WO2014021800A2 - Chaîne de fabrication de technologie verte de micro- et nanoparticules d'argile et de leurs nanohybrides polymères fonctionnels pour applications de nano-ingéniérie et de nano-médecine - Google Patents

Chaîne de fabrication de technologie verte de micro- et nanoparticules d'argile et de leurs nanohybrides polymères fonctionnels pour applications de nano-ingéniérie et de nano-médecine Download PDF

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WO2014021800A2
WO2014021800A2 PCT/TR2013/000240 TR2013000240W WO2014021800A2 WO 2014021800 A2 WO2014021800 A2 WO 2014021800A2 TR 2013000240 W TR2013000240 W TR 2013000240W WO 2014021800 A2 WO2014021800 A2 WO 2014021800A2
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montmorillonite
maleic anhydride
line according
technology line
mmt
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PCT/TR2013/000240
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WO2014021800A3 (fr
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Zakir Rzayev
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Rich Group Kimyevi Maddeler Insaat Sanayi Ve Ticaret Limited Sirketi
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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/10—Clay
    • C04B14/104—Bentonite, e.g. montmorillonite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/36—Polymerisation in solid state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the present invention relates to the field of inorganic mineral micro- and nanoparticles fabrication, modification and uses. More specifically, the present invention related to green technology line for preparation of micro- and nanoparticles of clays preferly bentonite and montmorillonite like clays from mineral resources of Turkey (BTT-TR and MMT-TR) and their novel functional organic and polymeric derivatives as reactive additives-nanofillers useful for utilization in situ polymer/clay processing to improve the important properties (mechanical, thermal, dynamic mechanical and etc.) of thermoplastic, thermoset and elastomer-rubber polymer materials, as well as to prepare novel preintercalated functional organic clays based polymer/biopolymer layered silicate nanomaterials by interlamellar copolymerization and graft copolymerization in the presence of MMT-TR and its various derivatives as catalyst-nanofillers.
  • Another aspect of this invention is use of nanoparticles and their organic derivatives, including reactive biopolymers, for nanoengineering and nanomed
  • inorganic mineral micro(nano)particles especially montmorillonite (MMT), bentonite (BTT) and their organically modified derivatives have a wide range of application areas as nanofillers in reinforced theroplastic, thermoset and elastomer-rubber polymer nanomaterials such as nanofilms, nanosheets, nanocoatings, nanofibers, nanofoams, and the like, which exhibit suitable flexibility and exellent mechanical strength and in medicine and pharmacy as additives in drug delivery systems, and the like, as well as in food and nonfood industry such as food packaging, paint-coating industry, agriculture, industrial wrapping applications, in building industry as heat transfer reducing agents-materials, electrical and electronic material industry and the like.
  • MMT montmorillonite
  • BTT bentonite
  • MMT was discovered in 1847 in Montmorillon in the Vienne prefecture of France, more than 50 years before the discovery of bentonite in the US. It is found in many locations world wide and known by other names [1], It is used in the oil drilling industry as a component of drilling mud, making the mud slurry viscous which helps in keeping the drill bit cool and removing drilled solids. It is also used as a soil additive to hold soil water in drought prone soils, to the construction of earthen dams and levees and to prevent the leakage of fluids. It is also used as a component of foundry sand and as a desiccant to remove moisture from air and gases [2].
  • MMT Similar to many other clays, MMT swells with the addition of water. However, some MMTs expand considerably more than other clays due to water penetrating the interlayer molecular spaces and concomitant adsorption. The amount of expansion is due largely to the type of exchangeable cation contained in the sample. The presence of sodium as the predominant exchangeable cation can result in the clay swelling to several times its original volume. Hence, sodium MMT has come to be used as the major constituent in non-explosive agents for splitting rock in natural stone quarries in order to limit the amount of waste, or for the demolition of concrete structures where the use of explosive charges is unacceptable.
  • MMT-containing bentonite useful also as an annular seal or plug for water wells and as a protective liner for landfills.
  • Other uses include as an anti-caking agent in animal feed, in paper making to minimize deposit formation and as a retention and drainage aid component.
  • MMT has also been used in cosmetics. MMT is known for its adsorbent qualities and has been used successfully in scientific trials to eliminate atrazine from water [3].
  • MMT clay is widely used in medicine and pharmacology. For internal use, MMT is effective in the treatment of irritable bowel syndrome. It is also used for the prevention of afla-toxicosis, and in the treatment of constipation. Also, a modified version inhibits intestinal absorption of cholesterol (nanotechnology research), and absorbs uric acid [1]. It is used in agriculture to improve growth performance of piglets and fish [1][3].
  • MMT is proven to be effective in use as an adsorptive of heavy metals, toxins, and hazardous chemicals[4]. Antibacterial effects of MMT are well demonstrated [5]. It has also shown itself useful for tissue engineering [6] [7].
  • MMT is widely used in pharmacology for a variety of application, such as stabilization of suspensions and emulsions, viscosizing, adhesion to the skin, and tablet making. It is also used as drug carrier, or as part of a drug delivery system, such as for controlled drug release; including for gene delivery, and for drug targeting to specific tissues. It is also used for stability enhancement in drug and nutrient application. There are also other similar uses [1]. MMT is also used in the production of pharmaceuticals, e.g. as a catalyst [8].
  • MMT and its organic derivatives are widely utilized in polymer nano- technology and nanoengineering processes as effective nano-fillers for preparation of polymer nanocomposites and nanomaterials with higher performance properties (mechanical, barrier, flame retardance, and etc.[USA Patent 2859198; USA Patents 3236802; 3328231; 3471435].
  • There is much interest in layered, clay-based polymer nanocomposites because of the improved properties exhibited by the nanocomposites. It is desirable to maximize delamination of the clay into individual platelet particles in order to maximize some property improvements, including barrier improvements, and to minimize deleterious effects on some properties including elongation-at- break.
  • the clay is exfoliated into particles with size less than about 100 nm in order to achieve clarity that is comparable to the clay-free polymer.
  • the only polymer/clay nanocomposites that meet this expectation are prepared by incorporation of organically treated clays during synthesis of the polymer from monomer.
  • the ealest patent on the polymerization of vinyl monomer(s) in the presence of clay belongs to Toyota [Kamigaito et al. Patent US 4384989, 1984].
  • the invention describes synthesis of intercalated clay composites by contacting MMT with a monomer (e.g., styrene, vinyl acetate) at room temperature, then mixing with dichlorodimethyl silane and in a few minutes effecting the polymerization.
  • a monomer e.g., styrene, vinyl acetate
  • dichlorodimethyl silane e.g., styrene, vinyl acetate
  • Some patents describe the blending of up to 60 weight percent of intercalated clay materials with a wide range of polymers including polyamides, polyesters, polyurethanes, polycarbonates, polyolefins, vinyl polymers, thermosetting resins and the like. Such high loadings with modified clays are impractical and useless with most polymers because the melt viscosity of the blends increases so much that they cannot be molded.
  • WO 93/04117 discloses a wide range of polymers melt blended with up to 60 weight percent of dispersed platelet particles.
  • WO 93/04118 discloses nanocomposite materials of a melt processable polymer and up to 60 weight percent of a clay that is intercalated with organic onium salts. The use of a mixture of swellable layered clays or a clay mixture intercalated with an onium ion is not contemplated nor disclosed.
  • U.S. Pat. No. 5,552,469 describes the preparation of intercalates derived from certain clays and water soluble polymers such as polyvinyl pyrrolidone, polyvinyl alcohol, and polyacrylic acid. The use of clay mixtures or mixtures intercalated with onium ions is specifically excluded.
  • JP Kokai patent no. 9-176461 discloses polyester bottles wherein the polyester contains unmodified sodium MMT. Incorporation of the clay into the polyester by melt compounding is disclosed; however the use of clay mixtures or clays intercalated with onium ions was neither contemplated nor disclosed.
  • Patent US 6,391,449, 2002 invention related to polymer-clay nano- composites and methods of fabrication comprising (a) a melt-process able matrix polymer such as poly(ethylene terephthalate) (PET), and incorporated therein (b) a mixture of at least to layered clay materials such as MMT clay and its various alkyl ammonium intercalated derivatives.
  • PET poly(ethylene terephthalate)
  • This invention also related to articles produced from a nanocomposites and a process for preparing a nanocomposites.
  • this invention comprises use of higher loading of clays and organoclays as well as mixtures of different clays to prepare only polyester (PET) based nanocomposites.
  • the mixture of micro- and nanostructures may be formed, which will be significantly decreased the engineering performance of prepared composites. In generally, these composites have a limited application areas.
  • Another US patent 10291141, 2002 describes preparation of clay/polymer nanocomposites by suspension polymerization of monomer(s) in the presence of hydrophobically modified clay, dispersed whithin the monomer phase.
  • the applications of the resulting nanicomposite range from coatings, sealants, caulks, adhesives, binders, traffic paints, to plastics additives.
  • Another patent from this series describes preparation of an aqueousnanocomposite dispersion [Lorah and Slone, 2002; patent US 2005580].
  • the goal of this invention is to protect modifications of the process with additional using a multivalent cation (Ca. Mg, Cu, Fe or Zr), which may improve the physical properties of clay/polymer nanocomposite via formation of strongly bended clay-polymer matrix.
  • composition and formulation of the layered silicate minerals strongly depend on the origin, geographic location, country and geophysical parameters of mineral welds, and therefore, different methods of their isolation and purification were utilized by many manufacturers from various countries (USA, Kanada, France, Germany, England, China, Japan, etc.)-
  • the results of geophysical and geochemical investigations of many Turkish researchers [12-16] were confirmed the presence of the mineral resources riched with layered smectite clay group.
  • nanofillers especially MMT-TR and organo-MMT-TR clays as renouncing nanoadditives for polymer nanotechnology
  • many Turkish industrial sectors such as plastics, packaging materials, paints, coatings, foams, etc., were exported the nanofillers and organo-nanofillers from various Firms-Manufactures (Aldrich-Sigma) through foreign trade.
  • the patent invention CN1369432A relates to nanocrystalline powder material preparation method, especially relate to one kind 2: 1 type stratiform montmorillonite mineral preparations of nanomaterials method .
  • this invention claimed a use of multicomponent system such as mixture of metatitatic acid butyl ether, alcohol (etanol, propyl alcohol or butanol), inorganic acids (hydrochloride acid or nitric acid) and powder MMT and two steps of reaction. After filtration, separation and washing processing of final product, many waste products were formed, purification of which is technologically difficult. From claim of this invention, a role of used row metatitanic acid is not explained.
  • prepared MMT clay has average grain diameter 380 nm and the specific surface area of nanometer montmorillonite powder is 200-410 m 2 /G. These particle parameters are higher as compared with MMT-TR clay particles of present invention (Fig. 4 and 5) which shown 286.5 and 373.1 nm for BTT (bentonite)-TR and 342.2 and 229.4 nm for MMT-TR in CHCI 3 and water solutions, respectively. All processing in the present invention were realized at room temperature unlike above mention Chine patent invention (temperature control (20-70°C or 30- 70°C at long time reactions 4-10 h, preferable 5-8 h).
  • this Chine invention disclosed the chemical processing for preparation of nanometer MMT clay (but no at nanoscale 0.1-100 nm) while the present invention only consisted the physical processing for preparation of MMT- TR clay.
  • This Chine patent invention claimed a use microwave-irradiation for disinfection- activation of MMT clay while present invention disclosed a use of microwave sonication of MMT- TR particles for the reduction of size, and therefore, significantly increasing in surface area of particles which allow future prepare polymer layered silicate nanohybrids or nancomposites with "core-shell" morphology and nanoscale (0.1-100 nm) particle size ( 85-100 nm, Fig. 8, TEM images).
  • This prototype technology line includes the following different physical processing steps:
  • Technology line also consists (i) a reactor for preparation novel reactive and non-reactive organic derivatives of MMT-TR clay, for synthesis novel functional (co)polymers/organo-MMT-TR nanohybrids by interlamellar radical and controlled/living (co)terpolymerization, preferable radical arrangement-fragmentation and chain termination (RAFT) copolymerization of preintercalated monomer...
  • RAFT radical arrangement-fragmentation and chain termination
  • organo-MMT-TR or terminating RAFT- agent...organo-MMT-TR complexes with various vinyl and acrylic monomers (ii) Lab. reactive extrusion system for preparation of a wide range of new generation of the polymer (thermoplastics, thermosets, rubbers and biopolymers)/organo-MMT-TR clay nanocomposites and nanomaterials (nanofilms, nanofibers, nanocoatings by in-line nanocoating method and the like).
  • This invention will causes to future Turkey industrial fabrication of BTT-TR and MMT-TR clays, their novel organic derivatives and polymer/organoclay hybrids, nanocomposites and nanomaterials with high performance parameters, especially Zheta-size (around 240-350 nm) and zheta-potential (> 70 mV) for a wide range of polymer nanoengineering and nanomedicine applications.
  • This invention discloses an utilization of mineral clay from resource of various regions in Turkey such as Nigde-Dikildas, Ordu-Llnye, Tokat-Resadiye, and etc.) which provides an independence of many Turkich industrial sectors from foreign firms on the nanofillers and organo-nanofillers, as well as causes significantly development of the polymer nanotechnology, nanoengineering and nanomedicine, paint, coating, building, and other industrial sectors.
  • Another aspects of the present invention are: (1) use of row mineral materials from different geophysical region of Turkey riches with mixtures of smectite clays, which are marked as BTT-TR and MMT-TR and significantly differ from conventional like clays by their purification degree, particle and composition parameters; (2) production technology line comprises green and recycling processes using deionized water as a medium at room temperature; (3) production technology line contains a combination of effective milling, microwave-sonication and purification processing; (4) production technology line permits the preparation of high performance of micro- and nanoparticles useful for a wide range of utilization in modern polymer nanotechnology and nano-engineering areas; (5) this invention discloses synthetic pathways for the preparation of a new generation of organic-polymeric derivatives of clay nanoparticles and their polymer/biopolymer layered silicate nanocomposites for the polymer nano-engineering, bioengineering and nanomedicine applications.
  • RAFT preintercalated terminating agent
  • This invention disclosed a novel prototype periodical green technology processing for preparation of micro- and nanoparticles of clays titled as BTT-TR and MMT-TR and their novel organic-polymeric intercalated derivatives and new generation of polymer layered silicate nanocomposites for nano- and bioengineering applications.
  • Fig. 1 Green Technology Line for Preparation of Clay (MMT-TR and BTT-TR) Micro and Nanoparticles from Turkey Mineral Resource and Their Polymer NAnocomposites
  • FIG. 3 SEM images (surface morphology with scale 1.0 and 10 ⁇ , xlO.000 and xlOOO magnification) of BTT-TR (left) and sodium MMT-TR (Na + -MMT-TR) (right) fabricated from mineral field of Ordu-lJniye (Turkey) using above mention technology line ( Figures 1 and 2)
  • Fig. 9 Synthetic pathways of preintercalated RAFT agent (S-l-dodecyl-S-(a,a'-dimethyl)-a"- acetic acid) through interlamellar complex-formation of non-reactive DMDA-MMT-TR and RAFT agent (A) and interlamellar amidizaton of reactive ODA-MMT-TR with RAFT agent (B) as a new generation of RAFT-agent-nanofllers Fig. 10. TEM micrographs of high resolution lattice images of terpolymer/ODA-MMT clay nanocomposite
  • This invention disclosed synthesis of a new generation of preintercalated radical arrangement-fragmentation chain termination (RAFT) agents ( Figure 5), preferable mono- and dicarboxyl-containing trithiocarbonates such as 5 -dodecyl-S-(a,a'-dimethyl-a"-acetic acid) and 5,.irbis(a,a'-dimethyl-a”-acetic acid) trithiocarbonates which are known as RAFT-1 and RAFT-2 agents, respectively, through physical (A) and chemical (B) in situ modification of organic derivatives of Na + -MMT-TR (dimethyldidodecyl ammonium cation, DM DA and octadecyl amine, ODA as non-reactive and reactive surfactant-intercalants, respectively).
  • RAFT preintercalated radical arrangement-fragmentation chain termination
  • novel RAFT agents/MTT-TR hybrids exhibit dual functions such as conventional chain terminating agents and as nanofillers useful for a widely utilization in interlamellar controlled/living RAFT (co)polymerization of vinyl, allyl, acrylic, strenic, and the like monomers for the preparation (co)polymer silicate layered nanocomposites.
  • Another aspect of this invention is use of these RAFT-agents/MTT-TR hybrids and their (co)polymer layered silicate nanocomposites for bioengineering (novel controlled drug delivery systems, enzyme carriers, the like) and nanomedicine (antimicrobial and selective anticancer agents, and the like) applications.
  • This invention disclosed synthesis of a new generation of functional copolymer- ⁇ - biopolymer layered silicate nanocomposites through interlamellar bulk graft copolymerization of lactic acid (or lactides, oligopeptides, DNA, Chitosan, carboxyl-functionalized polysaccharides, and like) onto maleic anhydride (MA)-containing homopolymer, random and alternating copolymers, graft copolymers (Polyolefins- ⁇ -MA, other thermoplastics-g-MA, rubber- ⁇ -MA and the like), preferable alternating (co)terpolymer of maleic anhydride(MA) [poly(MA-c?/f-a- olefinsC 2- i8), poly(MA-c?/i-alkyl vinyl ether), poly(MA- ⁇ ?/i-dihyropyran-co-/V-isopropyl acrylamide), poly(MA- ⁇ ?/i-2-vinyl
  • This disclosed method is significantly differ from known method of graft copolymerization of lactic acid which is provide the following advantages: (1) this method includes in situ self-catalysis process, (2) Synthesis procedure was realized at relatively lower temperature (60-80°C) and reaction time (35-50 min) as compared with known high temperature (120°C) catalytic graft copolymerization (with 3-6 h of reaction time), (3) grafting and graft copolymerization reactions occur between silicate galleries in nano- scale, (4) the formation of nanohybrid composites produced through in situ interfacial complex- formation (physical interaction) or amidization (chemical interaction), and in situ full exfoliation processing.
  • This invention also disclosed the preparation of biodegradable thermoplastic nanocomposites with high performance properties for a wide range of industrial and medical applications.
  • a novel carboxyl-trithiocarbonate functionalized polymer with super-selective antitumor activity was synthesized by a Reversible Addition-Fragmentation Chain Transfer (RAFT) controlled/living intercamellar polymerization of maleic anhydride (MA) with benzoyl peroxide as an initiator and preintercalated S-l-dodecyl-S-(a,a'-dimethyl-a"-acetic acid) trithiocarbonate/ ODA-MMT-TR as a RAFT agent-nanofiller and with the aim to design and synthesize an effective anticancer agent with minimum or without side effects.
  • RAFT Reversible Addition-Fragmentation Chain Transfer
  • the structure, molecular weights and composition of synthesized multifunctional polymer were investigated by ⁇ ( 1 C) NMR, MTDI- TOF-MAS and GPC analyses, respectively. It was demonstrated that RAFT polymerization of MA accompanied with partially controlled decarboxylation of anhydride units and formation of conjugated double bond fragments in backbone macromolecular chains.
  • the mechanism of interaction of pristine RAFT agent and PMA-RAFT polymer/ODA-MMT-TR nanocomposite with cancer (HeLa human cervix carcinoma) and normal (L929 Fibroblast) cells were investigated by using a combination of chemical, biochemical, statistical, spectroscopy (SEM and Fluorescence Inverted Microscope) and Real-Time Analysis (RTCA) methods.
  • Another aspect of this invention is preparation of novel smart bioengineeting functional copolymer silicate layered nanocomposites by microwave-assisted (500 W) interlamellar copolymerization of /V-isopropyl acrylamide (NIPAm, i) with maleic anhydride (MA, M 2 ) and terpolymerization of NIPAm with equimolar mixture of MA/dihyd ropy ran (M 3 ) comonomers in the presence of organoclay (ODA-MMT-TR).
  • NIPAm /V-isopropyl acrylamide
  • MA maleic anhydride
  • M 3 terpolymerization of NIPAm with equimolar mixture of MA/dihyd ropy ran
  • ODA-MMT-TR organoclay
  • Preparation of BTT-TR (bentonite-TR) and MMT-TR (Na + -MMT-TR) clays from mineral resources of various regions in Turkey includes a combination of effective milling, isolation, purification, microwawe-sonication, centrifugation or water-absorption via filter press, drying under vacuum at 100°C and particle separation cyclones, as well as recycling lines to utilize water/ethanol and salt water.
  • This prototype processing provides effective isolation of BTT-TR and its richen with Na-cation derivative (Na + -MMT-TR) via ion exchane reactions using 0.5-1.0 M NaCI (or NaC0 3 ), preferable 0.75 M water solution.
  • Ag + - and organic derivatives of Na + -MMT-TR were preparated by using known intercalation via ion exchange reactions using AgN0 3 , octadecyl amine or amide (ODA) as reactive intercalant and dimethydidodecyl ammonium bromide (DMDA) as non-reactive intercalant in deionized water solutions.
  • ODA octadecyl amine or amide
  • DMDA dimethydidodecyl ammonium bromide
  • Intercalated RAFT agents were prepared by the following synthesis procedure: Na + - MMT-TR, ODA-MMT-TR or DM DA- MMT-TR was dispersed in acetone (or methyl ethyl ketone (MEK) or deionized water) solution of RAFT (radical arrangement-fragmentation chain transfer) agents with intensive mixing at room temperature up to formation homogenous viscose system. Than intercalated product was isolated by evaporation or precipitation by ethanol and ultracentrifugation, draying under vacuum at 60°C. Physical and chemical structures of synthesized intercalated RAFT agents were confirmed by FTIR, ⁇ NMR, XRD and SEM-TEM morphology analyses.
  • Synthesis of polymer layered silicate nanocomposites were carried out by interlamellar controlled/living (co)polymerization of maleic anhydride (MA) and butyl methacrylate (BMA) in the presence of RAFT...ODA-MMT-TR (complex or amide form) or RAFT...DMDA-MMT-TR as a reactive or non-reactive nanofiller-terminating agent, respectively, and a radical initiator (A1BN) under a nitrogen atmosphere at 65°C in MEK or 1,4-dioxane solution.
  • MA maleic anhydride
  • BMA butyl methacrylate
  • RAFT...ODA-MMT-TR complex or amide form
  • RAFT...DMDA-MMT-TR reactive or non-reactive nanofiller-terminating agent
  • OMA-RAFT-1/ODA-MMT-TR silicate layered nanocomposite was synthesized by controlled/living RAFT heterogeneous polymerization of MA monomer in toluene under a nitrogen atmosphere in the presence of BP as a radical initiator and preintercalated RAFT agent... ODA-MMT-TR .
  • Ag + -MMT-TR clay was synthesized by ion-exchange reaction of Na + -MMT-TR and AgN0 3 in aqueous medium at 30-50°C for 3 h. Product of reaction was isolated by evaporation, drying under vacuum at 60°C. Above mention polymer/clays nanocomposites were isolated and purified by twice precipitation with ethanol (or deionizsed water), extraction with ethanol, centrifugation an than draying in vacuum at 60°C up to constant weight. Core-shell morphology images of nanocomposites are presented in Figure 8 (TEM images).
  • Na + -MMT-TR clay exhibits essentially lower average particle size (342 and 229 nm) and narrow particle size distribution as compared with known Na + -MMT (2535 nm) (Fgure 6).
  • Na+-MMT-TR clay exhibits higher exchange capacity and d(001)-spacing value (distance between silicate layers) as compared with a known Na+-MMT clay.
  • This patent invention firstly disclosed the preparation of functional copolymer- ⁇ - poly(lactic acid) / ODA-MMT organoclay (A and B) or Na (or Ag) + -MMT-TR (C and D) nanohybrid particles with high self-organized 'core-shell' inner morphology using preferable alternating copolymer of maleic anhydride and ⁇ -olefins, preferable olefin monomers with Ce-ie and self- catalysis interlamellar graft copolymerization method.
  • polymeric nanoparticles 120-100 nm
  • nanofillers-catalyst were formed by using Na + and Ag + -MMT-TR as : nanofillers-catalyst.
  • the observed highly selective antitumor activity of the PMA-RAFT copolymer is related to the presence and distribution of carboxyl and trithiocarbonate groups, which are capable of physical (carboxyl-amine H-bonding) and chemical (trithiocarbonate-amine reaction and termination of free radicals and other reactive species) interactions within a biological environment, as well as its amphiphilic character. These important factors contribute to the inhibition of the cancer cell growth via destruction of supramacromolecular assemblies.
  • the ⁇ -size and ⁇ -potential parameters of nanoparticles were performed by a Zetasizer 3000HSA (Malvern, UK) using 3 ml. of acetone solution of polymer samples with 0.01 g/ml_ concentration.
  • Microwave sonication was performed by Lab. SONMAK Ultrsonic Clainer (Falc Instrumeny, Italy) with capacity 4 L, power 400 W, frequency 40kHz and sonication time 15 min.
  • the surface morphology of nanocomposites was examinated using a scanning electron microscope (JSM-6400 JOEL SEM with scale: 1 and 10 ⁇ , xlO 4 and an accelaration voltage 20 kV). All speciments were freeze-dried and coated with a thin layer of gold before testing.
  • TEM transmission electron microscopy
  • Thermogravimetric (TGA) and differential scanning calorimetric (DSC) analyses were carried out using a EXTRAR600 TG-DTA6300 and Diamond DSC Perkin Elmer Thermal Analyzers and a linear heating rate of 10°C/min under nitrogen flow. Samples were measured in a sealed alumina pan with a mass of about 10 mg.
  • DMA Dynamic mechanical analysis
  • Zakir M. O. Rzayev (Review). In Book: Advanced polyolefin nanocomposites, Chapter 4. Polyolefin nanocomposites by reactive extrusion (Ed. V. Mittal), Taylor & Francis Ltd. Publisher, CRC Press, New York, 2011, pp. 87-127. 11. Zakir M. 0. Rzayev (Review). Nano methods in polymer synthesis and processing: Carboxyl/anhydride functionalzed copolymers for nanoengineering applications. Int. Rev. Chem. Eng., 2012, 3, 674-732.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
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  • Civil Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de technologie verte combinant des traitements prototypes pour la préparation, la purification et la modification de micro- et nanoparticules d'argile à partir de ressources minérales turques faisant appel à des agents intercalants fonctionnels organiques inédits en tant que nano-charges réactives, à des copolymères alternés d'anhydride maléique et à leurs formes greffées par des biopolymères en tant qu'agents compatibilisants réactifs et polymères matriciels bioactifs, à des thermoplastiques, des résines thermodurcissables et des caoutchoucs en tant que polymères matriciels transformables, lesdites micro- et nanoparticules pouvant être utilisées pour la préparation de nanomatériaux d'ingéniérie et de bio-ingéniérie haute performance stratifiés à base de polymères et de silicates inédits (nano-films, nano-revêtements, nanofibres, nano-médicaments, etc.).
PCT/TR2013/000240 2012-07-30 2013-07-09 Chaîne de fabrication de technologie verte de micro- et nanoparticules d'argile et de leurs nanohybrides polymères fonctionnels pour applications de nano-ingéniérie et de nano-médecine WO2014021800A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295858A (zh) * 2015-11-26 2016-02-03 天津滨海新区普瑞德石油科技有限公司 一种油基钻井液用增粘剂
CN109280256A (zh) * 2018-08-07 2019-01-29 中广核三角洲（苏州）高聚物有限公司 一种机车用低voc无卤阻燃聚烯烃电缆料
CN110911616A (zh) * 2019-11-26 2020-03-24 电子科技大学 一种锂硫电池用耐高温多功能隔膜及制备方法
CN113321861A (zh) * 2021-05-20 2021-08-31 苏州赛荣建筑装饰工程有限公司 一种防污阻燃高密度树脂及其制备方法

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CN105295858A (zh) * 2015-11-26 2016-02-03 天津滨海新区普瑞德石油科技有限公司 一种油基钻井液用增粘剂
CN109280256A (zh) * 2018-08-07 2019-01-29 中广核三角洲（苏州）高聚物有限公司 一种机车用低voc无卤阻燃聚烯烃电缆料
CN110911616A (zh) * 2019-11-26 2020-03-24 电子科技大学 一种锂硫电池用耐高温多功能隔膜及制备方法
CN113321861A (zh) * 2021-05-20 2021-08-31 苏州赛荣建筑装饰工程有限公司 一种防污阻燃高密度树脂及其制备方法
CN113321861B (zh) * 2021-05-20 2023-09-08 贵州联创管业有限公司 一种防污阻燃高密度树脂及其制备方法

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