WO2005028363A2 - Organophilic clays and their use in the preparation of nanocomposite materials - Google Patents
Organophilic clays and their use in the preparation of nanocomposite materials Download PDFInfo
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- WO2005028363A2 WO2005028363A2 PCT/EP2004/010693 EP2004010693W WO2005028363A2 WO 2005028363 A2 WO2005028363 A2 WO 2005028363A2 EP 2004010693 W EP2004010693 W EP 2004010693W WO 2005028363 A2 WO2005028363 A2 WO 2005028363A2
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- clay
- organophilic clays
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- polymerization
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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
Definitions
- the present invention relates to organophilic clays and their use in the preparation of nanocomposite materials . More specifically, the present invention relates to organophilic clays and their use with thermoplastic polymers in the preparation of nanocomposite materials with an improved structural resistance.
- Composite materials consisting of an organic-inorganic hybrid can have higher mechanical properties than those of single components evaluated individually.
- a polymeric composite material for example, can be easily obtained by adding an inorganic component to the polymer, improving not only its mechanical properties but also other properties such as electric conductivity or impermeability to gases such as oxygen or water vapour, or flame resistance, or thermal dilation.
- the lamellas which form the dispersed phase have a thickness in the order of a nanometer, whereas the other two dimensions can reach a micron (“lamellar" nanocomposites) .
- the latter is modified with organic cations, for example alkylammonium or alkylphosphonium ions, which, by substituting the alkaline or alkaline-earth metal ions interposed in the lamellar structure of the phyllosilicate, increase the dimension of the interlayer and make it organophilic favouring its interaction with the polymer.
- organic cations for example alkylammonium or alkylphosphonium ions, which, by substituting the alkaline or alkaline-earth metal ions interposed in the lamellar structure of the phyllosilicate, increase the dimension of the interlayer and make it organophilic favouring its interaction with the polymer.
- organophilic clays obtained by modifying a clay, for example a smectite clay, with one or more compounds of quaternary ammonium and one or more non-ionic or- ganic compounds.
- the organophilic clays thus modified have a swollen layered structure, as the interlayer spacing has increased after the chemical-organic treatment.
- This swollen structure makes organophilic clays particularly suitable for forming nanocomposites with thermoplastic polymers such as polyolefins, polyester resins, polyamides, etc.
- the Applicant has now found a new group of organophilic clays obtained by modifying lamellar-structured clays with organic compounds, which, after mixing with thermoplastic polymers, allow nanocomposites to be obtained with improved mechanical properties such as tensile strength, elastic modulus, flexural strength, HDT and with improved flame resistance and thermal dilation properties.
- organic compounds belong to a new group of polymers characterized by a highly branched structural architecture which has recently appeared in scientific literature. This group of polymers is called dendritical if: the structure has 100% of possible branchings, the polymer is defined as a dendrimer; the percentage is lower, due to accidental growth de- fects, the polymer is defined as hyperbranched.
- Dendritic polymers (dendrimers and hyperbranched polymers) have unusual properties, as described in "Synthesis and Properties of Dendrimers and Hyperbranched Polymers", J.M.J. Frechet and C.J. Hawker, Chapter 3 of “Comprehensive Polymer Science”, 2 nd Supplement Volume, Pergamon, Oxford 1996, or in "Dendrimers and other Dendritic Polymers", J.M.J. Frechet and D.A. Tomalia, Wiley, Chichester, 2001, which make them appropriate for being studied for new applications. Two general methods have been developed for preparing dendritic polymers, depending on the structural type of the one or other subset (dendrimers or hyperbranched macromole- cules) .
- a multi-step preparation is applied for the former group, described for example in the above references, which almost always involves protection, growth, deprotection cycles .
- a simpler single-step preparative procedure is used, on the contrary, for the second group, as described, for example, in "New Developments in Hyperbranched Polymers", B. Voit, "Journal of Polymer Science Part A: Polymer Chemistry” 38 (2000), 2505.
- the most interesting properties of dendritic polymers are linked to their globular or almost globular structure and to the high number of chain-ends carrying functional groups of the same type which, in the case of the present invention, have proved to be particularly suitable for modifying lamellar-structured clays to be used in the preparation of PLSN.
- An object of the present invention therefore relates to organophilic clays comprising a reaction product ioni- cally exchanged and obtained by the intercalation of: a) at least one lamellar-structured clay in powder form having an average particle size, measured according to ASTM B330/00, ranging from 10 nm to 25 ⁇ m; with b) a dendritic polymer selected from those having the general formula: [A(B) n ] m (I) wherein n is an integer greater than or equal to 2, preferably from 2 to 4, whereas m is an integer greater than or equal to 4, preferably from 10 to 2,000, A and B, the same or different, are functional groups capable of reacting with each other according to a polymerization mechanism selected from radicalic polymerization, controlled or living radicalic polymerization, ionic polymerization, polyconden- sation, polymerization by metathesis, polymerization by the opening of a non-aromatic cyclic ring possibly containing hetero-atoms, Zie
- the dendritic polymer consists of: a core (C) and growth generations (G) according to the general formula: C-(G) n -Ym (V) wherein C is a molecule with a functionality equal to or higher than 3, characterized by functional groups selected from those listed above in the definition of A and B; G consists of identical branches, wherein each branch is made up of constitutional repetition units attributable to the specific monomer used which units are selected
- These dendritic polymers have an av- erage molecular weight up to 140,000, especially from 500 to 120,000, preferably ranging from 500 to 30,000, especially from 14,000 to 30,000, more preferably from 1,500 to 20,000, for example from 2,000 to 10,000.
- Dendritic polymers which are particularly suitable for the present invention are those wherein A and B are selected from amines and/or amides and derivatives, carbox- ylic acids and their salts or derivatives, halogen derivatives, alcohols and phenols, n ranges from 2 to 3, whereas m ranges from 10 to 100. Examples of these products are those available on the market under the trade-name of PAMAM, and sold by SIGMA ALDRICH, or those described in "High Performance Polymers", 2001, 13, 545-559.
- the lamellar- structured clay is preferably a phyllo-silicate such as vermiculite, montmorillonite, cloisite, ectorite, saponite, beidellite, nontronite, stevensite and other analogous products. These products are well known in literature. Details on their chemical composition and structural morphology are available in "Crystal Structure of Clay Minerals and Their X-ray Diffraction", S.W. Bridley and G. Brown, Mineralogical Society, London 1980 and in “Science” 220, T.J. Pinnavaia, 365 (1983). Before treatment with the dendritic polymer, the clay is preferably converted, if not already so, into sodium form.
- the clay is diluted in water and the suspension thus prepared is percolated through a fixed bed of an ion exchange resin of the sodium type.
- the clay suspension is mixed with a sodium compound soluble in water, for example sodium car- bonate or bicarbonate or sodium hydroxide, and then stirred vigorously.
- a sodium compound soluble in water for example sodium car- bonate or bicarbonate or sodium hydroxide
- it is filtered, dried and added to the solution of dendritic polymer for the intercalation reaction.
- Any intercalation technique can be used for preparing the organophilic clays, object of the present invention.
- direct intercalation can be adopted, by adding the clay, under stirring, in powder form, in sodium form, to a solution of the dendritic polymer.
- the solution of dendritic polymer generally consists of an inert solvent, which said dendritic polymer is dissolved in weight concentrations ranging from 0.5 to 25%.
- solvents are polar solvents, such as dimethylformamide, dimethylacet- amide, N-methylpyrrolidone, dimethylsulfoxide, etc. for hy- drophobic systems; water and C1-C4 alcohols, such as metha- nol, ethanol or isobutanol, in the case of hydrophilic systems .
- the clay is added in weight concentrations ranging from 0.5% to 10% with respect to the total, the temperature being maintained at a value ranging from room temperature to the boiling point of the solvent, preferably from 25 to 100°C.
- the clay is added to the organic solution in powder form with an average parti- cle size ranging from 10 nm to 25 ⁇ m, preferably from 100 nm to 10 ⁇ m, suitably from 1 to 13 ⁇ m.
- Examples of clays in sodium form suitable for the present invention are listed below: “Cloisite Na + " commercialized by Southern Clay Products, Inc. (USA); "Somasif ME-100" commercialized by Unicoop Chemical Co.
- the clay in sodium form, is exchanged with one or more alkylphosphonium or alkylammonium salts having general formula (VI) and (VII) :
- Ri, R 2 , R 3 and R 4 are C ⁇ -C 20 (iso)alkyl or C ⁇ -C 2 o aryl or alkylaryl radicals, on the condition that at least one of Ri, R 2 , R 3 and R 4 is an (iso)alkyl radical with from 10 to 20 carbon atoms
- X represents an organic anion, for example an anion of carboxylic acid, mono- or multi-functional, C1-C10, or an inorganic an- ion such as, for example, a halide, a phosphate, a sulfate, a nitrate, a carbonate.
- the exchange operation with the products having general formula (VI) and (VII) substantially takes place with the same procedures described above for the preparation of clay in sodium form.
- the clay is treated with the solution of dendritic polymer under the same conditions described above.
- the organophilic clay is recovered with the known methods, for example by centrifugation, filtration and/or evaporation of the solvent.
- a further technique for effecting the intercalation reaction is polymerization in situ, i.e.
- the polymerization in the presence of the sodium clay in powder form optionally exchanged with the alkylammonium or alkylphosphonium salts having general formula (VI) or (VII), of the monomer or monomers forming the dendritic polymer.
- This technique can be carried out by dispersing the clay powder in the monomer or mixture of monomers and effecting the synthesis of the dendritic polymer according to the methods of the known art.
- the organic clay is recovered with the known filtration technique and evaporation of the reaction solvents and non- reacted monomers.
- a further object of the present invention relates to a nanocomposite material comprising: i) a thermoplastic polymer with a transformation temperature ranging from 90 to 400°C; and ii) an organophilic clay obtained by the intercalation reaction of at least one lamellar-structured clay in powder form having an average particle size, measured ac- cording to ASTM B330/00, ranging from 10 nm to 25 ⁇ m, with a dendritic polymer having the general formula: [A(B) thread] cohesive (I) wherein n is an integer greater than or equal to 2, preferably from 2 to 4, whereas m is an integer greater than or equal to 4, preferably from 10 to 2,000, A and B, the same or different, are functional groups, described above, capable of reacting with each other according to a polymerization mechanism selected from radicalic polymerization, controlled or living radicalic polymerization, ionic polymerization, polycondensation, polymerization by metathesis, polymerization by the opening of a non- aromatic
- thermoplastic polymer can be used in the preparation of the nanocomposite materials object of the present invention.
- Illustrative examples comprise: polyolefins, such as high, medium or low density polyethylene, linear polyethylene, polypropylene, poly (iso) butene, polymers and copolymers of styrene such as polystyrene, impact resistant polystyrene, styrene-acrylonitrile copolymer (SAN) , acrylo- nitrile-butadiene-styrene copolymer (ABS) , copolymers of styrene with ⁇ -methylstyrene, copolymers of styrene with C ⁇ C 4 esters of (meth) acrylic acid, polymers of C ⁇ C 4 esters of (meth) acrylic acid, thermoplastic condensation polymers such as thermoplastic (co) polyester resins, for example polyethyleneterephthalate (PET) , polybutyleneterephthalate (P
- the hybrids between thermoplastic polymer and organophilic clays, wherein the latter are dispersed in the poly- meric matrix at a nanoscopic level, can be subdivided into two groups, intercalated nanocomposites and delaminated or exfoliated nanocomposites.
- intercalated hybrid the single polymeric chains are interposed between the laminas of the clay whereas the latter maintains a well-defined layered structure characterized by the regular alternation of polymer and lamellas.
- the distance between the various laminas which represents the space occupied by the polymer, is generally a few nanometers .
- the clay In a delaminated hybrid, the clay is completely exfo- liated and is uniformly dispersed in the polymeric matrix. The clay has completely lost its ordinate structure and the distance between the lamellas is in the order of the gyration radius of the polymer. According to this subdivision, it can be said that an intercalated nanocomposite material forms a system with a limited miscibility whereas a delaminated nanocomposite material represents a system with a complete miscibility.
- the conventional composites have a microscopic distribution in the polymeric matrix, of the clay wherein the lamellar structure maintains its original layered aggregation state.
- the concentration of organophilic clays in the thermoplastic polymer ranges from 0.5 to 30% by weight, preferably from 2 to 6%.
- the nanocomposites, object of the present invention can be prepared with conventional methods.
- the organophilic clay can be added to the thermoplastic polymer in the molten state using equipment normally used for transforming thermoplastic polymers, for example single- or twin-screw extruders and internal mixers.
- This technique is particularly suitable for organophilic clays comprising dendritic polymers with a high thermal stability.
- Other methods comprise polymerization in situ and mixing in solution.
- the polymer is sold as an alcohol solution (10% by weight in methanol) and in order to be used as compatibi- lizing agent, it is dissolved in water. For this reason, the methanol was eliminated by treating the solution at a rotavapor and adding water to the partially anhydrous polymer.
- the clay is cloisite-Na + , purchased from Southern Clay Products, of which 90% has a particle size lower than 13 ⁇ m. 50 ml of demineralized water are poured into a beaker, containing non-modified clay, with stirring at room temperature.
- the beaker is then heated on a heating plate to about 100°C for approximately ten minutes and subsequently, the aqueous solution of the dendrimer is added, under constant stirring, in such a quantity as to form, after evaporation of the water, 30% by weight of the material obtained.
- the temperature is raised to about 150 °C and the stirring is continued until a homogeneous suspension is obtained. It is then left to evaporate, under bland stirring, until a gel is obtained.
- the gel is dried in an oven for a day at 50°C and subsequently for another day at 100°C.
- X-ray diffractometry and TEM analysis showed the intercalation of the dendritic polymer in the clay.
- Table 1 below indicates the data relating to the interplanar distances dooi which verify, through an increase in the inter- lamellar distances, the insertion of the dendrimer.
- thermogravimetric analysis in air and nitrogen was also carried out on this system, at a heating rate of 10°C/min and with a gas flow of 30 cm 3 /min, which allowed the protection effect of the clay on the dendrimer to be revealed.
- Table 2 indicates the results.
- EXAMPLE 2 The preparation was effected by exactly repeating the procedures described in Example 1, with the only difference that the dendritic polymer was polyamidoamine-NH 2 (4 th generation), again of Aldrich. X-ray diffractometry showed the intercalation of the polymer in the clay. Table 3 below indicates the data relating to the interlamellar distances dooi- Table 3
- EXAMPLE 3 The preparation was effected by exactly repeating the procedures described in Example 1, with the only difference that the dendritic polymer was polyamidoamine-NH 2 of the 5 th generation, again of Aldrich. X-ray diffractometry showed the intercalation of the polymer in the clay. Table 5 below indicates the data relating to the interlamellar distances d 0 o ⁇ . Table 5
- Examples 1-5 were used for preparing nanocomposite materials based on PBT (PIBITER of the Applicant) and PA 6 (VIVIONPLAST B again of the Applicant) containing 3.5% and 4.0% by weight of modified clays as indicated above, respectively.
- the nanocomposite materials were prepared in co-rotating twin-screw extruders, of the Werner ZSK 40 type, operating with a temperature profile of about 250°C. In all cases, composite materials were obtained in which the modified inorganic phase proved to be homogeneously dispersed in the polymer.
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ITMI2003A001806 | 2003-09-23 | ||
ITMI20031806 ITMI20031806A1 (it) | 2003-09-23 | 2003-09-23 | Argille organofiliche e loro impiego nella preparazione di materiali nanocompositi. |
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WO2005028363A2 true WO2005028363A2 (en) | 2005-03-31 |
WO2005028363A3 WO2005028363A3 (en) | 2005-10-27 |
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Cited By (6)
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FR2904620A1 (fr) * | 2006-08-02 | 2008-02-08 | Rhodia Recherches & Tech | Materiau a structure lamellaire modifie, de type polysilicate ou phosphate de zirconium et/ou de titane, modifie par un oligoamide, son procede de preparation et son utilisation. |
CN100443537C (zh) * | 2006-08-01 | 2008-12-17 | 扬州大学 | 双连续相结构的高分子合金基纳米复合材料及制备方法 |
US7928154B2 (en) * | 2006-06-26 | 2011-04-19 | Sabic Innovative Plastics Ip B.V. | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US8545975B2 (en) | 2006-06-26 | 2013-10-01 | Sabic Innovative Plastics Ip B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
US8568867B2 (en) | 2006-06-26 | 2013-10-29 | Sabic Innovative Plastics Ip B.V. | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
US9161440B2 (en) | 2006-06-26 | 2015-10-13 | Sabic Global Technologies B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
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EP1344794A1 (en) * | 2002-03-15 | 2003-09-17 | Eastman Kodak Company | Article comprising highly branched polymers and splay layered materials |
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WO2003016392A1 (en) * | 2001-08-16 | 2003-02-27 | Ecole Polytechnique Federale De Lausanne | Composites and methods for their production |
EP1344794A1 (en) * | 2002-03-15 | 2003-09-17 | Eastman Kodak Company | Article comprising highly branched polymers and splay layered materials |
Non-Patent Citations (3)
Title |
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ACOSTA ERICK J ET AL: "Dendritic surfactants show evidence for frustrated intercalation: A new organoclay morphology" CHEM. MATER.; CHEMISTRY OF MATERIALS JUL 29 2003, vol. 15, no. 15, 29 July 2003 (2003-07-29), pages 2903-2909, XP002336204 * |
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SINGH CHANDRALEKHA ET AL: "Effect of polymer architecture on the miscibility of polymer/clay mixtures" POLYM INT; POLYMER INTERNATIONAL MAY 2000 JOHN WILEY & SONS LTD, CHICHESTER, ENGL, vol. 49, no. 5, May 2000 (2000-05), pages 469-471, XP008021393 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7928154B2 (en) * | 2006-06-26 | 2011-04-19 | Sabic Innovative Plastics Ip B.V. | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US20110212314A1 (en) * | 2006-06-26 | 2011-09-01 | Sabic Innovative Plastics Ip Bv | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US8158243B2 (en) | 2006-06-26 | 2012-04-17 | Sabic Innovative Plastics Ip B.V. | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US20120190791A1 (en) * | 2006-06-26 | 2012-07-26 | Sabic Innovative Plastics Ip Bv | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US8278383B2 (en) | 2006-06-26 | 2012-10-02 | Sabic Innovative Plastics Ip B.V. | Methods of preparing polymer-organoclay composites and articles derived therefrom |
US8545975B2 (en) | 2006-06-26 | 2013-10-01 | Sabic Innovative Plastics Ip B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
US8568867B2 (en) | 2006-06-26 | 2013-10-29 | Sabic Innovative Plastics Ip B.V. | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
US9161440B2 (en) | 2006-06-26 | 2015-10-13 | Sabic Global Technologies B.V. | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
CN100443537C (zh) * | 2006-08-01 | 2008-12-17 | 扬州大学 | 双连续相结构的高分子合金基纳米复合材料及制备方法 |
FR2904620A1 (fr) * | 2006-08-02 | 2008-02-08 | Rhodia Recherches & Tech | Materiau a structure lamellaire modifie, de type polysilicate ou phosphate de zirconium et/ou de titane, modifie par un oligoamide, son procede de preparation et son utilisation. |
WO2008017757A2 (fr) * | 2006-08-02 | 2008-02-14 | Rhodia Operations | Materiau a structure lamellaire modifie, de type polysilicate ou phosphate de zirconium et/ou de titane, modifie par un oligoamide, son procede de preparation et son utilisation |
WO2008017757A3 (fr) * | 2006-08-02 | 2008-03-27 | Rhodia Operations | Materiau a structure lamellaire modifie, de type polysilicate ou phosphate de zirconium et/ou de titane, modifie par un oligoamide, son procede de preparation et son utilisation |
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ITMI20031806A1 (it) | 2005-03-24 |
WO2005028363A3 (en) | 2005-10-27 |
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