EP2956502A1 - Plastic material with improved properties comprising nanoclay - Google Patents

Plastic material with improved properties comprising nanoclay

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Publication number
EP2956502A1
EP2956502A1 EP14703883.0A EP14703883A EP2956502A1 EP 2956502 A1 EP2956502 A1 EP 2956502A1 EP 14703883 A EP14703883 A EP 14703883A EP 2956502 A1 EP2956502 A1 EP 2956502A1
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EP
European Patent Office
Prior art keywords
plastic material
din
material according
phosphor
tegostab
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP14703883.0A
Other languages
German (de)
French (fr)
Inventor
Sylvia R. Hofmann
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Individual
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Individual
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Publication date
Application filed by Individual filed Critical Individual
Priority to EP14703883.0A priority Critical patent/EP2956502A1/en
Publication of EP2956502A1 publication Critical patent/EP2956502A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a plastic material with improved properties comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.
  • isocyanates are considered an essential component for achieving desired material properties, in particular for providing reliable crosslinking during polyurethane manufacture.
  • isocyanates includes significant disadvantages due to their toxicity to both users and the environment. In consequence, there is absence strong demand in the plastics industry to provide materials which fulfil toxicological and environmental requirements without loss in material performance.
  • thermoplastic polyurethanes TPU
  • thermoplastic elastomers TPU
  • TPUs possess different cohesion energy densities in the segments. In an ideal situation a phase separation into crystalline "hard” and “soft” areas can take place. The resulting two-phase structure has up to now determined the property profile of TPU.
  • the soft segment one uses long-chain polyoles which significantly affect the compatibility with the medium and the consistency of the TPU materials, and for the hard segment one uses short-chain polyoles. The latter strongly affect the hardness of the material, and they are responsible for the physical cross- linking.
  • the present invention relates to plastic materials without, or with strongly reduced quantities, of isocyanate components, which demonstrate improved mechanical properties compared to similar TPU materials and greater flexibility with respect to a modification of their physical properties via the addition of further modifying components.
  • nanoclay components may be integrated into plastics in order to maintain the mechanical qualities of a synthetic material that has been modified with a self-extinguishing agent. Nanoclays have also been applied in order to enhance the adhesive properties of plastic materials intended for medical implants (US 2007/0249754). Despite such advances, there exists a need for further or improved plastic materials that incorporate less isocyanates and enable easily modifiable plastic properties.
  • the technical problem underlying the invention was the provision of a novel plastic material that overcomes the disadvantages of those materials known in the art.
  • the plastic material of the invention enables improved toxicological and environmental properties in order to provide users with safe materials that have improved product properties.
  • an object of the invention is to provide a plastic material comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.
  • the plastic material of the invention therefore represents an environmentally friendly plastic that requires no addition of isocyanates during manufacture, whereby the nanoclay component in combination with the other components in the material enables a stable plastic material with easily modified physical and mechanical properties.
  • polyurethane TPU
  • nanoclay N-(2-aminoethyl)
  • PC polycarbonate
  • PCL polycaprolactone
  • PC is a commercially available synthetic material
  • PCL is a special polymeric material which has the outstanding properties of relatively high heat- and impact resistance.
  • PCL is a resinous polymer which is biodegradable and non-poisonous. The presence of these components in combination with TPU, polyol and nanoclays enables a robust plastic material ideally suited for further modification with an additive as described herein.
  • the additive is or comprises substances that may also act as a filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer. Even with additives the manufacturing of the material is reliable and results in a plastic material with the desired properties.
  • the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is a phosphor component.
  • the plastic material of the present invention is characterised in that the phosphor component comprises salts that derive from phosphor with organic or inorganic acids, phosphites and/or phosphates.
  • the plastic material of the present invention is characterised in that the phosphor component is a phosphite component.
  • the plastic material of the present invention is characterised in that the phosphor component is trisnonylphenyl phosphite.
  • the plastic material of the present invention is characterised in that the phosphor component is bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di- t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
  • the phosphor component is bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di- t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
  • the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is carboxylated polypropylene, preferably a carboxylated polypropylene functionalised with maleic anhydride.
  • carboxylated polypropylene preferably functionalised with maleic anhydride
  • SCONA TPPP 21 12 FA from BYK carboxylated polypropylene
  • the combination of thermoplastic polyurethane (TPU), nanoclay, polyol, polycarbonate (PC) and polycaprolactone (PCL) represents an unexpectedly beneficial base for the addition of carboxylated polypropylene.
  • carboxylated polypropylene provides an improved distribution of nanoclays in the mixture and therefore enhanced uniformity in and stability of the plastic material produced.
  • a combination of carboxylated polypropylene with a PC and PCL- based polymer has not been previously described. It was surprising that the combination of these materials was easily created via extrusion procedures.
  • the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis-MPA) and/or 1 ,3-polyethylene glycol diol.
  • the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis-MPA) and/or 1 ,3-polyethylene glycol diol.
  • the plastic material of the present invention is characterised in that the additive additionally comprises one or more substances that act as a filler, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer.
  • the additive additionally comprises one or more substances that act as a filler, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer.
  • the plasticizer comprises Benzyl-2-ethylhexyl adipate, Alkyl sulfonic ester of phenol, Benzyl butyl phthalate and/or Polyadipate.
  • the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis- MPA), 1 ,3-polyethylene glycol diol, phosphor components with the chemical element phosphor, salts that derive from phosphor with organic or inorganic acids, phosphates, phosphites, bis (2,6- di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. It was a surprise that with the addition of stabilizer the manufacturing process is not affected and product performance can be enhanced.
  • the plastic material of the present invention is characterised in that the material comprises polyurethane in an amount of 20 to 80 %, preferably 30 to 70 %, more preferably 40 to 60% and most preferably 42 to 55 % by weight.
  • the amount of polyurethane present in the material has proven to be modifiable, so that over a relatively wide range of potential amounts of TPU the plastic material retains its structural integrity and ease of manufacturing.
  • a stabilizer such as a carboxylated polypropylene or phosphor component
  • TPU amount a stabilizer for example allows a greater variation in TPU amount.
  • the plastic material of the present invention is characterised in that the material comprises nanoclay in an amount of 0.00001 to 5 %, preferably 0.0001 to 4 %, more preferably 0.001 to 3 % and most preferably 0.01 to 2 % by weight.
  • the nanoclay component preferably in combination with the TPU, and more preferably in combination with polyol, PC and PCL, enables an isocyanate free (or low isocyanate) polymer to be produced with sufficient strength and stability, comparable to traditional polyurethane plastics.
  • the plastic material of the present invention is characterised in that the material comprises polyol in an amount of 5 to 45 %, preferably 6 to 35 %, more preferably 7 to 25 % and most preferably 8 to 15 % by weight.
  • polyol especially those polyols, such as polyesterpolyols, described herein, into the plastic material represents a surprising and unexpected result, whereby the polyol provides added flexibility to the product.
  • the plastic material of the present invention is characterised in that the material comprises polycarbonate in an amount of 5 to 60 %, preferably 10 to 50 %, more preferably 15 to 40 % and most preferably 20 to 30 % by weight.
  • PC provides increased sustainability and hardness to the product, in particular enhanced temperature and impact resistance.
  • the combination between polyol and PC, together in a nanoclay based plastic represents an entirely surprising result, combining the flexibility and hardness of both components to enable a strong, resistant but flexible material.
  • the plastic material of the present invention is characterised in that the material comprises polycaprolactone in an amount of 2 to 45 %, preferably 4 to 35 %, more preferably 6 to 25 % and most preferably 8 to 15 % by weight.
  • Addition of PCL to the plastic as described herein represents a surprising and beneficial result characterised by increased impact resistance.
  • the plastic material of the present invention is characterised in that the material comprises one or more additives in an amount of less than 20 %, preferably less than 15 %, more preferably less than 10% and most preferably less than 5 % by weight.
  • the additives are intended to fulfill various purposes as described herein and are intended to function at a relatively low total content in comparison to the remaining plastic base mixture (ie the TPU, nanoclay, PC, PCL, polyol base mixture).
  • the plastic material of the present invention is characterised in that the material comprises one or more additives in an amount of 0.1 % to 20%, 0.5% to 10%, or preferably 1 % to 5% by weight.
  • the plastic material of the present invention is characterised in that the material contains less than 10 % isocyanates, preferably less that 5 % isocyanates, more preferably less than 1 % isocyanates and most preferably less than 0.5 % isocyanates by weight.
  • isocyanate have been validated by chemical characterization and represent an improved standard for environmentally friendly plastic materials.
  • nanoclays in the amounts provided herein show such beneficial adhesive properties within these compounds, thereby forming a stable plastic without the need for isocyanate-based cross- linking. It was surprising that no additional isocyanates were required to produce a stable plastic material. Although some traces of isocyanate may be detectable in the final product likely due to residual isocyanate in the TPU products introduced into the plastic, the plastic is essentially isocyanate free and therefore represents an environmentally friendly product in comparison to similar plastics known in the art.
  • the plastic material comprises: polyurethane in an amount of 20 to 80 %, preferably 30 to 70 %, more preferably 40 to 60% and most preferably 42 to 55 %,
  • nanoclay in an amount of 0.00001 to 5 %, preferably 0.0001 to 4 %, more preferably 0.001 to 3 % and most preferably 0.01 to 2 %,
  • polyol in an amount of 5 to 45 %, preferably 6 to 35 %, more preferably 7 to 25 % and most preferably 8 to 15 %,
  • polycarbonate in an amount of 5 to 60 %, preferably 10 to 50 %, more preferably 15 to 40 % and most preferably 20 to 30 %,
  • polycaprolactone in an amount of 2 to 45 %, preferably 4 to 35 %, more preferably 6 to 25 % and most preferably 8 to 15 %, and
  • one or more additives in an amount of less than 20 %, preferably less than 15 %, more preferably less than 10% and most preferably less than 5 %, the additive may
  • plastic material alternatively be present at a percentage by weight of the plastic material of 0.1 % to 20%, 0.5% to 10%, or preferably 1 % to 5%,
  • polyurethane in an amount of 40 to 60% and most preferably 42 to 55 %
  • nanoclay in an amount of 0.001 to 3 % and preferably 0.01 to 2 %,
  • polyol in an amount of 7 to 25 % and preferably 8 to 15 %
  • polycarbonate in an amount of 15 to 40 % and preferably 20 to 30 %
  • polycaprolactone in an amount of 6 to 25 % and most preferably 8 to 15 %, and one or more additives at a percentage by weight of the plastic material of 0.5% to 10%, or preferably 1 % to 5%,
  • the additives may be present at a final % by weight in P0, P1 , P2 or P3 of 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 .0, 1 .1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1 .9, 2.0, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or 10 or any value between these values or ranges thereof.
  • PC and/or PCL is compatible with a plastic material that is easily modified with an additive, without a reduction in reliability of the manufacturing process.
  • the additive can be added to the plastic either before or after addition of PC and PCL, either of which leads to a stable plastic material that is not hindered in any way during manufacture.
  • carboxylated polypropylene such as SCONA TPPP 21 12 FA
  • a plasticizer preferably selected from Benzyl-2-ethylhexyl adipate, Alkyl sulfonic ester of phenol, Benzyl butyl phthalate and/or Polyadipate, or a stabilizer and/or elasticity modulator, preferably selected from polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis- MPA), 1 ,3-polyethylene glycol diol, phosphor components with the chemical element phosphor, salts that derive from phosphor with organic or inorganic acids, phosphates, phosphites, bis (2,6- di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di-t-butylphenyl)
  • One of the possible methods for production of the plastic material relates to a method comprising
  • Method step AP1 Mixture of thermoplastic polyurethane (TPU) and a nanoclay component, thereby producing PI, whereby AP1 may be carried out in two steps, for example by mixing TPU and nanoclay producing P0, then adding P0 to TPU in a second step producing P1 , whereby the additive may be added during P0 or P1 production,
  • TPU thermoplastic polyurethane
  • Method step AP2 Mixture of P1 with a polyol component and optionally additional TPU, thereby producing P2, whereby the additive may be added during P2 production,
  • Method step AP3 Mixture of P2 with a polycarbonate (PC) and polycaprolactone component (PCL), thereby producing P3, whereby the additive may be added during P3 production, whereby P3 may be subsequently processed to produce P4 in method step AP4 via extrusion, blowing, casting, grinding and/or spraying, to obtain particles, granules, films, fibres, foams, strands, sheets and/or foils.
  • PC polycarbonate
  • PCL polycaprolactone component
  • the additive may be added at any stage in the extrusion process, preferably to the AP2 or AP3 manufacturing steps.
  • the plastic material contains less than 10 % isocyanate, preferably less that 5 % isocyanate, more preferably less than 1 %, 0.5 %, 0.2 %, 0.1 % or less than 0.05% isocyanates by weight.
  • the plastic of the present invention is essentially isocyanate free.
  • One procedure for the quantitative determination of free isocyanates in synthetic materials is performed using the Kubitz quantitative test "Analytical Chemistry", Vol. 29, pages 814-816 (1957). The presence of isocyanate (for example at levels at or above 210 parts per million) causes the Kubitz reagent, which is a complex of n-butylamine and malacite green, to turn green.
  • the plastic material comprises phosphor, iron, magnesium, aluminium and/or silicon.
  • silicon, or silicium represents any substance comprising silicon.
  • the plastic material of the present invention is characterised in that the material comprises phosphor, iron, magnesium, aluminium and silicon.
  • the plastic material of the present invention is characterised in that the material comprises 10 to 1000 mg/kg phosphor, preferably 100 to 200 mg/kg phosphor, more preferably 150 mg/kg phosphor.
  • the plastic material of the present invention is characterised in that the material comprises 1 to 100 mg/kg iron, preferably 10 to 20 mg/kg iron, more preferably 15 mg/kg iron. In one embodiment the plastic material of the present invention is characterised in that the material comprises 1 to 100 mg/kg magnesium, preferably 5 to 15 mg/kg magnesium, more preferably 10 mg/kg magnesium.
  • the plastic material of the present invention is characterised in that the material comprises 1 to 500 mg/kg aluminium, preferably 10 to 100 mg/kg aluminium, more preferably 50 mg aluminium.
  • the plastic material of the present invention is characterised in that the material comprises 10 to 1000 mg/kg silicon, preferably 100 to 200 mg/kg silicon, more preferably 150 mg/kg silicon.
  • the plastic material comprises 10 to 1000 mg/kg phosphor of the total plastic material, preferably 100 to 200 mg/kg phosphor, more preferably 150 mg/kg phosphor, 1 to 100 mg/kg iron, preferably 10 to 20 mg/kg iron, more preferably 15 mg/kg iron, 1 to 100 mg/kg magnesium, preferably 5 to 15 mg/kg magnesium, more preferably 10 mg/kg magnesium, 1 to 500 mg/kg aluminium, preferably 10 to 100 mg/kg aluminium, more preferably 50 mg aluminium, and 10 to 1000 mg/kg silicon, preferably 100 to 200 mg/kg silicon, more preferably 150 mg/kg silicon.
  • Particular blends of nanoclay enables improved adhesion within the plastic in addition to beneficial distribution properties in the plastic, enabling improved uniform strength throughout the plastic.
  • a binary mixture comprising polyurethane and nanoclay comprises 0.1 to 10 mg/kg phosphor, preferably 0.5 to 5 mg/kg phosphor, more preferably 1 mg/kg phosphor, 10 to 1000 mg/kg iron, preferably 100 to 200 mg/kg iron, more preferably 130 mg/kg iron, 5 to 1000 mg/kg magnesium, preferably 10 to 100 mg/kg magnesium, more preferably 70 mg/kg magnesium, 50 to 5000 mg/kg aluminium, preferably 100 to 1000 mg/kg aluminium, more preferably 500 mg aluminium, and 100 to 10000 mg/kg silicon, preferably 1000 to 2000 mg/kg silicon, more preferably 1500 mg/kg silicon.
  • the plastic material is manufactured by hot melt extrusion.
  • Hot melt extrusion is considered to relate to an extrusion process for plastic materials at temperatures preferably between 80 and 250 deg C as known to a skilled person in the art.
  • plastics extrusion is a considered a high volume manufacturing process in which raw plastic material is melted and formed into a continuous profile.
  • raw thermoplastic compound material is typically applied as granulate or beads and is gravity fed from a top mounted hopper into the barrel of the extruder. Additives in either liquid or pellet form may be mixed into the resin prior to arriving at the hopper, or at specific points downstream of the initial feeder. Multiple inlets are possible.
  • a screw extruder is preferably applied.
  • the material enters preferably through a feeder and comes into contact with the screw.
  • the rotating screw forces the plastic beads forward into the barrel which is heated to the desired melt temperature of the molten plastic.
  • a heating profile is set for the barrel in which two or more independent heater zones gradually increase the temperature of the barrel from the rear (where the plastic enters) to the front. This allows the plastic to melt gradually as it is pushed through the barrel and lowers the risk of overheating which may cause degradation in the polymer.
  • the plastic material may be processed post-extrusion, or inline during the extrusion process, to produce a foam, particles, granules, film, fibres, strands, sheets and/or foils.
  • Fig. 7 is provided to demonstrate the processing of the intermediate product P3 in AP4 to produce the processed end product.
  • the plastic material is elastic with a rupture resistance of more than 100%, more than 200 %, preferably of more than 300%, more than 400 %, more than 500%, more preferably of more than 600 % and most preferably of more than 700 %.
  • the ability to resist breaking under tensile stress is one of the most important and widely measured properties of materials used in structural applications.
  • the force per unit area (MPa or psi) required to break a material in such a manner is the ultimate tensile strength or tensile strength at break.
  • ASTM D638 may also be used for determining either elasticity or rupture resistance. For this test, plastic samples are either machined from stock shapes or injection molded.
  • the tensile testing machine pulls the sample from both ends and measures the force required to pull the specimen apart and how much the sample stretches before breaking.
  • the analogous test to measure tensile properties in the ISO system is ISO 527.
  • the ultimate elongation of an engineering material is the percentage increase in length that occurs before it breaks under tension. Rigid plastics, especially fibre reinforced ones, often exhibit values under 5%. The combination of high ultimate tensile strength and high elongation leads to materials of high toughness.
  • the plastic material has a density of 100 to 10000 kg/m 3 , preferably 250 to 7500 kg/m 3 , more preferably 500 to 5000 kg/m 3 and most preferably 1000 to 1200 kg/m 3 .
  • DIN 53479 testing of Plastics and Elastomers; Determination of Density.
  • the plastic material is resistant against temperature of -100°C to +750°C, preferably to temperature of -75°C to +500°C, more preferably to temperature of -60°C to +250°C and most preferably to temperature of -40°C to +100°C.
  • the plastic material is resistant against chemical agents comprising solvents, softener, mineral oils, alkalis, acids and/or fuels.
  • the mixing of the different polymers is a possibility either to combine characteristic properties of the initial components into one blend and to optimize, or to develop entirely new properties through the formation of new supermolecular structures in the differentiated mixture. It was surprising that highly specialized plastic material of this invention with dedicated properties can be obtained and be custom made by targeted processing.
  • the plastic material in particular comprises binary partly-crystalline polymer blends.
  • the central problem in estimating the crystallization processes in such blends is their strong dependence on the different experimental parameters.
  • the structure formation is above all governed by the competition between kinetics and equilibrium thermodynamics. Experiments are conducted regarding the formation of a bi-crystalline polymer structure, in equilibrium thermodynamics the eutecticum. Because of its finely cross-linked crystalline structure, the plastic material has completely new mechanical properties.
  • a further advantage of the present invention in particular is the simplicity in processing and completeness in mixing. This becomes obvious with examinations of mixtures that decrease the mixed-glass temperature and of polymer crystallization.
  • Polymers like PCL and PC with the aid of an extruder, and certain additives provide unexpected results and material with improved properties.
  • the addition of PCL and/or PC which is an amorphous polymer and hence has no inclination whatever for crystallization, makes crystallization out of the melt possible. For example a crystallization tendency of 30% in the PC portion can be reached.
  • the polymer blend PCL/PC is a system in which the mixing partners separately crystallize depending on experimental conditions and composition, and in which they are embedded in an amorphous mixing matrix. As the examination shows, new areas of application can be developed through the plastic material of this invention. A mixture with suitable polymeric mixing partners is possible in order to achieve the simultaneous crystallization of both phases.
  • the plastic material comprises preferably a composition which is suitable to achieve a compound system with less isocyanates or which is free of isocyanates and a dedicated additive amount for obtaining the desired properties like elasticity, stability, resistance.
  • the plastic material can contain products from a multifunctional orthosilicate and/or tetraethyl orthosilicate and/or an alkyl polymer. This not only results in a financial advantage but also in an advantage in quality.
  • a silicate could be added to the composition, e.g. tetraethyl-orthosilicate in order to complete the hardening properties.
  • the silicate can be added under constant shear in the composition.
  • the silicate weight lies for example between 1.0 and 20 wt.% relative to the total weight of the composition.
  • the plastic material of the present invention relates to a plastic substance or polymer comprising of a cross-linked and/or adhesive mixture of thermoplastic polyurethane (TPU) and nanoclays.
  • TPU thermoplastic polyurethane
  • the product comprises a combination of TPU, nanoclays, polyol, polycarbonate (PC), polycaprolactone component (PCL) and an additive, determined according to the specific properties desired.
  • the plastic material produced through the method of the present invention exhibits a novel chemical structure, produced by the unique combination of components and processing steps as described herein.
  • the resulting chemical structure is preferably a combination of polymerisation and/or adhesion, whereby the nanoclay component acts as catalyst of a chemical reaction, leading to polymerisation and/or re-polymerisation of the reaction components, or as an adhesive component, providing strong adhesion between the components resulting in long-lasting and stable essentially isocyanate free plastic materials or plastic materials with low amount of isocyanates.
  • the polymerisation comprises additionally or exclusively of polyaddition reactions.
  • the synthetic material described herein may be described either as a polymer, a synthetic material, a plastic or a modified polyurethane, without intending to describe separate products.
  • the materials produced via the method of the invention show a novel structure that may be a combination of polymerisation and/or adhesion.
  • thermoplastic polyurethane in a preferred embodiment for example thermoplastic polyurethane (TPU), is a polymer composed of a chain of organic units joined by carbamate (urethane) links.
  • TPU is defined as any thermoplastic polyurethane.
  • the present invention may be carried out with any TPU.
  • TPU may be used in a milled or grinded grade. The following TPUs are preferred: Pearlcoat 162K, Pearlthane 16N80, Pearlthane Clear 15N80, Desmopan 385 S, Elastollan 1 185 A.
  • Pearlcoat 162K comprises a polyether based TPU, supplied in form of translucent, colourless pellets, combining hardness with excellent low temperature flexibility and very good hydrolysis resistance. Typical properties are listed in the following table:
  • Pearlcoat 162K is preferably used in melt coatings on textile substrates, for preferably end-uses in industrial coatings (for life-jackets, etc.) obtained by extrusion and calendering. Pearlcoat 162K is preferably used for obtaining extruded films and fabric coatings.
  • the preferred working instructions can be described as follows and the characteristics of the extruder that are suitable for processing Pearlcoat 162K are the following:
  • the extruder screw preferably has 3 or more zones and a compression
  • the extruder screw should preferably have a continuous regulation device and a working power higher than for processing other plastics.
  • the speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
  • the filters used should preferably be disks with holes of 1 .5 to 5 mm.
  • Pearlthane 16N80 comprises a polyether based TPU, preferably supplied in form of translucent, colourless pellets, combining hardness with excellent mechanical properties and an outstanding hydrolysis, microbial resistance. It can preferably be extruded and injection-moulded. Pearlthane 16N80 can preferably be used for blown- and cast films, cables, tubing and profiles. When processed by injection moulding, it can be used for making technical parts. Typical properties are listed in the following table:
  • Preferred working instructions are the following and for optimum results, previous drying of the product during 1 -2 hours at 100-1 10 °C is advisable, in a hot air circulatory, vacuum or desiccant- air dryer.
  • characteristics and the extruder that is suitable for processing Pearlthane 16N80 are the following:
  • the extruder screw preferably has 3 or more zones and a compression ratio in between 2:1 and 3:1 (usually, the screws that are used for Polyethylene extrusion give good results).
  • the extruder screw should preferably have a continuous regulation device and a working power higher than for processing other plastics.
  • the speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
  • the filters used should preferably be disks with holes of 1 .5 to 5 mm. (depending on the screw and the screen packs (the no. of meshes /cm 2 will depend on the end product that is processed), so as to create a pressure built-up.
  • the preferred parameter are the following: The obtained data are based on plaques produced in an injection moulding equipment with the following
  • Pearlthane Clear 15N80 comprises a polyether copolymer-based TPU, preferably supplied in form of translucent, colourless, combining low hardness with excellent mechanical properties and excellent hydrolysis resistance.
  • Pearlthane Clear 15N80 can preferably be extruded and injection-moulded.
  • Pearlthane Clear 15N80 is preferably used for making films, cables, tubing, profiles and different technical parts. To improve the microbiological protection of Pearlthane Clear 15N80, it could be necessary to add a biocide, preferably in form of TPU-based masterbatch. Typical properties are listed in the following table:
  • Preferred working instructions are the following and for optimum results, previous drying of the product during 1-2 hours at 210 - 230° F is advisable, in a hot air circulatory, vacuum or desiccant- air dryer.
  • characteristics and the extruder that is suitable for processing Pearlthane Clear 15N80 are the following:
  • the extruder screw preferably has 3 or more zones and a compression ratio between
  • the extruder screw should preferably have a continuous regulation device and a
  • the speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
  • the filters used should preferably be disks with holes of 1/16 to 3/16 in (depending on the screw and the die), and screen packs (the no. of meshes /in 2 will depend on the end product which is processed), so as to create a pressure built-up.
  • Desmopan 385 S comprises aromatic thermoplastic polyurethanes and/or polyurethane elastomers, preferably with less than 1 % 2,2',6,6'-Tetraisopropyldiphenyl Carbodiimide (CAS-No. 2162-74-5).
  • the preferred storage temperature maximum is 30 °C.
  • the material is hygroscopic and may absorb small amounts of atmospheric moisture. According to the present invention a polymer comprising Desmopan 385 S preferably shows the following physical and chemical properties:
  • Decomposition temperature Decomposition begins at 230 °C.
  • the injection molding grade preferably shows high mechanical strength and improved hydrolysis resistance.
  • the following table comprises preferred properties of the polymer to be used and/or obtained from the method of the present invention.
  • Elastollan 1 185 A comprises a thermoplastic polyether-polyurethane with outstanding hydrolysis resistance, low temperature flexibility and high resistance to microorganisms.
  • the polymer is processable preferably by injection moulding, extrusion and blow moulding.
  • a polymer comprising Elastollan 1 185 A preferably shows the following characteristics:
  • Test plaques are preferably manufactured by injection moulding from pre-dried granules and water content of less than 0.02%. Test plaques are preferably aged 20 hrs at 100°C. Specimens are cut from test plaques. Test conditions are 23°C ⁇ 2°C and 50% ⁇ 6% rel. humidity. Polymers comprising Elastollan are hygroscopic, therefore storage in dry conditions and original container is recommended. In a preferred form the polymer product comprises lentil shaped pellets. In a preferred embodiment the Elastollan polymer is processable at least for 6 months from delivery date in original sealed containers with cool dry storage.
  • Nanoclays are nanoparticles of layered mineral silicates. Depending on chemical composition and nanoparticle morphology, nanoclays are organized into several classes such as
  • Nanoclays are an attractive class of hybrid organic-inorganic nanomaterials with potential uses in polymer nanocomposites, as rheological modifiers, gas absorbents and drug delivery carriers. Nanoclays can come in the form of nanoplatelets.
  • the silicate platelets that the additives are derived from are about 1 nanometer thick and 70 - 150 nanometers across.
  • the platelets are surface modified with an organic chemistry to allow complete dispersion into and provide miscibility with the thermoplastic systems for which they were designed to improve.
  • the additives can reinforce thermoplastics by enhancing flexural and tensile modulus.
  • Nanoparticles preferably in the form of masterbatches, or so called nano masterbatches, influence the adhesion and/or crosslinking of the components during production, preferably polymerization, melting and/or extrusion. Furthermore it is preferred, that nano masterbatches influence the viscosity in the melt and surface properties of the hardened polymer.
  • a preferred nanoclay is Perkalite F100, or derivatives of and/or mixtures including Perkalite F100, which is an aluminum magnesium layered double hydroxide (LDH) modified with hydrogenated fatty acid.
  • LDH aluminum magnesium layered double hydroxide
  • composition on ingredients for Perkalite F100 is as follows:
  • Perkalite F100 Preferably the physical and chemical properties for Perkalite F100 are as follows:
  • Flash point not applicable. Product may contain flammable volatiles.
  • Flammability combustible material.
  • Nanoclays comprising nanocomposites are for example Cloisite products. These products are in particular super-charged nanoparticles. Nanoclays comprising Cloisite are in particular providing benefits to plastic material at very low loadings. Benefits can be summarized as follows: • flame retardant
  • Nanoclay comprising montmorillonite can be employed in the preparation of polymer-clay nanocomposites.
  • Typical performance advantages, of montmorillonite compared to traditional reinforcing agents for plastics are as follows: Montmorillonite will develop similar increase in modulus and tensile strength at 3-5% loading compared to 20-60% loading of conventional reinforcing agents such as kaolin, silica, talc, and carbon black. Implicit advantages include lighter plastic parts with greater transparency. With montmorillonite, the plastic will have increased barrier properties to moisture, solvents, chemical vapors, gases such as 02 and flavors. Particle shape is known to affect plastic barrier properties.
  • Montmorillonite is a nanoparticle with an anisotropic, plate-like, high aspect-ratio morphology. It is this morphology that leads to the improved permeation barrier through a tortuous path mechanism. With montmorillonite, the plastic will have increased dimensional stability at low reinforcement loading. Dramatic decreases in CLTE values are the result. The plastic has a higher heat distortion temperature. Only a few percent loading of montmorillonite increases the temperature at which the plastic begins to soften. This property is important, for example, in under-the-hood automotive applications. The thermoplastic polymer will be more recyclable. Montmorillonite performance actually improves upon recycling. Fiberglass products typically cannot be recycled for the same application, since the fibers are damaged during the recycling process. The plastic will dye easier.
  • Nanocomposites offer a synergistic flame-retardant approach.
  • the improved flame retardancy as measured by Cone Calorimetry shows a decrease in the Peak Heat Release Rate. Observed are a decrease in smoke and an increase in char formation.
  • Combination with traditional flame retardants can enable passage of specified flame tests.
  • the appearance of painted parts is improved compared to conventional reinforced parts.
  • the nanocomposite particles are much smaller than traditional reinforcing agents so the plastic surface is much smoother. There is reduced static cling in films containing nanocomposites.
  • Nanoclay comprises Montmorillonite.
  • Montmorillonite is a very soft phyllosilicate group of minerals that typically form in microscopic crystals, forming a clay.
  • Montmorillonite a member of the smectite family, is a 2:1 clay, meaning that it has 2 tetrahedral sheets sandwiching a central octahedral sheet. The particles are plate-shaped with an average diameter of approximately one micrometre. Members of this group include saponite.
  • Montmorillonite is the main constituent of the volcanic ash weathering product, bentonite. The water content of montmorillonite is variable and it increases greatly in volume when it absorbs water. Chemically it is hydrated sodium calcium aluminium magnesium silicate hydroxide (Na,Ca)o.33(AI,Mg)2(Si 4 0 o)(OH)2 nH 2 0.
  • Bentonite is an absorbent aluminium phyllosilicate, essentially impure clay consisting mostly of montmorillonite.
  • bentonite There are different types of bentonite, each named after the respective dominant element, such as potassium (K), sodium (Na), calcium (Ca), and aluminium (Al).
  • Bentonite is formed from weathering of volcanic ash, most often in the presence of water.
  • bentonite as well as a similar clay called tonstein, has been used to describe clay beds of uncertain origin.
  • K-bentonites In stratigraphy and tephrochronology, completely devitrified (weathered volcanic glass) ash-fall beds are commonly referred to as K-bentonites when the dominant clay species is illite.
  • Other common clay species, and sometimes dominant, are montmorillonite and kaolinite. Kaolinite-dominated clays are commonly referred to as tonsteins and are typically associated with coal.
  • nanoclay comprises different types of bentonite, for example sodium bentonite, calcium bentonite, potassium bentonite.
  • Sodium bentonite expands when wet, absorbing as much as several times its dry mass in water.
  • the property of swelling also makes sodium bentonite useful as a sealant, since it provides a self-sealing, low permeability barrier. It is used to line the base of landfills to prevent migration of leachate, for quarantining metal pollutants of groundwater, and for the sealing of subsurface disposal systems for spent nuclear fuel. Similar uses include making slurry walls, waterproofing of below-grade walls, and forming other impermeable barriers, e.g., to seal off the annulus of a water well, to plug old wells.
  • Sodium bentonite can also be "sandwiched" between synthetic materials to create geo-synthetic clay liners (GCL) for the aforementioned purposes. This technique allows for more convenient transport and installation, and it greatly reduces the volume of sodium bentonite required.
  • GCL geo-synthetic clay liners
  • Calcium bentonite acts preferably as adsorbent of ions in solution, as well as fats and oils, being a main active ingredient of fuller's earth, probably one of the earliest industrial cleaning agents.
  • Calcium bentonite may be converted to sodium bentonite (termed sodium beneficiation or sodium activation) to exhibit many of sodium bentonite's properties by a process known as "ion exchange". This means adding for example 5-10% of a soluble sodium salt such as sodium carbonate to wet bentonite, mixing well, and allowing time for the ion exchange to take place and water to remove the exchanged calcium.
  • Some properties, such as viscosity and fluid loss of suspensions, of sodium-beneficiated calcium bentonite (or sodium-activated bentonite) may not be fully equivalent to those of natural sodium bentonite. For example, residual calcium
  • Potassium bentonite also known as potash bentonite or K-bentonite
  • potassium bentonite is a potassium-rich illitic clay formed from alteration of volcanic ash.
  • Masterbaches comprise of a solid product of a plastic, rubber, polyol, elastomer and/or polymer in which pigments, additives, clays, nanoclays, silicates, composites and/or nanocomposites are optimally dispersed at high concentration in a carrier material.
  • the carrier material is compatible with the main plastic, rubber, polyol, elastomer and/or polymer in which it will be blended during molding, whereby the final plastic, rubber, polyol, elastomer and/or polymer obtains the color and/or properties from the masterbatch.
  • masterbatches preferably comprise clays, silicates and/or nanoclays and are preferably used according to the invention for the
  • masterbatches are preferably used for enhancing the monomers, oligomers, polymers and/or pre-polymers properties. These enhanced properties comprise in particular strength, hardness, elongation break, viscosity, handling, manufacturability, stability and/or processability. Additives and/or non-isocyanate polymerizing agents in
  • masterbatches comprise according to the present invention monomers, oligomers, polymers and/or pre-polymers. In a preferred embodiment masterbatches are used as non-isocyanate polymerizing agent. In a preferred embodiment a masterbatch is dispersed via extrusion in a polymer matrix. Masterbatches are preferably comprising a solid content of up to 50%, more preferably of up to 90% and most preferably of up to 99%.
  • a polyol is an alcohol containing multiple hydroxyl groups.
  • Polyol is defined as any polyol.
  • the present invention may be carried out with any polyol.
  • the following polyol components are preferred: Lupraphen 81 13, Lupraphen 8109, Lupraphen 8108, Lupraphen 8107, Lupraphen 8106, Lupraphen 8104, Lupraphen 8103, Lupraphen 8101 , Lupraphen 8008, Lupraphen 8007, Lupraphen 8004, Lupranol BALANCE 50, Lupranol VP 9390, Lupranol 4674-15, Lupraphen VP 9267.
  • the polyol comprises a di- or multifunctional, aliphatic, polyester polyol, such as Lupraphen.
  • Lupraphen 81 13 is preferably used for the production of polyurethane elastomers. Typical properties are listed in the following table:
  • Lupraphen 81 13 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 81 13 or its product groups are listed in the BgVV (Germany) as Codes of Practice No. XXVIII dated June 1 , 1981 , and XXXIX dated June 1 , 1998.
  • Lupraphen 81 13 The components of Lupraphen 81 13 or its product groups or the polyurethanes made from Lupraphen 81 13 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 81 13 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
  • Lupraphen 8109 comprises a partially-branched, aliphatic polyester polyol. Lupraphen 8109 is preferably used for the production of polyurethane flexible integral skin foams, elastomers and shoe sole systems. Typical properties are listed in the following table:
  • Lupraphen 8109 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive
  • Lupraphen 8109 has not to be marked according to the EC directive 67/548 and its guidelines.
  • Lupraphen 8108 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8108 is preferably used for the production of polyurethane flexible integral skin foams, elastomers and textile coatings. Typical properties are listed in the following table:
  • Lupraphen 8108 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 8108 or its product groups or the polyurethanes made from Lupraphen 8108 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8108 has not to be marked according to the EC directive 67/548 and its guidelines.
  • Lupraphen 8107 comprises a partially-branched, aliphatic, polyester polyol. Lupraphen 8107 is preferably used for the production of polyurethane slab stock foam. Typical properties are listed in the following table:
  • Lupraphen 8107 is a polymer or no-longer-polymer, made from monomers and additives, which are listed in the directive 90/128/EG (Europe) and its amendments (latest: 2004/19/EG), in annexe II, paragraph A or B or annex III, paragraph A or B.
  • the components of Lupraphen 8107 or its product groups or the polyurethanes made from Lupraphen 8107 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8107 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
  • Lupraphen 8106 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8106 is preferably used for the production of polyurethane elastomers. Typical properties are listed in the following table:
  • Lupraphen 8106 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 8106 or its product groups or the polyurethanes made from Lupraphen 8106 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8106 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
  • Lupraphen 8104 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8104 is preferably used for the production of compact and cellular polyurethane elastomers. Typical properties are listed in the following table:
  • Lupraphen 8104 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 8104 or its product groups or the polyurethanes made from Lupraphen 8104 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8104 has not to be marked according to the EC directive 67/548 and its guidelines.
  • Lupraphen 8103 comprises a difunctional, aliphatic polyester polyol.
  • Lupraphen 8103 is preferably used for the production of compact and cellular polyurethane elastomers. It is particularly suitable for the production of shoe sole systems. Typical properties are listed in the following table:
  • Lupraphen 8103 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 8103 or its product groups or the polyurethanes made from Lupraphen 8103 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8103 has not to be marked according to the EC directive 67/548 and its guidelines.
  • Lupraphen 8101 comprises a difunctional, aliphatic, polyester polyol. Lupraphen 8101 is preferably used to improve the fire retardancy of rigid foams, especially of PI R formulations. Typical properties are listed in the following table:
  • Lupraphen 8101 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • the components of Lupraphen 8101 or its product groups or the polyurethanes made from Lupraphen 8101 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8101 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
  • Lupraphen 8008 comprises a difunctional polyester polyol. It is based on aromatic dicarboxylic acids. Lupraphen 8008 is preferably used to improve the fire performance of rigid foams. It has been developed for the production of block foams and for the manufacture of rigid foam panels with flexible facings. It is especially recommended for the manufacture of PIR foams. Typical properties are listed in the following table:
  • Lupraphen 8008 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annexe II, paragraph A or B.
  • the components of Lupraphen 8008 or its product groups or the polyurethanes made from Lupraphen 8008 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8008 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
  • Lupraphen 8007 comprises a difunctional polyester polyol based on aromatic dicarbonic acids. Lupraphen 8007 is preferably used to improve the fire retardancy of rigid foams, especially of PIR formulations. Typical properties are listed in the following table:
  • Lupraphen 8007 is a polymer or no-longer-polymer, made from monomers and additives, which are listed in the directive 90/128/EG (Europe) and its amendments (latest: 2004/19/EG), in annex II, paragraph A or B or annex III, paragraph A or B.
  • the components of Lupraphen 8007 or its product groups or the polyurethanes made from Lupraphen 8007 are listed in the 21 CFR, part 175 105 (edition of April 1, 1998) of FDA (USA).
  • Lupraphen 8007 has not to be marked according to the EC directive 67/548 and its guidelines.
  • Lupraphen 8004 comprises a branched, aromatic-aliphatic polyester polyol. Lupraphen 8004 is preferably used for the production of polyurethane rigid foam systems. Typical properties are listed in the following table:
  • Lupraphen 8004 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B.
  • Lupraphen 8004 are listed in the 21st CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8004 has not to be marked according to the EC directive 67/548 and its guidelines.
  • PC Polycarbonate
  • PCL Polycaprolactone
  • PCL Polycaprolactone
  • PCL Polycaprolactone
  • the most common use of polycaprolactone is in the manufacture of speciality polyurethanes.
  • Polycaprolactones impart good water, oil, solvent and chlorine resistance to synthetic materials.
  • Preferred PCL components are: Perstorp Capa 6400, Perstorp Capa 6500, Perstorp Capa 6800.
  • the plastic material according to the present invention comprises additives.
  • additives are in particular organic or inorganic compounds. These additives are added, blended, mixed, processed, manufactured and/or compounded preferably together with educts, intermediates or end-products of the plastic material according to the present invention.
  • Fillers are in particular organic or inorganic compounds. These additives are added, blended, mixed, processed, manufactured and/or compounded preferably together with educts, intermediates or end-products of the plastic material according to the present invention.
  • Fillers improve performance and/or reduce production costs. Stabilizing additives and/or fire retardants for example lower the flammability of the material.
  • the plastic material contains for example fillers which are relatively inert and inexpensive materials that make the product cheaper by weight. Typically fillers are mineral in origin, e.g., chalk. Some fillers are more chemically active and are called reinforcing agents.
  • organic polymers are too rigid for particular applications, they are blended with plasticizers, such as oily compounds, that confer improved rheology.
  • additives comprise plasticizer.
  • Plasticizers are in particular substances, mainly esters, which are added to a polymer in order to improve its flexibility and/or extendability.
  • the addition of a plasticizer lowers melt viscosity, glass transition temperature and modulus of elasticity.
  • Plasticizers allow the manufacture of a broad spectrum of different materials. At the same time, they create the conditions required for the application of a large number of mild and energy-saving processing methods.
  • Plasticizers for plastics are to be understood as additives, and may relate to phthalate esters in PVC applications.
  • Plasticizers typically work by embedding themselves between the chains of polymers, spacing them apart (increasing the "free volume"), and thus significantly lowering the glass transition temperature for the plastic and making it softer.
  • the more plasticizer added the lower its cold flex temperature will be. This means that it will be more flexible and its durability will increase as a result of it.
  • Plasticizers make it possible to achieve improved compound processing characteristics, while also providing flexibility in the end-use product. Ester plasticizers are selected based upon cost- performance evaluation. The rubber compounder must evaluate ester plasticizers for
  • ester chemistries that are in production include sebacates, adipates, terephthalates, dibenzoates, gluterates, phthalates, azelates, and other specialty blends.
  • This broad product line provides an array of performance benefits required for the many elastomer applications such as tubing and hose products, flooring, wall-coverings, seals and gaskets, belts, wire and cable, and print rolls.
  • Plasticizer-elastomer interaction is governed by many factors such as solubility parameter, molecular weight and chemical structure.
  • Colorants are common additives, although their weight contribution is small. Additives may also include chain extenders, cross linkers, surfactants, flame retardants, blowing agents, pigments, and fillers.
  • the plastic material according to the present invention for example can be made in a variety of densities, viscosity, resistance, chemical stability, biological stability, physical stability, elasticity and/or hardnesses by varying the polyol, the polycarbonate, the polycaprolactone, the nanoclay and/or the additives.
  • Phosphor components Phosphor components:
  • Phosphor components can preferably act as additives, performing preferably as stabilizers, dispersion agents and/or elasticity modulators.
  • the phosphor components in particular the phosphite components described herein, provide advantageous effects with respect to enhancing the dispersion of nanoclay particles in the plastic material.
  • Dispersion is a description of a system or effect in which particles are dispersed in a continuous phase of a different composition.
  • the phosphor component enables enhanced dispersion of the nanoclay in the plastic material during manufacture, thereby resulting in improved homogenous distribution of the nanoclay. Improved dispersion and subsequently improved distribution of the nanoclay thereby assists in providing increased stability of the plastic material produced.
  • Increased stability of the plastic relates preferably to enhanced stability under various potential stresses.
  • the various molecules are distributed in a particular form and in particular relative amounts. Homogenous distribution of the various components enables greater stress resistance, which can be termed as greater stability.
  • Enhanced stability of a plastic material relates to enhanced tolerance of the individual molecules of the plastic to change, caused by structural, chemical or other forms of stress, before structural damage occurs.
  • Enhanced stability in one embodiment, relates to a reduced likelihood of, or greater resistance under mechanical stress to, the formation of e. g. stress whitening or crease whitening of the material.
  • the stability may also relate to an enhanced resistance to change in colour or formation of a turbid appearance.
  • Increased stability also relates to reduces in the frequency of
  • the phosphor components of the present invention provide an appropriate means for enhancing the stability of a plastic material.
  • the Charpy impact test may also be applied for ascertaining the stability of a plastic material. Also known as the Charpy V-notch test, the Charpy test is a standardized high strain-rate test which determines the amount of energy absorbed by a material during fracture. This absorbed energy is a measure of a given material's notch toughness and acts as a tool to study
  • the phosphor components as described herein also enable greater elasticity of the plastic materials described herein.
  • the elasticity of a material can be determined by various methods as described herein, such as ASTM D638, which may be used for determining either elasticity or rupture resistance.
  • ASTM D638 which may be used for determining either elasticity or rupture resistance.
  • plastic samples are either machined from stock shapes or injection moulded.
  • the tensile testing machine pulls the sample from both ends and measures the force required to pull the specimen apart and how much the sample stretches before breaking. Via this approach either elasticity or plasticity may be assessed, whereby the deformed plastic after stress application may wither revert to its original shape or maintain an elongated shape (in the case of stretching).
  • the materials as described herein show both enhanced elasticity and plasticity in comparison to materials without additives.
  • the final elastic and plastic properties of the materials will depend on the precise components used in the manufacturing process.
  • Phosphor components according to the present invention comprise for example phosphites.
  • phosphites are salts of phosphorous acid, H 3 PO 3 and following the lUPAC naming recommendations the phosphite ion would be P0 3 3 ⁇ a salt of P(OH) 3 .
  • Phosphite also comprises salts containing HP0 3 2 ⁇ .
  • Phosphor component comprises also the diprotic HP(0)(OH) 2 with for example the name phosphonic acid and suitable salts thereof. Substances comprising the formula HP0 3 2 ⁇ as ion substance with in particular the naming phosphonate also fall under the definition of phosphor component.
  • the term phosphor component also comprises phosphite ester, an organophosphorus compound with the formula P(OR) 3 .
  • Phosphor component according to the present invention comprises for example phosphates.
  • a phosphate is in particular an inorganic chemical, is a salt of phosphoric acid.
  • a phosphate, or organophosphate is an ester of phosphoric acid.
  • Inorganic phosphates are in particular mined to obtain phosphorus for use in agriculture and industry. At elevated
  • phosphates can condense to form pyrophosphates.
  • the chemical properties of phosphates relate in particular to its functional group. Phosphates derive in particular from phosphoric acid and the functional group of phosphates can be found in weakly acidic aqueous solution. In more basic aqueous solutions, the group donates the two hydrogen atoms and ionizes as a phosphate group with a negative charge of 2.
  • the phosphate ion is a polyatomic ion with the empirical formula P0 4 3" and a molar mass of 94.97 g/mol. It consists of one central phosphorus atom surrounded by four oxygen atoms in a tetrahedral arrangement.
  • the phosphate ion carries a negative three formal charge and is the conjugate base of the hydrogen phosphate ion, HP0 4 2" , which is the conjugate base of H 2 P0 4 " , the dihydrogen phosphate ion, which in turn is the conjugate base of H 3 P0 4 , phosphoric acid.
  • a phosphate salt forms when a positively charged ion attaches to the negatively charged oxygen atoms of the ion, forming an ionic compound.
  • Many phosphates are not soluble in water at standard temperature and pressure.
  • the sodium, potassium, rubidium, caesium and ammonium phosphates are all water soluble. Most other phosphates are only slightly soluble or are insoluble in water.
  • the hydrogen and dihydrogen phosphates are slightly more soluble than the corresponding phosphates.
  • the pyrophosphates are mostly water soluble.
  • Aqueous phosphate exists in four forms. In strongly basic conditions, the phosphate ion (P0 4 3" ) predominates, whereas in weakly basic conditions, the hydrogen phosphate ion (HP0 4 2" ) is prevalent. In weakly acid conditions, the dihydrogen phosphate ion (H 2 P0 4 " ) is most common. In strongly acidic conditions, trihydrogen phosphate (H 3 P0 4 ) is the main form.
  • phosphor component according to the present invention in particular comprises
  • Phosphate - OP(OR) 3 such as triphenyl phosphate
  • the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is a phosphor component, such as salts that derive from phosphor with organic or inorganic acids, phosphites and/or phosphates, for example trisnonylphenyl phosphite, bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4- di-t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
  • a phosphor component such as salts that derive from phosphor with organic or inorganic acids, phosphites and/or phosphates, for example trisnonylphenyl phosphite, bis (2,6-di-t-butylphenyl-4-methylpentaery
  • Phosphor components as stabilizers and/or elasticity modulators may also be selected from: Doverphos 4 (TNPP): Trisnonylphenol phosphite
  • TNPP Doverphos HiPure 4
  • TPP Triphenyl phosphite
  • DPP Diphenyl phosphite
  • Doverphos 7 Phenyl diisodecyl phosphite
  • DPDP Diphenyl isodecyl phosphite
  • DPIOP Diphenyl isooctyl phosphite
  • Doverphos 1 1 Tetraphenyl dipropyleneglycol diphosphite
  • Doverphos 12 Poly(dipropyleneglycol) phenyl phosphite
  • Doverphos 613 Alkyl (C12-C15 ) bisphenol A phosphite
  • Doverphos 675 Alkyl (C10) bisphenol A phosphite
  • TDP Triisodecyl phosphite
  • TTDP Tris (tridecyl) phosphite
  • TLP Trilauryl phosphite
  • Doverphos 72 Tris (dipropylene glycol) phosphite
  • Doverphos 253 Dioleyl hydrogen phosphite
  • Doverphos S-9228 Bis (2,4-dicumylphenyl) pentaerythritol diphosphite
  • Doverphos S-9228T Bis (2,4-dicumylphenyl) pentaerythritol diphosphite
  • Doverphos S-680 Distearyl pentaerythritol diphosphite
  • Doverphos S-682 Distearyl pentaerythritol diphosphite w/ ⁇ 1 % TIPA
  • the additives comprise stabilizers that are alternative to or in addition to the phosphor components mentioned herein.
  • the stabilizer in particular offer superior thermal stability and low volatility under extended high temperature conditions, excellent atmospheric stability and in-polymer hydrolytic stability, outstanding processing protection against
  • the stabilizer are suitable to enhance or stabilize the manufacturing process in order to achieve constant and reproducible product qualities with dedicated properties or the plastic material for the present invention.
  • Stabilizer can be of high or low molecular weight, they show preferably low volatility.
  • Stabilizer also comprises foam stabilizer.
  • TEGOSTAB B 1048 TEGOSTAB B 41 13, TEGOSTAB B 4690, TEGOSTAB B4900, TEGOSTAB B 8002, TEGOSTAB B 8040, TEGOSTAB B 8040 LV,
  • TEGOSTAB B 8234 TEGOSTAB B 8239, TEGOSTAB B 8242, TEGOSTAB B 8244,
  • TEGOSTAB B 8285 TEGOSTAB B 8300, TEGOSTAB B 8301 , TEGOSTAB B 8301 CL,
  • TEGOSTAB B 8444 TEGOSTAB B 8450, TEGOSTAB B 84503, TEGOSTAB B 8460,
  • TEGOSTAB B 8461 TEGOSTAB B 8462, TEGOSTAB B 8465, TEGOSTAB B 8466,
  • TEGOSTAB B 8492 TEGOSTAB B 8495, TEGOSTAB B 8496, TEGOSTAB B 8498,
  • TEGOSTAB B 8681 TEGOSTAB B 8707 LF2, TEGOSTAB B 8715 LF2, TEGOSTAB B 8716
  • TEGOSTAB B 8724 LF2 TEGOSTAB B 8724 LF2
  • TEGOSTAB B 8726 LF2 TEGOSTAB B 8727 LF2
  • TEGOSTAB B 8729 LF2 TEGOSTAB B 8732 LF2
  • TEGOSTAB B 8734 LF2 TEGOSTAB B 8736 LF2
  • a preferred additive of the present invention relates to polypropylene, preferably carboxylated polypropylene, more preferably a carboxylated polypropylene functionalised with maleic anhydride.
  • a substance may also be known as maleated polypropylene.
  • One example of such a compound is SCONA TPPP 21 12 FA, which is described as an adhesion promoter for polymer compounds and a dispersing agent for nano clays in polypropylene.
  • the carboxylated polypropylene as an adhesion promoter is used in granulate form.
  • a concentrate can be made from nano clay and the modifier is created by means of a twin-screw extruder with high shear forces first, which is then incorporated into the polymer.
  • the preferred method for testing plastic tensile strength and/or elasticity is ASTM D638.
  • This test method is designed to produce tensile property data for the control and specification of plastic materials.
  • Tensile properties may provide useful data for plastics engineering design purposes.
  • the "stiffness" or "rigidity” or “elasticity” of a plastic may be examined.
  • the exact stress- strain characteristics of plastic materials are highly dependent on such factors as rate of application of stress, temperature, previous history of specimen, etc.
  • stress-strain curves for plastics determined as described in this test method, almost always show a linear region at low stresses, and a straight line drawn tangent to this portion of the curve permits calculation of an elastic modulus of the usually defined type.
  • Such a constant is useful if its arbitrary nature and dependence on time, temperature, and similar factors are realized.
  • the ASTM D638 test method covers the determination of the tensile properties of unreinforced and reinforced plastics in the form of standard dumbbell-shaped test specimens when tested under defined conditions of pretreatment, temperature, humidity, and testing machine speed.
  • This test method can preferably be used for testing materials of any thickness up to 14 mm (0.55 in.).
  • method ASTM D882 is the preferred test method. Materials with a thickness greater than 14 mm (0.55 in.) should be reduced by machining.
  • This test method includes the option of determining Poisson's ratio at room temperature.
  • This test method and ISO 527-1 or -2 are technically equivalent.
  • This test method covers the determination of Poisson's ratio preferably obtained from strains resulting from uniaxial stress.
  • twin screw extrusion is used as method for mixing, compounding, or reacting polymeric materials in the present invention.
  • the flexibility of twin screw extrusion equipment allows this operation to be designed specifically for the formulation being processed.
  • the two screws may be co-rotating or counter-rotating, intermeshing or non-intermeshing.
  • the configurations of the screws themselves may be varied using forward conveying elements, reverse conveying elements, kneading blocks, and other designs in order to achieve particular mixing characteristics.
  • single screw configurations may be modified to enable different strengths or degrees of in homogenisation, for example by changing the structure of the screw in any given screw segment.
  • extrusion comprises a process to create objects of a fixed, cross-sectional profile.
  • the material is pushed or drawn through a die of the desired cross-section.
  • the two main advantages of this process over other manufacturing processes are its ability to create very complex cross- sections and work materials that are brittle, because the material only encounters compressive and shear stresses. It also forms finished parts with an excellent surface finish.
  • Extrusion may be continuous or semi-continuous. The process begins by heating the stock material (for hot or warm extrusion). Hot extrusion is a hot working process, which means it is done above the material's recrystallization temperature to keep the material from work hardening and to make it easier to push the material through the die.
  • calendering compression molding, injection molding, spread coating, milling, printing, dip coating, casting, spraying are preferred manufacturing techniques for production of the plastics material of the present invention.
  • Preferred extruders of the invention are:
  • the present method can also use recycled TPUs as starting materials of the present invention.
  • the method can be used for recycling polymers or recycled plastics (synonym use).
  • the mineral or organic nanocomposites the polymer contains between 0 to 99% of the virgin polymer and between 1 to 100% of a recycling polymer, which consists in the range of 0 to 100%.
  • the polymer melt contains less than 10% weight% as nanoclay before formation of the disclosed nanocomposite.
  • the polymer melt, polymerization before formation of the disclosed nanocomposite contains preferably less than 2%, more preferably less than 1 %, even more preferably less than 0.5% as a nanoclay.
  • the applicable nanoclays can be intercalated with organic molecules (e.g. ammonia ions) between the proximate layers.
  • organic molecules e.g. ammonia ions
  • the amount of the mixture, mixed with the recycling-polymer can vary. Clay loadings are in the range of approximately 0.01 to 40% weight%, preferably approximately 0.05 to 20%, more preferably 0.5 to 15% and most preferably 1 to 10% of the total composition. It is preferred that the clay contains less than 15% of the nanocomposite.
  • An additional aspect of the described process is the form stability (peeling) of the clays which are mechanically and chemically split.
  • the clays are finely dispersed and are in fact nanoclays.
  • the used nanocomposites refer to a mixture out of recycled polymer and a clay which is in minimum partly flaked off.
  • the nanocomposites can also be used as new material.
  • the type of mixture of the polymer melt and the clay can comprise compounding, extrusion, mixing or every other method for bringing polymer and resins together with in minimum partly individual platelets.
  • a recycling polymer is a polymer material which is implemented after a certain period of use.
  • the application can be intended for the casting formation of polymers and products or the application of a dedicated purpose.
  • post-industrial recycling polymers are these polymer-materials which derive from an industrial manufacturing process.
  • post-industrial recycling polymers do not get contaminated with other materials or polymers.
  • Recycled polymers can be used for new material, especially when use for superior physical properties. Furthermore, the described recycled polymer-nanocomposites show retention properties so that the physical properties remain without significant disadvantageous effect on the recycling via additional steps in comparison to polymers which are improved without nanoclays.
  • the synthetic materials comprising 47.784 % TPU, 12.0 % Polyol, 0.216 % Nanoclay, 28 % PC and 12 % PCL, in addition to the materials comprising 47.946 % TPU, 12.0 % Polyol, 0.054 % Nanoclay, 28 % PC and 12 % PCL are suitable for longer storage.
  • the substance shows surprisingly low tendency for degradation. In particular the handling process is enhanced.
  • the material resists temperature change processes with daily variation. Permanent temperature resistance.
  • part 7 - resistant and against flying sparks and heat radiation which is applicable for flat roof coatings.
  • the technical characteristics of the preferred embodiments of the synthetic material of the present invention may be determined by the following tests. A barrage of standard tests was carried out on the plastics of the present invention, as indicated herein, that have indicated desirable properties. The following tests are provided as examples of appropriate tests:
  • the modified thermoplastic polyurethanes (TPU) of the invention show the following properties: excellent material properties (vapour porosity, heat conductance, melting point), nano-absorber properties, flexible adaption for dedicated purpose, low material costs (100% lower than PTFE), processing with existing / available production lines without expensive new installations.
  • the plastic may be processed as a foil, which can be manufactured with environment friendly processes like blowing extrusion and it is possible to produce TPU foils in different types, for example 3, 4, 5, 6, 7, 8, 9; 12 my foils.
  • the foils are particularly resistant against microbes, fungus, UV radiation, yellowing, hydrolysis, enzymes, high humidity, chemicals, oils, fats, week acids, carbon acid, alkali, carbon oils, alcohols.
  • the compounds in the following examples are preferably processed via extrusion.
  • the compounds can also be manufactured via blowing, casting, grinding and/or spraying.
  • Extrusion is conducted with preferably a single or twin screw extruder.
  • the extruder is for example equipped with 1 to 15 temperature zones. Screw diameter may vary for example between 10 mm and 50 mm. The temperature range is in particular between 50 and 250°C.
  • As feeder main hopper and/or side feeder are used also liquid injection is a possible option.
  • the extruder comprises a degassing option. Screw speed is adjustable preferably between 0 and 1000 rpm.
  • the detailed configuration can be described as follows:
  • the extruder comprises 10 temperature zones, with increasing temperature, from 150 - 170 deg C, increasing to 180 - 200 deg C.
  • a screw speed of in particular 400 rpm is applied. As resulting pressure 8 bar was observed.
  • the extrusion efficacy was 20 %.
  • the strand pelletizer had a take-off speed of 30 m/min.
  • the output was in the range of 5 to 8 kg/h.
  • the substances reside in the extruder for 90 seconds.
  • a masterbatch is manufactured (P1 ).
  • this masterbatch generation 2 is manufactured in the following way:
  • thermoplastic polyurethane (TPU) and a nanoclay component Mixing of thermoplastic polyurethane (TPU) and a nanoclay component and thereby producing P1. It is preferred that P1 is produced in two steps, namely the mixture of thermoplastic polyurethane (TPU) and a nanoclay component, thereby producing P0 according to figure 7, followed by the mixture of thermoplastic polyurethane (TPU) and P0, thereby producing P1 .
  • This product P1 is called masterbatch generation 2. Further preferred is that variants of the masterbatch generation 2 according to the selected quality and quantity of nanoclay can be produced.
  • This P2 is in the next step mixed with a polycarbonate (PC) and polycaprolactone component (PCL), and optionally additional one or more additive, thereby producing P3 (according to figure 7).
  • PC polycarbonate
  • PCL polycaprolactone component
  • P3 optionally additional one or more additive
  • the P2 mixture may further contains in particular a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer.
  • a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer.
  • the additive was provided to AP3 during the PC and PCL mixture.
  • PC Polycarbonat
  • the mixture contains in particular a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer.
  • a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer.
  • Elasticity was assessed via ASTM D638. Assessment of various compositions as described herein was carried out and elongation with respect to rupture and elasticity were examined.
  • the Phosphor components in particular various phosphite components, such as trisnonylphenyl phosphite, were used in manufacture and the materials subsequently tested using ASTM D638. Unexpected benefits were seen regarding surprisingly enhanced elasticity after addition of the phosphor components.
  • the stability of the plastic material was assessed by empirical analysis of the frequency of polymer breaks post extrusion during application of the Charpy impact test.
  • the nanoclay component in combination with the other plastic components enables replacement of
  • the compound P3 comprising 5% additive relates to the embodiment described above, whereby a relatively smaller amount of nanoclay is provided during the AP1 process step, and 5% by weight additive is added at the AP3 step with a subsequent reduction in P2, PC and PCL.
  • the following composition(s) were obtained and tested as P3:
  • plastic material was produced with 5% additive (either the phosphor component or a combination of the phosphor component and carboxylated polypropylene), added at either AP2 or AP3 with either a reduction in the TPU, P1 or P2 quantity, or a reduction of all components at the respective mixture/extrusion step.
  • 5% additive either the phosphor component or a combination of the phosphor component and carboxylated polypropylene
  • compositions as follows may therefore be produced. These embodiments represent examples and do not limit the scope of the invention. Preliminary testing has revealed reliable manufacture for all compound mixtures and improved functional properties with respect to elasticity and stability of the products.
  • composition may be obtained: Component % by weight
  • the additive preferably a phosphor component and/or carboxylated polypropylene
  • the additive is added to either the AP2 or AP3 method steps at for example 5% to each of the respective mixtures with a proportionally equal reduction of all other components in the mixture, not just the TPU, P1 or P2 component as mentioned above.
  • Samples obtained from P1 and P3 were characterised via various analytical methods. Sample preparation related to mechanical separation of the target sample parts and preparation for the following investigation.
  • FT-IR Fourier-transformed IR spectroscopy
  • Two analyses are carried out before and after extraction of the granules.
  • GC-MS Gas chromatography-Mass spectrometry
  • the IR spectrum of the clear and colourless granules is shown in figure 1.
  • the spectrum was generated with the ATR technique (diamante crystal).
  • the spectrum shows that the plastic material, a polymer, is a polyurethane elastomer.
  • the granules were extracted either in chloroform or in methanol. During the extraction in methanol a strong swelling behaviour of the granules was observed.
  • the IR-spectrum of the chloroform extract in shown in figure 2. It has been compared with the IR spectrum of the starting product (granules). The spectra comparison shows that with chloroform parts of the polyurethane elastomer are becoming dissolved, probably due to the oligomeric components.
  • the isocyanate absorption (NCO) in the spectrum of the extract shows a residual monomer at extremely low quantity.
  • Peak (4) is the residual monomer 4, 4'-diphenylmethandiisocyanate with the following structural formula: A further isocyanate is indicated with peak (5). It is a residual 2,6-diisopropylphenylisocyanate with the following structural formula:
  • Plastic material P3 according to figure 7 with respect to the phosphor additive plastic
  • P1 and P3 reveal low isocyanate background contaminants, thereby enabling an environmentally friendly low-isocyanate product.
  • the phosphor and nanoclay components are present in the expected levels with respect to the original substance. Almost undetectable P is found in P1 , indicating that without addition of a dedicated phosphor component, no phosphor contaminant is present in the P1 mixture.
  • the elements present from the nanoclay components are also relatively reduced in quantity in P3, due to the additional components added during AP2 and AP3 (polyol, PC, PCL, additive).

Abstract

The invention relates to a plastic material comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.

Description

PLASTIC MATERIAL WITH IMPROVED PROPERTIES COMPRISING NANOCLAY
DESCRIPTION
The invention relates to a plastic material with improved properties comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.
BACKGROUND OF THE INVENTION
The importance of plastic material in various areas of industrial application has considerably increased in recent times. In the current state of the art in the plastics industry, isocyanates are considered an essential component for achieving desired material properties, in particular for providing reliable crosslinking during polyurethane manufacture. However, the use of isocyanates includes significant disadvantages due to their toxicity to both users and the environment. In consequence, there is absence strong demand in the plastics industry to provide materials which fulfil toxicological and environmental requirements without loss in material performance.
Furthermore, there are significant deficits in present plastic manufacturing capabilities when it comes to providing unique plastic materials with dedicated properties tailored to fulfil the customer's requirements. Special properties, like elastic behaviour, of plastic material are presently achieved by using thermoplastic polyurethanes (TPU), which are partly crystalline materials and belong to the class of thermoplastic elastomers.
For polyurethane elastomers the segmented structure of the macro-molecules is characteristic. TPUs possess different cohesion energy densities in the segments. In an ideal situation a phase separation into crystalline "hard" and "soft" areas can take place. The resulting two-phase structure has up to now determined the property profile of TPU. For the soft segment one uses long-chain polyoles which significantly affect the compatibility with the medium and the consistency of the TPU materials, and for the hard segment one uses short-chain polyoles. The latter strongly affect the hardness of the material, and they are responsible for the physical cross- linking.
However, up to now, toxic isocyanates have been used as cross-linking agents between the polyoles in order to obtain materials with certain desired properties. Such "traditional" TPU materials are not easily modified, as the addition of further components, such as a plasticizer or stabilizer, leads to reduced crosslinking due to the sub-optimal amounts of isocyanates present, which in turn potentially requires extensive re-working of the relative amounts of components provided to the material. Plastic materials at present often require significant effort and time- intensive experimentation to acquire workable modified materials tailored to provide specific mechanical or functional properties. There is a need in the art to provide plastic materials that may be easily modified by the simple addition of further stabilizing or plasticizing modifiers, that reliably lead to predictable outcomes with regard to strength, elasticity, fire resistance, formability etc.
In light of traditional TPUs, there exists a need in the art for the provision of novel and
environmentally beneficial cross-linking or adhesive strategies that enable reductions in the use of isocyanate and subsequent benefits in the workability of the plastic materials produced. The present invention relates to plastic materials without, or with strongly reduced quantities, of isocyanate components, which demonstrate improved mechanical properties compared to similar TPU materials and greater flexibility with respect to a modification of their physical properties via the addition of further modifying components.
The use of nanoclays in plastic materials has been described in the art. As shown in DE
102010007820, nanoclay components may be integrated into plastics in order to maintain the mechanical qualities of a synthetic material that has been modified with a self-extinguishing agent. Nanoclays have also been applied in order to enhance the adhesive properties of plastic materials intended for medical implants (US 2007/0249754). Despite such advances, there exists a need for further or improved plastic materials that incorporate less isocyanates and enable easily modifiable plastic properties.
SUMMARY OF THE INVENTION
In the light of the prior art the technical problem underlying the invention was the provision of a novel plastic material that overcomes the disadvantages of those materials known in the art. The plastic material of the invention enables improved toxicological and environmental properties in order to provide users with safe materials that have improved product properties.
The problem is solved by the features of the independent claims. Preferred embodiments of the present invention are provided by the dependent claims.
Therefore, an object of the invention is to provide a plastic material comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.
It was surprising that with this composition, a plastic material could be produced that required no additional isocyanate to be added in order to produce a stable and strong plastic material. A final product is obtained with less isocyanate than those plastic materials known in the art (low-content isocyanate, or preferably isocyanate-free). Surprisingly this mixture of components could be produced via standard extrusion methods. Furthermore, it was surprising that adding certain additives to the composition can easily be carried out without any difficulties in production, for example no problems in solubility or compatibility between the products during extrusion is observed.
The plastic material of the invention therefore represents an environmentally friendly plastic that requires no addition of isocyanates during manufacture, whereby the nanoclay component in combination with the other components in the material enables a stable plastic material with easily modified physical and mechanical properties.
The use of the synthetic materials Poly-Caprolactone (PCL) and Polycarbonate (PC), such as Bisphenol-A-Polycarbonate, provides distinct advantages when manufacturing the plastic material according to the present invention and targeting its properties. Until the present time, no synthetic material has been successfully developed incorporating PC and PCL in combination with a low- isocyanate nanoclay-based TPU synthetic material. The combination of thermoplastic
polyurethane (TPU), nanoclay, polyol, polycarbonate (PC) and polycaprolactone (PCL) represents an unexpectedly beneficial base mixture for the addition of further modifying compounds, for example a stabilizer plasticizer and/or elasticity modulator, which is not susceptible to unwanted fluctuations in stability during manufacture, regardless of the additive provided to the combination described.
PC is a commercially available synthetic material, and PCL is a special polymeric material which has the outstanding properties of relatively high heat- and impact resistance. PCL is a resinous polymer which is biodegradable and non-poisonous. The presence of these components in combination with TPU, polyol and nanoclays enables a robust plastic material ideally suited for further modification with an additive as described herein.
In a preferred embodiment the additive is or comprises substances that may also act as a filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer. Even with additives the manufacturing of the material is reliable and results in a plastic material with the desired properties.
In one embodiment the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is a phosphor component.
In one embodiment the plastic material of the present invention is characterised in that the phosphor component comprises salts that derive from phosphor with organic or inorganic acids, phosphites and/or phosphates.
In one embodiment the plastic material of the present invention is characterised in that the phosphor component is a phosphite component.
In one embodiment the plastic material of the present invention is characterised in that the phosphor component is trisnonylphenyl phosphite.
In one embodiment the plastic material of the present invention is characterised in that the phosphor component is bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di- t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
In one embodiment the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is carboxylated polypropylene, preferably a carboxylated polypropylene functionalised with maleic anhydride. One preferred embodiment of the invention relates to the use of carboxylated polypropylene (preferably functionalised with maleic anhydride), such as SCONA TPPP 21 12 FA from BYK, as an additive, preferably as a dispersing and/or stabilizing agent for the nanoclays in the compound mixture. The combination of thermoplastic polyurethane (TPU), nanoclay, polyol, polycarbonate (PC) and polycaprolactone (PCL) represents an unexpectedly beneficial base for the addition of carboxylated polypropylene. The addition of carboxylated polypropylene provides an improved distribution of nanoclays in the mixture and therefore enhanced uniformity in and stability of the plastic material produced. A combination of carboxylated polypropylene with a PC and PCL- based polymer has not been previously described. It was surprising that the combination of these materials was easily created via extrusion procedures.
In one embodiment the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis-MPA) and/or 1 ,3-polyethylene glycol diol.
In one embodiment the plastic material of the present invention is characterised in that the additive additionally comprises one or more substances that act as a filler, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer.
In a preferred embodiment the plasticizer comprises Benzyl-2-ethylhexyl adipate, Alkyl sulfonic ester of phenol, Benzyl butyl phthalate and/or Polyadipate.
In a preferred embodiment the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis- MPA), 1 ,3-polyethylene glycol diol, phosphor components with the chemical element phosphor, salts that derive from phosphor with organic or inorganic acids, phosphates, phosphites, bis (2,6- di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. It was a surprise that with the addition of stabilizer the manufacturing process is not affected and product performance can be enhanced.
In one embodiment the plastic material of the present invention is characterised in that the material comprises polyurethane in an amount of 20 to 80 %, preferably 30 to 70 %, more preferably 40 to 60% and most preferably 42 to 55 % by weight. The amount of polyurethane present in the material has proven to be modifiable, so that over a relatively wide range of potential amounts of TPU the plastic material retains its structural integrity and ease of manufacturing. Especially with respect to the modifiers of the invention, increased stability due to a stabilizer (such as a carboxylated polypropylene or phosphor component) for example allows a greater variation in TPU amount.
In one embodiment the plastic material of the present invention is characterised in that the material comprises nanoclay in an amount of 0.00001 to 5 %, preferably 0.0001 to 4 %, more preferably 0.001 to 3 % and most preferably 0.01 to 2 % by weight. The nanoclay component, preferably in combination with the TPU, and more preferably in combination with polyol, PC and PCL, enables an isocyanate free (or low isocyanate) polymer to be produced with sufficient strength and stability, comparable to traditional polyurethane plastics.
In one embodiment the plastic material of the present invention is characterised in that the material comprises polyol in an amount of 5 to 45 %, preferably 6 to 35 %, more preferably 7 to 25 % and most preferably 8 to 15 % by weight. The integration of polyol, especially those polyols, such as polyesterpolyols, described herein, into the plastic material represents a surprising and unexpected result, whereby the polyol provides added flexibility to the product.
In one embodiment the plastic material of the present invention is characterised in that the material comprises polycarbonate in an amount of 5 to 60 %, preferably 10 to 50 %, more preferably 15 to 40 % and most preferably 20 to 30 % by weight. PC provides increased sustainability and hardness to the product, in particular enhanced temperature and impact resistance. The combination between polyol and PC, together in a nanoclay based plastic represents an entirely surprising result, combining the flexibility and hardness of both components to enable a strong, resistant but flexible material.
In one embodiment the plastic material of the present invention is characterised in that the material comprises polycaprolactone in an amount of 2 to 45 %, preferably 4 to 35 %, more preferably 6 to 25 % and most preferably 8 to 15 % by weight. Addition of PCL to the plastic as described herein represents a surprising and beneficial result characterised by increased impact resistance.
In one embodiment the plastic material of the present invention is characterised in that the material comprises one or more additives in an amount of less than 20 %, preferably less than 15 %, more preferably less than 10% and most preferably less than 5 % by weight. The additives are intended to fulfill various purposes as described herein and are intended to function at a relatively low total content in comparison to the remaining plastic base mixture (ie the TPU, nanoclay, PC, PCL, polyol base mixture). In one embodiment the plastic material of the present invention is characterised in that the material comprises one or more additives in an amount of 0.1 % to 20%, 0.5% to 10%, or preferably 1 % to 5% by weight.
In one embodiment the plastic material of the present invention is characterised in that the material contains less than 10 % isocyanates, preferably less that 5 % isocyanates, more preferably less than 1 % isocyanates and most preferably less than 0.5 % isocyanates by weight. These relatively low quantities of isocyanate have been validated by chemical characterization and represent an improved standard for environmentally friendly plastic materials. Surprising was that nanoclays in the amounts provided herein show such beneficial adhesive properties within these compounds, thereby forming a stable plastic without the need for isocyanate-based cross- linking. It was surprising that no additional isocyanates were required to produce a stable plastic material. Although some traces of isocyanate may be detectable in the final product likely due to residual isocyanate in the TPU products introduced into the plastic, the plastic is essentially isocyanate free and therefore represents an environmentally friendly product in comparison to similar plastics known in the art.
In a preferred embodiment the plastic material comprises: polyurethane in an amount of 20 to 80 %, preferably 30 to 70 %, more preferably 40 to 60% and most preferably 42 to 55 %,
nanoclay in an amount of 0.00001 to 5 %, preferably 0.0001 to 4 %, more preferably 0.001 to 3 % and most preferably 0.01 to 2 %,
polyol in an amount of 5 to 45 %, preferably 6 to 35 %, more preferably 7 to 25 % and most preferably 8 to 15 %,
polycarbonate in an amount of 5 to 60 %, preferably 10 to 50 %, more preferably 15 to 40 % and most preferably 20 to 30 %,
polycaprolactone in an amount of 2 to 45 %, preferably 4 to 35 %, more preferably 6 to 25 % and most preferably 8 to 15 %, and
one or more additives in an amount of less than 20 %, preferably less than 15 %, more preferably less than 10% and most preferably less than 5 %, the additive may
alternatively be present at a percentage by weight of the plastic material of 0.1 % to 20%, 0.5% to 10%, or preferably 1 % to 5%,
wherein said components add to 100%; said percentages relate to % by weight.
In one embodiment the plastic material comprises:
polyurethane in an amount of 40 to 60% and most preferably 42 to 55 %,
nanoclay in an amount of 0.001 to 3 % and preferably 0.01 to 2 %,
polyol in an amount of 7 to 25 % and preferably 8 to 15 %,
polycarbonate in an amount of 15 to 40 % and preferably 20 to 30 %,
polycaprolactone in an amount of 6 to 25 % and most preferably 8 to 15 %, and one or more additives at a percentage by weight of the plastic material of 0.5% to 10%, or preferably 1 % to 5%,
wherein said components add to 100%; said percentages relate to % by weight.
The additives may be present at a final % by weight in P0, P1 , P2 or P3 of 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 .0, 1 .1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1 .9, 2.0, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or 10 or any value between these values or ranges thereof.
The addition of an additive to a preferred base mixture of mixture of TPU, Polyol, nanoclay, PC and PCL, can be carried out without having to significantly modify manufacturing proceedings. The extrusion process runs essentially unaltered without any additional issues arising with respect to poor mixing or distribution of components, or a lack in compatibility of the components.
In particular, it was a surprising and unexpected development that the presence of PC and/or PCL is compatible with a plastic material that is easily modified with an additive, without a reduction in reliability of the manufacturing process. The additive can be added to the plastic either before or after addition of PC and PCL, either of which leads to a stable plastic material that is not hindered in any way during manufacture. The addition of carboxylated polypropylene (Maleic anhydride), such as SCONA TPPP 21 12 FA, a plasticizer, preferably selected from Benzyl-2-ethylhexyl adipate, Alkyl sulfonic ester of phenol, Benzyl butyl phthalate and/or Polyadipate, or a stabilizer and/or elasticity modulator, preferably selected from polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis- MPA), 1 ,3-polyethylene glycol diol, phosphor components with the chemical element phosphor, salts that derive from phosphor with organic or inorganic acids, phosphates, phosphites, bis (2,6- di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphate, can be carried out by simple addition to the extruder of the additive, to either a pre-prepared base mixture, or with different combinations of the individual components during the extrusion process, as described herein.
One of the possible methods for production of the plastic material relates to a method comprising
Method step AP1 : Mixture of thermoplastic polyurethane (TPU) and a nanoclay component, thereby producing PI, whereby AP1 may be carried out in two steps, for example by mixing TPU and nanoclay producing P0, then adding P0 to TPU in a second step producing P1 , whereby the additive may be added during P0 or P1 production,
Method step AP2: Mixture of P1 with a polyol component and optionally additional TPU, thereby producing P2, whereby the additive may be added during P2 production,
Method step AP3: Mixture of P2 with a polycarbonate (PC) and polycaprolactone component (PCL), thereby producing P3, whereby the additive may be added during P3 production, whereby P3 may be subsequently processed to produce P4 in method step AP4 via extrusion, blowing, casting, grinding and/or spraying, to obtain particles, granules, films, fibres, foams, strands, sheets and/or foils.
With reference to Figure 7, the additive may be added at any stage in the extrusion process, preferably to the AP2 or AP3 manufacturing steps.
In a preferred embodiment the plastic material contains less than 10 % isocyanate, preferably less that 5 % isocyanate, more preferably less than 1 %, 0.5 %, 0.2 %, 0.1 % or less than 0.05% isocyanates by weight. In a preferred embodiment the plastic of the present invention is essentially isocyanate free. One procedure for the quantitative determination of free isocyanates in synthetic materials is performed using the Kubitz quantitative test "Analytical Chemistry", Vol. 29, pages 814-816 (1957). The presence of isocyanate (for example at levels at or above 210 parts per million) causes the Kubitz reagent, which is a complex of n-butylamine and malacite green, to turn green.
In a preferred embodiment the plastic material comprises phosphor, iron, magnesium, aluminium and/or silicon. The term silicon, or silicium, represents any substance comprising silicon. In one embodiment the plastic material of the present invention is characterised in that the material comprises phosphor, iron, magnesium, aluminium and silicon.
In one embodiment the plastic material of the present invention is characterised in that the material comprises 10 to 1000 mg/kg phosphor, preferably 100 to 200 mg/kg phosphor, more preferably 150 mg/kg phosphor.
In one embodiment the plastic material of the present invention is characterised in that the material comprises 1 to 100 mg/kg iron, preferably 10 to 20 mg/kg iron, more preferably 15 mg/kg iron. In one embodiment the plastic material of the present invention is characterised in that the material comprises 1 to 100 mg/kg magnesium, preferably 5 to 15 mg/kg magnesium, more preferably 10 mg/kg magnesium.
In one embodiment the plastic material of the present invention is characterised in that the material comprises 1 to 500 mg/kg aluminium, preferably 10 to 100 mg/kg aluminium, more preferably 50 mg aluminium.
In one embodiment the plastic material of the present invention is characterised in that the material comprises 10 to 1000 mg/kg silicon, preferably 100 to 200 mg/kg silicon, more preferably 150 mg/kg silicon.
In a preferred embodiment the plastic material comprises 10 to 1000 mg/kg phosphor of the total plastic material, preferably 100 to 200 mg/kg phosphor, more preferably 150 mg/kg phosphor, 1 to 100 mg/kg iron, preferably 10 to 20 mg/kg iron, more preferably 15 mg/kg iron, 1 to 100 mg/kg magnesium, preferably 5 to 15 mg/kg magnesium, more preferably 10 mg/kg magnesium, 1 to 500 mg/kg aluminium, preferably 10 to 100 mg/kg aluminium, more preferably 50 mg aluminium, and 10 to 1000 mg/kg silicon, preferably 100 to 200 mg/kg silicon, more preferably 150 mg/kg silicon. Particular blends of nanoclay enables improved adhesion within the plastic in addition to beneficial distribution properties in the plastic, enabling improved uniform strength throughout the plastic.
In a preferred embodiment a binary mixture comprising polyurethane and nanoclay comprises 0.1 to 10 mg/kg phosphor, preferably 0.5 to 5 mg/kg phosphor, more preferably 1 mg/kg phosphor, 10 to 1000 mg/kg iron, preferably 100 to 200 mg/kg iron, more preferably 130 mg/kg iron, 5 to 1000 mg/kg magnesium, preferably 10 to 100 mg/kg magnesium, more preferably 70 mg/kg magnesium, 50 to 5000 mg/kg aluminium, preferably 100 to 1000 mg/kg aluminium, more preferably 500 mg aluminium, and 100 to 10000 mg/kg silicon, preferably 1000 to 2000 mg/kg silicon, more preferably 1500 mg/kg silicon.
In a preferred embodiment the plastic material is manufactured by hot melt extrusion. Hot melt extrusion is considered to relate to an extrusion process for plastic materials at temperatures preferably between 80 and 250 deg C as known to a skilled person in the art. Generally, plastics extrusion is a considered a high volume manufacturing process in which raw plastic material is melted and formed into a continuous profile. In the extrusion of plastics, raw thermoplastic compound material is typically applied as granulate or beads and is gravity fed from a top mounted hopper into the barrel of the extruder. Additives in either liquid or pellet form may be mixed into the resin prior to arriving at the hopper, or at specific points downstream of the initial feeder. Multiple inlets are possible.
A screw extruder is preferably applied. The material enters preferably through a feeder and comes into contact with the screw. The rotating screw forces the plastic beads forward into the barrel which is heated to the desired melt temperature of the molten plastic. In most processes, a heating profile is set for the barrel in which two or more independent heater zones gradually increase the temperature of the barrel from the rear (where the plastic enters) to the front. This allows the plastic to melt gradually as it is pushed through the barrel and lowers the risk of overheating which may cause degradation in the polymer. In a preferred embodiment the plastic material may be processed post-extrusion, or inline during the extrusion process, to produce a foam, particles, granules, film, fibres, strands, sheets and/or foils. In one embodiment Fig. 7 is provided to demonstrate the processing of the intermediate product P3 in AP4 to produce the processed end product.
In a preferred embodiment the plastic material is elastic with a rupture resistance of more than 100%, more than 200 %, preferably of more than 300%, more than 400 %, more than 500%, more preferably of more than 600 % and most preferably of more than 700 %. The ability to resist breaking under tensile stress is one of the most important and widely measured properties of materials used in structural applications. The force per unit area (MPa or psi) required to break a material in such a manner is the ultimate tensile strength or tensile strength at break. ASTM D638 may also be used for determining either elasticity or rupture resistance. For this test, plastic samples are either machined from stock shapes or injection molded. The tensile testing machine pulls the sample from both ends and measures the force required to pull the specimen apart and how much the sample stretches before breaking. The analogous test to measure tensile properties in the ISO system is ISO 527. The values reported in the ASTM D638 and ISO 527 tests in general do not vary significantly and either test will provide good results early in the material selection process. The ultimate elongation of an engineering material is the percentage increase in length that occurs before it breaks under tension. Rigid plastics, especially fibre reinforced ones, often exhibit values under 5%. The combination of high ultimate tensile strength and high elongation leads to materials of high toughness.
In a preferred embodiment the plastic material has a density of 100 to 10000 kg/m3, preferably 250 to 7500 kg/m3, more preferably 500 to 5000 kg/m3 and most preferably 1000 to 1200 kg/m3. Preferably used is DIN 53479 (testing of Plastics and Elastomers; Determination of Density).
In a preferred embodiment the plastic material is resistant against temperature of -100°C to +750°C, preferably to temperature of -75°C to +500°C, more preferably to temperature of -60°C to +250°C and most preferably to temperature of -40°C to +100°C.
In a preferred embodiment the plastic material is resistant against chemical agents comprising solvents, softener, mineral oils, alkalis, acids and/or fuels.
DETAILED DESCRIPTION OF THE INVENTION
The advantages of plastic materials with less or without isocyanates are many, providing outstanding advantages regarding environmentally friendly and non-toxic solutions in the marketplace of the future. In this connection it is, however, under certain conditions necessary to adapt their properties to more specialized requirement profiles. A possibility for the optimization of their properties without requiring large amounts of isocyanates has until now not been satisfactorily described in the art. Novel combinations of raw materials are sought that enable simple manufacture and easy manipulation to extend the potential uses of common plastic materials in new technical applications. In this regard, mixable and non-mixable systems as well as systems that are partially mixable with reference to temperature and mixing proportion can be distinguished. The properties of the blends are determined by the molecular structures which occur because of the mixing / de-mixing processes. It is possible that, depending on experimental conditions, one observes homogeneous mixing- and de-mixing phases as well as crystallization and glassy consolidation during and after processing.
The mixing of the different polymers is a possibility either to combine characteristic properties of the initial components into one blend and to optimize, or to develop entirely new properties through the formation of new supermolecular structures in the differentiated mixture. It was surprising that highly specialized plastic material of this invention with dedicated properties can be obtained and be custom made by targeted processing. The plastic material in particular comprises binary partly-crystalline polymer blends. The central problem in estimating the crystallization processes in such blends is their strong dependence on the different experimental parameters. In addition, the structure formation is above all governed by the competition between kinetics and equilibrium thermodynamics. Experiments are conducted regarding the formation of a bi-crystalline polymer structure, in equilibrium thermodynamics the eutecticum. Because of its finely cross-linked crystalline structure, the plastic material has completely new mechanical properties.
A further advantage of the present invention in particular is the simplicity in processing and completeness in mixing. This becomes obvious with examinations of mixtures that decrease the mixed-glass temperature and of polymer crystallization. Polymers like PCL and PC, with the aid of an extruder, and certain additives provide unexpected results and material with improved properties. The addition of PCL and/or PC, which is an amorphous polymer and hence has no inclination whatever for crystallization, makes crystallization out of the melt possible. For example a crystallization tendency of 30% in the PC portion can be reached. The polymer blend PCL/PC is a system in which the mixing partners separately crystallize depending on experimental conditions and composition, and in which they are embedded in an amorphous mixing matrix. As the examination shows, new areas of application can be developed through the plastic material of this invention. A mixture with suitable polymeric mixing partners is possible in order to achieve the simultaneous crystallization of both phases.
An advantage of the present invention is that a compound system is available that possesses reproducible qualities. The plastic material comprises preferably a composition which is suitable to achieve a compound system with less isocyanates or which is free of isocyanates and a dedicated additive amount for obtaining the desired properties like elasticity, stability, resistance.
The plastic material can contain products from a multifunctional orthosilicate and/or tetraethyl orthosilicate and/or an alkyl polymer. This not only results in a financial advantage but also in an advantage in quality. In the course of the implementation a silicate could be added to the composition, e.g. tetraethyl-orthosilicate in order to complete the hardening properties. The silicate can be added under constant shear in the composition. The silicate weight lies for example between 1.0 and 20 wt.% relative to the total weight of the composition. The plastic material of the present invention relates to a plastic substance or polymer comprising of a cross-linked and/or adhesive mixture of thermoplastic polyurethane (TPU) and nanoclays. In a preferred embodiment the product comprises a combination of TPU, nanoclays, polyol, polycarbonate (PC), polycaprolactone component (PCL) and an additive, determined according to the specific properties desired. The plastic material produced through the method of the present invention exhibits a novel chemical structure, produced by the unique combination of components and processing steps as described herein. The resulting chemical structure is preferably a combination of polymerisation and/or adhesion, whereby the nanoclay component acts as catalyst of a chemical reaction, leading to polymerisation and/or re-polymerisation of the reaction components, or as an adhesive component, providing strong adhesion between the components resulting in long-lasting and stable essentially isocyanate free plastic materials or plastic materials with low amount of isocyanates. Preferably the polymerisation comprises additionally or exclusively of polyaddition reactions. The synthetic material described herein may be described either as a polymer, a synthetic material, a plastic or a modified polyurethane, without intending to describe separate products. The materials produced via the method of the invention show a novel structure that may be a combination of polymerisation and/or adhesion.
Polyurethane
Polyurethane, in a preferred embodiment for example thermoplastic polyurethane (TPU), is a polymer composed of a chain of organic units joined by carbamate (urethane) links. TPU is defined as any thermoplastic polyurethane. The present invention may be carried out with any TPU. TPU may be used in a milled or grinded grade. The following TPUs are preferred: Pearlcoat 162K, Pearlthane 16N80, Pearlthane Clear 15N80, Desmopan 385 S, Elastollan 1 185 A.
In a preferred embodiment Pearlcoat 162K comprises a polyether based TPU, supplied in form of translucent, colourless pellets, combining hardness with excellent low temperature flexibility and very good hydrolysis resistance. Typical properties are listed in the following table:
Physical Property Test Method Values
Density @ 20°C DIN 53.479 1.1 1 g/cm3
Shore Hardness DIN 53.505 82 A
Tensile Strength DIN 53.504 30 MPa
Modulus @ 100% Elongation DIN 53.504 5 MPa
Modulus @ 300% Elongation DIN 53.504 10 MPa
Elongation @ Break DIN 53.504 550 %
Abrasion Loss DIN 53.516 25 mm3
Melting Range (MFI=10**) MQSA 1 1 1 145 - 155 °C
Tg (DSC, 10°C / min.) DIN 51 .007 -42 °C
** Temperature at which MFI = 10 g/10 min @ 21.6 kg.
Pearlcoat 162K is preferably used in melt coatings on textile substrates, for preferably end-uses in industrial coatings (for life-jackets, etc.) obtained by extrusion and calendering. Pearlcoat 162K is preferably used for obtaining extruded films and fabric coatings. The preferred working instructions can be described as follows and the characteristics of the extruder that are suitable for processing Pearlcoat 162K are the following:
1 . L/D ratio between 25: 1 and 30: 1
2. The extruder screw preferably has 3 or more zones and a compression
ratio in between 2:1 and 3:1 (Usually, the screws that are used for Polyethylene extrusion give good results).
3. The extruder screw should preferably have a continuous regulation device and a working power higher than for processing other plastics.
4. The speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
5. The filters used should preferably be disks with holes of 1 .5 to 5 mm.
(depending on the screw and the die), and screen packs (the number of meshes /cm2 will depend on the end product that is processed), so as to create a pressure built-up.
For optimum results, previous drying of the product during 2 hours at 90-100° C is advisable, in a hot air circulatory, vacuum or desiccant-air dryer. The suggested processing-temperature profiles for film extrusion (flat film) are given in the table below.
Preferred process parameter (extruder and conditions) can be described as follows: TYPE.- 30/25D (L/D=25:1 ), COOLING.- Air, SCREW.- 3:1 , SPEED.- 50 rpm BREAKER PLATE.- -, FILTER PACK.- -, THICKNESS DIE.- 0,2 mm, PRE-DRYING.- 1 h @100
In a preferred embodiment Pearlthane 16N80 comprises a polyether based TPU, preferably supplied in form of translucent, colourless pellets, combining hardness with excellent mechanical properties and an outstanding hydrolysis, microbial resistance. It can preferably be extruded and injection-moulded. Pearlthane 16N80 can preferably be used for blown- and cast films, cables, tubing and profiles. When processed by injection moulding, it can be used for making technical parts. Typical properties are listed in the following table:
Physical Property Test Method Values
Density @ 20°C ISO 2781 1.09 g/cm3 Shore Hardness ISO 868 81 A
Tensile Strength ISO 527 35 MPa
Elongation @ Break ISO 527 760 %
Modulus @ 100% Elongation ISO 527 5 MPa
Modulus @ 300% Elongation ISO 527 8 MPa Tear Strength ISO 34-1 B 80 kN/m Abrasion Loss ISO 4649 20 mm3
Compression Set (70 h. 23°C) ASTM D395B 30 %
Compression Set (24 h. 70°C) ASTM D395B 42 %
Moisture Content MQSA 44 < 0.1 %
Melting Range (MFI=10**) MQSA 1 1 1 160-170 °C
Tg (DSC, 10°C /min.) ISO 1 1357-2 -47 °C
Temperature at which MFI = 10 g/10 min @ 21.6 kg.
Preferred working instructions are the following and for optimum results, previous drying of the product during 1 -2 hours at 100-1 10 °C is advisable, in a hot air circulatory, vacuum or desiccant- air dryer. In extrusion processes the characteristics and the extruder that is suitable for processing Pearlthane 16N80 are the following:
1. L/D ratio between 25:1 and 30:1
2. The extruder screw preferably has 3 or more zones and a compression ratio in between 2:1 and 3:1 (usually, the screws that are used for Polyethylene extrusion give good results).
3. The extruder screw should preferably have a continuous regulation device and a working power higher than for processing other plastics.
4. The speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
5. The filters used should preferably be disks with holes of 1 .5 to 5 mm. (depending on the screw and the screen packs (the no. of meshes /cm2 will depend on the end product that is processed), so as to create a pressure built-up.
The preferred processing-temperature profiles for film extrusion (flat films) are given in the table below:
Preferred process parameter can be described as follows: Type- 30/25d (l/d = 25:1 ), Cooling. - Air, Screw.- 3:1 , Speed.- 50 rpm Breaker plate.— Filter.— . Thickness Die.- 0,2 mm, Pre-heating.- 1 h @ 105°C. For injection moulding the preferred parameter are the following: The obtained data are based on plaques produced in an injection moulding equipment with the following
characteristics and suggested processing conditions: Feeding zone 180°C
Compression zone 190°C
Metering zone 195°C
Nozzle 195°C
Mould temperature 35°C
Closing force 30 tons
Screw diameter 26 mm
L/D ratio 23
Maximum hydraulic pressure 210 bar
Mould Plaque 120x120x2
In a preferred embodiment Pearlthane Clear 15N80 comprises a polyether copolymer-based TPU, preferably supplied in form of translucent, colourless, combining low hardness with excellent mechanical properties and excellent hydrolysis resistance. Pearlthane Clear 15N80 can preferably be extruded and injection-moulded. Pearlthane Clear 15N80 is preferably used for making films, cables, tubing, profiles and different technical parts. To improve the microbiological protection of Pearlthane Clear 15N80, it could be necessary to add a biocide, preferably in form of TPU-based masterbatch. Typical properties are listed in the following table:
Physical Property Test Method Values
Specific Gravity ASTM D-792 1.05
Shore Hardness ASTM D-2240 82 A
Tensile Strength ASTM D-412 5076 psi.
Elongation @ Break ASTM D-412 740 %
Modulus @ 100% Elongation ASTM D-412 725 psi.
Modulus @ 300% Elongation ASTM D-412 1 160 psi.
Tear Strength ASTM D-624 (Die C) 460 lb/in
Abrasion Loss DIN 53.516 25 mm3
Compression Set (70 h. @ 73° F) ASTM D-395 24 %
Compression Set (24h. @ 158°F) ASTM D-395 38 %
Moisture Content MQSA 44 < 0.1 %
Melting Range (MFI = 10**) MQSA 1 1 1 385 - 400 °F
Tg (DSC, 10°/10min) DIN 51.007 - 65 °F
** Temperature at which MFI = 10 g/10 mm @ 21.6 kg.
Preferred working instructions are the following and for optimum results, previous drying of the product during 1-2 hours at 210 - 230° F is advisable, in a hot air circulatory, vacuum or desiccant- air dryer. In extrusion processes the characteristics and the extruder that is suitable for processing Pearlthane Clear 15N80 are the following:
1 . L/D ratio between 25:1 and 30:1
2. The extruder screw preferably has 3 or more zones and a compression ratio between
2:1 and 3:1 . (Usually, the screws that are used for Polyethylene extrusion give good results).
3. The extruder screw should preferably have a continuous regulation device and a
working power higher than for processing other plastics. 4. The speed of the extruder should preferably be low (12 to 60 rpm, depending on its diameter), so as to avoid material degradation due to shearing.
5. The filters used should preferably be disks with holes of 1/16 to 3/16 in (depending on the screw and the die), and screen packs (the no. of meshes /in2 will depend on the end product which is processed), so as to create a pressure built-up.
The preferred processing-temperature profiles for film extrusion (flat film) are given in the table below:
Preferred process parameter (extruder and conditions) can be described as follows: TYPE.- 30/25D (L/D=25:1 ), COOLING.- Air, SCREW.- 3:1 , SPEED.- 25 rpm., BREAKER PLATE.- -, FILTER PACK.- -, THICKNESS DIE.- 0,2 mm, PRE-DRYING.- 1 h @ 220 °F
Preferred characteristic of the film are the following:
Appearance: Colourless, elastic, translucent
Softening point: 310-330 °F (MQSA 91 (Kofler))
Dry cleaning resistance: Excellent
Hydrolysis resistance: Excellent
Based on an injection molding equipment with the following characteristics
Closing force: 30 tons
Screw diameter: 1.02 in
UD ratio: 23
Maximum hydraulic pressure: 3050 psi.
Mold: Plaque 4.7x4.7x0.08 in,
the preferred processing conditions for injection molding are as follows:
Injection pressure 1450 psi
Injection time 4 sec
Holding pressure 700 psi
Holding time 10 sec
Cooling time 30 sec
Feed zone 365°F
Compression zone 375°F
Metering zone 385°F
Nozzle 390°F
Mold temperature 95° F
Screw speed : approx. 142 rpm. In a preferred embodiment Desmopan 385 S comprises aromatic thermoplastic polyurethanes and/or polyurethane elastomers, preferably with less than 1 % 2,2',6,6'-Tetraisopropyldiphenyl Carbodiimide (CAS-No. 2162-74-5). The preferred storage temperature maximum is 30 °C. The material is hygroscopic and may absorb small amounts of atmospheric moisture. According to the present invention a polymer comprising Desmopan 385 S preferably shows the following physical and chemical properties:
Form: solid
Appearance: pellets
Color: Natural
Odor: Odorless
pH: not applicable
Melting Point: 220 °C (428 °F)
Flash point: 250 °C (482 °F)
Lower explosion limit: not applicable
Upper explosion limit: not applicable
Specific Gravity: 1.1
Solubility in Water: insoluble
Autoignition temperature: > 210 °C (> 410 °F)
Decomposition temperature: Decomposition begins at 230 °C.
Softening point: 180 °C (356 °F)
Bulk density: 500 - 700 kg/m3
Hazardous Reactions: Hazardous polymerisation does not
Stability: Stable
Materials to avoid: None known.
Conditions to avoid: None known.
In a further preferred embodiment the injection molding grade preferably shows high mechanical strength and improved hydrolysis resistance. The following table comprises preferred properties of the polymer to be used and/or obtained from the method of the present invention.
temperature
In a preferred embodiment Elastollan 1 185 A comprises a thermoplastic polyether-polyurethane with outstanding hydrolysis resistance, low temperature flexibility and high resistance to microorganisms. The polymer is processable preferably by injection moulding, extrusion and blow moulding. According to the present invention a polymer comprising Elastollan 1 185 A preferably shows the following characteristics:
Property Unit Value
Test method according to Hardness Shore A 87
DIN 53505 Shore D 36
DIN EN ISO
Density g/cm3 1 , 12
1183-1 -A
Tensile strength MPa 45 DIN 53504-S2
Elongation at break % 600 DIN 53504-S2
Stress at 20 % elongation MPa 2,5 DIN 53504-S2
Stress at 100 % elongation MPa 6 DIN 53504-S2
Stress at 300 % elongation MPa 10 DIN 53504-S2
Tear strength N/mm 70 DIN ISO 34-1 Bb
Abrasion loss mm3 25 DIN ISO 4649-A
Compression set 23°C / 72 hrs % 25 DIN ISO 815
Compression set 70°C / 24 hrs % 45 DIN ISO 815
Tensile strength after storage in water
MPa 32 DIN 53504-S2 at 80°C for 42 days
Elongation at break after storage in water
% 600 DIN 53504-S2 at 80°C for 42 days
Notched impact strength (Charpy) + 23°C kJ/m2 no break DIN EN ISO 179-
- 30°C kJ/m2 no break 1
Flammability rating HB UL 94
Test plaques are preferably manufactured by injection moulding from pre-dried granules and water content of less than 0.02%. Test plaques are preferably aged 20 hrs at 100°C. Specimens are cut from test plaques. Test conditions are 23°C ± 2°C and 50% ± 6% rel. humidity. Polymers comprising Elastollan are hygroscopic, therefore storage in dry conditions and original container is recommended. In a preferred form the polymer product comprises lentil shaped pellets. In a preferred embodiment the Elastollan polymer is processable at least for 6 months from delivery date in original sealed containers with cool dry storage.
Nanoclavs
Nanoclays are nanoparticles of layered mineral silicates. Depending on chemical composition and nanoparticle morphology, nanoclays are organized into several classes such as
montmorillonite, bentonite, kaolinite, hectorite, and halloysite. Organically-modified nanoclays (organoclays) are an attractive class of hybrid organic-inorganic nanomaterials with potential uses in polymer nanocomposites, as rheological modifiers, gas absorbents and drug delivery carriers. Nanoclays can come in the form of nanoplatelets. The silicate platelets that the additives are derived from are about 1 nanometer thick and 70 - 150 nanometers across. The platelets are surface modified with an organic chemistry to allow complete dispersion into and provide miscibility with the thermoplastic systems for which they were designed to improve. The additives can reinforce thermoplastics by enhancing flexural and tensile modulus. Nanoparticles, preferably in the form of masterbatches, or so called nano masterbatches, influence the adhesion and/or crosslinking of the components during production, preferably polymerization, melting and/or extrusion. Furthermore it is preferred, that nano masterbatches influence the viscosity in the melt and surface properties of the hardened polymer.
A preferred nanoclay is Perkalite F100, or derivatives of and/or mixtures including Perkalite F100, which is an aluminum magnesium layered double hydroxide (LDH) modified with hydrogenated fatty acid.
Preferably the composition on ingredients for Perkalite F100 is as follows:
Preferably the physical and chemical properties for Perkalite F100 are as follows:
Appearance: powder
Colour: offwhite
Odour: characteristic
Melting point/freezing point : >500 Ό / >932 F
Flash point: not applicable. Product may contain flammable volatiles.
Flammability: combustible material.
Explosive properties: no
Oxidising properties: no
Vapour pressure: not applicable
Density:
1378 kg/m3 (20O / 68'F)
Specific gravity = 1.378 (20Ό / 68 )
Bulk density:
211-219 kg/m3 (20O / 68'F)
Specific gravity = 0.211 - 0.219 (20Ό / 68 )
Solubility in water: Insoluble (20Ό/68 )
Preferred nanoclays, comprising nanocomposites are for example Cloisite products. These products are in particular super-charged nanoparticles. Nanoclays comprising Cloisite are in particular providing benefits to plastic material at very low loadings. Benefits can be summarized as follows: • flame retardant
• increased modulus and tensile
• improved barrier properties
• dimensional stability increased
• recyclable thermoplastic
• clarity
• increased HDT
• reinforcement
• low density
Nanoclay comprising montmorillonite can be employed in the preparation of polymer-clay nanocomposites. Typical performance advantages, of montmorillonite compared to traditional reinforcing agents for plastics are as follows: Montmorillonite will develop similar increase in modulus and tensile strength at 3-5% loading compared to 20-60% loading of conventional reinforcing agents such as kaolin, silica, talc, and carbon black. Implicit advantages include lighter plastic parts with greater transparency. With montmorillonite, the plastic will have increased barrier properties to moisture, solvents, chemical vapors, gases such as 02 and flavors. Particle shape is known to affect plastic barrier properties. Montmorillonite is a nanoparticle with an anisotropic, plate-like, high aspect-ratio morphology. It is this morphology that leads to the improved permeation barrier through a tortuous path mechanism. With montmorillonite, the plastic will have increased dimensional stability at low reinforcement loading. Dramatic decreases in CLTE values are the result. The plastic has a higher heat distortion temperature. Only a few percent loading of montmorillonite increases the temperature at which the plastic begins to soften. This property is important, for example, in under-the-hood automotive applications. The thermoplastic polymer will be more recyclable. Montmorillonite performance actually improves upon recycling. Fiberglass products typically cannot be recycled for the same application, since the fibers are damaged during the recycling process. The plastic will dye easier. Due to the colloidal nature, high surface area, and surface treatability of montmorillonite, it can serve as an active site to fix dyes into plastic. Nanocomposites offer a synergistic flame-retardant approach. The improved flame retardancy as measured by Cone Calorimetry shows a decrease in the Peak Heat Release Rate. Observed are a decrease in smoke and an increase in char formation.
Combination with traditional flame retardants can enable passage of specified flame tests. The appearance of painted parts is improved compared to conventional reinforced parts. The nanocomposite particles are much smaller than traditional reinforcing agents so the plastic surface is much smoother. There is reduced static cling in films containing nanocomposites.
Nanoclay comprises Montmorillonite. Montmorillonite is a very soft phyllosilicate group of minerals that typically form in microscopic crystals, forming a clay. Montmorillonite, a member of the smectite family, is a 2:1 clay, meaning that it has 2 tetrahedral sheets sandwiching a central octahedral sheet. The particles are plate-shaped with an average diameter of approximately one micrometre. Members of this group include saponite. Montmorillonite is the main constituent of the volcanic ash weathering product, bentonite. The water content of montmorillonite is variable and it increases greatly in volume when it absorbs water. Chemically it is hydrated sodium calcium aluminium magnesium silicate hydroxide (Na,Ca)o.33(AI,Mg)2(Si40 o)(OH)2 nH20.
Potassium, iron, and other cations are common substitutes; the exact ratio of cations varies with source. It often occurs intermixed with chlorite, muscovite, illite, cookeite, and kaolinite. Nanoclay comprises Bentonite. Bentonite is an absorbent aluminium phyllosilicate, essentially impure clay consisting mostly of montmorillonite. There are different types of bentonite, each named after the respective dominant element, such as potassium (K), sodium (Na), calcium (Ca), and aluminium (Al). Bentonite is formed from weathering of volcanic ash, most often in the presence of water. However, the term bentonite, as well as a similar clay called tonstein, has been used to describe clay beds of uncertain origin. For industrial purposes, two main classes of bentonite exist: sodium and calcium bentonite. In stratigraphy and tephrochronology, completely devitrified (weathered volcanic glass) ash-fall beds are commonly referred to as K-bentonites when the dominant clay species is illite. Other common clay species, and sometimes dominant, are montmorillonite and kaolinite. Kaolinite-dominated clays are commonly referred to as tonsteins and are typically associated with coal.
In particular nanoclay comprises different types of bentonite, for example sodium bentonite, calcium bentonite, potassium bentonite. Sodium bentonite expands when wet, absorbing as much as several times its dry mass in water. The property of swelling also makes sodium bentonite useful as a sealant, since it provides a self-sealing, low permeability barrier. It is used to line the base of landfills to prevent migration of leachate, for quarantining metal pollutants of groundwater, and for the sealing of subsurface disposal systems for spent nuclear fuel. Similar uses include making slurry walls, waterproofing of below-grade walls, and forming other impermeable barriers, e.g., to seal off the annulus of a water well, to plug old wells. It is also used to form a barrier around newly planted trees to constrain root growth so as to prevent damage to nearby pipes, footpaths and other infrastructure. Sodium bentonite can also be "sandwiched" between synthetic materials to create geo-synthetic clay liners (GCL) for the aforementioned purposes. This technique allows for more convenient transport and installation, and it greatly reduces the volume of sodium bentonite required. Various surface modifications to sodium bentonite improve some rheological or sealing performance in various applications for example geoenviromental applications, for example, the addition of polymers.
Calcium bentonite acts preferably as adsorbent of ions in solution, as well as fats and oils, being a main active ingredient of fuller's earth, probably one of the earliest industrial cleaning agents. Calcium bentonite may be converted to sodium bentonite (termed sodium beneficiation or sodium activation) to exhibit many of sodium bentonite's properties by a process known as "ion exchange". This means adding for example 5-10% of a soluble sodium salt such as sodium carbonate to wet bentonite, mixing well, and allowing time for the ion exchange to take place and water to remove the exchanged calcium. Some properties, such as viscosity and fluid loss of suspensions, of sodium-beneficiated calcium bentonite (or sodium-activated bentonite) may not be fully equivalent to those of natural sodium bentonite. For example, residual calcium
carbonates (formed if exchanged cations are insufficiently removed) may result in inferior performance of the bentonite in geosynthetic liners. Potassium bentonite, also known as potash bentonite or K-bentonite, potassium bentonite is a potassium-rich illitic clay formed from alteration of volcanic ash.
Masterbatch
Masterbaches comprise of a solid product of a plastic, rubber, polyol, elastomer and/or polymer in which pigments, additives, clays, nanoclays, silicates, composites and/or nanocomposites are optimally dispersed at high concentration in a carrier material. The carrier material is compatible with the main plastic, rubber, polyol, elastomer and/or polymer in which it will be blended during molding, whereby the final plastic, rubber, polyol, elastomer and/or polymer obtains the color and/or properties from the masterbatch.
In a preferred embodiment of the present invention masterbatches preferably comprise clays, silicates and/or nanoclays and are preferably used according to the invention for the
manufacturing, polymerisation and/or recycling of monomers, oligomers, polymers and/or pre- polymers. It is further preferred that masterbatches are preferably used for enhancing the monomers, oligomers, polymers and/or pre-polymers properties. These enhanced properties comprise in particular strength, hardness, elongation break, viscosity, handling, manufacturability, stability and/or processability. Additives and/or non-isocyanate polymerizing agents in
masterbatches comprise according to the present invention monomers, oligomers, polymers and/or pre-polymers. In a preferred embodiment masterbatches are used as non-isocyanate polymerizing agent. In a preferred embodiment a masterbatch is dispersed via extrusion in a polymer matrix. Masterbatches are preferably comprising a solid content of up to 50%, more preferably of up to 90% and most preferably of up to 99%.
Polyol
A polyol is an alcohol containing multiple hydroxyl groups. Polyol is defined as any polyol. The present invention may be carried out with any polyol. The following polyol components are preferred: Lupraphen 81 13, Lupraphen 8109, Lupraphen 8108, Lupraphen 8107, Lupraphen 8106, Lupraphen 8104, Lupraphen 8103, Lupraphen 8101 , Lupraphen 8008, Lupraphen 8007, Lupraphen 8004, Lupranol BALANCE 50, Lupranol VP 9390, Lupranol 4674-15, Lupraphen VP 9267.
In a preferred embodiment the polyol comprises a di- or multifunctional, aliphatic, polyester polyol, such as Lupraphen. Lupraphen 81 13 is preferably used for the production of polyurethane elastomers. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow solid
OH Number 55 mg KOH/g DIN 53 240
Viscosity at 75 °C 580 mPa*s DIN EN 12092
Water Content < 0.015 % DIN 51 777
Acid Number < 0,45 mg KOH/g DIN EN ISO 21 14
Density at 50 °C 1.2 g/cm3 DIN 51 757
Flash point > 160 °C DIN EN 22 719
Lupraphen 81 13 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 81 13 or its product groups are listed in the BgVV (Germany) as Codes of Practice No. XXVIII dated June 1 , 1981 , and XXXIX dated June 1 , 1998. The components of Lupraphen 81 13 or its product groups or the polyurethanes made from Lupraphen 81 13 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 81 13 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments. In a preferred embodiment Lupraphen 8109 comprises a partially-branched, aliphatic polyester polyol. Lupraphen 8109 is preferably used for the production of polyurethane flexible integral skin foams, elastomers and shoe sole systems. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow, viscous liquid
OH Number 55 mg KOH/g DIN 53 240
Viscosity at 75 °C 700 mPa*s DIN 53 015
Water Content < 0.10 % by weight DIN 51 777
Acid Number < 1.0 mgKOH/g DIN EN ISO 3682
Density at 25 °C 1.2 g/cm3 DIN 51 757
Flash point > 160 °C DIN EN 22 719
Lupraphen 8109 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive
90/128/EG (Europe) and its amendments (latest: 96/11/EC), in annex II, paragraph A or B. The components of Lupraphen 8109 or its product groups or the polyurethanes made from Lupraphen 8109 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8109 has not to be marked according to the EC directive 67/548 and its guidelines.
In a preferred embodiment Lupraphen 8108 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8108 is preferably used for the production of polyurethane flexible integral skin foams, elastomers and textile coatings. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow, viscous liquid
OH Number 56 mg KOH/g DIN 53 240
Viscosity at 75 °C 613 mPa*s DIN 53 015
Water Content < 0.07 % DIN 51 777
Acid Number < 0.4 mgKOH/g DIN EN ISO 3682
Density at 25 °C 1.15 g/cm3 DIN 51 757
Colour < 3 Iodine DIN 6162
Flash point > 160 °C DIN EN 22 719
Lupraphen 8108 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8108 or its product groups or the polyurethanes made from Lupraphen 8108 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8108 has not to be marked according to the EC directive 67/548 and its guidelines.
In a preferred embodiment Lupraphen 8107 comprises a partially-branched, aliphatic, polyester polyol. Lupraphen 8107 is preferably used for the production of polyurethane slab stock foam. Typical properties are listed in the following table:
Appearance: Colourless to pale yellow, viscous liquid
OH Number 61 mg KOH/g DIN 53 240
Viscosity at 25 °C 19000 mPa s DIN 53 015
Viscosity at 75 °C 1050 mPa s DIN 53 015
Water Content < 0.07 % DIN 51 777 Acid Number < 1 .5 mgKOH/g DIN EN ISO 21 14
Density at 25 °C 1.19 g/cm3 DIN 51 757
Colour < 2 Iodine DIN 6162
Flash point > 1 60 °C DIN EN 22 719
Lupraphen 8107 is a polymer or no-longer-polymer, made from monomers and additives, which are listed in the directive 90/128/EG (Europe) and its amendments (latest: 2004/19/EG), in annexe II, paragraph A or B or annex III, paragraph A or B. The components of Lupraphen 8107 or its product groups or the polyurethanes made from Lupraphen 8107 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8107 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
In a preferred embodiment Lupraphen 8106 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8106 is preferably used for the production of polyurethane elastomers. Typical properties are listed in the following table:
Appearance: white to slightly yellow, solid product
OH Number 56 mg KOH/g DIN 53 240
Viscosity at 75 °C 563 mPa*s DIN 53 015
Water Content < 0.06 % by weight DIN 51 777
Acid Number < 0.8 mg KOH/g DIN EN ISO 3682
Density at 25 °C 1.15 g/cm3 DIN 51 757
Flash point > 160 °C DIN EN 22 719
Lupraphen 8106 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8106 or its product groups or the polyurethanes made from Lupraphen 8106 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8106 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
In a preferred embodiment Lupraphen 8104 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8104 is preferably used for the production of compact and cellular polyurethane elastomers. Typical properties are listed in the following table:
Appearance: slightly yellow, waxlike product
OH Number 56 mg KOH/g DIN 53 240
Viscosity at 75 °C 650 mPa*s DIN 53 015
Water Content < 0.10 % by weight DIN 51 777
Acid Number < 1.2 mgKOH/g DIN EN ISO 3682
Density at 25 °C 1.16 g/cm3 DIN 51 757
Flash point > 160 °C DIN EN 22 719 Lupraphen 8104 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8104 or its product groups or the polyurethanes made from Lupraphen 8104 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8104 has not to be marked according to the EC directive 67/548 and its guidelines.
In a preferred embodiment Lupraphen 8103 comprises a difunctional, aliphatic polyester polyol. Lupraphen 8103 is preferably used for the production of compact and cellular polyurethane elastomers. It is particularly suitable for the production of shoe sole systems. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow viscous liquid
OH Number 56 mg KOH/g DIN 53 240
Viscosity at 75 °C 525 mPa*s DIN 53 015
Water Content < 0.06 % DIN 51 777
Acid Number < 0.8 mg KOH/g DIN EN ISO 3682
Density at 25 °C 1.20 g/cm3 DIN 51 757
Colour < 75 Pt/Co,APHA DIN ISO 6271
Flash Point > 160 °C DIN EN 22 719
Lupraphen 8103 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8103 or its product groups or the polyurethanes made from Lupraphen 8103 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8103 has not to be marked according to the EC directive 67/548 and its guidelines.
In a preferred embodiment Lupraphen 8101 comprises a difunctional, aliphatic, polyester polyol. Lupraphen 8101 is preferably used to improve the fire retardancy of rigid foams, especially of PI R formulations. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow viscous liquid
OH Number 55 mg KOH/g DIN 53 240
Viscosity at 75 °C 625 mPa*s DIN 53 015
Water Content < 0.03 % DIN 51 777
Acid Number < 0.9 mgKOH/g DIN EN ISO 3682
Density at 25 °C 1.16 g/cm3 DIN 51 757
Colour 50 Pt/Co, APHA DIN ISO 6271
Flash point > 160 °C DIN EN 22 719
Lupraphen 8101 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8101 or its product groups or the polyurethanes made from Lupraphen 8101 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8101 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
In a preferred embodiment Lupraphen 8008 comprises a difunctional polyester polyol. It is based on aromatic dicarboxylic acids. Lupraphen 8008 is preferably used to improve the fire performance of rigid foams. It has been developed for the production of block foams and for the manufacture of rigid foam panels with flexible facings. It is especially recommended for the manufacture of PIR foams. Typical properties are listed in the following table:
Appearance: colourless to pale yellow viscous liquid
OH Number 238 mg KOH/g DIN 53 240
Viscosity at 25 °C 3300 mPa*s DIN 53 015
Water Content < 0.1 % DIN 51 777
Density at 25 °C 1.23 g/cm3 DIN 51 757
Flash point > 160 °C DIN EN 22 719
Lupraphen 8008 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annexe II, paragraph A or B. The components of Lupraphen 8008 or its product groups or the polyurethanes made from Lupraphen 8008 are listed in the 21 CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8008 is not classified as dangerous for supply according to the EC directive 67/548 and its amendments.
In a preferred embodiment Lupraphen 8007 comprises a difunctional polyester polyol based on aromatic dicarbonic acids. Lupraphen 8007 is preferably used to improve the fire retardancy of rigid foams, especially of PIR formulations. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow, viscous liquid
OH Number 240 mg KOH/g DIN 53 240
Viscosity at 25 °C 12 500 mPa*s DIN 53 015
Viscosity at 75 °C 175 mPa*s DIN 53 015
Water Content < 0.07 % DIN 51 777
Acid Number < 1 .8 mg KOH/g DIN EN ISO 21 14
Density at 25 °C 1.2 g/cm3 DIN 51 757
Colour < 2 iodine DIN 6162
Flash point > 160 °C DIN EN 22 719
Lupraphen 8007 is a polymer or no-longer-polymer, made from monomers and additives, which are listed in the directive 90/128/EG (Europe) and its amendments (latest: 2004/19/EG), in annex II, paragraph A or B or annex III, paragraph A or B. The components of Lupraphen 8007 or its product groups or the polyurethanes made from Lupraphen 8007 are listed in the 21 CFR, part 175 105 (edition of April 1, 1998) of FDA (USA). Lupraphen 8007 has not to be marked according to the EC directive 67/548 and its guidelines. In a preferred embodiment Lupraphen 8004 comprises a branched, aromatic-aliphatic polyester polyol. Lupraphen 8004 is preferably used for the production of polyurethane rigid foam systems. Typical properties are listed in the following table:
Appearance: colourless to slightly yellow solid
OH Number 383 mg KOH/g DIN 53 240
Viscosity at 75 °C 1 363 mPa*s DIN 53 015
Water Content < 0.08 % DIN 51 777
Acid Number < 1.2 mg KOH/g DIN EN ISO 3682
Density at 25 °C 1.1 1 g/cm3 DIN 51 757
Colour < 10 iodine DIN 6162
Flash point > 160 °C DIN EN 22 719
Lupraphen 8004 is a polymer or no-longer-polymer, made from monomers, which are listed in the German consumer goods regulation, annex 3, paragraph A or B as well as in the directive 90/128/EG (Europe) and its amendments (latest: 96/1 1/EC), in annex II, paragraph A or B. The components of Lupraphen 8004 or its product groups or the polyurethanes made from
Lupraphen 8004 are listed in the 21st CFR, part 175 105 (edition of April 1 , 1998) of FDA (USA). Lupraphen 8004 has not to be marked according to the EC directive 67/548 and its guidelines.
Polycarbonate (PC)
Polycarbonates relate to polymers containing carbonate groups (-0-(C=0)-0-). Most polycarbonates of commercial interest are derived from rigid monomers, which due to their final structure are very durable materials. Although it has high impact-resistance, it has low scratch- resistance and unlike most thermoplastics, polycarbonate can undergo large plastic deformations without cracking or breaking. A balance of useful features including temperature resistance, impact resistance and optical properties position polycarbonates between commodity plastics and engineering plastics. Preferred PC components are: Makrolon 2400, Makrolon 2405, Makrolon 2800, Makrolon 2805.
Polycaprolactone (PCL)
Polycaprolactone (PCL) is biodegradable polyester with a low melting point of around 60°C and a glass transition temperature of about -60°C. The most common use of polycaprolactone is in the manufacture of speciality polyurethanes. Polycaprolactones impart good water, oil, solvent and chlorine resistance to synthetic materials. Preferred PCL components are: Perstorp Capa 6400, Perstorp Capa 6500, Perstorp Capa 6800.
Additives:
It is preferred that the plastic material according to the present invention comprises additives. These additives are in particular organic or inorganic compounds. These additives are added, blended, mixed, processed, manufactured and/or compounded preferably together with educts, intermediates or end-products of the plastic material according to the present invention. Fillers:
Fillers improve performance and/or reduce production costs. Stabilizing additives and/or fire retardants for example lower the flammability of the material. The plastic material contains for example fillers which are relatively inert and inexpensive materials that make the product cheaper by weight. Typically fillers are mineral in origin, e.g., chalk. Some fillers are more chemically active and are called reinforcing agents.
Plasticizers:
Since many organic polymers are too rigid for particular applications, they are blended with plasticizers, such as oily compounds, that confer improved rheology.
It is further preferred that additives comprise plasticizer. Plasticizers are in particular substances, mainly esters, which are added to a polymer in order to improve its flexibility and/or extendability. The addition of a plasticizer lowers melt viscosity, glass transition temperature and modulus of elasticity. Plasticizers allow the manufacture of a broad spectrum of different materials. At the same time, they create the conditions required for the application of a large number of mild and energy-saving processing methods.
Plasticizers for plastics are to be understood as additives, and may relate to phthalate esters in PVC applications. Plasticizers typically work by embedding themselves between the chains of polymers, spacing them apart (increasing the "free volume"), and thus significantly lowering the glass transition temperature for the plastic and making it softer. For plastics such as PVC, the more plasticizer added, the lower its cold flex temperature will be. This means that it will be more flexible and its durability will increase as a result of it.
Plasticizers make it possible to achieve improved compound processing characteristics, while also providing flexibility in the end-use product. Ester plasticizers are selected based upon cost- performance evaluation. The rubber compounder must evaluate ester plasticizers for
compatibility, processibility, permanence and other performance properties. The wide variety of ester chemistries that are in production include sebacates, adipates, terephthalates, dibenzoates, gluterates, phthalates, azelates, and other specialty blends. This broad product line provides an array of performance benefits required for the many elastomer applications such as tubing and hose products, flooring, wall-coverings, seals and gaskets, belts, wire and cable, and print rolls. Plasticizer-elastomer interaction is governed by many factors such as solubility parameter, molecular weight and chemical structure.
Colorants:
Colorants are common additives, although their weight contribution is small. Additives may also include chain extenders, cross linkers, surfactants, flame retardants, blowing agents, pigments, and fillers. The plastic material according to the present invention for example can be made in a variety of densities, viscosity, resistance, chemical stability, biological stability, physical stability, elasticity and/or hardnesses by varying the polyol, the polycarbonate, the polycaprolactone, the nanoclay and/or the additives. Phosphor components:
Phosphor components can preferably act as additives, performing preferably as stabilizers, dispersion agents and/or elasticity modulators.
The phosphor components, in particular the phosphite components described herein, provide advantageous effects with respect to enhancing the dispersion of nanoclay particles in the plastic material.
Dispersion is a description of a system or effect in which particles are dispersed in a continuous phase of a different composition. In the context of the present invention, the phosphor component enables enhanced dispersion of the nanoclay in the plastic material during manufacture, thereby resulting in improved homogenous distribution of the nanoclay. Improved dispersion and subsequently improved distribution of the nanoclay thereby assists in providing increased stability of the plastic material produced.
Increased stability of the plastic relates preferably to enhanced stability under various potential stresses. During plastic manufacture the various molecules are distributed in a particular form and in particular relative amounts. Homogenous distribution of the various components enables greater stress resistance, which can be termed as greater stability. Enhanced stability of a plastic material relates to enhanced tolerance of the individual molecules of the plastic to change, caused by structural, chemical or other forms of stress, before structural damage occurs.
Enhanced stability, in one embodiment, relates to a reduced likelihood of, or greater resistance under mechanical stress to, the formation of e. g. stress whitening or crease whitening of the material. The stability may also relate to an enhanced resistance to change in colour or formation of a turbid appearance. Increased stability also relates to reduces in the frequency of
compatibility problems between components during manufacture, which may occur if the various components are not sufficiently homogenously mixed. The phosphor components of the present invention provide an appropriate means for enhancing the stability of a plastic material.
The Charpy impact test may also be applied for ascertaining the stability of a plastic material. Also known as the Charpy V-notch test, the Charpy test is a standardized high strain-rate test which determines the amount of energy absorbed by a material during fracture. This absorbed energy is a measure of a given material's notch toughness and acts as a tool to study
temperature-dependent ductile-brittle transition.
The phosphor components as described herein also enable greater elasticity of the plastic materials described herein. The elasticity of a material can be determined by various methods as described herein, such as ASTM D638, which may be used for determining either elasticity or rupture resistance. For this test, plastic samples are either machined from stock shapes or injection moulded. The tensile testing machine pulls the sample from both ends and measures the force required to pull the specimen apart and how much the sample stretches before breaking. Via this approach either elasticity or plasticity may be assessed, whereby the deformed plastic after stress application may wither revert to its original shape or maintain an elongated shape (in the case of stretching). Preferably the materials as described herein show both enhanced elasticity and plasticity in comparison to materials without additives. The final elastic and plastic properties of the materials will depend on the precise components used in the manufacturing process.
Phosphor components according to the present invention comprise for example phosphites. In particular phosphites are salts of phosphorous acid, H3PO3 and following the lUPAC naming recommendations the phosphite ion would be P03 3~ a salt of P(OH)3. Phosphite also comprises salts containing HP03 2~. Phosphor component comprises also the diprotic HP(0)(OH)2 with for example the name phosphonic acid and suitable salts thereof. Substances comprising the formula HP03 2~ as ion substance with in particular the naming phosphonate also fall under the definition of phosphor component. The term phosphor component also comprises phosphite ester, an organophosphorus compound with the formula P(OR)3.
Phosphor component according to the present invention comprises for example phosphates. A phosphate is in particular an inorganic chemical, is a salt of phosphoric acid. In organic chemistry, a phosphate, or organophosphate, is an ester of phosphoric acid. Inorganic phosphates are in particular mined to obtain phosphorus for use in agriculture and industry. At elevated
temperatures in the solid state, phosphates can condense to form pyrophosphates. The chemical properties of phosphates relate in particular to its functional group. Phosphates derive in particular from phosphoric acid and the functional group of phosphates can be found in weakly acidic aqueous solution. In more basic aqueous solutions, the group donates the two hydrogen atoms and ionizes as a phosphate group with a negative charge of 2. The phosphate ion is a polyatomic ion with the empirical formula P04 3" and a molar mass of 94.97 g/mol. It consists of one central phosphorus atom surrounded by four oxygen atoms in a tetrahedral arrangement. The phosphate ion carries a negative three formal charge and is the conjugate base of the hydrogen phosphate ion, HP04 2", which is the conjugate base of H2P04 ", the dihydrogen phosphate ion, which in turn is the conjugate base of H3P04, phosphoric acid. A phosphate salt forms when a positively charged ion attaches to the negatively charged oxygen atoms of the ion, forming an ionic compound. Many phosphates are not soluble in water at standard temperature and pressure. The sodium, potassium, rubidium, caesium and ammonium phosphates are all water soluble. Most other phosphates are only slightly soluble or are insoluble in water. As a rule, the hydrogen and dihydrogen phosphates are slightly more soluble than the corresponding phosphates. The pyrophosphates are mostly water soluble. Aqueous phosphate exists in four forms. In strongly basic conditions, the phosphate ion (P04 3") predominates, whereas in weakly basic conditions, the hydrogen phosphate ion (HP04 2") is prevalent. In weakly acid conditions, the dihydrogen phosphate ion (H2P04 ") is most common. In strongly acidic conditions, trihydrogen phosphate (H3P04) is the main form.
The term phosphor component according to the present invention in particular comprises
• Hypophosphite - H2P02 "
• Organophosphorus compounds
• Phosphate for conversion coating
• Phosphine - PR3
• Phosphine oxide - OPR3
• Phosphinite - P(OR)R2
• Phosphonite - P(OR)2R
• Phosphite - P(OR)3 • Phosphinate - OP(OR)R2
• Phosphonate - OP(OR)2R
• Phosphate - OP(OR)3, such as triphenyl phosphate
• Polyphosphate - Pn03n+i(n+2)"
• Substances used during Phosphorylation
• Pyrophosphate - P2O74"
In one embodiment the plastic material of the present invention is characterised in that the stabilizer and/or elasticity modulator is a phosphor component, such as salts that derive from phosphor with organic or inorganic acids, phosphites and/or phosphates, for example trisnonylphenyl phosphite, bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4- di-t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
Phosphor components as stabilizers and/or elasticity modulators may also be selected from: Doverphos 4 (TNPP): Trisnonylphenol phosphite
Doverphos 4-HR (TNPP): Trisnonylphenol phosphite +0.75% triisopropanolamine
Doverphos 4-HR Plus (TNPP): Trisnonylphenol phosphite +1.0% triisopropanolamine
Doverphos HiPure 4 (TNPP): Trisnonylphenol phosphite 0.1 % max. free nonylphenol
Doverphos HiPure 4-HR (TNPP): Trisnonylphenol phosphite 0.1 % max. free nonylphenol (+0.75% triisopropanolamine)
Doverphos 10 (TPP): Triphenyl phosphite
Doverphos 10 HR (TPP): Triphenyl phosphite +0.5% triisopropanolamine
Doverphos 213 (DPP): Diphenyl phosphite
Doverphos 7 (PDDP): Phenyl diisodecyl phosphite
Doverphos 8 (DPDP): Diphenyl isodecyl phosphite
Doverphos 9 (DPIOP): Diphenyl isooctyl phosphite
Doverphos 1 1 : Tetraphenyl dipropyleneglycol diphosphite
Doverphos 12: Poly(dipropyleneglycol) phenyl phosphite
Doverphos 613: Alkyl (C12-C15 ) bisphenol A phosphite
Doverphos 675: Alkyl (C10) bisphenol A phosphite
Doverphos 6 (TDP): Triisodecyl phosphite
Doverphos 49 (TTDP): Tris (tridecyl) phosphite
Doverphos 53 (TLP): Trilauryl phosphite
Doverphos 72: Tris (dipropylene glycol) phosphite
Doverphos 253: Dioleyl hydrogen phosphite
Doverphos S-9228: Bis (2,4-dicumylphenyl) pentaerythritol diphosphite
Doverphos S-9228T: Bis (2,4-dicumylphenyl) pentaerythritol diphosphite
Doverphos S-9228PC: Bis (2,4-dicumylphenyl) pentaerythritol diphosphite
Doverphos S-480: Tris (2,4-di-tert-butylphenyl) phosphite
Doverphos S-680: Distearyl pentaerythritol diphosphite
Doverphos S-682: Distearyl pentaerythritol diphosphite w/<1 % TIPA
Stabilizer: It is further preferred that the additives comprise stabilizers that are alternative to or in addition to the phosphor components mentioned herein. The stabilizer in particular offer superior thermal stability and low volatility under extended high temperature conditions, excellent atmospheric stability and in-polymer hydrolytic stability, outstanding processing protection against
discoloration and thermal degradation. Furthermore, the stabilizer are suitable to enhance or stabilize the manufacturing process in order to achieve constant and reproducible product qualities with dedicated properties or the plastic material for the present invention. Stabilizer can be of high or low molecular weight, they show preferably low volatility. Stabilizer also comprises foam stabilizer.
Further preferred additives are TEGOSTAB B 1048; TEGOSTAB B 41 13, TEGOSTAB B 4690, TEGOSTAB B4900, TEGOSTAB B 8002, TEGOSTAB B 8040, TEGOSTAB B 8040 LV,
TEGOSTAB B 8052, TEGOSTAB B 81 10, TEGOSTAB B 8150, TEGOSTAB B 8221 ,
TEGOSTAB B 8225, TEGOSTAB B 8228, B 8229, TEGOSTAB B 8232, TEGOSTAB B 8233,
TEGOSTAB B 8234, TEGOSTAB B 8239, TEGOSTAB B 8242, TEGOSTAB B 8244,
TEGOSTAB B 8247, TEGOSTAB B 8255, TEGOSTAB B 8260, TEGOSTAB B 8275,
TEGOSTAB B 8285, TEGOSTAB B 8300, TEGOSTAB B 8301 , TEGOSTAB B 8301 CL,
TEGOSTAB B 8315, TEGOSTAB B 8317, TEGOSTAB B 8324, TEGOSTAB B 8325,
TEGOSTAB B 8330, TEGOSTAB B 8334, TEGOSTAB B 8356, TEGOSTAB B 8366,
TEGOSTAB B 8404, TEGOSTAB B 8407, TEGOSTAB B 8408, TEGOSTAB B 8409,
TEGOSTAB B 8418, TEGOSTAB B 8423, TEGOSTAB B 8433, TEGOSTAB B 8443,
TEGOSTAB B 8444, TEGOSTAB B 8450, TEGOSTAB B 84503, TEGOSTAB B 8460,
TEGOSTAB B 8461 , TEGOSTAB B 8462, TEGOSTAB B 8465, TEGOSTAB B 8466,
TEGOSTAB B 8467, TEGOSTAB B 8469, TEGOSTAB B 8470, TEGOSTAB B 8474,
TEGOSTAB B 8476, TEGOSTAB B 8481 , TEGOSTAB B 8484, TEGOSTAB B 8485,
TEGOSTAB B 8486, TEGOSTAB B 8487, TEGOSTAB B 8490, TEGOSTAB B 8491 ,
TEGOSTAB B 8492, TEGOSTAB B 8495, TEGOSTAB B 8496, TEGOSTAB B 8498,
TEGOSTAB B 8512, TEGOSTAB B 8513, TEGOSTAB B 8517, TEGOSTAB B 8522,
TEGOSTAB B 8523, TEGOSTAB B 8526, TEGOSTAB B 8629, TEGOSTAB B 8680,
TEGOSTAB B 8681 , TEGOSTAB B 8707 LF2, TEGOSTAB B 8715 LF2, TEGOSTAB B 8716
LF2, TEGOSTAB B 8724 LF2, TEGOSTAB B 8726 LF2, TEGOSTAB B 8727 LF2, TEGOSTAB B 8729 LF2, TEGOSTAB B 8732 LF2, TEGOSTAB B 8734 LF2, TEGOSTAB B 8736 LF2,
TEGOSTAB B 8737 LF2, TEGOSTAB B 8738 LF2, TEGOSTAB B 8742 LF2, TEGOSTAB B 8745 LF2, TEGOSTAB B 8863 Z, TEGOSTAB B 8870, TEGOSTAB B 8871 , TEGOSTAB B 8905, TEGOSTAB B 8930, TEGOSTAB B 8936, TEGOSTAB B 8946 PF, TEGOSTAB B 8948,
TEGOSTAB B 8950, TEGOSTAB B 8951 , TEGOSTAB B 8952, TEGOSTAB B 8954,
TEGOSTAB B 8960, TEGOSTAB B 8993, TEGOSTAB BF 2270, TEGOSTAB BF 2370,
TEGOSTAB BF 2470 BF.
A preferred additive of the present invention relates to polypropylene, preferably carboxylated polypropylene, more preferably a carboxylated polypropylene functionalised with maleic anhydride. Such a substance may also be known as maleated polypropylene. One example of such a compound is SCONA TPPP 21 12 FA, which is described as an adhesion promoter for polymer compounds and a dispersing agent for nano clays in polypropylene. For adhesion formulations, it is recommended that the carboxylated polypropylene as an adhesion promoter is used in granulate form. A concentrate can be made from nano clay and the modifier is created by means of a twin-screw extruder with high shear forces first, which is then incorporated into the polymer.
Physical and chemical properties of SCONA TPPP 21 12 FA
Appearance : powder
Colour : light yellow
Odour : characteristic
Flash point : not applicable
Ignition temperature : not applicable
Lower explosion limit : not applicable
Upper explosion limit : not applicable
pH : not applicable
Melting point/range : 155 - 170 °C (DIN 53461 )
Initial boiling point : not applicable
Vapour pressure : not applicable
Density : 0,89 - 0,92 g/cm3 at 20 °C (1 .013 hPa; Method: DIN 53479)
Bulk density : 0,45 - 0,55 kg/m3 (method: DIN 53466)
Elasticity tests
The preferred method for testing plastic tensile strength and/or elasticity is ASTM D638. This test method is designed to produce tensile property data for the control and specification of plastic materials. Tensile properties may provide useful data for plastics engineering design purposes. In general, the "stiffness" or "rigidity" or "elasticity" of a plastic may be examined. The exact stress- strain characteristics of plastic materials are highly dependent on such factors as rate of application of stress, temperature, previous history of specimen, etc. However, stress-strain curves for plastics, determined as described in this test method, almost always show a linear region at low stresses, and a straight line drawn tangent to this portion of the curve permits calculation of an elastic modulus of the usually defined type. Such a constant is useful if its arbitrary nature and dependence on time, temperature, and similar factors are realized.
The ASTM D638 test method covers the determination of the tensile properties of unreinforced and reinforced plastics in the form of standard dumbbell-shaped test specimens when tested under defined conditions of pretreatment, temperature, humidity, and testing machine speed. This test method can preferably be used for testing materials of any thickness up to 14 mm (0.55 in.). However, for testing specimens in the form of thin sheeting, including film less than 1.0 mm (0.04 in.) in thickness, method ASTM D882 is the preferred test method. Materials with a thickness greater than 14 mm (0.55 in.) should be reduced by machining. This test method includes the option of determining Poisson's ratio at room temperature. This test method and ISO 527-1 or -2 are technically equivalent. This test method covers the determination of Poisson's ratio preferably obtained from strains resulting from uniaxial stress.
Extrusion
Preferably, either single, twin or multiple screw extrusion is used as method for mixing, compounding, or reacting polymeric materials in the present invention. The flexibility of twin screw extrusion equipment allows this operation to be designed specifically for the formulation being processed. For example, the two screws may be co-rotating or counter-rotating, intermeshing or non-intermeshing. In addition, the configurations of the screws themselves may be varied using forward conveying elements, reverse conveying elements, kneading blocks, and other designs in order to achieve particular mixing characteristics. Alternatively, single screw configurations may be modified to enable different strengths or degrees of in homogenisation, for example by changing the structure of the screw in any given screw segment. According to the present invention, extrusion comprises a process to create objects of a fixed, cross-sectional profile. The material is pushed or drawn through a die of the desired cross-section. The two main advantages of this process over other manufacturing processes are its ability to create very complex cross- sections and work materials that are brittle, because the material only encounters compressive and shear stresses. It also forms finished parts with an excellent surface finish. Extrusion may be continuous or semi-continuous. The process begins by heating the stock material (for hot or warm extrusion). Hot extrusion is a hot working process, which means it is done above the material's recrystallization temperature to keep the material from work hardening and to make it easier to push the material through the die. In addition to extrusion also calendering, compression molding, injection molding, spread coating, milling, printing, dip coating, casting, spraying are preferred manufacturing techniques for production of the plastics material of the present invention.
Extruder
Preferred extruders of the invention are:
1. Coperion ZSK 32 MC Extruder ( Coperion GmbH)
Twin screw extruder
- screw diameter: 32 mm
- screw length: 48 D
- through put: 10 bis 200 kg/h
2. Leistritz Extruder Micro 27-36D (LEISTRITZ EXTRUSIONSTECHNIK GMBH)
Twin screw extruder
- screw diameter: 27 mm
- through put: 3-30 kg/h
- screw length (2): 36 D
3. Granulator Pell-tec SP 50 EN (PELL-TEC Pelletizing Technology GmbH)
Strand granulator for up to 8 strands
Strand velocity: 15-60 m/min
Granulate length between 2-15mm 4. Gala LPU (Gala Kunststoff- und Kautschukmaschinen GmbH)
Below water granulation, Granulation energy consumption: 2 to 150 kg/h
5. Melt equipment Concept B/12/1 Premelter KPC 12 (Robatech GmbH)
Hot melt pump for feeding the polyols
6. Brabender DDW MD-FW40N/5plus-50 (Brabender Technologie KG)
Gravimetric dosing balance with operation unit Congrav OP 5 - Touch
7. Brabender DDW MD2-DDSR 20-10Q (Brabender Technologie KG)
Gravimetric dosing balance with operation unit Congrav OP 5 - Touch
8. Single screw extruder (similar to Buss-Ko-Kneter)
The extruder is a 44D extruder, meaning 44x53 = 2,33 m. There are 1 1 temperature zones along the extruder, and 8 in the die, sieve and neck. Every temperature zone is 212 mm (21 .2 com). The screw is 53mm, co-rotating, 3 lobs, 44D.
Further preferred embodiments
The incorporation of nanoclays into the TPU composites of the present invention enables a novel polymerization and/or adhesion and therefore a reduction of process steps in the production of such synthetic materials.
The present method can also use recycled TPUs as starting materials of the present invention. The method can be used for recycling polymers or recycled plastics (synonym use). In the preferred embodiment the mineral or organic nanocomposites the polymer contains between 0 to 99% of the virgin polymer and between 1 to 100% of a recycling polymer, which consists in the range of 0 to 100%.
Preferably the polymer melt contains less than 10% weight% as nanoclay before formation of the disclosed nanocomposite. The polymer melt, polymerization before formation of the disclosed nanocomposite contains preferably less than 2%, more preferably less than 1 %, even more preferably less than 0.5% as a nanoclay.
The applicable nanoclays can be intercalated with organic molecules (e.g. ammonia ions) between the proximate layers. The incorporation of polymers between the layers with a minimum of 3A, preferably 5A and for the interim layer (interlaminar) with a distance of approximately 10- 15A and up to 100A, is performed for example via mixing and higher shear. Clays possess the property of flaking. The amount of the mixture, mixed with the recycling-polymer can vary. Clay loadings are in the range of approximately 0.01 to 40% weight%, preferably approximately 0.05 to 20%, more preferably 0.5 to 15% and most preferably 1 to 10% of the total composition. It is preferred that the clay contains less than 15% of the nanocomposite.
An additional aspect of the described process is the form stability (peeling) of the clays which are mechanically and chemically split. For gaining the full advantage out of the process and composition the clays are finely dispersed and are in fact nanoclays. The used nanocomposites refer to a mixture out of recycled polymer and a clay which is in minimum partly flaked off. The nanocomposites can also be used as new material. The type of mixture of the polymer melt and the clay can comprise compounding, extrusion, mixing or every other method for bringing polymer and resins together with in minimum partly individual platelets.
A recycling polymer is a polymer material which is implemented after a certain period of use. The application can be intended for the casting formation of polymers and products or the application of a dedicated purpose. Two different types of recycling polymers exist: post-industrial and post- consumer. In general post-industrial recycling polymers are these polymer-materials which derive from an industrial manufacturing process. Usually post-industrial recycling polymers do not get contaminated with other materials or polymers.
Recycled polymers can be used for new material, especially when use for superior physical properties. Furthermore, the described recycled polymer-nanocomposites show retention properties so that the physical properties remain without significant disadvantageous effect on the recycling via additional steps in comparison to polymers which are improved without nanoclays.
Due to the nano technology described herein it is possible to produce polymers via essentially HFCKW (comprises CFC - chloroflurocarbon) free processes.
The synthetic materials comprising 47.784 % TPU, 12.0 % Polyol, 0.216 % Nanoclay, 28 % PC and 12 % PCL, in addition to the materials comprising 47.946 % TPU, 12.0 % Polyol, 0.054 % Nanoclay, 28 % PC and 12 % PCL are suitable for longer storage. The substance shows surprisingly low tendency for degradation. In particular the handling process is enhanced.
Surprisingly these substances are less irritant, inert, easier to process and show stronger mechanical properties than conventional synthetic materials.
The polymers of the present invention exhibit the following advantages:
Non-poisonous
Lighter than known materials
Reduction in production and material costs
Simpler production processes
Emission avoidance
Low hydrolysis hazards
Simple to store and transport
The following disadvantages of those materials known in the art are avoided:
contamination of drinking water
danger to health of end-users (avoidance of potential cancer risk) contamination of foodstuffs via packaging materials
agricultural damage due to toxic substances in soil.
Further advantages of the subject matter of the invention relate to:
The material resists temperature change processes with daily variation. Permanent temperature resistance.
Maximal short term temperature resistance is +250°C.
Fire behaviour:
- according to DIN 4102: part 1 - construction material class B2
- according to DIN 4107, part 7 - resistant and against flying sparks and heat radiation, which is applicable for flat roof coatings.
The technical characteristics of the preferred embodiments of the synthetic material of the present invention may be determined by the following tests. A barrage of standard tests was carried out on the plastics of the present invention, as indicated herein, that have indicated desirable properties. The following tests are provided as examples of appropriate tests:
Plastic property tested Normalised test
bending test DIN EN ISO 178
Charpy notched impact strength DIN EN ISO 179-1/1 eA
Charpy notched impact strength DIN EN ISO 179-1/1 eU
Glow wire test ( GWFI ) DIN EN 60695-2-12
Glow wire test ( GWIT ) DIN EN 60695-2-13
Residue on ignition DIN EN IS03451
Residual moisture determination DIN EN ISO 15515
Melt volume-flow rate MVR DIN EN ISO 1 133
Shore A DIN EN ISO 868
Shore D DIN EN ISO 868
density testing DIN 53479 Auftriebsverfahren tensile test DIN EN ISO 527
Permeation ( hollow body ) DIN EN ISO 15105/1
Permeation ( hollow body ) DIN EN ISO 15105/2
density testing DIN EN ISO 1 133
ash determination DIN EN ISO 3451-1
color measurement DIN 6164
density DIN EN ISO 1 183-1
Determination of viscosity number EN ISO 1628
Moisture Determination by Karl Fischer DIN EN ISO 15512-B
Color measurement DIN 5033
Color measurement DIN 5033
Hot storage test DIN 53497
Tension modulus DIN 53504
tensile strength DIN 53504
elongation at break DIN 53504
tensile strength DIN 53504
Stress at 10 % elongation DIN 53504
Stress at 50 % elongation DIN 53504 Stress at 100 % elongation DIN 53504
Stress at 300 % elongation DIN 53504
Tension E modulus DIN EN ISO 527 tensile strength DIN EN ISO 527 elongation at Yield DIN EN ISO 527 yield stress DIN EN ISO 527
Elongation at tensile strength DIN EN ISO 527
Flexural modulus DIN EN ISO 178 flexural strength DIN EN ISO 178
Flexural strain at flexural strength DIN EN ISO 178
Vicat softening temperature DIN EN ISO 306
Shape maintenance HDT (0.45 MPa) DIN EN ISO 75-2
Shape maintenance HDT (1.8 MPa) DIN EN ISO 75-2
MFR / MVR DIN EN ISO 1 133 rheology ISO 1 1443
Residue on ignition DIN EN ISO 3451-1 density DIN EN ISO 1 183-1-A
Ball indentation hardness DIN EN ISO 2039-1 burning rate FMVSS 302
Flame resistance UL 94 DIN EN 60695-1 1-10 glow-wire resistance GWFI IEC 60695-2-12 glow-wire resistance GWIT IEC 60695-2-13
Volume resistivity IEC 60093 flowability DIN EN ISO 6186 sieve analysis DIN 66165
Tensile Test climate 23/50 -40 0 C to 200 0 C DIN EN ISO 527 foam production DIN 53571 elastomer properties DIN 53504
Tear Resistance DIN ISO 34-1
Hydrostatic test DIN EN ISO 604
Climate 23/50 , -10 0 C to 200 0 C DIN 53421
Climate 23/50 , -10 0 C to 200 0 C DIN 53421
Torsion pendulum ( forced oscillation ) ASTM D 4065
Vickers hardness test ( microhardness ) DIN EN ISO 6507-1
Impact Test ( Izod ) DIN EN ISO 180
Impact test ( Dynstat ) DIN 53435
Tensile impact DIN EN ISO 8256
Tensile creep DIN EN ISO 899-1
Creep - 3-point bending tests DIN EN ISO 899-2
Determining the compression set after DIN 53517
Determination of tension DIN ISO 2285
Fatigue test (DIN 50100) Coefficient of linear expansion DIN 53752
Thermal penetration measurement ISO 1 1359-1
Thermogravimetric analysis TGA DIN 51006
30 deg C to 1000 deg C DIN EN ISO 1 1358
Examination of the dimensional stability DIN 53462
Testing the Vicat softening temperature (air) DIN ISO 306
Examination of the deflection temperature HDT DIN EN ISO 75
Thermal conductivity of solid substances EN ISO 22007
extraction guantitatively DIN EN ISO 1407
Residue on ignition (plastics, elastomers) DIN 53568 T1
Loss on ignition (GRP) (DIN EN 60)
carbon black content quantitatively DIN 53585
Measurement of density , buoyancy method DIN 53479
Measurement of bulk density with a varying filling level DIN 53468
Determination of water content DIN EN ISO 12937
water absorption DIN EN ISO 62
Fogging (reflectometer ) DIN 75201 A
odor performance VDA 270
Solution viscosity , viscosity DIN EN ISO 1628
Measurement of filled and unfilled samples at DIN EN ISO 307
23 0 C to 80 0 C , and temperatures DIN EN ISO 1628
Melt index , melt volume flow rate , melt density DIN EN ISO 1 133
thermal analysis DIN EN ISO 1 1358 und DIN 51006
KGV ISO 13320-1
Karl Fischer test DIN EN ISO 15512
moisture determination In Anlehnung an die Norm DIN EN density determination DIN EN ISO 1 183-3 Helium-
MFR / MVR DIN EN ISO 1 133
B2 fire test DIN 4102, Teil 1
A number of properties have been identified for which the plastic material as described herein demonstrates beneficial characteristics:
Density Approximately 1 .000 to 1 .200 kg / nT3
Humidity absorbs no humidity
Changement of measurement values after None
thermal storage
Tension properties Equivalent or better then Thermoplast / PE
Elastic tension properties Equivalent or better then Thermoplast / PE
Elastic stretch properties Equivalent or better then Thermoplast / PE
Tension resistance Equivalent or better then Thermoplast / PE
Soot content none with PU-basis
Soot distribution none with PU-basis
Permanent temperature resistance -40 to +100C
Max. shorttime thermal load +250°C Rupture restistance over 200%, preferably over 700%
Chemical resistance resistant against aggressive chemicals
Further chemical resistance solvents, softeners, mineral oils, alkalis, fuels, emissions
Biological resistance fungus, microbs, roots growth, deterioration, putrefaction
Further biological resistance acc. to DIN 53930-31 and DIN 4062
Mechanical resistance Improved
Environmental impact none
Humidity behavior conform DIN 4108
Vapour diffision resistance factor Q 50 acc. DIN 52615
UV-resistance Little or no influence from UV
Strength of root acc. DIN 4062
Processing advantage Seamless
Ground water risks none as there is no embrittlement of material due to PUR-basis
Compression properties Sufficient compression resistance according to
DIN 53421
Thermal insulation properties Beneficial thermal insulation according to DIN
52615
The modified thermoplastic polyurethanes (TPU) of the invention show the following properties: excellent material properties (vapour porosity, heat conductance, melting point), nano-absorber properties, flexible adaption for dedicated purpose, low material costs (100% lower than PTFE), processing with existing / available production lines without expensive new installations. The plastic may be processed as a foil, which can be manufactured with environment friendly processes like blowing extrusion and it is possible to produce TPU foils in different types, for example 3, 4, 5, 6, 7, 8, 9; 12 my foils. The foils are particularly resistant against microbes, fungus, UV radiation, yellowing, hydrolysis, enzymes, high humidity, chemicals, oils, fats, week acids, carbon acid, alkali, carbon oils, alcohols.
FIGURES
The figures provided herein represent examples of particular embodiments of the invention and are not intended to limit the scope of the invention. The figures are to be considered as providing a further description of possible and potentially preferred embodiments that enhance the technical support of one or more non-limiting embodiments.
Short description of the Figures
Figure 1 IR-spectrum (ATR) of the sample P1
Figure 2 IR-spectra comparison: starting granules - chloroform extract
Figure 3 Gas chromatogram of the methanolic extract of the sample P1
Figure 4 IR-spectrum of the granules P3
Figure 5 IR-spectrum of the methanolic extract of the sample P3
Figure 6 Gas chromatogram of the methanolic extract of the sample P3
Figure 7 Manufacturing flow chart EXAMPLES
The examples provided herein represent practical support for particular embodiments of the invention and are not intended to limit the scope of the invention. The examples are to be considered as providing a further description of possible and potentially preferred embodiments that demonstrate the relevant technical working of one or more non-limiting embodiments.
Investigation of different mixtures and additives
The compounds in the following examples are preferably processed via extrusion. However, the compounds can also be manufactured via blowing, casting, grinding and/or spraying. Extrusion is conducted with preferably a single or twin screw extruder. The extruder is for example equipped with 1 to 15 temperature zones. Screw diameter may vary for example between 10 mm and 50 mm. The temperature range is in particular between 50 and 250°C. As feeder main hopper and/or side feeder are used, also liquid injection is a possible option. Preferably the extruder comprises a degassing option. Screw speed is adjustable preferably between 0 and 1000 rpm.
In a preferred embodiment a co-rotating double screw extruder is used (Leistritz Micro 27 - 36D, screw diameter = 27 mm; L/D = 36) together with a strand granulating system. The detailed configuration can be described as follows: The extruder comprises 10 temperature zones, with increasing temperature, from 150 - 170 deg C, increasing to 180 - 200 deg C. A screw speed of in particular 400 rpm is applied. As resulting pressure 8 bar was observed. The extrusion efficacy was 20 %. The strand pelletizer had a take-off speed of 30 m/min. The output was in the range of 5 to 8 kg/h. The substances reside in the extruder for 90 seconds.
The manufacturing is conducted in several steps (see figure 7). In a first step a masterbatch is manufactured (P1 ). In a preferred embodiment this masterbatch generation 2 is manufactured in the following way:
Mixing of thermoplastic polyurethane (TPU) and a nanoclay component and thereby producing P1. It is preferred that P1 is produced in two steps, namely the mixture of thermoplastic polyurethane (TPU) and a nanoclay component, thereby producing P0 according to figure 7, followed by the mixture of thermoplastic polyurethane (TPU) and P0, thereby producing P1 . This product P1 is called masterbatch generation 2. Further preferred is that variants of the masterbatch generation 2 according to the selected quality and quantity of nanoclay can be produced.
After having manufactured the masterbatch generation 2 the following further process steps are carried out. A mixture of P1 with a polyol component, and optionally additional TPU and/or one or more additive, is prepared resulting in the production of P2 (according to figure 7). This P2 is in the next step mixed with a polycarbonate (PC) and polycaprolactone component (PCL), and optionally additional one or more additive, thereby producing P3 (according to figure 7). After having produced P3 it is further processed via extrusion, blowing, casting, grinding and/or spraying, to obtain particles, granules, films, fibres, foams, strands, sheets and/or foils (P4 according to figure 7).
In detail for example the following mixture was produced investigating and optimizing the composition of the plastic material. P2 (manufacturing step AP 2 according to figure 7):
20% Lupranol 4674-15 (polyol component)
15% Masterbatch generation 2
65% Desmopan 385S (TPU component)
The P2 mixture may further contains in particular a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer. In this particular example the additive was provided to AP3 during the PC and PCL mixture.
P2 was produced without any major problems. The extrusion was stable and the extruded fibres were dry but slightly sticky. The fibres were very smooth, yellowish/white in colour and rubbery. In conclusion, the combination of 15% masterbatch generation 2 with 65% TPU and 20% polyol was easily processed, without any air inclusions or phase separation.
Process step AP 3 according to figure 7:
Compounding of P2 with PC/PCL
- Mixture 1 (P2): 20% Lupranol 4674-15
15% Masterbatch generation 2
65% Desmopan 385S
- Polycarbonat (PC): Makrolon 2405
- Polycaprolacton (PCL): CAPA 6400
- Additive Stabilizer, plasticizer or elasticity modulator
The mixture contains in particular a suitable additive selected from the group filler, stabilizer, elasticity modulator, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent, abrasion reducer.
In this experiment the mixture produced via single screw extrusion (P2 according to figure 7), as described above is compounded with makrolon (PC) and PCL. As result granules (P3) were obtained that have white colour and an even round form. Three additives were tested in sucession, namely Stabilizer (Polysiloxane polyoxyalkylene block copolymer), Plasticizer (Polyadipate) and Elasticity modulator (phosphor component; trisnonylphenyl phosphite).
In this experiment, the additive was added to the AP3 method step, whereby the relative proportions of P2, PC and PCL whereby reduced according to the additional additive. Test runs were performed with 5, 10 or 15% additive.
Elasticity was assessed via ASTM D638. Assessment of various compositions as described herein was carried out and elongation with respect to rupture and elasticity were examined. The Phosphor components, in particular various phosphite components, such as trisnonylphenyl phosphite, were used in manufacture and the materials subsequently tested using ASTM D638. Unexpected benefits were seen regarding surprisingly enhanced elasticity after addition of the phosphor components.
The stability of the plastic material was assessed by empirical analysis of the frequency of polymer breaks post extrusion during application of the Charpy impact test. The nanoclay component in combination with the other plastic components enables replacement of
isocyanates, essentially replacing a cross-linking agent during plastic extrusion. Effective nanoclay distribution is therefore required for sufficient structural stability of the material. After multiple production rounds, the addition of 5% stabilizer at either AP2 or AP3 (tests were conducted with Polysiloxane polyoxyalkylene block copolymer added in AP3 with subsequent foam production, carboxylated polypropylene (Scona TPPP 21 12 FA) added during AP2, and trisnonylphenyl phosphite as a stabilizer by addition in AP2) lead to reduced material breaks post- production, enhanced homogenous distribution of all components in the mixture and reduced frequency of solubility issues during extrusion of AP3. Conclusion:
In conlcusion, the method as described above produced a novel plastic material, which was produced surprisingly without any manfucaturing difficulties. The single screw extrusion mixture to produce P2 was especially beneficial. The compound P3 was finally produced.
The compound P3 comprising 5% additive relates to the embodiment described above, whereby a relatively smaller amount of nanoclay is provided during the AP1 process step, and 5% by weight additive is added at the AP3 step with a subsequent reduction in P2, PC and PCL. The following composition(s) were obtained and tested as P3:
Additional variations on the plastic material were produced with 5% additive (either the phosphor component or a combination of the phosphor component and carboxylated polypropylene), added at either AP2 or AP3 with either a reduction in the TPU, P1 or P2 quantity, or a reduction of all components at the respective mixture/extrusion step.
Compositions as follows may therefore be produced. These embodiments represent examples and do not limit the scope of the invention. Preliminary testing has revealed reliable manufacture for all compound mixtures and improved functional properties with respect to elasticity and stability of the products.
For example when 5% phosphor component (in this series of examples phosphite components, such as trisnonylphenyl phosphite was preferably used) is added at the AP2 step with a subsequent reduction of 5% P1 , and AP3 is subsequently carried out; the following composition may be obtained:
For example when 3% phosphor component and 2% carboxylated polypropylene is added at the AP2 step with a subsequent reduction of 5% P1 , and AP3 is subsequently carried out; the following composition may be obtained: Component % by weight
TPU 44,730%
nanoclay 0,270%
Polyol 12,000%
PC 28,000%
PCL 12,000%
Phosphite component 1 ,800%
Carbox. Polypro. 1 ,200%
Total 100%
For example when 5% phosphor component is added at the AP3 step with a subsequent reduction of 5% P2, the following composition may be obtained:
For example when 3% phosphor component and 2% carboxylated polypropylene is added at the AP3 step with a subsequent reduction of 5% P2, the following composition may be obtained:
In a further embodiment, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 5% phosphor component is added at the AP2 step with a subsequent reduction of 5% P1 , and AP3 is subsequently carried; the following composition may be obtained:
In a further embodiment, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 3% phosphor component and 2% carboxylated polypropylene is added at the AP2 step with a subsequent reduction of 5% P1 , and AP3 is subsequently carried out; the following composition may be obtained:
In a further embodiment, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 5% phosphor component is added at the AP3 step with a subsequent reduction of 5% P2, the following composition may be obtained:
In a further embodiment, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 3% phosphor component and 2% carboxylated polypropylene is added at the AP3 step with a subsequent reduction of 5% P2, the following composition may be obtained:
In further embodiments of the invention, the additive (preferably a phosphor component and/or carboxylated polypropylene) is added to either the AP2 or AP3 method steps at for example 5% to each of the respective mixtures with a proportionally equal reduction of all other components in the mixture, not just the TPU, P1 or P2 component as mentioned above.
For example, when 5% phosphor component (or a combination of phosphor component and carboxylated polypropylene amounting to 5% by weight, for example 3% phosphor component and 2% carboxylated polypropylene) is added at the AP2 step with a subsequent reduction of P1 , polyol and TPU, and AP3 is subsequently carried out; the following composition may be obtained: Component % by weight
TPU 45,326%
nanoclay 0,274%
Polyol 1 1 ,400%
PC 28,000%
PCL 12,000%
Additive (Phosphite component, or phosphite
component and carbox. polypro.) 3,000%
Total 100%
For example, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 5% phosphor component (or a combination of phosphor component and carboxylated polypropylene amounting to 5% by weight, for example 3% phosphor component and 2% carboxylated polypropylene) is added at the AP2 step with a subsequent reduction of P1 , polyol and TPU, and AP3 is subsequently carried out; the following composition may be obtained:
For example, when 5% phosphor component (or a combination of phosphor component and carboxylated polypropylene amounting to 5% by weight, for example 3% phosphor component and 2% carboxylated polypropylene) is added at the AP3 step with a subsequent reduction in P2, PC and PCL, the following composition may be obtained:
For example, if a relatively smaller amount of nanoclay is provided during the AP1 process steps, when 5% phosphor component (or a combination of phosphor component and carboxylated polypropylene amounting to 5% by weight, for example 3% phosphor component and 2% carboxylated polypropylene) is added at the AP3 step with a subsequent reduction in P2, PC and PCL, the following composition may be obtained: Component % by weight
TPU 45,549%
nanoclay 0,051 %
Polyol 1 1 ,400%
PC 26,600%
PCL 1 1 ,400%
Additive (Phosphite component, or phosphite
component and carbox. polypro.) 5,000%
Total 100%
Characterization methods
Samples obtained from P1 and P3 were characterised via various analytical methods. Sample preparation related to mechanical separation of the target sample parts and preparation for the following investigation.
The following methods (amongst others) may be applied for characterisation of the products:
o ICP-MC-Anaylsis for determining the yield of the elements phosphor, iron, magnesium, aluminium and silicon,
o Determination of the annealing residue at 550°C
o Fourier-transformed IR spectroscopy (FT-IR) for integral identification of complex organic compounds. Two analyses are carried out before and after extraction of the granules. o Gas chromatography-Mass spectrometry (GC-MS) from the extract for identifying and quantifying of soluble organic substances.
Chemical analysis
Binary mixture of polyurethane and nanoclay (P1 according to figure 7)
The IR spectrum of the clear and colourless granules is shown in figure 1. The spectrum was generated with the ATR technique (diamante crystal). The spectrum shows that the plastic material, a polymer, is a polyurethane elastomer. For the investigation of the ingredients the granules were extracted either in chloroform or in methanol. During the extraction in methanol a strong swelling behaviour of the granules was observed.
The IR-spectrum of the chloroform extract in shown in figure 2. It has been compared with the IR spectrum of the starting product (granules). The spectra comparison shows that with chloroform parts of the polyurethane elastomer are becoming dissolved, probably due to the oligomeric components. The isocyanate absorption (NCO) in the spectrum of the extract shows a residual monomer at extremely low quantity.
In figure 3 the detailed description of the chromatogram is shown. In this figure less intensive peaks are considered. Peak (4) is the residual monomer 4, 4'-diphenylmethandiisocyanate with the following structural formula: A further isocyanate is indicated with peak (5). It is a residual 2,6-diisopropylphenylisocyanate with the following structural formula:
It was surprising that such a small amount of isocyanate was determined. Estimates from the analytical experimentation described herein reveal that less than 1 % isocyanate is present in the final mixture, which represents a significant reduction in comparison to known plastics, which comprise generally between 10% and 20% per weight, and therefore enables subsequently an environmentally-friendly product. Any isocyanate identified likely represents residual
contamination from the original TPU used in the reaction.
In order to further assess the quantity of isocyanate present in the plastic material, additional experimentation using a procedure for free isocyanate determination was performed. The Kubitz quantitative test according to "Analytical Chemistry", Vol. 29, pages 814-816 (1957) was applied to provide more accurate quantifications of the isocyanates present.
Samples were treated with N-butylamine, which is capable of reacting with isocyanate groups. The amount of unreacted n-Butylamine is then detected by reaction with the malachite green reagent. After creation of an appropriate calibration curve the samples were analysed and UVVIS-spectrum obtained.
According to the Kubitz test, quantities of less than 0.05 % by weight were detected in P1 and P3 samples. This indicates that only extremely low levels of residual isocyanate is present from the starting TPU materials. Considering the low amounts of isocyanates, the stability and internal adhesion properties of the plastic material can not be attributed to any kind of residual isocyanate activity. The ability to produce a sufficiently stable material without isocyanate, based on a PC, PCL, TPU, polyol synthetic material, represents an unexpected and advantageous aspect of the invention with respect to production cost, environmental effects and the structural and mechanical properties of the plastic.
Plastic material (P3 according to figure 7 with respect to the phosphor additive plastic)
The IR spectrum of the white granules is shown in figure 4. The spectrum is dominated by polycarbonate (PC) and polyesterurethane (PU). Also a strong swelling during the extraction with chloroform could be observed. Due to this reason the methanol extract was used for the GC-MS analysis.
With regard to the IR spectrum of the methanolic extract in figure 5; except the isocyanate absorption band (low quantities) all other bands can be allocated to polyesterpolyol. The gas chromatogram of the methanolic extract is shown in figure 6. The chromatogram comparison of the extracts shown in figure 9 leads to the conclusion that the main components in both samples P1 and P3 are the same. Of the different peaks, peak (10) is specific to P3 and represents the residual monomer of the polycarbonate (PC), the bisphenol A with the following structural formula:
Elementary analysis and annealing residue; The results are shown in the following table:
Summary of chemical analysis
The chemical analysis of P1 and P3 reveal low isocyanate background contaminants, thereby enabling an environmentally friendly low-isocyanate product. As can be seen from the additional elementary analysis, the phosphor and nanoclay components are present in the expected levels with respect to the original substance. Almost undetectable P is found in P1 , indicating that without addition of a dedicated phosphor component, no phosphor contaminant is present in the P1 mixture. The elements present from the nanoclay components are also relatively reduced in quantity in P3, due to the additional components added during AP2 and AP3 (polyol, PC, PCL, additive).

Claims

Claims
1. Plastic material comprising thermoplastic polyurethane, nanoclay, polyol, polycarbonate, polycaprolactone and one or more additives selected from a stabilizer and/or elasticity modulator, whereby the nanoclay is a silicate substance which comprises silicon and/or aluminium.
2. Plastic material according to claim 1 ,
characterized in that
the stabilizer and/or elasticity modulator is a phosphor component.
3. Plastic material according to one or more of the preceding claims
characterized in that
the phosphor component comprises salts that derive from phosphor with organic or inorganic acids, such as phosphites and/or phosphates.
4. Plastic material according to one or more of the preceding claims
characterized in that
the phosphor component is a phosphite component.
5. Plastic material according to one or more of the preceding claims
characterized in that
the phosphor component is trisnonylphenyl phosphite.
6. Plastic material according to one or more of the preceding claims
characterized in that
the phosphor component is bis (2,6-di-t-butylphenyl-4-methylpentaerythritol) diphosphite, tris (2,4-di-t-butylphenyl) phosphite and/or bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite.
7. Plastic material according to one or more of the preceding claims
characterized in that
the stabilizer and/or elasticity modulator is carboxylated polypropylene, preferably a carboxylated polypropylene functionalised with maleic anhydride.
8. Plastic material according to one or more of the preceding claims
characterized in that
the stabilizer and/or elasticity modulator comprises Polysiloxane polyoxyalkylene block copolymer, polyethylene glycol (PEG), dimethylol propionic acid (Bis-MPA) and/or 1 ,3- polyethylene glycol diol.
9. Plastic material according to claim 1
characterized in that
the additive additionally comprises one or more substances that act as a filler, viscosity modulator, plasticizer, colorant, fire retardant, emulsifier, surfactant, dispersing agent, antistatic agent, pigment, brightener, blowing agent, absorbent, antioxidants, antistatic agent, softening agent and/or abrasion reducer.
10. Plastic material according to one or more of the preceding claims
characterized in that
the plastisizer comprises Benzyl-2-ethylhexyl adipate, Alkyl sulfonic ester of phenol, Benzyl butyl phthalate and/or Polyadipate.
1 1. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises polyurethane in an amount of 20 to 80 %, preferably 30 to 70 %, more preferably 40 to 60% and most preferably 42 to 55 % by weight.
12. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises nanoclay in an amount of 0.00001 to 5 %, preferably 0.0001 to 4 %, more preferably 0.001 to 3 % and most preferably 0.01 to 2 % by weight.
13. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises polyol in an amount of 5 to 45 %, preferably 6 to 35 %, more preferably 7 to 25 % and most preferably 8 to 15 % by weight.
14. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises polycarbonate in an amount of 5 to 60 %, preferably 10 to 50 %, more preferably 15 to 40 % and most preferably 20 to 30 % by weight.
15. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises polycaprolactone in an amount of 2 to 45 %, preferably 4 to 35 %, more preferably 6 to 25 % and most preferably 8 to 15 % by weight.
16. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises one or more additives in an amount of less than 20 %, preferably less than 15 %, more preferably less than 10% and most preferably less than 5 % by weight.
17. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises one or more additives in an amount of 0.1 % to 20%, 0.5% to 10%, or preferably 1 % to 5% by weight.
18. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material contains less than 10 % isocyanates, preferably less that 5 % isocyanates, more preferably less than 1 % isocyanates and most preferably less than 0.5 % isocyanates by weight.
19. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises phosphor, iron, magnesium, aluminium and silicon.
20. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises 10 to 1000 mg/kg phosphor, preferably 100 to 200 mg/kg phosphor, more preferably 150 mg/kg phosphor.
21. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises 1 to 100 mg/kg iron, preferably 10 to 20 mg/kg iron, more preferably 15 mg/kg iron.
22. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises 1 to 100 mg/kg magnesium, preferably 5 to 15 mg/kg magnesium, more preferably 10 mg/kg magnesium.
23. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material comprises 1 to 500 mg/kg aluminium, preferably 10 to 100 mg/kg aluminium, more preferably 50 mg aluminium.
24. Plastic material according to one or more of the preceding claims
characterized in that the plastic material comprises 10 to 1000 mg/kg silicon, preferably 100 to 200 mg/kg silicon, more preferably 150 mg/kg silicon.
25. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material is manufactured by hot melt extrusion.
26. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material is present as foam, particles, granules, film, fibres, strands, sheets and/or foils.
27. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material has a density of 100 to 10000 kg/m3, preferably 250 to 7500 kg/m3, more preferably 500 to 5000 kg/m3 and most preferably 1000 to 1200 kg/m3 by measurement via DIN 53479.
28. Plastic material according to one or more of the preceding claims
characterized in that
the plastic material is elastic with a rupture resistance of more than 100%, more than 200 %, preferably of more than 400 %, more preferably of more than 600 % and most preferably of more than 700 % by measurement via ASTM D638 or ISO 527.
EP14703883.0A 2013-02-12 2014-02-12 Plastic material with improved properties comprising nanoclay Withdrawn EP2956502A1 (en)

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CN107001789B (en) * 2014-12-12 2021-02-02 路博润先进材料公司 Halogen-free flame-retardant composition
PL3268408T3 (en) * 2015-03-09 2019-07-31 Basf Se Polyurethane molded bodies having excellent flexibility at low temperature
CN106189187A (en) * 2016-07-29 2016-12-07 华蓥伟创立电子科技有限公司 A kind of earphone encapsulated plastic material
CN109705562A (en) * 2017-10-26 2019-05-03 江苏瑞凌新能源科技有限公司 A kind of flame retardant automotive accessory plastic formula
CN109988296B (en) 2018-01-02 2021-09-10 财团法人工业技术研究院 Process for producing polycarbonate polyol and polycarbonate polyol composition
JP2023511415A (en) * 2020-01-24 2023-03-17 チェッカースポット， インコーポレイテッド Use of microbial-derived materials in thermosetting applications
WO2023043945A2 (en) 2021-09-17 2023-03-23 Checkerspot, Inc. High oleic oil compositions and uses thereof
WO2023102069A1 (en) 2021-12-01 2023-06-08 Checkerspot, Inc. Polyols, polyurethane dispersions, and uses thereof

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