Classifications

• • 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
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/06—Hydrocarbons
  • C08F12/08—Styrene
• • 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
  • C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F12/36—Divinylbenzene
• • 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
  • C08F2/34—Polymerisation in gaseous 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
  • 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
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials

Definitions

• the present invention relates to a process for manufacturing nanocomposites of layered material and organic polymers, the thus obtained nanocomposites and their use.
• Polymer nanocomposites containing layered material for instance phyllosilicates, have been attracting increasing interest over the past two decades as inorganic fillers.
• intercalation The most common morphology for miscible polymer-clay dispersions is known as intercalation.
• the host polymer penetrates the space between the clay platelets/layers, but separating them only slightly and maintaining the parallel, regular structure of the platelets.
• Intercalated polymer-clay nanocomposites are often observed to have measurable improvements in physical properties, but are typically less favorable compared to the corresponding nanocomposites having a morphology known as exfoliation. Although exfoliation is much more desirable, it is less common and more difficult to obtain.
• exfoliation is much more desirable, it is less common and more difficult to obtain.
• the clay platelets are thoroughly separated from each other by the host polymer, so that their original crystallographic register is lost.
• the fully exfoliated polymer-clay nanocomposites are notoriously difficult to obtain.
• the clay phase should also be rendered compatible with the polymer matrix in which it should be bedded.
• the challenge in achieving these objectives arises from the fact that unmodified clay surfaces are hydrophilic, whereas a vast number of polymers of technological importance are hydrophobic in nature.
• Montmorillonite a kind of smectite, has been most frequently used for preparing the polymer nanocomposites.
• montmorillonite consists of silicate platelets that are about 1 nm thick and about 100-200 nm wide.
• Each platelet, or layer is typically composed of two silica tetrahedral sheets and one alumina octahedral sheet sandwiched between the silica sheets, where adjacent sheets share some of the oxygen atoms.
• a metal e.g. magnesium and iron(ll) for aluminum
• negative charges are generated within the layers.
• the (alumina-) silicate layers aggregate and form stacked structure with e.g. sodium or potassium ions between the layers to neutralize the negative charges.
• montmorillonite Since montmorillonite is hydrophilic as described above, it does not homogeneously mingle with hydrophobic polymers. Therefore, it has to be organically modified prior to its use.
• the alkali metal ions within the pristine clay mineral are typically replaced with organic cations, e.g. alkylammonium cations.
• the organically modified montmorillonite is dispersed into the polymer matrix basically by means of either melt mixing or in-situ polymerization.
• thermoplastic polymer at a temperature higher than its melting or softening point is mechanically mixed with filler
• WO00/29467 teaches a process for producing a polymer nanocomposite by dispersing a polyvalent anionic organic edge coated quaternary ammonium intercalated multi-layered silicate material into a thermoplastic polymer, admitting some of the silicate layers are present as multiple layers, i.e. intercalates, in the product.
• Transition metal compounds e.g. group IV metallocenes
• the supported catalyst is dispersed into an organic medium for the (co)polymerization of olefins such as ethylene, propylene and the like.
• olefins such as ethylene, propylene and the like.
• Heinemann and coworkers in: Macromol. Rapid Commun. 20 (1999) pp. 423)
• Dubois and coworkers in: Macromol. Symp. 194 (2003) 13
• Jin and coworkers in: Macromol. Rapid Commun. 23, (2002) pp.
• catalytic activity of methylaluminoxane/rac- dimethylsilylene-bis(2-methylbenz[e]indenyl)zirconium chloride supported on dimethylstearylbenzylammonium-modified Na-bentonite for ethylene/1 -octene copolymerization is 1 ,500 kg/(mol-M-h), compared with 253,800 kg/(mol-M-h) of ordinary, unsupported catalyst system, calculated from mass of polymer, catalyst concentration, monomer concentration, and polymerization time (Macromol. Rapid Commun. 20 (1999), page 426, Table 2).
• the catalytic activities of ordinary catalyst systems are so high there is no need to remove the residual catalyst. In the case of nanocomposites thus obtained, however, a substantial amount of catalyst remains in the product and the residual metal compound may have adverse effects on the product such as yellowing.
• Some examples of the moiety for free radical generation are azo (Fan et al. in: Langmuir 19 (2003) pp. 4381), nitroxy (Weimer et al. in: J. Amer. Chem. Soc. V2 ⁇ _ (1999) pp. 1615), and bromoalkyl (Zhao et al. in: J. Polym. ScL Part A: Polym. Chem. 42 (2004) 916).
• the other one, "monomer type” modifier has a polymerizable moiety like methacryloyloxy or vinylbenzyl as well as a quaternary ammonium moiety.
• silicate platelets and matrix polymer chains are firmly bound through ionic and covalent bonds, which helps to homogeneously disperse the silicate platelets into polymer matrix.
• one aim of the present invention is to eliminate the use of the costly, custom-made quaternary ammonium salts, and to make it possible to use standard commercially available organically modified clay minerals.
• Yet another aim of the present invention is to provide nanocomposites with a high content of inorganic phase.
• Conventional in-situ polymerization of vinyl monomers in liquid phase can achieve a clay content of about 10 % at most. From industrial point of view, this is problematic because no compounders can use the product as a masterbatch. Masterbatch products could for instance be used for further melt mixing. In other words, molders and/or compounders would be able to optimize the clay content in their products by adjusting the mixing ratio of the masterbatch to pristine polymers.
• nanocomposites comprising a content of clay mineral, for instance as high as 30 to 40 % by weight or even higher, for use as a masterbatch.
• the present invention provides a process for producing a nanocomposite comprising a radical polymerization of at least one ethylenically unsaturated monomer species in the presence of a system comprising at least one initiator species, which is associated to the layer surfaces and interlayer spaces of at least one organoclay species, characterized in that the at least one ethylenically unsaturated monomer species is supplied to the radical polymerization in the gaseous state.
• Nanocomposite shall mean a composite material wherein at least one component comprises an inorganic phase, such as a smectite clay, with at least one dimension in the 0.1 to 100 nanometer range.
• “Layered material” shall mean an inorganic material such as a smectite clay that is in the form of a plurality of adjacent bound layers.
• Platelets shall mean individual layers of the layered material.
• Intercalation shall mean the insertion of one or more foreign molecules or parts of foreign molecules between platelets of the layered material, usually detected by X-ray diffraction technique, as illustrated in US 5 891 611 (line 10, col.5 - line 23, col. 7).
• Intercalant shall mean the aforesaid foreign molecule inserted between platelets of the aforesaid layered material.
• Exfoliation or “delamination” shall mean separation of individual platelets in to a disordered structure without any stacking order.
• substantially completely exfoliated is meant that at least 90 percent of the original background- subtracted X-ray diffraction peak intensity (height) due to the (001) basal plane has been lost, as shown by a standard measurement in conformity with the type of measurements provided in Examples below.
• the term "(001) basal plane” shall refer to the spacing between a layer of silicate atoms in one plane to the corresponding layer of silicate atoms in another plane, including any material present between layers. This can also be referred to as basal plane spacing or d(001).
• Intercalated shall refer to layered material that has at least partially undergone intercalation. This can also include material that has undergone both partial intercalation and partial exfoliation.
• Organicclay shall mean clay material modified by organic molecules.
• “Swellable” shall refer to a layered material capable of showing an increase or expansion in spacing between layers resulting from insertion of species into the said layered material, in particular resulting from intercalation of organic molecules, for instance resulting in the formation of an organoclay.
• the layers of the organoclay are substantially completely exfoliated, which results in a random dispersion into the polymer matrix.
• the clay material suitable to prepare an organoclay can comprise any inorganic phase comprising layered materials in plates or other shapes with a significantly high aspect ratio.
• the clay materials suitable for this invention include phyllosilicates, e.g., montmorillonite, particularly sodium montmorillonite, potassium montmorillonite, magnesium montmorillonite, and/or calcium montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, svinfordite, vermiculite, magadiite, kenyaite, talc, mica, kaolinite, and mixtures thereof.
• Other useful layered materials include illite, mixed layered illite/smectite minerals, such as ledikite and admixtures of illites with the clay minerals named above.
• Preferred clays are swellable. These swellable clays include phyllosilicates of the 2:1 type, as defined in clay literature (for example: H. van Olphen in: An Introduction to Clay Colloid Chemistry, John Wiley & Sons Publishers, 1977). Typical phyllosilicates possess an ion exchange capacity of 50 to 300 milliequivalents per 100 grams, more preferably 50 to 200 milliequivalent per 100 grams.
• Preferred clays for the present invention include smectite clay such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, svinfordite, halloysite, magadiite, kenyaite and vermiculite as well as layered double hydroxides or hydrotalcites.
• the most preferred clays include montmorillonite, hectorite and hydrotalcites, because of their effectiveness in the present invention and/or the commercial availability of these materials.
• Particularly preferable is a montmorillonite having a cation exchange capacity of 50 to 200 milliequivalents per 100 grams.
• the aforementioned clays can be natural or synthetic, for example synthetic smectite clay. This distinction can influence the particle size and/or the level of associated impurities.
• synthetic clays are relatively smaller than natural clays in lateral dimension, and therefore possess smaller aspect ratios.
• synthetic clays are purer and are of narrower size distribution, compared to natural clays, and may not require any further purification or separation.
• the clay particles typically have (on average) a lateral dimension of between 0.01 ⁇ m and 5 ⁇ m, and preferably between 0.05 ⁇ m and 2 ⁇ m, and more preferably between 0.1 ⁇ m and 1 ⁇ m.
• the thickness or the vertical dimension of the clay particles typically varies (on average) between 0.5 nm and 10 nm, and preferably between 1 nm and 5 nm.
• the aspect ratio which is the ratio of the largest and smallest dimension of the clay particles is preferably >10:1, and more preferably >100:1 for use in compositions of this invention.
• the aforementioned values regarding the size and shape of the particles are designed to ensure best improvements in some properties of the nanocomposites without deleteriously affecting others. For example, a large lateral dimension may result in an increase in the aspect ratio, a desirable criterion for improvement in mechanical and barrier properties.
• the aforementioned layered materials are basically hydrophilic and need to be organically modified/treated to become compatible with organic polymers.
• the thus modified or treated clays can be described by the term organoclays.
• Organoclays can be produced by interacting the unfunctionalized clay with suitable intercalants.
• intercalants which are also referred to as "swelling agents" are typically organic cationic compounds.
• Useful compounds are cationic surfactants including onium species such as ammonium (primary, secondary, tertiary, and quaternary), phosphonium, or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides.
• onium ions can cause intercalation in the layers through ion exchange with the metal cations of the preferred smectite clay.
• a number of commercial organoclays, which may be used in the practice of this invention, are available from clay vendors.
• the organoclay Cloisite 2OA which is a dimethyl dihydrogenated tallow ammonium- modified montmorillonite supplied by Southern Clay Products, Inc. can be conveniently used for the purpose of the present invention.
• the intercalation of the onium species can for instance be accomplished according to well-established methods. For example, an excess of an aqueous quaternary alkyl ammonium salt containing solution can be added gradually to an aqueous dispersion of the smectite clay under vigorous stirring, yielding precipitates. The precipitates can be separated and washed with water to remove the unreacted quaternary alkylammonium salt, and dried in vacuo.
• the onium salt is a quaternary ammonium salt with one or more organic group(s) which render the clay compatible with organic materials, for instance radical initiators, ethylenically unsaturated monomers, and polymers resulting from the polymerization of ethylenically unsaturated monomers.
• organic materials for instance radical initiators, ethylenically unsaturated monomers, and polymers resulting from the polymerization of ethylenically unsaturated monomers.
• Quaternary alkyl amines containing at least one alkyl group with a carbon number of 8 and more are preferably used.
• alkyl ammonium salts are for instance trimethyl(octyl) ammonium chloride, trimethyl(decyl) ammonium chloride, trimethyl(dodecyl) ammonium chloride, trimethyl(tetradecyl) ammonium chloride, trimethyl(hexadecyl) ammonium chloride and trimethyl(stearyl) ammonium chloride.
• the organoclay has to be "doped” or “impregnated” with one or more radical initiators.
• "doping” or “impregnating” means bringing the initiator in contact with the layered material, i.e. the organoclay, so that the initiator molecules are associated to the layers of the organoclay.
• An association to the layers can be accomplished in different ways. One possibility is, that the initiator molecules are only loosely bound to the layer surfaces, e.g. by dipolar forces or by van der Waals forces. It is, however, also possible to use initiators which are bound to the surface of the substrate by ionic bonds or covalent bonds. Such association of the free radical initiator to the organoclay can be effected prior to and/or during the polymerization.
• monomers can be used yielding radicals on suitable activation like hydroperoxides, especially cumene hydroperoxide or tert. -butyl hydroperoxide, organic peroxides like dibenzoyl peroxide, dilauric peroxide, dicumene peroxide, di-tert.
• -butyl peroxide methyl ethyl ketone peroxide, tert.-butyl benzoyl peroxide, diisopropyl peroxy dicarbonate, dicyclohexyl peroxy dicarbonate, di-tert.-butyl peroxalate, inorganic peroxides like potassium persulfate, potassium peroxydisulfate or hydrogen peroxide, azo compounds like azo bis(isobutyro nitrile), 1 ,1'-azo bis(1-cyclohexane nitrile), 2,2'-azo bis(2-methyl butyronitrile), 2,2'-azo bis(2,4-dimethyl valeronitrile), 1 ,1 '-azo bis(1-cyclohexane carbonitrile), dimethyl-2,2'-azobisisobutyrate, 4,4'-azo bis(4-cyano valeric acid) or triphenyl methyl azobenzene, redox systems like mixtures
• initiators are combinations of dialkylanilines and halogen compounds, boron alkyls and oxidizing agents, organometallic compounds and oxidizing agents and metal acetylacetonates.
• a polymerization according to the present invention can also be initiated by photochemical initiators or initiating systems with radioactive sources or electron beams, iniferters like dithiocarbamate compounds, monosulfides, cyclic and acyclic disulfides, nitroxides including stable, free radical species and their adducts or oxidation adducts of borabicyclononane compounds.
• initiation procedure generally all procedures which initiate a propagating species are acceptable in the present context.
• the initiator or the mixture of two or more initiators are subjected to an energy source which causes the generation of a species able to initiate a propagation step which causes the polymerization.
• Suitable types of energy comprise thermal energy, radiation like laser-light, UV-light or gamma rays or high energy particles, e.g., from radioactive sources.
• the above-mentioned initiators can be used alone or as combinations of two or more of the above-mentioned initiators.
• initiators are preferred which, upon heating or irradiation with a source of high energy radiation, decompose to form an initiating species, e.g., two radicals. It is, according to the present invention, most preferred to use as initiators an initiator from the group consisting of peroxides or azo compounds.
• the initiator or the combination of initiators employed in the process according to the present invention is selected from the group consisting of a cumene hydroperoxide, tert.-butyl hydroperoxide, dibenzoyl peroxide, dilauric peroxide, dicumene peroxide, di-tert.-butyl peroxide, methyl ethyl ketone peroxide, tert.-butyl benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert.-butyl peroxalate, potassium persulfate, potassium peroxydisulfate, hydrogen peroxide, azo bis(isobutyro nitrile), 1,1 '-azo bis(1-cyclohexane carbonitrile) 4,4'-azo bis(4-cyano valeric acid) or triphenyl methyl azobenzene.
• the concentration of the initiators on layer surface is generally in a range of from about 0,01 to about 50 ⁇ mol/cm 2 , preferably from about 0,05 to about 10 ⁇ mol/cm 2 or from about 0,1 to about 5 ⁇ mol/cm 2 , and/or 0.005 to about 1 gram per gram of organoclay, preferably from about 0.01 to about 0.5 gram per gram of organoclay, more preferably from about 0.05 to about 0.25 gram per gram of organoclay.
• an initiator which is firmly bound to the platelet surfaces of the organoclay by ionic or by covalent bonds
• the above-mentioned types of initiators must be equipped with a functional group that allows for the above-mentioned type of bonding to the substrate surface.
• the modification of a substrate surface with a functional initiator molecule is generally achieved by using initiator molecules that have at least one anchor group which is able to react with functional groups on the clay platelet surfaces. In general, all types of reactions can be used to achieve an ionic or a covalent bond between the surfaces and an initiator molecule. If the type of bond is ionic, usually suspending the substrate in a solution of the respective initiator molecule is sufficient to achieve a substrate with a modified surface that can be used according to the present invention.
• the bonding between the substrate and the initiator is to be covalent, only reactions that lead to a covalent bond between the substrate surface and the initiator molecule can be employed.
• the contact between initiator and organoclay can generally be established by all contacting methods known to the skilled person which lead to the desired type of bonding between the initiator and the substrate surface.
• the initiators are contacted with the organoclay preferably by way of contacting the substrate and the initiator compounds or a mixture of two or more initiator compounds, dissolved in a liquid phase.
• the impregnation of the organoclay is preferably achieved by contacting a solvent or solvent mixture containing the initiator or the initiators with the organoclay, where the organoclay is inert against the initiator and/or the initiator components and where the solvent or the solvent mixture can be removed, preferably completely removed, from the impregnated organoclay.
• the amount of solvent or solvent mixture remaining on the substrate is low, e.g. less than 0.1 or less than 0.01 % by weight, relative to the weight of the initiator or the mixture of two or more initiators.
• the impregnation of the organoclay can also be achieved by contacting the organoclay and the initiator or the initiators in a fluidized bed.
• the organoclay is fluidized by a flow of inert gas and the solution containing the initiator or the initiators is brought into contact with the substrate e.g. by spraying.
• the inert gas can be, after it was stripped from solvents and initiators, circulated back to the reactor. This process can be run batchwise or continuously.
• the solvent or the solvent mixture is removed as completely as possible, for instance by distillation.
• the distillation is carried out, depending on the boiling temperature of the solvent or the solvent mixture and the pressure during the distillation, at a temperature of about 10 to about 150 0 C, preferably at 10 to 70 0 C, and at pressures of 0.001 up to about 20 bar, preferably at about 0.001 mbar up to about ambient pressure.
• the distillation temperature has to be lower than the activation temperature of the initiator, if the initiator is thermally activable.
• the initiator bearing organoclay is preferably kept at or below a temperature where premature decomposition of the initiator can be avoided.
• the ethylenically unsaturated monomers used according to the present invention can be any ethylenically unsaturated compounds that are capable of being polymerized by free radical initiators.
• the preferred monomers include those of the formula (I)
• alkyl alkenyl and alkynyl refer to straight-chain or branched groups.
• aryl refers to phenyl, naphthyl, phenanthryl, phenylenyl, anthracenyl, triphenylenyl, fluoroanthenyl, pyrenyl, chrysenyl, naphthacenyl, hexaphenyl, picenyl and perylenyl (preferably phenyl and naphthyl), in which each hydrogen atom may be replaced with alkyl of from 1 to 20 carbon atoms (preferably from 1 to 6 carbon atoms and more preferably methyl), alkyl of from 1 to 20 carbon atoms (preferably from 1 to 6 carbon atoms and more preferably methyl) in which each of the hydrogen atoms can be independently replaced by a halide (for example by a fluoride or a chloride), alkenyl of from 2 to 20 carbon atoms, alkynyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 6 carbon
• aryl also applies to the aryl groups in “aryloxy” and “aralkyl”).
• phenyl may be substituted from 1 to 5 times and naphthyl may be substituted from 1 to 7 times (preferably, any aryl group, if substituted, is substituted from 1 to 3 times) with one of the above substituents.
• aryl refers to phenyl, naphthyl, phenyl substituted from 1 to 5 times with fluorine or chlorine, and phenyl substituted from 1 to 3 times with a substituent selected from the group consisting of alkyl of from 1 to 6 carbon atoms, alkoxy of from 1 to 4 carbon atoms and phenyl. Most preferably, “aryl” refers to phenyl and tolyl.
• heterocyclyl refers to pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazonyl, pyrimidinyl, pyridazinyl, pyranyl, indolyl, isoindolyl, indazoiyl, benzofuryl, isobenzofuryl, benzothienyl, isobenzothienyl, chromenyl, xanthenyl, purinyl, piperidinyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phenoxathiinyl, carbazolyl, cinnolinyl, phenanthridinyl, acridinyl, 1 ,10-phenanthrolinyl, phenazinyl,
• Preferred heterocyclyl groups include pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl and indolyl, the most preferred heterocyclyl group being pyridyl.
• suitable vinyl heterocyclyls to be used as a monomer in the present invention include 2-vinyl pyridine, 4-vinyl pyridine, 2-vinyl pyrrole, 2-vinyl pyrrole, 2-vinyl oxazole, 4-vinyl oxazole, 9-vinyl oxazole, 2-vinyl thiazole, 4-vinyl-thiazole, 5-vinyl-thiazole, 2-vinyl imidazole, 4-vinyl imidazole, 3-vinyl pyrazole, 4-vinyl pyrazole, 3-vinyl pyridazine, 4-vinyl pyridazine, 3-vinyl isoxazole, 3-vinyl isothiazoles, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 5-vinyl pyrimidine, and any vinyl pyrazine.
• the vinyl heterocycles mentioned above may bear one or more (preferably 1 or 2) CrC 6 alkyl or alkoxy groups, cyano groups, ester groups or halogen atoms, either on the vinyl group or the heterocyclyl group. Further, those vinyl heterocycles which, when unsubstituted, contain an N-H group may be protected at that position with a conventional blocking or protecting group, such as a CrC 6 alkyl group, a tris-Ci-C 6 alkylsilyl group, an acyl group of the formula R 9 CO (where R 9 is alkyl of from 1 to 20 carbon atoms, in which each of the hydrogen atoms may be independently replaced by halide, preferably fluoride or chloride), alkenyl of from 2 to 20 carbon atoms (preferably vinyl), alkenyl of from 2 to 10 carbon atoms (preferably acetylenyl), phenyl which may be substituted with from 1 to 5 halogen atoms or alkyl groups of from 1 to 4 carbon
• preferred monomers include (but not limited to) styrene, vinyl acetate, acrylate and methacrylate esters of C 1 -C20 alcohols, acrylic acid, methacrylic acid, t-butyl acrylate, hydroxyethyl-methylacrylate, isobutene, acrylonitrile, and methacrylonitrile.
• Most preferred monomers are acrylic and methacrylic acid esters having from 1 to about 20 carbon atoms in the alcohol moiety, styrene, vinyl substituted styrene, such as ⁇ -alkyl styrene or ring substituted styrene such as p-alkyl styrene; such monomers are commercially available or can be easily prepared by known esterification processes.
• Preferred esters are n-butyl acrylate, ethyl acrylate, methyl methacrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, t-butylacrylate, hydroxyethylmethylacrylate, acrylate and methacrylate esters of C 1 -C20 fluorinated alcohols; preferred styrenic monomers are styrene, ⁇ -methyl styrene, p-methyl styrene, p-tert-butyl styrene, p-acetoxy styrene and ring-halogenated styrene.
• the organoclay associated with the radical initiator is brought into contact with one or more ethylenically unsaturated monomers present in the gas phase.
• the term "in the gas phase” means that the monomer or the mixture of two or more monomers contact the initiator or a propagating species by direct access from the gas phase without interaction in a liquid phase.
• the gas phase in the process according to the present invention must be completely free from “liquids”. It is also within the scope of the present invention that the gas phase contains microdroplets of monomers which can be spread in the gas phase by a carrier gas, depending on the method of introduction of the monomer or the monomer mixture into the gas phase. It is, however, preferred that the gas phase in the process according to the present invention is essentially free of such microdroplets, preferably free of microdroplets.
• the process according to the present invention will not require a solvent or a liquid monomer phase for the polymerization according to the present invention. It is, however, not excluded that the gas phase contains molecules that do not take part in the polymerization process, such as solvent molecules. It is also not excluded that the gas phase contains molecules other than the polymerizable monomers, such as a carrier gas or a mixture of two or more carrier gases.
• Carrier gases are substances which are in a gaseous state at the operating temperature of the present invention.
• compounds are used as carrier gases which are in a gaseous state at the reaction temperature and pressure, preferably at a temperature of 80 0 C or less, more preferably at a temperature of 50 or 30 0 C or less.
• Suitable carrier gases are essentially inert towards the monomers, the initiators and the organoclay under the reaction conditions and thus do not take part in the polymerization itself. Gases like He, Ne, Ar, N2, CO2, H 2 O and the like.
• the polymerization itself takes place in a reactor which can generally have any shape or size as long as it is able to host the initiator impregnated organoclay. Suitable reactors can be tightly sealed against the surrounding atmosphere.
• the ethylenically unsaturated monomer is introduced into a reactor in the gaseous state. This can generally be done by all methods known to the skilled person like vaporizing under reduced pressure, vaporizing by heating, bubbling with carrier gas flow or sublimating by heating under reduced pressure.
• the ethylenically unsaturated monomers can be introduced into the reactor before during or after the activation of the initiator.
• the monomers are introduced before or during the activation of the initiator.
• the one or more ethylenically unsaturated monomers are consumed from the gas phase and polymer is formed on the surface of and between the layers of the organoclay material resulting in a substantially complete exfoliation of the organoclay.
• the reaction time according to the present invention depends upon the desired molecular weight of the polymer and the speed of the reaction.
• the reaction speed can be varied in conventional ways known to the skilled person, e.g. by variation of the monomer type, monomer concentration, reaction temperature, flow rate of the carrier gas, the surface area of the organoclay doped or impregnated with the initiator or accelerators such as light.
• the reaction can generally be performed at a temperature of from about -80 to about 200 0 C, depending on the type of initiator, the type of activation and the monomer types.
• the reaction temperature is from about 0 0 C to about 150 0 C or from about 20 to about 100 0 C or from about 40 to about 70 0 C, especially from about 45 to about 65 0 C.
• the reaction time can essentially last for any time specified by the operator, as long as the chain ends of the polymers are still "alive" and the polymerization can still propagate.
• the reaction time per step for instance for a chosen type of monomer or for a chosen monomer composition, the reaction time can vary in broad ranges, for example between about 10 minutes to about 5 days, depending on the type of monomers, the desired molecular weight, the initiator, the organoclay and the desired organoclay concentration in the nanocomposite.
• the reaction time for one polymerization step is in the order of from about 1 to about 50 h, preferably from about 2 to about 40 h.
• organoclays used for the present invention are usually in the form of powder, the organoclays can efficiently contact the monomer in a reactor equipped with mechanical stirrers or in a fluidized bed reactor. Suitable reactors can be tightly sealed against the surrounding atmosphere. Since the impregnation of organoclay powders with the initiators can also be carried out in a fluidized bed reactor, one and the same reactor can be used to impregnate the organoclay and host the polymerization reaction.
• regulators can be present.
• Regulators are substances which can influence the polymerization reaction and the structure of the polymer obtained. Suitable regulators are described, for instance, in Ullmanns Enzyklopadie der ischen Chemie, vol. 15, pages 188 and ff.
• Suitable regulators are, e.g., aromatic hydrocarbons like triphenylmethane, nitro- or nitrosoaromatics like nitrobenzene, nitrotoluene or nitrosobenzene, organic halogen compounds like tetrachloromethane, tetrabromomethane or bromotrichloromethane, organic sulphur compounds like alkylmercaptanes and xanthogenedisulfides, e.g., n-dodecylmercaptane, tert- dodecylmercaptane, butylmercaptane, tert.-butylmercaptane, dibutyldisulfide, diphenyldisulfide, benzyldiethyldithiocarbamate or 2-phenylethyldiethyl- dithiocarbamate, or compounds bearing carbonyl functions like ketones and aldehydes, especially ace
• the invention also provides nanocomposites, which are obtainable according to the method of the present invention.
• such nanocomposites comprise at least 10 % by weight, more preferably at least 15 or 20 % by weight of the essentially completely exfoliated organoclay material, based on the total weight of the nanocomposite. Even more preferable the nanocomposites comprise at least 25 % by weight and most preferable at least 30 % by weight of the essentially completely exfoliated organoclay material, based on the total weight of the nanocomposite.
• the invention also relates to the use of the nanocomposites of the invention or obtained according to the process of the invention as reinforced material and/or masterbatch, which e.g. can be used to supplement a pristine polymer for instance in a melt-blending process by means of extruders.
• Inorganic montmorillonite clay that is characterized by a cation exchange capacity of 108.6 meq/100g, and stearyltrimethylammonium-modified montmorillonite were supplied by Kunimine Industries Co. and used as received.
• CloisiteTM C20A a natural montmorillonite modified with dimethyl di(hydrogenated tallow) ammonium chloride was supplied by Southern Clay Products, Inc. and used as received.
• Stearyltrimethylammonium chloride Nacalai Tesque, Inc. was used as received.
• Vinyl monomers, methyl methacrylate (MMA) and styrene (St), and radical initiator, 2,2'-azobis(isobutyronitrile) (AIBN) were purchased from Wako Pure Chemical Industries, and were purified by fractional distillation over calcium hydride and recrystallization from methanol, respectively.
• Number and weight-average molecular weights were measured on a Tosoh HPLC-8220 gel permeation chromatography system equipped with a polystyrene gel column (TSK gel super HM-H: 6.0 mm I.D. ⁇ 150 mm, linearity range, 10 3 - 8x10 6 ; molecular weight exclusion limit, 4x10 8 ) and detectors, i.e.
• Montmorillonite clay (2.5 g) was dispersed into 3 L of deionized water, and the dispersion was stirred vigorously overnight at room temperature. The suspension was then ultrasonicated for 5 hours, resulting in a homogeneous dispersion. Stearyltrimethylammonium chloride was dissolved in deionized water to make a 10 % aqueous solution. An excess amount of the ammonium salt solution (14 g, about 50 % excess) to fully replace the Na counterions in the montmorillonite was slowly added to the montmorillonite dispersion while it was being stirred. The mixture was then stirred for another 12 hours.
• the resulting white precipitate was separated by filtration, washed with deionized water to remove the unattached ammonium salt, and dried in vacuo at 45 0 C for 24 hours.
• the c/(001)-spacing of the organically modified montmorillonite was 2.08 nm according to XRD analysis and Bragg equation.
• the organically modified montmorillonite particles (60 mg) and AIBN (2.0 mg) were dissolved in 200 ⁇ l_ of acetone and mixed by stirring in a glass vial. Then, acetone was slowly and completely eliminated under a reduced pressure.
• the glass vial containing the clay was placed in a glass reactor for subsequent gas-phase polymerization.
• Liquid MMA monomer (about 4 ml_) and A-tert- butylpyrocatechol (about 25 mg) as an inhibitor were introduced into a separated area in the reactor under argon gas flow.
• the reactor was degassed by three times of freeze-pump-thaw cycle and then sealed off in vacuo.
• the reactor was maintained at 70 0 C for 1 hour.
• the MMA monomer evaporates at least partly and comes via gas phase into the above mentioned glass vial, where it comes into contact with the clay. After the prescribed time of polymerization, the product was taken out and adsorbed/absorbed MMA monomer was completely desorbed in vacuo at 45 0 C.
• the final weight of the product was 315 mg, containing about 19 % of the modified montmorillonite.
• Mn and Mw were 276,000 and 1 ,880,000, respectively.
• XRD analysis of the product showed no peak, meaning complete exfoliation of the silicate platelets.
• a composite material comprising polyMMA and montmorillonite was prepared in the same manner as in Example 1 , except that decyltrimethylammonium chloride was used for the modification of montmorillonite and the amount of AIBN was 4.0 mg.
• the modified montmorillonite had d(001)-spacing of 1.59 nm before polymerization.
• the final weight of the product after gas-phase polymerization was 216 mg, containing about 28 % of the modified montmorillonite.
• Mn and Mw were 41 ,000 and 283,000, respectively. XRD analysis of the product showed no peak, meaning complete exfoliation of the silicate platelets.
• a composite material was prepared in the same manner as in Example 2, except that styrene was used for the polymerization.
• the final weight of the product after gas-phase polymerization was 322 mg, containing about 19 % of the modified montmorillonite.
• Mn and Mw were 222,000 and 997,000, respectively.
• XRD analysis of the product showed no peak, meaning complete exfoliation of the silicate platelets.
• CloisiteTM C20A (12.0 g), a natural montmorillonite modified with dimethyl di(hydrogenated tallow) ammonium chloride and AIBN (400 mg) were dissolved in 2 L of acetone and mixed by stirring for 4 hours in a beaker. Then, acetone was slowly and completely eliminated under a reduced pressure. The organoclay thus impregnated with AIBN was collected and crushed into powder in a mortar, and was used as filler in the preparation of a nanocomposite as follows.
• Gas-phase deposition polymerization was carried in a dumbbell-shaped glass reactor that has two round-shaped vessels and a short pipe (bridge) to unite the vessels to each other, where each vessel has a volume of 150 ml_ and is equipped with a neck for introducing and taking out materials.
• the powdered organoclay (10 g) impregnated with AIBN was introduced into one of the vessels of the reactor and liquid MMA monomer (20 ml_), including 4-tert-butylpyrocatechol (100 mg) as an inhibitor, was introduced into the other.
• the reactor was degassed by three times of freeze-pump-thaw cycle and then sealed off in vacuo.
• the reactor was put in an oven maintained at 60 0 C for 17 hours; while the reactor was slowly and continuously rotated in order to maintain impartial contact between the clay and vaporized MMA, which diffused from the monomer vessel to the clay vessel through the bridge.
• the product was taken out and the adsorbed/absorbed monomer was completely desorbed in vacuo at 45 0 C.
• the final weight of the product was 27.57 g, containing about 36.3 % of the organically modified montmorillonite.
• Mn and Mw of the polymer extracted from the composite were 200,000 and 1 ,088,000, respectively.
• Wide angle XRD analysis of the product showed no peak in the range of 2 ⁇ > 2°. Thus, complete exfoliation of the silicate platelets was achieved, as opposed to the original CloisiteTM C20A with d(001)-spacing of 2.50 nm. Comparative example 1
• CloisiteTM C20A (0.5 g) was impregnated with AIBN as explained in Example 4. Then MMA monomer (2 ml_) was added together with toluene (4 ml_) in a glass vial. The solution was subjected to three times of freeze-pump-thaw cycle to eliminate oxygen from the reaction system. Then, the solution was maintained at 60 0 C for 6 hours with stirring under argon gas flow. After the prescribed time of polymerization, the product was taken out and precipitated in methanol, yielding 2.33 g of polyMMA/clay composite that contained about 21.5 % of the organically modified montmorillonite. XRD pattern of the composite showed a peak corresponding to d(001)-spacing of 3.30 nm. Thus, by this process complete exfoliation was not achieved.
• the clay/polyMMA nanocomposite (16.7 parts) obtained in Example 4 was melt- mixed, as a masterbatch, with AcrypetTM VH001 (83.3 parts), a commercial polyMMA supplied by Mitsubishi Rayon, in a kneader (PBV-0.3, lrie Shokai Co. Ltd., Tokyo) at 210 0 C and a rotational speed of 15 rpm.
• PBV-0.3 lrie Shokai Co. Ltd., Tokyo
• a rotational speed of 15 rpm a rotational speed of 15 rpm.
• the compound contained 6 wt % of organoclay.
• the compound was subsequently molded into a sheet (150mm X 150mm X 4mm) by using a hot press, at 220 0 C and 7 MPa.
• the sheet was cut into the shapes of test pieces, which were subjected to measurement of flexural properties, Izod impact strength, temperature of deflection under load, and gas transmission rate, in accordance with ISO standards.
• a composite made of CloisiteTM C20A (6 parts) and AcrypetTM VHO01 (94 parts) was prepared under the same conditions as Example 5, and its properties were also measured under the same conditions as Example 5.
• the composite containing the ornagoclay that was subjected to gas-phase polymerization showed greater flexural and impact strength, flexural modulus, gas barrier, and transparency to visible light, in comparison with the organoclay without gas-phase polymerization treatment.
• a composite material comprising an organoclay and a copolymer consisting of MMA and styrene was prepared in the same manner as in Example 4, except that MMA and styrene were simultaneously polymerized, as follows.
• the powdered organoclay (5.0 g) impregnated with AIBN (167 mg) was introduced into the smaller vessels of the reactor and a mixture of MMA (30 ml_) and styrene (90 ml_) monomers, including 4-tert-butylpyrocatechol (600 mg) as an inhibitor, was introduced into the larger vessel, respectively.
• the reactor was degassed by three times of freeze-pump-thaw cycle and then sealed off in vacuo.
• the reactor was put in an oven maintained at 70 0 C for 24 hours; while the reactor was slowly and continuously rotated in order to maintain impartial contact between the clay and vaporized monomers, which diffused from the monomer vessel to the clay vessel through the bridge.
• the product was taken out and the adsorbed/absorbed monomers were completely desorbed in vacuo at 45 0 C.
• the final weight of the product was 17.6 g, containing about 23.4 % of the organically modified montmorillonite.
• Wide angle XRD analysis of the product showed no peak in the range of 2 ⁇ > 2°.
• complete exfoliation of the silicate platelets was achieved, as opposed to the original stearyltrimethyl ammonium-modified montmorillonite with d(001)-spacing of 2.10 nm.
• Polymer was extracted from the composite with tetrahydrofuran using a Soxhlet's apparatus for 48 hours and subjected to characterization.
• a composite material comprising an organoclay and a copolymer consisting of MMA and styrene was prepared in the same manner as in Example 1 , except that MMA and styrene were consecutively introduced to the reactor and polymerized stepwise, as follows.
• the first-stage polymerization i.e. polymerization of MMA was carried out for 18 hours in an oven maintained at 60 0 C. After the prescribed time of polymerization, the unreacted MMA monomer was completely eliminated from the reactor by using a syringe and a vacuum pump, followed by the introduction of styrene (2.0 ml_, including 13 mg of 4-tert-butylpyrocatechol) into the reactor.
• the second-stage polymerization i.e.
• polymerization of styrene was carried out the in same way as the first-stage polymerization, but the reactor was maintained at 80 0 C for 11 hours. After the prescribed time of polymerization, the product was taken out and adsorbed/absorbed styrene monomer was completely desorbed in vacuo at 45 0 C. The final weight of the product was 555 mg, containing about 19 % of stearyltrimethyl ammonium-modified montmorillonite. XRD analysis of the product showed no peak in the range of 2 ⁇ ⁇ 2°, meaning complete exfoliation of the silicate platelets, as opposed to the original stearyltrimethyl ammonium-modified montmorillonite with d(001)-spacing of 2.10 nm.
• Polymer was extracted from the composite with tetrahydrofuran and subjected to characterization. Mn and Mw were 680,000 and 1 ,496,000, respectively.
• a composite material comprising polyMMA and montmorillonite was prepared in the same manner as in Example 1 , except that a mixture of stearyltrimethylammonium chloride and 6-
• Montmorillonite clay (2.0 g) was dispersed into 2 L of deionized water, and the dispersion was stirred vigorously overnight at room temperature. The suspension was then ultrasonicated for 5 hours, resulting in a homogeneous dispersion.
• Stearyltrimethylammonium chloride (0.75 g, 2.15 mmol)
• 6- (methacryloyloxy)hexyltriethylammonium bromide (0.20 g, 0.57 mmol) were mixed and dissolved in 200 ml_ of deionized water and slowly added to the montmorillonite dispersion while it was being stirred. The mixture was then stirred for another 12 hours.
• the organically modified montmorillonite powder (102 mg) impregnated with AIBN (3.4 mg) was placed in a glass reactor for subsequent gas-phase polymerization.
• Liquid MMA monomer (about 2 ml_) and 4-te/f-butylpyrocatechol (about 13 mg) as an inhibitor were introduced into a separated area in the reactor under argon gas flow.
• the reactor was degassed by three times of freeze-pump-thaw cycle and then sealed off in vacuo.
• the reactor was maintained at 70 0 C for 3 hour. After the prescribed time of polymerization, the product was taken out and adsorbed/absorbed MMA monomer was completely desorbed in vacuo at 45 0 C.
• the final weight of the product was 613 mg, containing about 17 % of the modified montmorillonite.
• Mn and Mw of the polymer were 499,000 and 1,301 ,000, respectively.
• XRD analysis of the product showed no peak, meaning complete exfoliation of the silicate platelets.

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