Patent Application
20080262126
The following disclosure relates to a novel polymeric composite including a nanoparticle filler, and a process for making the composite using a masterbatch. More particularly, the disclosure provides a novel method for the production of a nanocomposite including a polymer and a halloysite nanoparticle filler, the filler having the general shape of a cylinder or rolled scroll-like element, in which the diameter of the cylinder is less than about 500 nm. The advantages of the nanoparticle filler (e.g., reinforcement, flame retardant, improved or equivalent mechanical performance) are provided as a result of the ability to disperse the nanoparticle within and/or on the surface of a polymeric structure.
The addition of various nano-clay materials to polymer systems can lead to improved mechanical properties (such as toughness/ductility, fatigue resistance or strength), improved processability and/or thermodynamic stability. Details of such advantages as well as alternative materials and their characteristics are found, for example, in several prior patent applications relating to halloysite nanocomposites and applications thereof, including U.S. patent application Ser. No. 11/469,128 for a “POLYMERIC COMPOSITE INCLUDING NANOPARTICLE FILLER,” by S. Cooper et al., filed Aug. 31, 2006; U.S. application Ser. No. 11/531,459 for “Radiation Absorptive Composite and Methods for Production” filed Sep. 13, 2006 by A. Wagner et al.; and U.S. Provisional Application 60/867,369 for “POLYPROPYLENE NANOCOMPOSITE MASTER BATCH COMPOSITION AND METHOD OF MANUFACTURE,” filed Nov. 27, 2006 by B. Dillon Boscia et al., the disclosures of all of the above-identified applications being hereby incorporated by reference in their entirety.
Composite materials have become well known as man-made materials are increasingly substituted for naturally occurring materials in construction, parts manufacture and the like (e.g., automobiles, building materials, food packaging and textiles). A polymer composite in this context includes at least one polymer matrix or material in combination with at least one particulate filler material. The polymer matrix material may be any of a number of polymers including themoplastics such as polyamide (Nylon), poly-urethane, polyolefins, vinyl polymers, and the like, thermosets, and elastomers. As structure-property relationships of composites become better understood, the use of nanoparticles is of increasing interest in the formation of composites—referred to as nanocomposites. Some of the most common nanoparticle fillers are two-dimensional nanoclays, one-dimensional carbon nanotubes, and zero-dimensional metal oxide nanoparticles such as Zinc Oxide (ZnO), Titanium Dioxide (Ti02), and Zirconia (ZrO). Composites offer the potential of materials having properties that are not often available in naturally occurring materials (e.g., U.S. Pat. No. 6,518,324 to Kresta et al. for a Polymer Foam Containing Nanoclay).
There are several known ways in which to form polymer nanocomposites utilizing nanoclay materials. These processes include melt compounding, precipitation, and utilization of a masterbatch. The following disclosure is directed, in one embodiment, to the use of a masterbatch as the means by which a polymer nanocomposite is produced. A masterbatch includes a high concentration of halloysite nanoparticles (e.g., up to 50% by weight of halloysite nanotubes), and is produced and then subsequently combined with neat polymer, for example in an extrusion or molding process, to form the final nanocomposite.
The advantages of using a concentrated masterbatch in the preparation of final nanocomposite materials, particularly those produced in accordance with the description below, are numerous. One advantage is that the final composite may exhibit better dispersion of the nanoparticles within the final material/product, further resulting in improved mechanical properties because of the more consistent dispersion. Defects in the final composite, due to poor dispersion, would lead to weak points in the final part formed, thus potentially compromising its mechanical properties. The nanotubes are well dispersed when the masterbatch is formed, making dilution to the final use composition for extrusion or molding an easy task. This two step process allows two opportunities to fully separate the tubes for maximum effectiveness. Also, making a concentrate limits the amount of polymer that must go through a separate compounding step and, therefore, reduces the operational cost of using the composite.
In melt compounding processes for nanomaterial fillers there is typically an upper limit to the amount of filler which can be incorporated. There is usually an increase in viscosity at high loading levels, resulting in high shear that will cause the polymer system to degrade to the detriment of the final mechanical properties. This requires high energy utilization and thus high cost, relative to standard polymer composite processing. For platy clays in particular the problem is made worse because the filler must be fully exfoliated during the extrusion process. Exfoliation requires the use of significant amounts of organic treatment agents that interfere with the polymer processing. In addition, to fully exfoliate and disperse a material such as a platy clay, a barrel length-to-diameter (L/D) ratio much greater than 40:1 is required and therefore necessitates specialized extrusion equipment.
For halloysite materials high concentrations of halloysite nanotube filler (e.g., HNT™ from NaturalNano, Inc.) are easily obtained for masterbatches for two reasons. First, the halloysite has already been processed to produce a primary particle that does not need to be exfoliated. Therefore, neither large amounts of organic additives are required nor unusual processing equipment or formulations. Second, the addition of the halloysite nanotubes does not produce significant increases in melt rheology and, in fact, for most polymers reduces the resistance to melt flow—producing a polymer composite formation process that is easier to run than simply melting the polymer itself. Composites made using the halloysite nanotube masterbatches (e.g. HNT™ from NaturalNano, Inc.) provide excellent ductility, elongation and fatigue resistance. By using a masterbatch, the material may also be provided in commercial quantities to facilitate use of the nanoparticle filler, yet avoiding inherent problems with handling clays (e.g., dusting).
Disclosed in embodiments herein is a method of producing a polymer nanocomposite, comprising: surface treating a nanofiller; forming a masterbatch by blending the nanofiller and polymer; forming particles (e.g., precipitate, pellets, flakes, etc.) of the masterbatch; dry blending masterbatch material with neat polymer to form a mixture; melt blending the mixture; and forming a final product using the melt-blended mixture.
Also disclosed in embodiments herein is a polymer nanocomposite masterbatch for letdown with a neat polymer, comprising: from about 5 wt % to about 50 wt % of a nanoparticulate filler (or about 5 wt % to about 60 wt %) and a polymer.
The various embodiments described herein are not intended to limit the invention to those embodiments described. On the contrary, the intent is to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the appended claims.
As more particularly set forth below, the disclosed compositions and methods for manufacture disclosed herein are directed to a masterbatch of high nanoparticle (e.g., nanotubular) concentration polymer additive, which is then further combined with a neat polymer to obtain a nanocomposite. The term “particulate” has been used herein in a general sense to represent an intermediate, concentrated form of nanocomposite, and includes, but is not limited to, pellets, flakes or powders as they may be formed from melt compounding or blending techniques and precipitates as they may be formed from blending techniques involving solvent blending and precipitation.
This present disclosure includes the description of a method for production of a polymer nanocomposite. The nanoclay material used for property enhancement is, in one of the disclosed embodiments, halloysite. Also disclosed herein, is a process for making a “masterbatch” of a high nanoparticle (e.g., halloysite) concentration with a polymer, such as nylon, polypropylene, or other melt processable polymer, to form a concentrated nanocomposite that can then be further compounded with the pure polymer to yield a final nanocomposite composition exhibiting superior properties. For example, the master or concentrated batch or composite is an intimate mixture of about 5 wt % to about 60 wt % of halloysite, preferably approximately 10% to about 40% by weight, and more preferably about 20% to about 30% by weight, of halloysite nanotubes, and approximately 40% to 95% by weight of polymer (based upon the range of preferable halloysite filler).
Typical let-down ranges for the concentrate to final nanocomposite (i.e., ratios of concentrated masterbatch material to neat polymer) are on in the range of about 1:1 up to about 1:10. The final nanocomposite that may be produced utilizing the masterbatch disclosed herein is likely to include between about 1 wt % to about 20 wt % halloysite nanotubes in polymer, preferably 5 wt % to 10 wt % halloysite in polymer. For example, to form a 5 wt % halloysite nanotube composite, 16.67% of a 30 wt % masterbatch could be melt blended with 83.33% of pure or neat polymer.
The masterbatch material is formed, in one embodiment, using a process that includes a solvent dissolution/mixing step, where a polymer such as polypropylene is dissolved in a solvent to produce a polymer solution. The polymer may include any material that may be dissolved by the solvent, including but not limited to themoplastics such as polyamides (Nylon), polyurethanes, polyolefins, vinyl polymers, and the like, thermosets, and elastomers, and more particularly including acrylic urethane latex, nylon, polyvinylpyrole, and acrylic latex polymers, polycarbonates, polyesters, polyvinyl chloride (PVC), polystyrenes and polypropylenes.
Added to the polymer solution is at least one dispersing aid or agent suitable for favorably affecting the dispersion of the halloysite in the polymer solution. The dispersing aid is typically a surfactant or compatibilizing agent, which has one functional group that is compatible with the solvent and/or polymer and one component that is compatible with the halloysite material. The dispersing agent may be selected from the group including, but not limited to, quaternary amines (quaternary compounds such as benzalkonium chloride (BAC)), silanes, titanates, organic acids, coupling agents and block co-polymers.
In one embodiment, the polymer is polypropylene, and the chemical compound is a quaternary ammonium compound (anhydrous or hydrated form) such as a surface affecting/treatment material (e.g., benzalkonium chloride (BAC)) added to the polymer solution.
A processed clay-based material, such as nanotubular halloysite, is then added to the polymer solution, to produce a composite solution, via agitation (e.g., sonic/ultrasonic), that is then suitable to be precipitated.
As will be appreciated, the nanoclay material (e.g., halloysite) may be treated using a dispersant or similar surface treatment. In addition to halloysite, alternative (layered or unlayered) inorganic clay materials may be employed, including but not limited to smectite, kaolin, boulangerite, and imogolite. The following examples suggest the use of benzalkonium chloride and/or benzylcetyl dimethylammonium chloride monohydrate in solvent as these materials have been demonstrated to permit the addition of up to approximately thirty-two times the mass of the BAC salt before flocculation occurs. In one example, 0.025 g BAC in 25 ml xylene is believed suitable to suspend up to about 0.785 g of halloysite clay, and twice the amount of BAC can suspend approximately twice the amount of clay. Up to flocculation, the clay finely disperses and suspends in the solvent (e.g., xylene) and remains in suspension in response to simple stirring or shaking.
Although various solvents may be employed, and depend upon the particular polymer being used for the masterbatch nanocomposite, the disclosed embodiments specifically contemplate the use of polypropylene (PP) as the polymeric material, and the use of xylene or tetrachloroethylene (TCE) as the solvents in which the material is dissolved. Preferably the solvent is chosen such that the solubility of the polymer is at least about 5% (at a temperature below the solvent boiling point and atmospheric conditions).
Another variable related to the solvent selection is the material into which the dissolved solution of polymer is to be introduced to cause precipitation. Alternatives that could be considered include any liquid that would not similarly act as a solvent for the polymer and which is miscible with the solvent used to dissolve the polymer. In the case of polypropylene, methanol and acetone were considered for use. As described in the examples below, methanol and acetone are believed particularly suitable for use with the polypropylene as the base polymer. These “non-solvents” preferably result in roughly immediate precipitation of the composite, are separable from solvent via distillation, and are easily removed from the resulting nanocomposite.
As will be appreciated, the precipitated material may be subsequently filtered, dried, or similar processed so as to produce the masterbatch material. After completion the masterbatch may be used in its highly-concentrated state, or may be further compounded with additional polymer material (virgin or reground/recycled) to produce a nanocomposite with a desired halloysite concentration and a satisfactory dispersion of halloysite in the nanocomposite.
The masterbatch, in an alternative embodiment, may be formed using a twin-screw extrusion process to produce a concentrated HNT polymer blend, typically 20-60 wt % HNT in polymer, and more preferably 30-50 wt % HNT in polymer.
After formation of the masterbatch, the final nanocomposite is formed through melt blending in an extrusion or molding process, such as a blown film molder, an injection molder or a single screw film extrusion process. Masterbatch pellets, flake or powder are, as one method contemplated herein, dry blended with neat polymer and fed into the molding or extrusion machine. A typical nanocomposite formed through this invention has 5-10 wt % nanofiller, so is formed through dry blending a 10-20 wt % masterbatch with 80-90 wt % neat polymer. Additional additives, such as compatibilizers, plasticizers, stabilizers, and the like, may be included in the blending operation.
It should be further appreciated that the halloysite nanotubes may be surface treated prior to incorporation in the masterbatch.
The practice of one or more aspects of the invention are illustrated in more detail in the following non-limiting examples:
To make a nylon nanocomposite:
1. A commercial grade of Nylon-6 resin named Ultramid® B3K is obtained from BASF and dried at 85° C. under vacuum for 16 hours. In addition, Halloysite MP-SM1 material obtained from Imerys New Zealand China Clays is also placed in a vacuum oven at 110° C. for 16 hours.
2. The dry Nylon-6 resin is fed at a controlled rate to a Werner and Pfleiderer ZSK-30 twin screw extruder operating at a 44:1 L/D ratio. The setup of this extruder is seen in
3. A metered amount of Halloysite MP-SM1 is added to the extrusion process so as to result in a masterbatch of about 30% Halloysite by weight.
4. The molten extrudate is passed through a water bath to cool and excess water is removed via an air knife. The cooled extrudate is then cut in regular sized increments to result in a pelletized material.
5. The resultant HNT/nylon masterbatch may then be dry blended with neat Nylon-6, so that the final mixture contains about 7.5 wt % Halloysite.
6. Subsequently, the final mixture may be molded in an injection molder to form a nanocomposite material via standard nylon-6 molding temperatures, pressures, and times.
7. Tensile testing is conducted according to ASTM D638 standards.
An alternative method for making a nanocomposite masterbatch is as follows (Yield approx. 26.25 g):
1. In a 2 liter beaker or glass reaction vessel, heat 500 ml mixed xylenes (e.g., mono or mixed isomers) with mild vortex stirring to about 115° C.
2. Dissolve 25 grams polypropylene (PP), such as Exxon-Mobil PP1024E4, into xylene, maintaining temperature and stirring, keeping boiling to a minimum. Depending on the size of PP particles (beads, powder, etc.), the time to complete dissolution varies from minutes to hours. Maintain approximate volume of solution by adding xylene as needed, or by refluxing.
3. Suspend and/or dissolve 0.39 g of benzalkonium chloride (BAC) in 25 ml xylene in a glass vial. Utilize either a horn sonicator or an ultrasonic bath for this purpose while maintaining constant room temperature.
4. Add 1.25 g of dried halloysite (Premium EG, NancoClay and Technologies, air milled and dried at 110° C.) to the 25 ml xylene/BAC mixture and pulse sonicate with a horn sonicator or ultrasonic bath.
5. Pour the contents of this vial (xylene, BAC and halloysite) into the hot stirring solution of PP and xylene. Rinse/shake the vial with xylene and add to solution.
6. Allow the mixture to stir for approximately 5-10 minutes to ensure homogeneity.
7. Prepare a vessel containing at least 500 ml of acetone or any other polypropylene non-solvent such as a low molecular weight anhydrous alcohol (methanol). The liquid should be stirred at an angle (or with baffles) with a high-torque stirrer.
8. Add the PP solution into the vessel of liquid slowly by either dropping or a slow stream and allow to stir for 10 min. The composite precipitates rather quickly and produces masterbatch particles such as those generally depicted in
9. Filter the precipitate over vacuum in a Büchner funnel. Rinse with fresh acetone three or more times, and allow to dry over vacuum for approximately 30 minutes.
10. Break up filter cake and place in a vented sparkless oven at 110° C. overnight.
11. Pulverize material in a blade grinder or other such device and add to an injection molder for nanocomposite piece formation (e.g. test dog-bones as depicted in
To make a nylon nanocomposite using melt compounding:
1. A commercial grade of Nylon-6 resin named Ultramid® B3K is obtained from BASF and dried at 85° C. under vacuum for 16 hours. In addition, Halloysite MP-SM1 material obtained from Imerys New Zealand China Clays is also placed in a vacuum oven at 110° C. for 16 hours.
2. The dry Nylon-6 resin is fed at a controlled rate to a Werner and Pfleiderer ZSK-30 twin screw extruder operating at a 44:1 L/D ratio. The setup of this extruder is seen in
3. A metered amount of Halloysite MP-SM1 is added to the extrusion process so as to result in a compound of about 7.5% Halloysite by weight.
4. Subsequently, the compound may be molded in an injection molder to form a nanocomposite material via standard nylon-6 molding temperatures, pressures, and times.
Test Results: As depicted in the table of
It will be appreciated that various of the above-disclosed embodiments, examples and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or methods. Also, various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.
This application claims priority from U.S. Provisional Patent Application 60/888,685 for a “NANOCOMPOSITE METHOD OF MANUFACTURE,” filed Feb. 7, 2007, by C. Fleischer et al., which is also hereby incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 60888685 | Feb 2007 | US |
