WO2003059917A1 - Synthetic hydrotalcites, syntheses and uses - Google Patents
Synthetic hydrotalcites, syntheses and uses Download PDFInfo
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- WO2003059917A1 WO2003059917A1 PCT/US2003/000478 US0300478W WO03059917A1 WO 2003059917 A1 WO2003059917 A1 WO 2003059917A1 US 0300478 W US0300478 W US 0300478W WO 03059917 A1 WO03059917 A1 WO 03059917A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Definitions
- the synthetic hydrotalcites of the present invention can be made from organic anions longer than C 4 , and also from organic anions with functional groups including saturated carboxylates of C 6 , C 8 , Cio, and C ⁇ 8 , straight chain acids; aromatics such as benzoates, chlorobenzoates, naphthoates, and p-hydroxybenzoates; carboxylates of acrylic, methacrylic, vinylacetic acids and mixtures of these organic anions.
- the synthetic hydrotalcites of the present invention can also be made from carboxylates of C 2 and higher organic acids containing heteroatoms such as nitrogen, sulfur, phosphorous and halogens.
- Hydrotalcites are derivatives of brucite, a naturally-occurring, layered, magnesium hydroxide mineral. Synthetic hydrotalcites can be made by substituting a trivalent metal cation, such as aluminum, for some of the magnesium cations normally present in a layer. The magnesium cations can also be substituted by other divalent cations. This substitution will result in a net positive charge residing on the layer, which requires an intercalating anion to achieve a net neutral charge for the molecule. The following general formula has been derived for synthetic hydrotalcites:
- M magnesium and/or other divalent cation
- M aluminum and/or other trivalent cation
- a n ⁇ is an anion.
- water is also a part of the lattice structure.
- hydrotalcites with a unique sheet- like morphology is described in U.S. Pat. No. 5,399,329, issued to Schutz, et al., and assigned to the assignee of the present invention.
- the entire contents of the Schutz '329 patent are incorporated herein by reference.
- the hydrotalcites of the Schutz '329 patent are comprised of anions derived from Ci to C 4 saturated carboxylic acids.
- the general synthetic method of the Schutz '329 patent involves the reaction of an alumina source with a carboxylic acid in water followed by the reaction of the resulting mixture with a magnesium source.
- the approximate molar ratio of the reagents is as follows: 2 Mg : 1 Al : 1 anion; with the anion being the carboxylate of the acid used.
- carboxylate anion hydrotalcites of the Schutz '329 patent exhibit a unique morphology, termed therein "sheet-like".
- the distance between the hydrotalcite layers, as measured by d spacing, depends on the size of the intercalating anion.
- carboxylate hydrotalcites from the following anions produced by the method of the Schutz '329 patent have a d spacing of: formate 7.64 A, acetate 12.3 A, propionate 13.02 A, and isobutyrate 15.15A.
- Hydrotalcites have many uses, including such applications as catalysts or catalyst precursors, ion exchangers, ion absorbers, ion-scavengers, and medical uses as antacids. Hydrotalcites are also used as nanocomposites in polymers to provide various property enhancements. Hybrid composites of polymer and other inorganic components such as clays and mica have been described in the prior art as having improved mechanical properties. The term nanocomposites reflects the dispersion of nano-scale particulates of the inorganic component of the hybrid in the polymer matrix.
- Nanocomposites are believed to disperse in the polymer in one of the following two ways:
- the polar functionality of the modified polypropylene is able to interact with the polar character of the nanoparticle, and the nonpolar portion of the modified polypropylene interacts with the polypropylene matrix.
- the interaction between the two polar functionso ⁇ ,alities provides both exfoliation and compatiblization, thereby resulting in a nanocomposite with uniform distribution of the nanoparticles.
- U.S. Patent No. 5,973,053 describes a layered composite clay material wherein organic onium ions and primary and secondary organic "guest" molecules are introduced into the interlayer space to increase the interlayer distance.
- the introduction of the organic onium ion acts to increase the compatibility of the clay with polymer and facilitate the dispersion of the clay in the hybrid composite.
- modified hydrotalcites made from carboxylates of C 2 and higher organic acids containing heteroatoms such as nitrogen, sulfur, phosphorous and halogens, which can be used in polymer nanocomposites and are more easily dispersed in a non-polar polymer without the necessity of using a compatibilizer.
- the present invention provides a synthetic hydrotalcite of the general formula,
- M 2+ 1-x M 3+ x (OH) 2 ] x+ [A n - ⁇ /n .mH 2 0] ⁇ -
- M 2+ is a divalent cation
- M 3+ is a trivalent cation
- a n" is an organic anion selected from straight chain carboxylates of C 5 -C ⁇ 8 acids, carboxylates of aromatic acids, carboxylates of acrylic acid, unsaturated carboxylates of methacrylic acid and unsaturated carboxylates of vinylacetic acid.
- the present invention also provides a synthetic hydrotalcite of the general formula
- M 2+ is a divalent cation
- M 3+ is a trivalent cation
- a n" is an anion comprising a mixture of at least two members of the group consisting of straight chain saturated carboxylates of C 2 -C 4 acids, carboxylates of aromatic acids, carboxylates of acrylic acid, unsaturated carboxylates of methacrylic acid and unsaturated carboxylates of vinylacetic acid.
- the present invention also provides a synthetic hydrotalcite of the general formula
- M 2+ 1-x M 3+ x (OH) 2 ] x+ [A n - ⁇ /n -mH 2 0] ⁇ -
- M 2+ is a divalent cation
- M 3+ is a trivalent cation
- a n" is an organic anion comprising a carboxylate of a C 2 or higher acid containing a heteroatom such as nitrogen, sulfur, phosphorous or a halogen.
- the heteroatom is nitrogen in the form of an amino acid.
- the acid end of the amino acid binds to cation sites on platelets of the hydrotalcite leaving the amine end to interact or react with solvents or polymer molecules.
- the amine is free to react with the acid moiety in the polymer to form an amide or imide.
- the synthetic hydrotalcite may be directly bonded to the polymer.
- the amino acid is a straight chain alkyl. More preferably, the amino acid intercalated hydrotalcite is capable of self and/or reversible exfoliation. Even more preferably the amino- acid is 4-aminobutyric or 6-aminocaproic acid.
- Modified hydrotalcites, or organo-hydrotalcites according to the current invention can be used to for polymer nanocomposites, and do not necessarily require the use of compatibilizers to effect dispersion of the hydrotalcite through the polymer.
- the synthetic hydrotalcite is capable of self exfoliation in a solvent, it may be maintained as a colloidal suspension after synthesis rather than being collected and dried.
- the present invention further provides for a method of making a synthetic hydrotalcite of the general formula
- M 2+ is a divalent cation source
- M 3+ is a trivalent cation source
- a n" is an organic anion source selected from straight chain carboxylates of C 5 -C ⁇ 8 acids, carboxylates of aromatic acids, carboxylates of acrylic acid, unsaturated carboxylates of methacrylic acid, unsaturated carboxylates of vinylacetic acid and carboxylates of C 2 and higher acids containing heteroatoms such as nitrogen, phosphorous, sulfur and halogens, the method comprising: reacting the trivalent cation source with the organic anion source to produce an intermediate and reacting the intermediate with the divalent cation source to produce the synthetic hydrotalcite.
- the present invention still further provides for a synthetic hydrotalcite polymer blend comprising a poly- addition polymer and a synthetic hydrotalcite of the general formula,
- M 2+ is a divalent cation
- M 3+ is a trivalent cation
- a ⁇ " is an organic anion selected from straight chain carboxylates of C 5 -C ⁇ 8 acids, carboxylates of aromatic acids, carboxylates of acrylic acid, unsaturated carboxylates of methacrylic acid, unsaturated carboxylates of vinylacetic acid and carboxylates of C 2 and higher acids containing heteroatoms such as nitrogen, phosphorous, sulfur and halogens.
- the organic anion in the synthetic hydrotalcite is an amino acid.
- the amino acid is one that promotes self and/or reversible exfoliation of the synthetic hydrotalcite.
- the polymer may be modified or functionalized, such as with maleic acid.
- an amino acid intercalated hydrotalcite may be bonded to the polymer via an amide or imide formed by reaction of the amine function with the acid modified polymer.
- the present invention yet further provides a method for making a synthetic hydrotalcite-polymer blend comprising: mixing an emulsion comprising a poly-addition polymer with a synthetic hydrotalcite of the general formula,
- M 2+ is a divalent cation source
- M 3+ is a trivalent cation source
- a n" is an organic anion source selected from straight chain carboxylates of C 5 -C] 8 acids, carboxylates of aromatic acids, carboxylates of acrylic acid, unsaturated carboxylates of methacrylic acid and unsaturated carboxylates of vinylacetic acid, and carboxylates of C 2 and higher acids containing heteroatoms such as nitrogen, phosphorous, sulfur and halogens, to obtain the blend.
- the organic anion in the synthetic hydrotalcite is an amino acid.
- the amino acid is one that promotes self and reversible exfoliation of the synthetic hydrotalcite.
- the polymer may be modified or functionalized, such as with maleic acid.
- an amino acid intercalated hydrotalcite may be bonded to the polymer via an amide or imide formed by reaction of the amine function with the acid modified polymer.
- Figure 1 is a micrograph of a synthetic hydrotalcite made in Example 1 ;
- Figure 2 is a micrograph of a synthetic hydrotalcite made in Example 2;
- Figure 3 is a micrograph of a benzoic acid-derived synthetic hydrotalcite
- Figure 4 is a micrograph of a methacrylic acid-derived synthetic hydrotalcite
- Figure 5 is a micrograph of an acrylic acid-derived synthetic hydrotalcite
- Figure 6 illustrates the predicted relationship between interlayer distance and the number of carbon atoms in an anion
- Figure 7 is a micrograph of a mixture of acetic, hexanoic, and stearic acids- derived synthetic hydrotalcite demonstrating a "semi cabbage” morphology;
- Figure 8 is a micrograph of a blend of about 81% hydrotalcite with polypropylene demonstrating the preferred "cabbage morphology";
- Figure 9 is a micrograph of a blend of about 5% hydrotalcite with polypropylene demonstrating a "doughnut" morphology.
- Figure 10 is a micrograph of a blend of methacrylic acid-derived hydrotalcite with polypropylene.
- Figure 11 shows XRD scans of an 8 wt% slurry of the hydrotalcite wet; an air-
- Figure 12 shows XRD scans of a 10 wt% slurry of the hydrotalcite wet; an air- dried sample of hydrotalcite from an 10 wt% slurry; a sample of the 10 wt% slurry dried at 100° C and a sample of the 10 wt% slurry dried at 150° C.
- Step I Trivalent Cation Source + Organic Anion — > Intermediate
- Step III Dry (evaporate/dry under vacuum, filter/dry under vacuum or spray-dry) or Step III: Maintain Wet (colloidal suspension/evaporate to concentrate or paste)
- Step I Success in preparing the synthetic hydrotalcites of the present invention depends greatly on the complete reaction in Step I, i.e., the trivalent cation reacting with the specific carboxylic acid.
- the preparation of hydrotalcites from longer chain than C 4 carboxylic acids, heteroatom containing acids and water-insoluble aromatic acids is accomplished by driving the reaction of Step I closer to completion preferably by utilizing one or more of the following approaches: 1) the reaction time for Step I can be increased from 30 minutes, as in the Schutz '329 patent, to from 4 to 8 hours;
- inert organic solvents can be used as a reaction media for water insoluble- organic carboxylic acids with the trivalent cation source
- Step I can be carried out in a melt of the organic anion.
- Trivalent cation source unless otherwise specified was CATAPAL® alumina which is aluminum oxide monohydroxide from Vista Chemical Corporation; divalent cation source: Martin Magnesia Specialties Inc. MAGCHEM® 200D (a high purity, highly reactive magnesium oxide powder); acids were from Aldrich Chemical Company; and maleated polypropylene emulsion with nonionic emulsifiers was from CHEMCOR containing 39-41% non-volatiles, Trade Name: POLY EMULSION 43N40® (used in the hydrotalcite-polypropylene blend preparation). For aminoacid intercalated hydrotalcite-polypropylene blend preparation, maleated polypropylene produced by Aristech, Trade Name: UNITE 1000®, was used.
- SEM scanning electron microscopy
- Spray-drying of the synthetic hydrotalcites of the present invention can preferably be performed by using a Niro-2 fluid nozzle spray-dryer with the following settings: heat at 5.5, air pressure to the nozzle at 1 bar and the inlet temperature maintained at desired set range of 200-230°C by varying the liquid feed rate (4-5 liters/hr). Water can preferably be fed to the spray-dryer after the temperature is stabilized to estimate the required feed rate and to remove any material remaining from a previous use. Colloidal Suspension, Condensed Suspension or Paste
- the synthetic hydrotalcite may be maintained in a wet or moist state. Maintenance of the synthetic hydrotalcite in a wet or moist state is particularly desirable in embodiments of the invention where the synthetic hydrotalcite is capable or self exfoliation on contact with a solvent.
- the product can be isolated directly from the synthesis as a colloidal suspension of the exfoliated hydrotalcite and taken on without further processing. Alternatively, the suspension may be evaporated to form a concentrate of the suspension or a doughy paste.
- Step I the organic anion source is reacted with a trivalent cation source, preferably Al 3+ , but as demonstrated in U.S. Pat. No. 5,518,704 incorporated herein in its entirety by reference, mixtures of Al 3+ and up to 50% of at least one of the other trivalent cations, Cr 3+ and Fe 3+ , may also be used in synthetic hydrotalcite preparation.
- Step II is the reaction of the mixture from Step I with a divalent cation source, preferably Mg 2+ , but as demonstrated in U.S. Pat. No.
- Step III is drying the resultant synthetic hydrotalcite.
- the hydrotalcite is maintained as a wet colloidal suspension, slurry or as a paste.
- a synthetic hydrotalcite that is capable of self and/or reversible exfoliation is maintained in an exfoliated state as a slurry or paste.
- Step I of the preparation may be carried out in water, in an organic solvent, or in an acid melt, depending on the water solubility of the organic anion.
- Step II preferably is carried out in water.
- the resulting material can preferably be dried in one of two ways: a) in an air oven at 130°C until a semi-dry solid is obtained, which is further dried in a vacuum oven at 80°C overnight; or b) by spray-drying at approximately 200°C inlet temperature and about 100°C outlet temperature.
- the powder obtained after drying the material is the intended synthetic hydrotalcite.
- 33 In water medium, a smaller than usual amount of water preferably is used, otherwise the acid may float above the alumina suspension in the water and slow the reaction rate.
- the product of this reaction was a greasy oil that was denser than the medium and settled to the bottom of the reaction vessel. In such a medium, some of the alumina and the free acid may be trapped and either reacts very slowly, or not at all, because mixing of the reagents becomes highly limited.
- the synthetic hydrotalcite made by this approach was not very homogenous as can be seen by reference to Figure 1, which is a scanning electron micrograph of the sample.
- Example 2 Step I Carried Out in Organic Solvent(s)
- the reaction of the trivalent cation source and carboxylic acids that are water immiscible, such as stearic acid, can preferably be carried out in an organic solvent, such as refluxing hexane.
- an organic solvent such as refluxing hexane.
- CATAPAL® alumina (0.26 moles) was suspended in 200 ml hexane in a 4- liter beaker and the acid (0.23 moles) was added to the stirred suspension.
- the beaker was fitted with a crystallizing dish filled with ice water to condense volatiles in the beaker as it was heated to about 65°C and the temperature was maintained for 4 to 8 hours.
- the solvent may preferably be removed by evaporation or filtration. Water was added to the resulting residue.
- Step I Carried Out in an Acid Melt
- Synthetic hydrotalcites from the following organic anion sources were prepared by the methods of the present invention and some properties of these synthetic hydrotalcites are summarized in Table II: stearic acid; glycolic acid; acetic acid; acrylic acid; v-butyrolactone; ethanesulfonic acid; lactic acid; hexanoic acid; octanoic acid; decanoic acid; benzoic acid; chlorobenzoic acid; cinnamic acid; naphthoic acid; methacrylic acid; acrylic acid, vinylacetic acid; a mixture of acrylic, acetic, and stearic acids; and a mixture of acetic, hexanoic, and stearic acids.
- the d-spacing is indicative of the distance between the layers in the hydrotalcite, because it is dependent upon the size and the shape of the anion in the hydrotalcite and is given for each of the synthetic hydrotalcites in Table II.
- interlayer distance obtained for the synthetic hydrotalcite made from stearic acid is 21.6 A
- the preferred morphology for hydrotalcites of the present invention is sheetlike, herein termed "cabbage". Excellent examples of this morphology were obtained for the synthetic hydrotalcites prepared from the following anions: acetic, ethanesulfonic, octanoic, benzoic, chlorobenzoic, methacrylic, acrylic, and vinylacetic acids.
- this semi-cabbage mo ⁇ hology may be that the size and/or shape of the organic anion prevents it from conforming to the true cabbage formation within the crystal structure.
- the long carbon chain anion and the interlayer water molecules in the synthetic hydrotalcite structure may repel each other, thereby leading to a distortion in the crystal structure. It is also possible that an incomplete reaction with the trivalent cation in Step I of the hydrotalcite synthesis may lead to a semi-cabbage mo ⁇ hology.
- the average size of the particles was measured in microns using the rulers shown in the SEM micrographs. A smaller particle size is preferred when the intended use for the synthetic hydrotalcite is in a nanocomposite.
- the particles of the synthetic hydrotalcites of the present invention are generally in the micron range as can be appreciated from a review of the data contained in Table II. The method of drying the synthetic hydrotalcites of the present invention did not seem to have any effect on the particle size. Comparative Examples 22-24
- Step I of preparation was carried out in hexane solvent. 2 Step I of preparation was carried out in stea ⁇ c acid melt without a solvent 3 M ⁇ xture molar composition- 3 76 acrylic acid: 1 14 acetic acid: 0 57 stea ⁇ c acid. 4 M ⁇ xture molar composition. 1.34 acetic acid: 0.6 hexanoic acid- 0.8 stearic acid. 5 T ⁇ valent cation source was flash calcined alumina (FCA).
- Example 51 The same procedure was repeated as in Example 25 except that 6-aminocaproic acid was used in place of 4-aminobutyric acid. The resulting slurry was a stable viscous suspension, and the solid component did not precipitate. The powder obtained after drying the material was the intended synthetic hydrotalcite. The re-wetted powder made a stable suspension again.
- Example 27 Synthesis with 4-aminobenzoic acid
- hydrotalcite is not observed in the wet sample, which indicates that the hydrotalcite is exfoliated in the wet state. Similar results are observed for 6-aminocaproic acid. This indicates that these organo hydrotalcites are self exfoliated on addition to a solvent. The data for 4-aminobenzoic acid indicate that this organo hydrotalcite is not self exfoliated on addition to a solvent.
- Blends with HTC-0498-10 (LaRoche) from 5% to 81% by weight in the solid weight of polypropylene were prepared as indicated in Table IV and analyzed by XRD, SEM, differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA).
- Example 32 a SEM micrograph of Example 32, a blend containing about 81% hydrotalcite, showed a cabbage mo ⁇ hology that was better defined than that of the hydrotalcite from which it was obtained.
- the SEM shown in Figure 9, of a similar blend with 5% hydrotalcite from Example 28, however, had a what the Inventors herein term a "doughnut" mo ⁇ hology. Without being limited to any specific theory, the Inventors believe that the doughnut mo ⁇ hology may result from the hydrophilic portion of the synthetic hydrotalcite forming a circular core while the hydrophobic portion, which comprises stearate or octanoate anion mixed with the polymer matrix, surrounds the circular core. The radii of the doughnut particles ranged from 2-3 microns.
- the blend of Example 28 may have the hydrotalcite so highly dispersed in the polymer matrix that it no longer exists in a layered form.
- the DSC transition temperatures represent the temperature at which phase changes take place in the blend and are indicative of minimum temperature required for processing these materials in polymer applications.
- the first phase transition temperature occurred at approximately 150°C for the blends. Some of these materials exhibited lower transition temperatures that can be attributed to a loss of water.
- Synthetic hydrotalcite-polypropylene blends of stearic acid, octanoic acid, methyl methacrylic acid and acrylic acid were also prepared in a manner that required the addition of the polypropylene emulsion to the un-isolated synthetic hydrotalcite in the preparations.
- the resulting blend was isolated by spray-drying in the manner described above.
- Example 34 a methacrylic acid-derived synthetic hydrotalcite polypropylene blend, did not exhibit the doughnut mo ⁇ hology, nor was it what could be referred to as semi-cabbage.
- the particle size of the methacrylic acid-derived synthetic hydrotalcite-polypropylene blend averaged 5X3 angstroms.
- the residue percentages from TGA for the synthetic hydrotalcites made from anions other than acetate correlate with the hydrotalcite percentages in the blends when corrections are made for the contribution of the weight of the anion.
- the DSC transition temperatures for these materials were similar to those materials derived from HTC- 0498-10, as the first transition temperatures ranged from 148°-152°C. These materials can therefore be processed with polymers at normal temperatures.
- Co-polymerizing the synthetic hydrotalcite derived from methacrylic acid with methyl methacrylate demonstrates that master-batch materials may be prepared. Blends with poly-addition polymers, such as polypropylene, can then be prepared from these master batches. With the Aerosol OT surfactant, the copolymer was expected to be evenly slurried in the water in which the reaction was carried out. In all the examples, slurry formation occurred only at the beginning of the polymerization. As the polymer amount increased, the suspended particles coalesced into a ball or into chunks that forced the early termination of the polymerization because of difficulty with stirring. The product obtained was a tan, tough and stiff polymer.
- Amino acid intercalated synthetic hydrotalcites according to the current invention are particularly useful for preparing inorganic polymer blends according to the current invention.
- the amino acid intercalated synthetic hydrotalcite is capable of self exfoliation when introduced into a solvent.
- the amino acid intercalated synthetic hydrotalcite is maintained as a slurry, suspension or paste when it is isolated from the synthesis.
- the amino acid intercalated hydrotalcite is isolated from the synthesis and is maintained in an exfoliated state.
- the amino acid intercalated synthetic hydrotalcite is dried after isolation and may be subsequently added to a solvent to induce self exfoliation.
- the hydrotalcite is added to the molten polymer as a slurry, suspension or paste. Because the amino acid intercalated synthetic hydrotalcite is capable of self-exfoliation it can be more easily dispersed in a polymer blend without the use of a compatiblizer. Although a compatiblizer is not required, amino acid intercalated synthetic hydrotalcites according to this embodiment of the invention can be used with compatiblizer molecules.
- the amino acid intercalated synthetic hydrotalcite is compounded with a modified poly-addition polymer.
- the modified poly-addition polymer is an acid modified polyolefin, such as maleated polypropylene.
- the hydrotalcite may be compounded with either the acid modified polymer alone or with a mixture of modified and unmodified polymers.
- the amino acid intercalated synthetic hydrotalcite is compounded with a molten acid modified polyolefin, such as maleated polypropylene, to produce a "master batch" of amino acid intercalated synthetic hydrotalcite and acid modified polyolefin. This "master batch” may then be compounded with unmodified poly- addition polymers to produce a final nanocomposite.
- 74 XRD was performed on a ground sample of UNITE 1000® and the 50/50 UNITE/hydrotalcite mixed material, as well as on wet and air-dried hydrotalcite from a batch of hydrotalcite prepared in an 8 wt% slurry.
- the 6 wt% slurry is not viscous enough to perform XRD on in the wet state, so an 8 wt% preparation was used for this comparison.
- the 6 wt% and 8 wt% hydrotalcite slurries were prepared in the same manner, so no real difference would be expected between the two.
- Figure 11 shows from bottom to top XRD scans of an 8 wt% slurry of the hydrotalcite wet; an air-dried sample of hydrotalcite from an 8 wt% slurry; a sample of UNITE
- Figure 12 shows the evolution of the hydrotalcite structure from heating.
- Figure 12 shows from bottom to top XRD scans of a 10 wt% slurry of the hydrotalcite wet; an air-dried sample of hydrotalcite from an 10 wt% slurry; a sample of the 10 wt% slurry dried at 100° C and a sample of the 10 wt% slurry dried at 150° C.
- the air dried sample second from bottom
- the peaks due to 6-aminocaproic acid appear in the region of about 12° to about 37°.
Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03729590A EP1472262A1 (en) | 2002-01-11 | 2003-01-08 | Synthetic hydrotalcites, syntheses and uses |
AU2003216043A AU2003216043A1 (en) | 2002-01-11 | 2003-01-08 | Synthetic hydrotalcites, syntheses and uses |
JP2003560020A JP2005515230A (en) | 2002-01-11 | 2003-01-08 | Synthesis and use of synthetic hydrotalcite |
CA002471032A CA2471032A1 (en) | 2002-01-11 | 2003-01-08 | Synthetic hydrotalcites, syntheses and uses |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/044,360 | 2002-01-11 | ||
US10/044,360 US6846870B2 (en) | 2001-08-23 | 2002-01-11 | Hydrotalcites, syntheses, and uses |
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WO2003059917A1 true WO2003059917A1 (en) | 2003-07-24 |
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PCT/US2003/000478 WO2003059917A1 (en) | 2002-01-11 | 2003-01-08 | Synthetic hydrotalcites, syntheses and uses |
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US (3) | US6846870B2 (en) |
EP (1) | EP1472262A1 (en) |
JP (1) | JP2005515230A (en) |
CN (1) | CN1615312A (en) |
AU (1) | AU2003216043A1 (en) |
CA (1) | CA2471032A1 (en) |
TW (1) | TW200413397A (en) |
WO (1) | WO2003059917A1 (en) |
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US9676920B2 (en) | 2007-11-27 | 2017-06-13 | Basell Poliolefine Italia S.R.L. | Polyolefin nanocomposites materials |
US10214632B2 (en) | 2015-12-17 | 2019-02-26 | Indian Oil Corporation Limited | Crystallinity modifier for polyolefins |
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- 2003-01-08 CN CNA038021552A patent/CN1615312A/en active Pending
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1514842A1 (en) * | 2003-09-12 | 2005-03-16 | Rohm And Haas Company | Nanoclay modified waterborne compositions for coating plastic and methods for making the same |
JP2005238194A (en) * | 2004-02-27 | 2005-09-08 | National Institute Of Advanced Industrial & Technology | Colloid particulate hydroxide base compounding agent for resin and resin composition containing the same |
JP4572289B2 (en) * | 2004-02-27 | 2010-11-04 | 独立行政法人産業技術総合研究所 | Colloidal particle-formed hydroxide resin compounding agent and resin composition containing the same |
US9676920B2 (en) | 2007-11-27 | 2017-06-13 | Basell Poliolefine Italia S.R.L. | Polyolefin nanocomposites materials |
US10214625B2 (en) | 2007-11-27 | 2019-02-26 | Basell Poliolefine Italia S.R.L. | Polyolefin nanocomosites materials |
US10214632B2 (en) | 2015-12-17 | 2019-02-26 | Indian Oil Corporation Limited | Crystallinity modifier for polyolefins |
Also Published As
Publication number | Publication date |
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JP2005515230A (en) | 2005-05-26 |
AU2003216043A1 (en) | 2003-07-30 |
EP1472262A1 (en) | 2004-11-03 |
US20030114699A1 (en) | 2003-06-19 |
US20050080178A1 (en) | 2005-04-14 |
US6846870B2 (en) | 2005-01-25 |
CA2471032A1 (en) | 2003-07-24 |
TW200413397A (en) | 2004-08-01 |
US20050080177A1 (en) | 2005-04-14 |
CN1615312A (en) | 2005-05-11 |
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