WO2013185196A1 - Utilisation d'une argile nanostructurée organophile exempte de sel d'ammonium dans du polyéthylène - Google Patents

Utilisation d'une argile nanostructurée organophile exempte de sel d'ammonium dans du polyéthylène Download PDF

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Publication number
WO2013185196A1
WO2013185196A1 PCT/BR2013/000207 BR2013000207W WO2013185196A1 WO 2013185196 A1 WO2013185196 A1 WO 2013185196A1 BR 2013000207 W BR2013000207 W BR 2013000207W WO 2013185196 A1 WO2013185196 A1 WO 2013185196A1
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Prior art keywords
clay
polyethylene
organophilic
free
application
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PCT/BR2013/000207
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English (en)
Portuguese (pt)
Inventor
Bianca Iodice
Reinaldo Yoshio MORITA
Juliana Regina KLOSS
Gilson Luiz Torrens
Ronilson Vasconcelos Barbosa
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Ioto International Indústria E Comércio De Produtos Aromáticos Ltda.
Universidade Federal Do Paraná
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Publication of WO2013185196A1 publication Critical patent/WO2013185196A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen

Definitions

  • the present invention is concerned with the incorporation of an ammonium salt free nanostructured organophilic clay into polyethylene.
  • This clay was obtained from the chemical treatment of a pure natural clay with a carboxylic acid or alkyl sulfate or propyl sulfate derived surfactant and from a chemical that modifies the surfactant within the clay and the clay itself. (patent-pending methodology - DEPR 015100000646)
  • Polyethylene is one of the most widely used polyolefin polymers and can be produced in different forms.
  • polyethylenes which vary in number and size of branches beyond molecular weight distribution [Pettarin, V .; Frontini, P. M; Pita, V.J. R. R .; Dias, M.L .; Diaz, F. V.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • PEUAMM ultra high molar mass polyethylene
  • PEUBD ultra low density polyethylene
  • Green Polyethylene a 100% renewable source (sugar cane)
  • This polymer combines environmental benefits and technical advantages with the easily processable forms of olefins.
  • Packaging In the polyethylene market, one of the trends is in the packaging for marketing meat, chicken, cheese and cold both in the domestic and export markets.
  • Packaging in this case, has to meet a range of requirements ranging from better product visualization and increased shelf life to barrier resistance, in addition to thickness, another important factor, making better packaging with less raw material is current market trend, and meets another concern that is sustainability [HAYASAKI, M. Commitment to Innovation. PACK Packaging, Technology and Innovation, n. 10, year 10, p. 19-21, 2008].
  • a product needs to provide consumer appeal while offering less environmentally friendly packaging around it and creating a lower cost opportunity that will be passed on to the community [Monteiro, S. Environmentally Friendly Packaging environment: where to start? PACK Packaging, Technology and Innovation, n.10, year 10, p. 38-39, 2008].
  • organophilic clays also known as nanoargils or nanoparticulate clays, which are obtained from bentonites, a very fine-grained clay composed essentially of smecite group clay minerals, with montmorillonite in concentrations ranging from 60% more common. 95% [PAIVA, LB; MORALES, AR 51st Brazilian Congress of Ceramics, 2007].
  • Nanocomposites have great advantages over virgin material or conventional micro or macro composites, because with the use of low fillers (up to 5% by mass), which differentiates them from traditional composites where the mass percentage can reach At 40%, a significant increase in modulus, tensile strength and thermal distortion temperature can be achieved, decreased permeability and flammability, and increased biodegradability in biodegradable polymers without significantly increasing material density while maintaining brightness and transparency, with strategic applications in the modern industrial park, including the automotive and packaging area [Saminathan, K .; Selvakumar, P .; Bhatnagar, N. Fracture studies of polypropylene / nanoclay composite. Part I: Effect of loading rates on essential work of fracture. Polymer Testing, v. 27, no. 3, p.
  • Interleaved structure nanocomposites formed when the polymeric chain is interspersed between the silicate lamellae, resulting in a morphology of well-ordered multilayer, alternating between inorganic and organic phases; / ' /) Exfoliated structure nanocomposites: These are formed when the lamellae of clays are uniformly dispersed (exfoliated) as individual entities in a continuous polymeric matrix [Camargo, PH C; Satyanarayana, KG; Wypych, F. .. Nanocomposites: Synthesis, Structure, Properties and New Application Opportunities. Materials Research, 12, 1-39, 2009]. Analyzes by X-ray diffraction and transmission electron microscopy are usually employed in the structural characterization of these materials [Patent, PI 0601384-8 A].
  • the exfoliation-adsorption process is a particular case of the simple component mixing method used in the preparation of composites at industrial level.
  • the fillers generally used are lamellar structures that can be partially or totally delaminated with the introduction of chemical species between the inorganic layers.
  • the preparation of a nanocomposite by the exfoliation-adsorption process is feasible only if the polymer in question is soluble in a particular solvent in which the inorganic material can be delaminated, because when added to the polymer solution the lamellae are spontaneously organized to form ordered nanocomposites [Esteves, AC C; Barros-Timmons, A .; Trindade, T. Polymeric matrix nanocomposites: Synthesis strategies of hybrid materials. New Chemistry, v. 27, no.
  • the intercalative in situ polymerization technique consists of swelling of the clay in the monomer or a solution of the monomer and subsequently, the polymerization is conducted by heating or radiation in the presence or absence of initiator. This procedure also allows the formation of intercalated and / or exfoliated structures, given the possibility of polymerization in the interlamellar region [Alexandre, M .; Dubois, P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Materials Science and Engineering, v. 28, pp. 1-63, 2000].
  • the physical and chemical properties of nanocomposites obtained by this process can be influenced by the choice of polymerization method.
  • An example is the advantage of producing nanocomposites via emulsion polymerization due to molecular weight control and molecular weight distribution of the polymer [Esteves, A. C. C; Barros-Timmons, A .; Trindade, T. Polymeric matrix nanocomposites: Synthesis strategies of hybrid materials. New Chemistry, v. 27, no. 5, p. 798-806, 2004].
  • amorphous polymer nanocomposites such as polystyrene (PS) and polymethyl methacrylate (PMMA).
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • the reactive site for polymerization resides in the interlamellar galleries and the driving force generated in the polymerization reaction promotes the effect of dispersing the clay lamellae
  • Polystyrene-clay nanocomposites prepared with polymerizable imidazolium surfactants Macromolecular Rapid Communications, v. 24, no. 8, p.
  • Fu and Qutubuddin (2001) using the in situ polymerization method obtained nanocomposites with a high degree of exfoliation and better mechanical and thermal properties than pure polymer [Fu, X .; Qutubuddin, S. Polymer-clay nanocomposites: exfoliation of organophilic montmorillonite nanolayers in polystyrene. Polymer, v. 42, p. 807-813, 2001].
  • Patent document PI0704383-0 describes the procedure for obtaining interleaved or exfoliated polyolefin nanocomposites using a modified clay to prepare a solid metallocene catalyst for in situ olefin polymerization reactions.
  • Evidence of nanocomposite structures was investigated by X-ray diffraction and transmission electron microscopy techniques [Patent, PI0704383-0].
  • the properties of the nanocomposite are given in some way by the polymeric matrix that acts as a mold.
  • This technique is widely used in the preparation of nanocomposites with double lamellar hydroxides and is often adapted for aqueous solution systems.
  • the method proceeds by crystallizing layered ordered structures from an aqueous solution of the inorganic precursors containing the polymer. In this way, the polymer is trapped within the layers during the inorganic crystal formation process [Esteves, A. C. C; Barros-Timmons, A .; Trindade, T. Polymeric matrix nanocomposites: Synthesis strategies of hybrid materials. New Chemistry, v. 27, no. 5, p. 798-806, 2004].
  • the molten polymer is mixed with the clay to allow interleaving of the polymeric chains between the coverslips.
  • the polymeric materials resulting from finite expansion of the lamellae produce intercalated nanocomposites.
  • a delaminated nanocomposite is obtained, where the lamellae behave as individual entities dispersed in the polymeric matrix [Paul , DR; Roberson, LM. Polymer nanotechnology: Nanocomposites. Polymer, v. 49, p. 3187-3204, 2008].
  • the nanocomposites obtained through this process have been intensively researched, mainly with the polyolefin class polymeric matrices [Barbosa, R .; Ara ⁇ jo, MS; Maia, LF; Pereira, OD; Melo, TJA; Ito, EN Morphology of polyethylene and polyamide-6 nanocomposites containing national clay.
  • Polymers Science and Technology, v. 16, no. 3, p. 246-251, 2006; Pettarin, V .; Frontini, PM, Pita, VJRR; Dias, M.L; Diaz, FV Polyethylene / (organo-montmorillonite) modified composites with ethylene / methacrylic acid copolymer: morphology and mechanical properties.
  • montmorillonite smectitic clay mineral one of the most common and used, presents a 2: 1 stacked face-to-face layered structure forming a crystalline reticulum.
  • the layers or sheets are comprised of two sheets of silica (nSi0 2) and richly distributed tetraed an alumina sheet (NAI 2 0 3) therebetween and distributed octahedrally chemically bonded.
  • the general chemical composition of montmorillonite is given by the formula:
  • the chemical composition of montmorillonites may vary, as isomorphic substitutions occur in the crystal structure by exchanging Si 4+ ions from tetrahedral leaves with Al 3+ ions and the other part, Al 3+ ions from octahedral leaves can be replaced by ions. Mg 2+ or Fe 3+ .
  • the unit clay cell becomes negatively charged and the electric balancing is done by the presence of a positive ion, known as an exchangeable cation.
  • the cation represented by M + occupies the interlamellar space or commonly called galleries, thus remaining between the stacked layers [Bergaya, F .; Theng, BKG; Lagaly, G.
  • Montmorillonite like other clay minerals, has the capacity to swell in the presence of water, because interlamellar hydration occurs. spacing of the coverslips allowing the accessibility of exchangeable ions. Therefore, ions are relatively more readily available for exchange with other ions or ionic structures.
  • CTC ion exchange capacity
  • Modification of the clays employing the ammonium salts introduces a hydrophobic character to the clay, reducing its surface tension and consequently improving compatibility with the polymer matrix. This process increases the spacing between the coverslips, facilitating polymer intercalation and thereby delamination of the clay.
  • clays are known as organophilic clays. These clays are currently one of the main precursors for obtaining polymeric nanocomposites, however, they have some limitations compared to the requirements in the area of composite materials [Patent, PI 0601384-8 A].
  • ammonium salts block the access of polymer chains to the polar polar sites is what causes the weak interaction between the polymer and this charge.
  • ammonium salts commonly employed in chemical modification do not have functional groups in their structures capable of promoting chemical bonding with clay or even proper interaction with this matrix [Pinavaia, T. J .; et al. Homostructured mixed organic and inorganic cation exchange tapered compositions. Int C13B22 C01 B 033/24. US 5,993,769. 14 May 1998, 30 Nov. 1999].
  • the use of ammonium modifiers becomes restrictive due to the low thermal stability, because depending on the type of processing employed in obtaining nanocomposites the temperature leads to the thermal degradation process [Park, C. I .; et al. The manufacture of syndiotactic polystyrene / organophilic clay nanocomposites and their properties. Polymer, v. 42, p. 7465-7475, 2001].
  • the principal method of obtaining the nanocomposite is via melt polymer intercalation. In this method, the polymer is mixed with clay in equipment such as extruders, calenders, internal mixers, among others. The polyethylene / clay mixture is subjected to high temperatures and high shear rates.
  • ammonium salt degradation products can act as degradants of the polymeric matrix, inducing color appearance and compromising the thermal stability and properties of the final product [ Patent, PI 0601384-8 A].
  • the present invention relates to different methodologies for the production of ammonium salt-free modified polyethylene / clay nanocomposites, i.e. chemical modification by a surfactant derived primarily from a carboxylic acid, or other surfactant having the desired characteristics, such as for example, an alkyl or propyl sulfate derivative.
  • Figure 1- X-ray diffractograms of low density polyethylene films (melt index around 7.0 g / 10 min) with LDPE / modified clay concentrate (70/30) inside, in the proportions of 3 (a) and 5% (b) (w / w).
  • the nanocomposite in question in the present invention will be prepared by the melt polymer intercalation technique through three different forms of processing employing a polymer belonging to the polyolefin family, preferably a polyethylene (low density, high density, low linear density). ) and a natural clay, belonging to the family of phyllosilicates, preferably from the 2: 1 group, modified with a surfactant derived from Recommended carboxylic acid for this invention is sodium stearate, CH 3 (CH 2 ) i 6 COO " Na + or sodium lauryl sulfate, CH 3 (CH 2 ) iSO 4 " Na + (methodology under production of DEPR 015100000646), ie surfactant other than ammonium salt.
  • a polymer belonging to the polyolefin family preferably a polyethylene (low density, high density, low linear density).
  • a natural clay belonging to the family of phyllosilicates, preferably from the 2: 1 group, modified with a surfactant derived from
  • the amount of polymeric material was between 50 to 50 to
  • ammonium salt-free modified clay ranged from 1 to 10% based on the final mass of the nanocomposite obtained.
  • the amounts may be increased depending on the expected properties of the final product or in the case of preparation of a polymer / clay concentrate (concentration of 20 to 50% of modified clay).
  • the concentrate (polyethylene / modified clay), after cooling, was granulated and mixed in the percentages of 3 and 5% to low density polyethylene - LDPE (flow rate around 7.0 g / 10 min), to obtain thin films prepared in a laboratory balloon extruder with the following temperature profile 130 - 135 - 140 - 140 ° C from the feed to the die and also in the percentages of 5 and 10% to low density polyethylene (LDPE) flow rate around 30.0 g / 10 min) to obtain the injected compound, in a 65 tonne closing force injector, screw L / D ratio of 20 and 35 mm thread diameter and 180 to 200 ° C.
  • LDPE low density polyethylene
  • EXAMPLE 2 Preparation of Nanocomposite with Addition of Specific Percentages of Modified Polyethylene (PE) Clay
  • PE Modified Polyethylene
  • This example consists of a mixture of polyethylene (melt index around 30.0 g / 10 min), generally 98.5 and 97%, and different amounts of modified clay, generally 1, 5 and 3.0%.
  • m / m in an intensive homogenizer at 3600 revolutions per minute for approximately two 10 second cycles. After mixing, the material was extruded in pellet form in a laboratory single-screw extruder with the following temperature profile 140 - 150 - 160 - 160 ° C from the feed to the die.
  • the extruded nanocomposites were granulated and injected, with a closing force of 65 tons, screw L / D ratio of 20 and a thread diameter of 35 mm and a process temperature of 180 to 200 ° C.
  • the third form consists of the processing of polyethylene (flow rate around 30.0 g / 10 min), generally 98.5 and 97%, and modified clay, generally 1, 0 and 3.0% m / m, in a co-rotating twin screw extruder with the following temperature profile 140 - 150 - 160 - 160 ° C from feed to die or in a twin screw mixer.
  • the extruded nanocomposites were granulated and injected, with a closing force of 65 tons, screw L / D ratio of 20 and a thread diameter of 35 mm and a process temperature of 180 to 200 ° C.
  • the mechanical tests were performed in a universal testing machine, using specimens according to ASTM D 638-08.
  • the clearance speed between the claws was 50 mm-min "1 and load cell of 500 kgf. 10 specimens per composition were analyzed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'une argile nanostructurée organophile exempte de sel d'ammonium dans du polyéthylène, consistant en la préparation d'un nanocomposite au moyen de la technique d'intercalation du polymère fondu, par trois modes de traitement distincts, faisant intervenir un polymère appartenant à la famille des polyoléfines, de préférence un polyéthylène (basse densité, haute densité, basse densité linéaire) et une argile naturelle appartenant à la famille des phyllosilicates, de préférence du groupe 2:1, modifiée avec un agent tensioactif dérivé de l'acide carboxylique. Le composé recommandé pour cette invention est le stéarate de sodium, CH3(CH2)16COO-Na+ ou o lauril sulfato de sódio, CH3(CH2)11SO4"Na+ (méthodologie en phase d'obtention de brevet - DEPR 015100000646), soit un agent tensioactif différent du sel d'ammonium.
PCT/BR2013/000207 2012-06-13 2013-06-11 Utilisation d'une argile nanostructurée organophile exempte de sel d'ammonium dans du polyéthylène WO2013185196A1 (fr)

Applications Claiming Priority (2)

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BR102012014230A BR102012014230A2 (pt) 2012-06-13 2012-06-13 Aplicação de uma argila nanoestruturada organofilica livre de sal de amônimo em polietileno.
BRBR1020120142309 2012-06-13

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412018A (en) * 1980-11-17 1983-10-25 Nl Industries, Inc. Organophilic clay complexes, their preparation and compositions comprising said complexes
US6521690B1 (en) * 1999-05-25 2003-02-18 Elementis Specialties, Inc. Smectite clay/organic chemical/polymer compositions useful as nanocomposites
US20030176537A1 (en) * 2002-03-18 2003-09-18 The University Of Chicago Composite materials with improved phyllosilicate dispersion
US20100274036A1 (en) * 2009-04-23 2010-10-28 National Taiwan University Organic/inorganic compositive dispersant including inorganic clay and organic surfactant
BRPI1001312A2 (pt) * 2010-03-10 2011-11-01 Ioto Internat Ind E Com De Produtos Aromaticos Ltda processo de obtenção de nanoargila modificada para a produção de nanocompósitos poliméricos e nanoargila modificada

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412018A (en) * 1980-11-17 1983-10-25 Nl Industries, Inc. Organophilic clay complexes, their preparation and compositions comprising said complexes
US6521690B1 (en) * 1999-05-25 2003-02-18 Elementis Specialties, Inc. Smectite clay/organic chemical/polymer compositions useful as nanocomposites
US20030176537A1 (en) * 2002-03-18 2003-09-18 The University Of Chicago Composite materials with improved phyllosilicate dispersion
US20100274036A1 (en) * 2009-04-23 2010-10-28 National Taiwan University Organic/inorganic compositive dispersant including inorganic clay and organic surfactant
BRPI1001312A2 (pt) * 2010-03-10 2011-11-01 Ioto Internat Ind E Com De Produtos Aromaticos Ltda processo de obtenção de nanoargila modificada para a produção de nanocompósitos poliméricos e nanoargila modificada

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