Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C08K5/19—Quaternary ammonium compounds
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
  • Y10T428/1345—Single layer [continuous layer]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1397—Single layer [continuous layer]

Definitions

• the present invention relates to the modified phyllosilicate composition comprising a mixture of modifying agents, its preparation process and its uses.
• the modified materials are used at relatively high temperature in different application, for example the production of food packaging. These materials at high temperature can be unstable.
• the patent application EP1787918 describes a biodegradable polyester resin reinforced by a modified phyllosilicate.
• the phyllosilicate is substituted with ammonium, pyridinium, imidazolium, or phosphonium ions.
• ammonium ions include tetraethylammonium,
• modified phyllosilicate describes in this patent application presents one type of modifying agent.
• modified phyllosilicate compositions comprising hexadecyltrimethyl ammonium cations and acetylcholine or choline are more stable at high temperatures than the phyllosilicate compositions comprising only hexadecyltrim ethyl ammonium cations.
• this modified phyllosilicate composition can be obtained at higher temperatures since no degradation of phyllosilicate compositions occurs which have the advantages of higher yields.
• phyllosilicate composition comprising a modifying agent which is hexadecyl trimethyl ammonium cations which are intercalated between the layers of the phyllosilicate and an additional modifying agent selected from the group consisting in acetylcholine and choline.
• the silicate used in the invention belongs to the family of phyllosilicates, preferably smectite group. These compounds are characterized by their swelling properties and high cation-exchange capacities.
• Another aspect of the present invention relates to a process for the production of a modified phyllosillicate as defined above, that is a phyllosilicate
• a modified phyllosilicate composition of the invention comprising a modifying agent which is hexadecyl trimethyl ammonium cations which are intercalated between the layers of the phyllosilicate and optionally an additional modifying agent which is acetylcholine or choline, the process comprising (a) dispersing the phyllosillicate in water and an d-do alcohol; (b) applying ultrasonic wave; (c) optionally adding choline salt or acetylcholine salt (d) adding hexadecyl trimethyl ammonium salt; (e) maintaining the mixture of step (d) at a temperature comprised between 20°C and 120°C; (f) isolating the compound obtained in step (d), wherein the step a), b), c), and d) can be carried out in any order.
• the incorporation of a modified phyllosilicate composition of the invention to a polymer results in a polymer nanocomposite showing improved thermal
• Another aspect of the present invention relates to the use of the modified phyllosilicate of the invention as a reinforcing agent of polymers.
• FIG. 1 shows a thermogravimetric analysis up to 700°C performed over the modified phyllosilicates.
• FIG. 2 shows the young Modulus (GPa), (white column) and the elongation at break (mm), (black column) of different samples.
• FIG. 3 shows the young Modulus (GPa), (white column) and the elongation at break (mm), (black column) of different samples.
• FIG. 4 shows a plot of the heat flow versus temperature of different samples.
• an aspect of the present invention relates to a modified phyllosilicate compositions comprising hexadecyltrim ethyl ammonium cations and acetylcholine or choline.
• phyllosilicates refers to layered silicates in which the SiO 4 tetrahedra are linked together in two dimensional sheets and are condensed with layers of ⁇ or MgO octahedra in the ratio 2: 1 or 1 : 1 .
• the negatively charged layers attract positive cations (e.g. Na + , K + , Ca 2+ , Mg 2+ .) which can hold the layers together.
• positive cations e.g. Na + , K + , Ca 2+ , Mg 2+ .
• Non phyllosilicate which may be used within the scope of the present invention are sodium
• the phyllosilicate is sodium montmorillonite.
• modified phyllosilicates refers to phyllosilicates wherein the positive cations (e.g. Na + , K + , Ca 2+ , Mg 2+ ), are exchanged by ion exchange reactions with alkylammonium cations as modifying agents.
• positive cations e.g. Na + , K + , Ca 2+ , Mg 2+
• the modified phyllosilicate of the present invention comprises hexadecyl trimethyl ammonium and, optionally acetylcholine or choline cations, as modifying agents.
• These modifiers are added in excess to the cation exchange capacity (CEC) of the phyllosilicate and it was established a value of 0.5-10 times the CEC as the optimum.
• CEC cation exchange capacity
• the amount of acetylcholine or choline is 0.20-0.75 meq/1 OOg the value of the phyllosilicate CEC and the amount of hexadecyl trimethyl ammonium cation is 5.25-5.80 meq/1 OOg the value of the phyllosilicate CEC.
• the amount of acetylcholine or choline is 0.25-0.50 meq/1 OOg the value of the phyllosilicate CEC and the amount of hexadecyl trimethyl ammonium cation is 5.55-5.75 meq/1 OOg the value of the phyllosilicate CEC.
• the modified phyllosilicate of the present invention that is a phyllosilicate comprising a modifying agent which is hexadecyl trimethyl ammonium cations which are intercalated between the layers of the
• acetylcholine or choline can be prepared by a process comprising (a) dispersing the phyllosillicate in water and an d-do alcohol; (b) applying ultrasonic wave; (c) optionally adding choline salt or acetylcholine salt (d) adding hexadecyl trimethyl ammonium salt; (e) maintaining the mixture of step (d) at a temperature comprised between 20°C and 120°C; (f) isolating the compound obtained in step (d), wherein the step a), b), c), and d) can be carried out in any order.
• the phyllosilicate is dispersed in water and ethanol.
• the choline salt added is choline halide. In a more preferred embodiment the choline salt adding is choline chloride. In a preferred embodiment, the acetylcholine salt added is acetylcholine halide. In a more preferred embodiment the acetylcholine salt added is acetylcholine chloride. In a preferred embodiment the hexadecyl trimethyl ammonium salt added is hexadecyl trimethyl ammonium halide. In a more preferred embodiment the hexadecyl trimethyl ammonium salt added is hexadecyl trimethyl ammonium bromide. In a preferred embodiment the optionally addition of choline salt or
• acetylcholine salt and the addition of hexadecyl trimethyl ammonium salt is carried out slowly.
• the mixture of step (d) is maintained at a temperature comprised between 20°C and 90°C. In another preferred embodiment the mixture of step (d) is maintained at a temperature comprised between 50°C and 90°C. In a more preferred embodiment the mixture of step (d) is maintained at a temperature comprised between 65°C and 75°C.
• the isolating step f) comprises purifying of the modified phyllosilicate prepared. In a more preferred embodiment the phyllosilicate is purified with a solution of water: ethanol, in particular, the solution is added to the modified phyllosilicate, and the mixture is maintained under stirring at a temperature comprised between 50°C-90°C . The product is filtered and the conductivity of the mother liqueours is measured. This process is repeated until the mother liqueours have a conductivity below 5-30 ⁇ / ⁇ .
• the isolating step comprises a drying step of the phyllosilicate after the purification.
• the drying step is carried out at a temperature comprised between 70°C-90°C. It can be carried out in a conventional oven, by lyophilisation or by atomization. Generally, the drying process last at least 12 hours.
• the phyllosilicate can be milled, and sieved. Generally it is sieved to a particle size below 25 microns.
• the modified phyllosilicate of the invention can be used in the reinforcement of polymers. Preferably in the reinforcement of polymers used in food packaging.
• PE polyethylenes
• PP polypropylenes
• EVA poly(ethylene-vinyl acetates
• PS polystyrenes
• PVC polyvinyl chlorides
• I polyethylene terephthalates
• PET polyvinyl acetates
• PC polycarbonates
• PA polyamides
• PA polyvinyl alcohols
• PVDC polyvinylidene chlorides
• a modified phyllosilicate of the invention to a biodegradable polymer, in particular polylactic polymer (PLA) results in a polymer nanocomposite showing not only improved mechanical properties but also improved barrier properties and thermal resistance.
• PVA polylactic polymer
• the fact that the polymer nanocomposite shows excellent barrier properties is advantageous on the one hand, for its use for storage of aqueous drinks (e.g. water, juice, milk) since the lost of water vapour through the wall of the bottles is minimized.
• aqueous drinks e.g. water, juice, milk
• the polymer nanocomposite of the present invention shows excellent mechanical strength and less rigidity which is an advantage for packaging long term storage, avoiding the polymer nanocomposite deformation and cracking.
• a polymer nanocomposite comprising a polylactic polymer and a modified phyllosilicate composition comprising a modifying agent which is hexadecyl trimethyl ammonium cations which are intercalated between the layers of the phyllosilicate and an additional modifying agent selected from the group consisting acetylcholine and choline are also part of the invention.
• a modifying agent which is hexadecyl trimethyl ammonium cations which are intercalated between the layers of the phyllosilicate and an additional modifying agent selected from the group consisting acetylcholine and choline
• Example 1 Preparation of montmorillonite modified with hexadecyltrimethyl ammonium cations and acetylcholine or choline
• Example 1 a montmorillonite with 5.5 CEC of HDTA and 0.5 CEC of ACQ
• Purified sodium montmorillonite (Closiste ® Na + ) was purchased from Southern Clay Products, with moisture content between 4 and 9 % CEC of sodium montmorillonite was 92.6 mequiv/1 OOg.
• Quaternary ammonium salts were supplied by Acros Organics. Choline (CO) chloride, acetylcholine (ACO) chloride, and hexadecyltrimethyl ammonium (HDTA) bromide with 99 % of purity, and trimethyloctadecylammonium bromide 98% was purchased from Fluka.
• Choline (CO) chloride, acetylcholine (ACO) chloride, and hexadecyltrimethyl ammonium (HDTA) bromide with 99 % of purity, and trimethyloctadecylammonium bromide 98% was purchased from Fluka.
• Next step includes drying of the phyllosilicate at 70°C during at least 12 hours. Finally, phyllosilicate were milled, and sieved to a particle size below 25 microns.
• the modified phyllosilicate obtained is a Cloisite (CLO) with 5.5 CEC of HDTA and 0.5 CEC of ACO.
• Example 1 b montmorillonite with 5.75 CEC of HDTA and 0.25 CEC of ACQ
• Example 1 c montmorillonite with 5.75 CEC of HDTA and 0.25 CEC of CO
• Example 1 For the production of the montmorillonite modified with hexadecyltrimethyl ammonium cations, the same process of Example 1 was carried out but starting from 40.50 grams of hexadecyltrimethyl ammonium bromide which have been dissolved in 500 ml of ethanol. The modified phyllosilicate obtained is a CLO with 6 CEC of HDTA. Comparative Example 1 : Preparation of montmorillonite modified with trimethyloctadecyl ammonium (ODTA) cations
• Example 2 For the production of the montmorillonite modified with (ODTA) cations the same process of Example 2 was carried out but starting from 43.62 grams of (ODTA) bromide.
• the modified phyllosilicate obtained is a CLO with 6 CEC of ODTA.
• Example 2 For the production of the montmorillonite modified with (ACO) cations the same process of Example 2 was carried out but starting from 10.09 grams of (ACO) chloride.
• the modified phyllosilicate obtained is a CLO with 3 CEC of ACO.
• Example 2 For the production of the montmorillonite modified with (CO) cations the same process of Example 2 was carried out but starting from 7.76 grams of (CO) chloride.
• the modified phyllosilicate obtained is a CLO with 3 CEC of
• Example 3 Thermal characterization of phyllosilicates with mixture of modifiers.
• Phyllosilicates prepared with a mixture of modifiers present different weight changes, which are the contribution of both modifiers.
• it was included in this Figure modified phyllosilicates with only one modifier (hexadecyltrimethylammonium, acetylcholine or choline). It was observed that the modified phyllosilicate, montmorillonite with octadecyltnmethylammonium was the less thermally stable, with big difference with the other modified phyllosilicates.
• Example 4 Preparation of PLA-phyllosilicate nanocomposites
• Example 4a PLA4042-phyllosilicate (montmorillonite with 5.5 CEC of HDTA and 0.5 CEC of ACQ)
• PLA nanocomposites samples were obtained with the modified phyllosilicate prepared in Example 1 a, and PLA 4042.
• a DSM Xplore Microcom pounder 15 cc was used.
• PLA pellets (dried overnight at 60°C) were blended with 4% in weight of modified phyllosilicate in this co-rotating twin screw micro-extruder.
• the temperature of processing was 200°C.
• the rotation speed of the screw was maintained at 100 r.p.m., and residence time was set to 10 min.
• Example 4b PLA4042-phyllosilicate (montmorillonite with 5.75 CEC of HDTA and 0.25 CEC of ACQ)
• Example 4a The same process of Example 4a was carried out but with the modified phyllosilicate prepared in Example 1 b.
• Example 4c PLA4042-phyllosilicate (montmorillonite with 5.75 CEC of HDTA and 0.25 CEC of CO)
• Example 4a The same process of Example 4a was carried out but with the modified phyllosilicate prepared in Example 1 c.
• Example 4d PLA4042-phyllosilicate (montmorillonite with HDTA)
• Example 4a The same process of Example 4a was carried out but with the modified phyllosilicate prepared in Example 2.
• Example 4e PLA2002-phyllosilicate (montmorillonite with 5.75 CEC of HDTA and 0.25 CEC of ACQ) The same process of Example 4a was carried out but with PLA2002 and the modified phyllosilicate prepared in Example 1 b.
• Example 4f PLA2002-phyllosilicate (montmorillonite with HDTA) The same process of Example 4a was carried out but with PLA2002 and the modified phyllosilicate prepared in Example 2.
• Example 4a The same process of Example 4a was carried out but with the modified phyllosilicates prepared in Comparative example 1 .
• Example 5 Characterization of the PLA-phyllosilicate nanocomposites of
• Results were presented in FIG. 2 show the Young Modulus and the elongation at break of PLA, (nanocomposites obtained in Example 4a, 4b, and 4c).
• Comparative results of nanocomposites based on PLA 4042 are shown in FIG. 3. It can be seen that the use of modified phyllosilicate of the present invention produces an increase in Young Modulus, and also an increase in the elongation at break, as occurred previously in respect of the nanocomposite of comparative example 4. Elongation at break reaches higher values when nanocomposites prepared in Example 4f and 4b were used.
• VWTR Water Vapour Transmission Rate
• Results are shown in Table 1 .
• the nanocomposites of the inventions show a high reduction of WVTR when the phyllosilicates is added. This reduction is higher than the PLA pure and the one showed by the closest prior art phyllosilicate (comparative example 5). Best results were reached with the nanocomposite prepared in Example 4f, with an improvement of 67 %. Oxygen transmission rate evaluation over samples prepared with PLA thermoforming grade (PLA2002D).
• Oxygen transmission rate was evaluated following standard ASTM D3985: "Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor".
• Experimental equipment was an OX-TRAN 2/20 SM. The measurements conditions were 23 °C and 50% relative humidity. The test was performed with oxygen (100 %).
• Results are presented in Table 3. The results show the reduction in oxygen permeability of the nanocomposites of the invention. The best improvement is observed with the nanocomposite prepared in Example 4b, with a reduction in oxygen permeability of almost 15%.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Wrappers (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Biological Depolymerization Polymers (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Saccharide Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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