and the like. The process should subject the mixture with sufficient shear to delaminate at least 90% by weight of the intercalated material into individual layers. The polyester composite prepared in this manner may also be treated with solid state polymerization to attain sufficient inherent viscosity to permit melt processing.
In the expansion of organoclays from a solvent, it is preferred that the expanding agent be present in an amount sufficient to provide a fully expanded 2 0 organoclay. Examples of expanded organoclays from a solvent methylene chloride are shown in Table 1.
In the expansion of organoclays in water, a fully expanded organoclay is obtained when the clay content is more than 20% but less than 60% by weight of clay.
Examples of expanded organoclays from water are shown in Table 2.
2 5 The expanding agents that are useful for this invention encompass a wide range of polymer compositions from oligomers with low molecular weight to high molecular weight polymers. In method 2 described above, preferred polymers are P,~'J~cvD~D SHEET
9: , , , ; , ,' ' : .
those that are soluble or will suspend readily in organic solvents, such as methylene chloride or toluene. Preferred organoclays are those that can be swelled by these solvents, thus allowing easy access of the expanding agent to the interlayer spacing of the organoclay. Preferred polymers used as expanding agents should be compatible or miscible with the polyester used to form the final article if clarity is needed in the product.
Suitable expanding agents are poly(caprolactone), poly(dimethylsiloxane), polyepoxides, polystyrene, polyacrylates, polycarbonates, polyurethanes, polysulfones, polyethers, polyketones, polyamides, and polyesters comprising residues from at least one dibasic acid and one glycol. In some cases in the preparation of polyesters it may be necessary to use more than one glycol to improve miscibility of the expanding agent in organic solvents. The primary dibasic acids are terephthalic, isophthalic, octadecyloxyisophthalic acid, naphthalenedicarboxylic, 1,4-cyclohexanedicarboxylic acid, sodiosulfbisophthalic acid and the like. Typical glycols used in the polyester 2 o include those containing two to about ten carbon atoms. Preferred glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanedimethanol, and 1,4-cyclohexanedimethanol. Molecular weights of these polymers can range from 250 to 25,000. Monomeric species may also act as expanding agents. Among these are Zonyl A and vitamin E.
2 5 For convenience in this work, the expanded organoclay was coated on the surface of the polyester pellets prior to extrusion. This was accomplished by blending polyester pellets with the expanded organoclay in methylene chloride followed by evaporation of the methylene chloride.
3 o Pol;~m_e~
The treated organoclay of the present invention may be combined with a wide variety of polymers including thermoplastic polymers and mixtures thereof and vulcanized and thermoplastic resins. Thermoplastic resins include polylactones, polyurethanes, linear long chain diols, polyether diols, polysulfones, polyether ether 3 5 ketones, polyamides, polyesters, polyesteramides, poly(arylene)oxides, polyarylene sulfides, polyetherimides, vinyl polymers and their copolymers, AMENDED SHEET
s.
ethylene acrylic acid copolymers, ethylene vinyl alcohol copolymers, acrylonitrile copolymers, methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers, methacryalted butadiene-styrene compolymers, polyolefins, cellulose ester elastics and the like: Many suitable polymers are disclosed in W4 93/04118 .
Particularly suitable are polyesters 20 J for incorporation of the expanded organoclays which include at least one dibasic acid and at least one glycol. 'The primary dibasic acids are terephthalie, isophthalic, naphthalenedicarboxylic, 1,4-cyclohexanedicarboxy~ic acid and the like. The various isomers of naphthalenedicarboxylic acid or n~i~tures of isomers may be used, but the 1,4-, I,5-, 2,~-, and 2,7-isomers are preferred. The 1,4-cyclohexanedicarboxylic acid may be in the form of cis, trans, or cis/trans mixtures.
In addition to the acid forms, the lower alkyl esters or acid chlorides,may.be alsa be used_ The dica.rboxylic acid component of the polyester may optionally be modified with up to about SO mole percent of one or more different dicarboxylic acids. Such additional dicarboxylic acids include dicarboxylic acids having from 6 to about 40 carbon atoms, and more preferably dicarboxyfic acids selected from aromatic dicarboxyIic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarbaxplic acids preferably having 8 to 12 carbon atoms.. Examples of suitable 2 5 dicacboxyiic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalene- 2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, gtutaric acid, adipic acid, azelaic acid, sebacic acid, diglycolic acid, 1,3-phenylenedioxy diacetic acid and the like_ Polyesters may be prepared from two or more of the above dicarboxylic acids.
The polymer may also contain small amounts of trifunctionat or tetrafunctional comonomers to provide controlled branching in the polymers.
Such comonomers include trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, trimellitic acid, pyromellitic acid and other polyester forming polyacids or polyols generally known in the art:
; ; 11'. .,' , .. ..
Typical glycols used in the polyester include aliphatic glycols containing from two to about ten carbon atoms, aromatic glycols containing from about 6 to about 15 carbon atoms and cycloaliphatic glycols containing from about 7 to about 14 carbon atoms. Preferred glycols include ethylene glycol, 1,4-butanediol, 1,6 hexanediol, 1,4 cyclohexanedimethanol, diethylene glycol and the like. Resorcinol and hydroquinone are preferred aromatic glycols. The glycol component may optionally be modified with up to about 50 mole percent of one or more additional diols. Such additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols include:
diethylene glycol, triethylene glycol, 1,4 cyclohexanedimethanol, propane- 1,3-diol, butane- 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4 trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(2-hydroxyethoxy)-benzene, 1,3-di-(2 hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy 1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2 bis-(4-hydroxypropoxyphenyl)-propane and the like. 1,4-Cyclohexanedimethanol may be used as the cis, trans or cis/trans mixtures.
Polyesters may be prepared from one or more of the above diols.
Bifunctional compounds such as hydroxybenzoic acid may also be included.
2 5 The amount of expanded organoclay incorporated into the polyester may vary widely depending on the intended use of the composite. The amount of material employed, based on the clay content, is preferably from about 2 to 20 % by weight of the mixture.
The polyester containing the homogeneously distributed layered clay can be 3 0 formed into film by suitable filin-forming methods, such as extrusion or pressing, or when the appropriate polyester is used, may be blown into bottles.
All inherent viscosities are determined at 25° C using 0.5 g of polymer per 100 mL of a solvent consisting of 60 parts by weight phenol and 40 parts by weight tetrachloroethane. The melting temperatures are determined by differential scanning 35 calorimetry (DSC) on the second heating cycle at a scanning rate of 20° C per minute AM~NDtD S~'~~ET
: l~ '' , ' .'..
after the sample has been heated to melting and quenched to below the glass transition temperature of the polymer. Oxygen permeability measurements were obtained according to ASTM D-3985 using a MOCON Oxtran-1000 instrument at 30 C and 68% relative humidity with pure oxygen permeant and nitrogen gas carrier. WARS
measurements of the spacings of the <001 > plane were performed on powdered samples using a 2 circle Scintag PAD V diffractometer equipped with a Pettier solid state detector using Cu Ka radiation from a closed tube operated at 20 ma and 45 kV.
Exam~ile 1 This example illustrates the method for preparing the organoclay materials used in this invention. Sodium montmorillonite ( 10 grams, 9.5 milliequivalents, clay supplied by Southern Clay Products and reported to have a cation exchange capacity of 95 milliequivalents/100 grams) was mixed with 490 ml of water at 60°C in a Vitamix blender to form a 2% by weight slurry of clay in water. Bis(2-hydroxyethyl) 2 0 methyl tallow ammonium chloride (4.0 grams, 9.5 milliequivalents) commercially available as a 74% solution as Ethoquad T/12 was added to the Vitamix blender and the mixture blended at high speed for one minute. The solids formed were removed by filtration on a Buchner funnel. The product was reslurned in 250 ml of water in a Vitamix blender, filtered again, and dried in a circulating air oven at 60°C for 16 2 5 hours. The product exhibited a basal spacing by X-ray diffraction of 2.0 nanometers.
le 2 This example illustrates the method used for preparing the expanded organoclay materials used in this invention from an organic solvent. The expanding 3 0 agent polydimethylsiloxane, carbinol terminated (Petrarch Systems, Inc.) (2.26 grams), was dissolved in 60 ml of methylene chloride. The organoclay bis(2 hydroxyethyl) methyl tallow ammonium montmorillonite (2.73 grams) was then added and the mixture blended at high speed in a Vitamix blender. The solvent was then allowed to evaporate to provide a solid material having a basal spacing by X-ray 3 5 diffraction of 4.5 nanometers.
Ar~,~~"D~D S~tEET
Examples 3 -16 -The compositions are prepared according to the procedure set forth in Example 2 and are listed in Table 1. The organoclay used is bis(2-hydroxyethyl) methyl tallow ammonium montmorilionite and the weight percent of clay used in each example based on total weight of expanded organoclay is 40 weight percent.
Ethoquad 18-25 is commercially available from AKZO Chemical Company.
PD7610 is commercially available from Anderson Chemical Company. AQ55 and PETG 6763 are commercial available polyesters made by Eastman Chemical Company. Epon 828 is available from Shell Chemical Company. SCX800 is made by S. C. Johnson V~ax, Co.
Table 1 Example Expanding X-Ray Basal, A ent nm Comparative Exam 1e 1 None 2.0 Polyethylene 3 glycol 4.2 distearate 4 Zon 1 A 3.8 5 Polysar 101 3.7 of st ene 6 Vitamin E 3.6 7 Eth uad 18-25 3.5 8 Polyglycidylacrylate3.4 9 A 55 3.2 10 PETG 6763 3. I
11 E on 828 3.1 12 Polycapro- 3.0 lactone 13 Polymethacry 3.0 late SCX800B
14 Polyvinyl 2.9 olidone 15 Makrolon 2608 2.9 Poi carbonate 16 Polyethylene oxide) 2.4 mw 3350 14 ~, ' ,..' ', . " ..
This example illustrates the method used for preparing the expanded organoclay materials from an aqueous medium. The water soluble polyester AQ 55 (5.0 grams) was dissolved in 250 ml of hot water in a Vitamix blender. Sodium montmorillonite (5.0 grams, 4.75 milliequivalents, clay supplied by Southern Clay Products and reported to have a cation exchange capacity of 95 milliequivalents/100 grams) was added to the blender and blended for one minute. Octadecyl bis(polyoxyethylene[5]amine (2.32 grams, 4.75 meq), commercially available as Ethomeen 18/15 from AKZO Chemical Company, was suspended in 25 mI of water and 4.88 g of 0.973 N HCl was added to form the ammonium salt which immediately dissolved. This ammonium salt solution was then added to the Vitamix blender containing the AQ 55 and clay and the mixture was blended at high speed for one minute. The solids formed were removed by filtration on a Buchner funnel. The 2 0 product was reslurned in 250 ml of water in a Vitamix blender, filtered again, and dried in an air circulating oven at 60°C for 16 hours. The product exhibited a basal spacing by X-ray diffraction of 4.1 nanometers.
2 5 Examples 18-25 The compositions are prepared according to the procedure set forth in Example 17 and are listed in Table 2. The expanding agent in each case is AQ 55 and the weight percent of clay used in each example based on total weight of expanded organoclay is 3 0 40 weight percent.
AMENDED SHEET
1$ ~.. ,., .. ,... , ,.
Table 2 Examples Onium ion used with X-Ray Basal,X-Ray Basal, sodium montmorillonite nm Organo- nm Expanded clay Organo-clay 18 Octadecyl trimethyl 2.0 3.9 ammonium 19 Octadecyl dihydroxyethyl1.7 3.8 ammonium 20 Octadecyl benzyldimethyl2.1 3.8 ammonium 21 Tallow methyl 1.9 3.6 dihydroxyethyl ammonium 22 Dodecyltrymethyl 1.6 3.2 ammonium 23 Hexadecyltrimethyl 2.2 3.1 ammonium 24 Octadecylammonium 1.7 3.1 25 Dodecylammonium 1.4 3.0 Comparative Tridodecylammonium 2.5 2.7 Example 2 Comparative Tetramethyl 1.4 1.4 Example 3 Comparative Example 1 The procedure of Example 2 was repeated except that no expanding agent was used. The basal spacing of the product was 2.0 omparative Exam a 2 10 The procedure of Example 17 was repeated except that tridodecylammonium chloride was used. The product had a basal spacing of 2.7 nanometers.
AMENOEO SHAT
Comparative Example 3 The procedure of Example 17 was repeated except that tetramethylammonium chloride was used. The product had a basal spacing of 1.4 nanometers.
This example illustrates the method used for preparing the expanded organoclay materials from an aqueous medium. The water soluble polyester AQ 55 (5.0 grams) was dissolved in 250 ml of hot water in a Vitamix blender. Sodium montmorillonite (5.0 grams, 4.75 milliequivalents, clay supplied by Southern Clay Products and reported to have a cation exchange capacity of 95 milliequivalents/100 grams) was added to the blender and blended for one minute. Octadecyl bis(polyoxyethylene[5]amine (2.32 grams, 4.75 meq), commercially available as Ethomeen 18/15 from AKZO Chemical Company, was suspended in 25 mI of water and 4.88 g of 0.973 N HCl was added to form the ammonium salt which immediately dissolved. This ammonium salt solution was then added to the Vitamix blender containing the AQ 55 and clay and the mixture was blended at high speed for one minute. The solids formed were removed by filtration on a Buchner funnel. The 2 0 product was reslurned in 250 ml of water in a Vitamix blender, filtered again, and dried in an air circulating oven at 60°C for 16 hours. The product exhibited a basal spacing by X-ray diffraction of 4.1 nanometers.
2 5 Examples 18-25 The compositions are prepared according to the procedure set forth in Example 17 and are listed in Table 2. The expanding agent in each case is AQ 55 and the weight percent of clay used in each example based on total weight of expanded organoclay is 3 0 40 weight percent.
AMENDED SHEET
1$ ~.. ,., .. ,... , ,.
Table 2 Examples Onium ion used with X-Ray Basal,X-Ray Basal, sodium montmorillonite nm Organo- nm Expanded clay Organo-clay 18 Octadecyl trimethyl 2.0 3.9 ammonium 19 Octadecyl dihydroxyethyl1.7 3.8 ammonium 20 Octadecyl benzyldimethyl2.1 3.8 ammonium 21 Tallow methyl 1.9 3.6 dihydroxyethyl ammonium 22 Dodecyltrymethyl 1.6 3.2 ammonium 23 Hexadecyltrimethyl 2.2 3.1 ammonium 24 Octadecylammonium 1.7 3.1 25 Dodecylammonium 1.4 3.0 Comparative Tridodecylammonium 2.5 2.7 Example 2 Comparative Tetramethyl 1.4 1.4 Example 3 Comparative Example 1 The procedure of Example 2 was repeated except that no expanding agent was used. The basal spacing of the product was 2.0 omparative Exam a 2 10 The procedure of Example 17 was repeated except that tridodecylammonium chloride was used. The product had a basal spacing of 2.7 nanometers.
AMENOEO SHAT
Comparative Example 3 The procedure of Example 17 was repeated except that tetramethylammonium chloride was used. The product had a basal spacing of 1.4 nanometers.
Claims (23)
1. A composition comprising (i) a layered clay material which has been cation exchanged with an organic cation salt represented by formula I:
wherein M represents either nitrogen or phosphorus; X- represents an anion selected from the group consisting of a halide, hydroxide, or an acetate anion; R1 is a straight or branched chain alkyl group having at least 8 carbon atoms;
R2, R3, and R4 are independently hydrogen or a branched alkyl group having 1 to 4 carbon atoms; and (ii) at least one expanding agent, wherein the cation-exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is a polymer or vitamin E.
wherein M represents either nitrogen or phosphorus; X- represents an anion selected from the group consisting of a halide, hydroxide, or an acetate anion; R1 is a straight or branched chain alkyl group having at least 8 carbon atoms;
R2, R3, and R4 are independently hydrogen or a branched alkyl group having 1 to 4 carbon atoms; and (ii) at least one expanding agent, wherein the cation-exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is a polymer or vitamin E.
2. The composition of claim 1, wherein X- represents chloride or bromide.
3. The composition of claim 1, wherein the expanding agent is a low molecular weight oligomer.
4. The composition of claim 1, where R1 is selected from the group consisting of straight and branched alkyl groups having between 8 and 25 carbon atoms.
5. The composition of claim 1, wherein R1 is selected from the group consisting of straight and branched alkyl groups having between 12 and 20 carbon atoms.
6. The composition of claim 1, wherein R2, R3, and R4 are independently selected from straight or branched alkyl groups having 1 to four carbon atoms and at least one of R2, R3, and R4 is methyl.
7. The composition of claim 1, wherein R2, R3, and R4 are each methyl.
8. A composite composition comprising at least one polymer selected from the group consisting of thermoplastic polymers and mixtures thereof and vulcanized and thermoplatic resins having dispersed therein the composition of claim 1, 5, 6 ar 7 wherein said expanding agent is compatible with said polymer.
9. The composition of claim 8, wherein said polymer is at least one thermoplastic resin selected from the group consisting of a polylactone, polyurethane, linear long chain diol, polyether diol, polysulfone, polyether ether ketone, polyamide, polyester, polyesteramide, poly(arylene) oxide, poly(arylene) sulfide, polyetherimide, vinyl polymer, vinyl copolymer, ethylene acrylic acid copolymer, ethylene vinyl alcohol copolymer, acrylonitrile copolymer, methacrylate-styrene copolymer, ethylene-ethyl acrylate copolymer, methacrylated butadiene-styrene copolymer, polyolefin, and cellulose ester plastic.
10. The composition of claim 8, wherein said polymer is at least one polyester, and R2, R3 and R4 are independently H.
11. The composition of claim 10, wherein said polyester is derived from at least one dibasic acid and at least one glycol.
12. The composition of claim 11, wherein said dibasic acid comprises terephthalic, isophthalic, naphthalenedicarboxylic, 1,4-cyclohexanedicarboxylic acid and mixtures thereof.
13. The composition of claim 12, wherein said dibasic acid further comprises up to about 50 mole percent of one or more second dicarboxylic acids selected from the group consisting of an aromatic dicarboxylic acid having 8 to 12 carbon atoms, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and a cycloaliphatic dicarboxylic acid having 8 to 12 carbon atoms.
14. The composition of claim 11, wherein the glycol is selected from the group consisting of an aliphatic glycol containing from 2 to about 10 carbon atoms, an aromatic glycol containing from about 6 to about 15 carbon atoms and a cylcoaliphatic glycol containing from about 7 to about 14 carbon atoms.
15. The composition of claim 14, wherein said glycol further comprises up to about 50 mole percent of one or more additional diols selected from the group consisting of a cycloaliphatic diol having 6 to 20 carbon atoms and an aliphatic diol having 3 to 20 carbon atoms.
16. The composition of claim 1, wherein said layered clay material is incorporated in an amount between about 2 to 20% by weight of the mixture.
17. A composition comprising at least one polymer having dispersed therein at least one layered clay material which has been cation exchanged with an organic cation salt having one substituent R1 selected from the group consisting of a straight and a branched alkyl group having at least 8 carbon atoms; and at least one expanding agent which is compatible with said polymer, wherein basal spacing between the layers of the layered clay material is greater than about 3.4, and wherein the cation exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is a polymer or vitamin E.
18. The composition of claim 17, wherein the expanding agent is a low molecular weight oligomer.
19. A composition comprising at least one polyester having dispersed therein at least one layered clay material which has been cation exchanged with an organic cation salt having one substituent R1 selected from the group consisting of a straight and a branched alkyl group having at least 8 carbon atoms; and at least one expanding agent which is compatible with said polymer, wherein said basal spacing between the layers of the layered clay material is greater than about 3, and wherein the cation exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is polymer or vitamin E.
20. The composition of claim 18, wherein the expanding agent is a low molecular weight oligomer.
21. A composition comprising a polymer having dispersed therein (i) a layered clay material that has been cation-exchanged with an organic cation salt represented by Formula (I):
wherein M is nitrogen or phosphorous, X- is a halide, hydroxide, or acetate anion, RI is a straight or branched alkyl group having at least 8 carbon atoms, and R2, R3, and R4 are independently hydrogen or a straight or branched alkyl group having 1 to 22 carbon atoms; and (ii) at least one expanding agent, wherein the cation-exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is a polymer or vitamin E.
wherein M is nitrogen or phosphorous, X- is a halide, hydroxide, or acetate anion, RI is a straight or branched alkyl group having at least 8 carbon atoms, and R2, R3, and R4 are independently hydrogen or a straight or branched alkyl group having 1 to 22 carbon atoms; and (ii) at least one expanding agent, wherein the cation-exchanged clay material contains platelet particles, the expanding agent separates the platelet particles into individual platelet particles and small tactoids, and the expanding agent is a polymer or vitamin E.
22. The composition of claim 21, wherein X- is chloride or bromide.
23. The composition of claim 21, wherein the polymer comprises a polyester, the expanding agent is a low molecular weight oligomer and the polyester and oligomer are compatible.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/995,178 | 1997-12-22 | ||
| US08/995,178 US6034163A (en) | 1997-12-22 | 1997-12-22 | Polyester nanocomposites for high barrier applications |
| PCT/US1997/024103 WO1999032403A1 (en) | 1997-12-22 | 1997-12-30 | Polyester nanocomposites for high barrier applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2315076A1 CA2315076A1 (en) | 1999-07-01 |
| CA2315076C true CA2315076C (en) | 2004-04-20 |
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ID=25541482
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002315076A Expired - Fee Related CA2315076C (en) | 1997-12-22 | 1997-12-30 | Polyester nanocomposites for high barrier applications |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6034163A (en) |
| EP (1) | EP1040081B1 (en) |
| JP (1) | JP2001526313A (en) |
| AR (1) | AR011332A1 (en) |
| BR (1) | BR9714936A (en) |
| CA (1) | CA2315076C (en) |
| DE (1) | DE69723887T2 (en) |
| ES (1) | ES2205278T3 (en) |
| WO (1) | WO1999032403A1 (en) |
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- 1997-12-22 US US08/995,178 patent/US6034163A/en not_active Expired - Fee Related
- 1997-12-30 WO PCT/US1997/024103 patent/WO1999032403A1/en active IP Right Grant
- 1997-12-30 AR ARP970106272A patent/AR011332A1/en unknown
- 1997-12-30 DE DE69723887T patent/DE69723887T2/en not_active Expired - Fee Related
- 1997-12-30 JP JP2000525345A patent/JP2001526313A/en active Pending
- 1997-12-30 CA CA002315076A patent/CA2315076C/en not_active Expired - Fee Related
- 1997-12-30 EP EP97954281A patent/EP1040081B1/en not_active Expired - Lifetime
- 1997-12-30 ES ES97954281T patent/ES2205278T3/en not_active Expired - Lifetime
- 1997-12-30 BR BR9714936-5A patent/BR9714936A/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| CA2315076A1 (en) | 1999-07-01 |
| EP1040081B1 (en) | 2003-07-30 |
| DE69723887T2 (en) | 2004-03-11 |
| EP1040081A1 (en) | 2000-10-04 |
| ES2205278T3 (en) | 2004-05-01 |
| BR9714936A (en) | 2000-10-24 |
| DE69723887D1 (en) | 2003-09-04 |
| JP2001526313A (en) | 2001-12-18 |
| WO1999032403A1 (en) | 1999-07-01 |
| AR011332A1 (en) | 2000-08-16 |
| US6034163A (en) | 2000-03-07 |
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