# Patent

## Title
Suspension polymerization and foaming of water containing activated carbon-nano/microparticulate polymer composites

## Abstract

Synthesis of polystyrene and/or other thermoplastic polymers or polymer blends which, for example, contain activated carbon and/or bamboo carbon carrying a co-blowing agent such as water and/or at least one of 1-dimensional, 2-dimensional, and 3-dimensional nano/micro-materials in suspension polymerization without using the inverse emulsion process. CO2 or other blowing agent based foaming processes such as extrusion, batch foaming, and injection molding may then be carried out to produce polymer foams that have low density, high-R value, bimodal structures, good mechanical properties, and high fire retardance.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/188,624, filed on Aug. 11, 2008, which is hereby incorporated by reference in its entirety. This application also claims the benefit of PCT Application No. PCT/US09/45511, filed on May 28, 2009, which claims the benefit of U.S. Provisional Application No. 61/130,061, filed on May 28, 2008, each of which is hereby incorporated by reference in its entirety.


STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The present invention was made with United States Government support under Grant No. OII-0620502 by the National Science Foundation. The United States Government may have certain rights to this invention under 35 U.S.C. §200 et seq.


TECHNICAL FIELD OF THE INVENTION
Exemplary embodiments of the present invention relate to polymeric foams and methods for their production and articles made therefrom.
BACKGROUND AND SUMMARY OF THE INVENTION
With the soaring cost of energy, it is essential to develop new light-weight materials that can provide better thermal insulation performance in housing and construction industries and high structural strength for automotive, aerospace, and electronic applications.
For example, in the housing industry, doubling the ‘R’ value of current thermal insulation materials can save $200 million annually in heating/cooling costs for families in the U.S. In today's average vehicles, as much as 5-10% in fuel savings can be achieved through a 10% weight reduction. Polymeric foams have been used in many applications because of their excellent strength-to-weight ratio, good thermal insulation and acoustic properties, materials savings, and other factors. By replacing solid plastic with cells, polymeric foams use fewer raw materials and thus reduce the cost and weight for a given volume. The North American market for foamed plastic insulations exceeds $3 billion annually, while global demand is above $13 billion. However, polymer foams, except sandwich composite foams, are rarely used as structural components in the automotive, aerospace, and construction industries because of poor mechanical strength and low dimensional and thermal stability, when compared to bulk polymers.
In recent years, several researchers have reported that foams can possess excellent mechanical strength if the cell size is smaller than the typical flaw size in bulk polymers, i.e., <10 μm. Microcellular foams can reduce material usage and improve mechanical properties simultaneously. They have been commercialized for some applications (i.e., MuCell by Trexel). However, they require specially designed processing equipment, have a narrow process window, and are still not strong enough for structural applications.
Closed-cell plastic foams have better thermal insulation efficiency than glass fiber or plywood insulation materials, but the application of plastic foams in the housing industry is limited due to their poor fire resistance. A drastic reduction of thermal conductivity has been observed when the cell size is reduced to the nanoscale, e.g., aerogel. These nanofoams are currently made of ceramics in thin films and are very expensive. Foams with ultra-low density also provide better thermal insulation. To increase the expansion ratio during foaming in order to achieve ultra-low density, an expensive vacuum system is often needed in the industrial foam extrusion line.
Another critical issue faced by the foam industry is the blowing agent. Traditional chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) blowing agents cause ozone depletion and will be banned by 2010 according to the Montreal Protocol. Carbon dioxide (CO2) is an attractive replacement for the ozone-depleting blowing agents because it is low-cost, non-toxic, nonflammable, and not regulated by the Environmental Protection Agency (EPA). Since insulation foams used in houses dramatically reduce energy consumption and thus decrease the pollution generated by power plants, the use of CO2 has both a direct and an indirect benefit to the environment. However, CO2 has a lower solubility in most polymers than traditional blowing agents. It also has a higher diffusivity leading to a quick escape from the foam after processing. While this ensures fast mixing, it also offers a quick escape from the foam after processing resulting in a lower expansion ratio (i.e., higher foam density). The presence of CO2 complicates the manufacturing process and thus results in a high processing cost.
An exemplary embodiment of the present invention seeks to dramatically improve the insulation performance of polymer foams using zero-ozone depleting blowing agents such as, but not limited to, CO2 and/or water. In addition to enhancing the insulation value, which may lower the energy cost of the building, exemplary embodiments of the present invention include developing and manufacturing new truly green polymer insulation foam products.
An exemplary embodiment of the present invention may use at least one blowing agent that has minimal impact on the environment (e.g., zero-ozone depleting blowing agents such as CO2 and/or water). One exemplary embodiment of the present invention relates to polystyrene and/or thermoplastic polymer or polymer blend composite foam or a foamable polymeric material precursor, which contains foaming facilitating material and/or at least one of 1-dimensional, 2-dimensional, and 3-dimensional nano/micro-materials in a polystyrene and/or thermoplastic polymer and/or polymer blend matrix to carry a co-blowing agent such as water without using any surfactant-like molecules and/or polymers, having or adapted to have the properties of low density, high-R value, good mechanical properties, and fire retardance thereof. Exemplary embodiments of the present invention include various manufacturing methods, which are not limited to extrusion, batch molding, and injection molding. One example includes synthesis and CO2 and water-based extruded foaming of such a material. Exemplary embodiments of the present invention also include products made from the materials and/or methods discussed herein.
In addition to the novel features and advantages mentioned above, other benefits will be readily apparent from the following descriptions of the drawings and exemplary embodiments.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows examples of several SEM micrographs of extrusion foams for comparative purposes: Foaming conditions—CO2 as the blowing agent (200° C.; CO2 pressure=890 Psi; CO2 flow rate=3 g/min; die pressure=1200 psi; screw rotation speed=50 rpm; feeding rate=50 rpm): (a) PS foam (no water); (b) PS/1% AC/0.01% water; (c) PS/1% AC/0.08% water; (d) PS/1% AC/0.36% water; and (e) PS/1% AC/0.54% water.
FIG. 2 is a graph of cell size distribution of PS and PS/AC foams blown by CO2 and water, in accordance with embodiments of the present invention.
FIG. 3 shows a single SEM micrograph of extrusion foam in accordance with one embodiment of the present invention.
FIGS. 4(a) through 4(d) show examples of SEM micrographs of foam morphologies of water expandable PS/3.0% AC foams with different water contents in oil bath at 135° C. for 15 seconds: FIG. 4(a) dried beads; FIG. 4(b) 5.2 wt % water; FIG. 4(c) 10.1 wt % water; and FIG. 4(d) 12.3 wt % water. The scale bar is 500 μm.
FIGS. 5(a) through 5(d) show examples of foam morphologies of water expandable PS/3.0% AC foams with different water contents expanded by using the combination of water and CO2 as blowing agents in oil bath at 135° C. for 15 seconds: FIG. 5(a) dried beads; FIG. 5(b) 5.2 wt % water; FIG. 5(c) 10.1 wt % water; and FIG. 5(d) 12.3 wt % water. The scale bar is 200 μm.
FIGS. 6(a) through 6(c) show examples of foam morphologies and cell size distributions: FIG. 6(a) PS/1.0% talc; FIG. 6(b) PS/3.0% AC; and FIG. 6(c) water expendable PS/3.0% AC foams. The scale bar is 1 mm.
FIG. 7 is a chart of the thermal conductivity of different examples of foams.
FIG. 8 is a chart of IR absorption at 5 seconds exposure and bulk density of different foam examples.
FIGS. 9(a) through 9(c) show pictures of examples after IR absorption with different exposed times.



DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENT(S)
In accordance with the foregoing summary, the following presents a detailed description of the exemplary embodiments of the present invention, which are presently considered to be the best mode thereof.
An exemplary embodiment of the present invention relates to the synthesis of nanocomposites using particulate-like, plate-like, and fiber-like nanoparticles with, for example, high CO2 and/or water affinity. Polymers or polymer blends including a minor phase with high CO2 solubility may be used as the matrix material. These polymer or polymer blend nanocomposites may then be used to produce high-performance foam products aimed, for example, at both insulation and structural applications. The presence of nanoparticles and polymer blends may allow better control of cell morphology and foam density in the manufacturing process. The low density (ρ<0.04 g/cm3) foams with better thermal insulation, fire resistance, and mechanical strength may be particularly useful for thermal insulation applications, while the high-density (ρ>0.5 g/cm3) nanocomposite foams and sandwich foams with a similar mechanical strength as solid polymers may be particularly useful for structural insulation applications. Successful implementation of this novel technology may lead to significant energy savings, material savings, and enhanced environmental protection, all of which are critical to the economy and societal health.
One exemplary embodiment of the present invention relates to synthesis and CO2-based extrusion foaming of polystyrene (PS) and/or other thermoplastic polymers or polymer blends, which contain activated carbon and/or at least one of 1-dimensional, 2-dimensional, and 3-dimensional nano/micro-materials in the polymer matrix. The proposed process includes a co-blowing agent such as water (which may be used alone as the blowing agent in some examples) without using any surfactant-like molecules and/or polymers, to produce a material with low density, high-R value, bimodal structures, good mechanical properties, and fire retardance thereof.
As used herein, “surfactant-like molecules and/or polymers” refers to molecules and/or polymers that are used to mediate the admixture or dissolution of water into base polymers such as those used in accordance with an exemplary embodiment of the present invention. Some commonly encountered surfactants of each type include: ionic surfactants such as anionic surfactants (typically based on sulfate, sulfonate, or carboxylate anions), bis(2-ethylhexyl) sulfosuccinate, sodium salt, sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, and other alkyl sulfate salts, sodium laureth sulfate, also known as sodium lauryl ether sulfate (SLES), alkyl benzene sulfonate, soaps, and fatty acid salts; cationic surfactants (typically based on quaternary ammonium cations) such as, but not limited to, cetyl trimethylammonium bromide (CTAB), a.k.a. hexadecyl trimethyl ammonium bromide, and other alkyltrimethylammonium salts, cetylpyridinium chloride (CPC), polyethoxylated tallow amine (POEA), benzalkonium chloride (BAC), benzethonium chloride (BZT), zwitterionic (amphoteric), dodecyl betaine, dodecyl dimethylamine oxide, cocamidopropyl betaine, and coco ampho glycinate; and nonionic surfactants such as, but not limited to, alkyl poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called poloxamers or poloxamines), and alkyl polyglucosides, including, but not limited to, octyl glucoside, decyl maltoside, fatty alcohols, cetyl alcohol, oleyl alcohol, cocamide MEA, and cocamide DEA.
Typical values for high R-value extruded polystyrene foam are R=5.4 per inch thickness or higher. For low density, the presence of activated carbon may lead to higher water content in the pellets or beads and reduced the water loss during storage and foaming. The presence of water cavities may significantly enlarge the cell size and lead to a foam product with ultra-low density ( ̃0.03 g/cc) and low thermal conductivity.
Polymeric foams are widely used in certain applications such as insulation, cushions, absorbents, and scaffolds for cell attachment and growth. Polystyrene (PS) foams are the second largest volume use among different foam materials. The extrusion and batch foaming processes are the two major techniques to produce PS foams. For extrusion foaming, hydrogen-containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC) are currently used as blowing agents in the foam industry. Recently, supercritical CO2 is an alternative choice because of its low cost, non-toxic, and non-flammable properties, and relatively high solubility in many polymers.
In the batch foaming process, expandable PS (EPS) is generally prepared by the modified styrene suspension polymerization method. In general, an organic blowing agent such as pentane is used during polymerization. When heating the pentane-containing PS beads up to their glass transition temperature, PS foams are obtained. Flammable blowing agents, e.g., pentane, hexane, etc., however, are not suitable for continuous extrusion foam processing due to safety concerns. Thus, the concept of water expandable polystyrene (WEPS) was proposed. Crevecoeur et al. reported a two-step synthesis method, i.e., inverse emulsion and water suspension, to entrap water in the PS matrix. Pallay et al. used starch as a water absorbent to replace the emulsifier in the inverse emulsion. After suspension polymerization, water was directly absorbed into the starch inclusions. This method requires surfactants to stabilize water, which is unfavorable for fire resistance properties.
Until now, it is difficult to produce ultra-low density foams by extrusion using only CO2 as the blowing agent because of the low solubility and high diffusivity of CO2 in polymers. Thus, it is necessary to introduce a co-blowing agent such as water in the CO2 foaming process. Although previous studies have demonstrated that it is possible to obtain PS foams with ultra-low density ( ̃0.03 g/cc) for WEPS and water expandable polystyrene-clay nanocomposites (WEPSCN), the work was mainly based on the batch foaming process and surfactants are also needed to trap water as a co-blowing agent.
In an exemplary embodiment of the present invention, an extrusion foaming process involves using suspension polymerization to directly entrap a co-blowing agent such as water into polymer-activated carbon nanocomposites without adding a surfactant as the stabilizer. Instead, examples of a suspension stabilizer for use in exemplary embodiments of the invention include hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), and mixtures thereof.
For thermal insulation applications, the thermal insulation efficiency is dependent on the average cell size of the foams, the polymer used, and the blowing agent used. It is known that extruded polystyrene foam blown by CFC has a higher thermal insulation value than that previously blown by CO2, resulting from the low thermal conductivity of CFC. Foams containing infrared attenuating agents also could enhance the thermal insulation value. However, such addition of infrared attenuating agent will reduce the cell size and increase the bulk density.
An exemplary embodiment of the present invention may produce PS (or other polymer) nanocomposite foams with a lower bulk density and better infrared (IR) absorption than conventional PS/Talc foams under the same extrusion conditions without using any inverse emulsion surfactant. These attributes may enhance thermal insulation efficiency.
To achieve this goal, water may be introduced as a co-blowing agent with CO2 to control the bulk density, bubble size, and expansion ratio in the extrusion process. PS and most other polymers are hydrophobic, and will not absorb any water. Thus, a carrier may be used to carry water into the extruder. This carrier preferably does not reduce the bubble size or increase the bulk density of the foam. Activated carbon (AC) is a good absorbent for liquids and gases with high thermal stability. Therefore, an exemplary embodiment of the present invention may feature the use of activated carbon as a water carrier. The results described below elucidate its effect in the PS foaming process.
Preliminary results showed that there are no significant differences in the properties of PS/AC foams blown by CO2 with/without the presence of water (see FIG. 1).
It was also observed that the average bubble sizes of PS/AC foams are 3 times smaller than that of PS foams (FIG. 2). Activated carbon has a higher CO2 affinity than pure PS and more nucleation centers are generated by activated carbon in the PS matrix. Although not limited to the theory upon which the invention operates, it is believed that this may explain why the cell size decreases when activated carbon is present in the foaming process. The cell size, however, may be similar to that of the PS/TiO2 foams and much larger than that of PS/nanoclay foams. For thermal insulation foams, this is a positive result. However, the water absorbed by AC did not show any significant effect on the cell size in the extrusion process (FIG. 2). Again though theory does not limit an exemplary embodiment of the present invention, it is believed that the water evaporated in the first zone of the extruder and then escaped from the feeding hopper due to the high operation temperature,  ̃200° C., in the extruder.
PS/AC/water samples from different zones in the extruder were examined, and it was found that the water content was very low in the extracted samples. For example, when 1.33% w/w of water in PS with 1.0% AC was loaded into the extruder, the sample extracted from the middle zone showed only 0.012% w/w of water remaining in the PS/0.03% AC. Most of the water ( ̃70% by wt) evaporated due to the high temperature but some voids resulting from the 30% wt of remaining water could be observed in the extracted samples (FIG. 3).
The macro/meso/micropores in an AC matrix may become an excellent reservoir for liquids such as water, ethanol, hexane, etc. These liquids may act as a co-blowing agent to assist PS composite foaming. This novel water encapsulation technique is intended to overcome the problem arising from water evaporation in the extrusion process.
In an exemplary embodiment, the liquid media may diffuse into the pores of the activated carbon when the Styrene/PS/AC composite is suspended and then polymerized in water. Examples of suspension liquids include chemical agents that evaporate, decompose, or react under the influence of heat to form a gas, ranging from hydrocarbons (e.g., butane, pentane, hexane, cyclohexane, petroleum ether, natural gases, etc.), halogenated hydrocarbons (e.g., methylene chloride, dioctyl phthalate, etc.), alcohols (e.g., methanol, ethanol, isoproponal, etc.), dihydric alcohol, polyhydric alcohol, ketones, esters, ethers, amides, acids, aldehydes, water, or mixtures thereof.
In an exemplary embodiment, the suspension polymerization may be completed under pressure (e.g., typically at or above atmospheric to about 2000 psi or higher, preferably 100 psi) and at a temperature below or above Tg of the base polymer (typically more than 20 degrees above Tg). These conditions are maintained for a period of time sufficient to substantially or totally consume the styrene monomer. The pellets, upon cooling to room temperature and returning to atmospheric pressure, may be further handled for extrusion processing, batch forming processing, or injection molding.
An exemplary process of the present invention may be carried out with any primary blowing agent, such as CO2 or N2 or hydrofluorocarbon or fluorocarbon or mixtures thereof. Fluorocarbon and hydrofluorocarbon may include such substances as CFC11, HCFC 123, or HCFC 141b. In exemplary embodiments of the invention, an environmentally friendly blowing agent is preferred as previously noted.
The blowing agent(s) may also be any liquid(s) that evaporate, decompose, or react under the influence of heat to form a gas, and activated carbon, for example, may be used as a carrier to carry these blowing liquids into foamable polymers. Water is a preferred liquid for some exemplary embodiments of the invention. As previously mentioned, these liquid blowing agents include chemical agents that evaporate, decompose, or react under the influence of heat to form a gas, ranging from, but not limited to, hydrocarbons (e.g., butane, pentane, hexane, cyclohexane, petroleum ether, natural gases, etc.), halogenated hydrocarbons (e.g., methylene chloride, dioctyl phthalate, etc.), alcohols (e.g., methanol, ethanol, isoproponal, etc.), dihydric alcohol, polyhydric alcohol, ketones, esters, ethers, amides, acids, aldehydes, water, or mixtures thereof.
In studies, high-pressure reaction chambers at the controlled temperature, 100 ̃130° C., were used to conduct post-cure experiments involving the methods and compositions of exemplary embodiments of the present invention. The preliminary results are very promising. In examples, water was entrapped into the polymer composite matrix and may survive extrusion foam processing.
The methods and compositions of exemplary embodiments of the present invention may use any polystyrene and other polymer composites which contain, for example, activated carbon and/or at least one of 1-dimensional (e.g, smectite clays (organoclays) or nanographites (graphite, graphene, and graphene oxide)), 2-dimensional (e.g., carbon nanofibers, multiwall carbon nanotubes, single wall carbon nanotubes, conducting polymer nanofibers/nanotubes, polymer nanofibers/nanotubes, etc.), and 3-dimensional (e.g, quantum dots, polyoctahedralsilasesquioxanes (FOSS), silica, TiO2, ZnO or Fe3O4 nanoparticles, soybean hulls and other natural materials, etc.), nano/micro-materials in the polymer matrix to carry water without using any surfactant-like molecules and/or polymers. Low density material with high-R value, a bimodal structure, good mechanical properties, and high fire retardance may be produced.
The polymers used in accordance with exemplary embodiments of the present invention may be macromolecules that include polystyrene, polystyrene/PMMA blends, polystyrene/PPO blends, polystyrene/high-impact polystyrene (HIPS) blends, and mixtures of any of the foregoing.
Foamed Polymer Method—Water and Blowing Agent
Generally, one example of the method of the present invention may be summarized as a method of making an extruded foamed polymer comprising: (a) preparing a foamable polymeric material precursor comprising: (1) suspension polymerization of a mixture comprising (i) styrene monomer; (ii) a polymeric material selected from the group consisting of polystyrene, thermoplastic polymers, and polymer blends thereof; (iii) a foaming facilitating material having water or other blowing agent affinity comprising activated carbon, charcoal (especially bamboo charcoal), and/or selected additional material selected from the group consisting of activated carbon, charcoal (especially bamboo charcoal), 1-dimensional, 2-dimensional, and 3-dimensional nano/micro-materials and mixtures of two or more thereof; and (iv) the foaming facilitating material adapted to absorb water in the absence of any surfactant-like molecules or polymers before mixing with styrene (or other monomers) and/or polystyrene (or other polymer) mixtures and suspension polymerization; and (2) a blowing agent; and (b) preparing a foamed polymer from the foamable polymeric material precursor.
One may use known processing techniques for formulating and extruding the foamable polymeric material precursor.
In an exemplary embodiment, it may be preferred that the polymeric material is polystyrene, but it may include any thermoplastic materials such as those set forth herein.
It may also be preferred that the polymeric material in an exemplary embodiment is polystyrene and that the foaming facilitating material comprises activated carbon.
Preferred amounts of the foaming facilitating material and the polymeric material may be in relative amounts in a weight ratio in the range of 20% to 0.01% in exemplary embodiments of the invention.
The 1-dimensional, 2-dimensional, and 3-dimensional nano/micro-material may be selected from any material capable of containing small amounts of water, such as those as those set forth herein.
In an exemplary embodiment of the present invention, bamboo charcoal is another excellent water affinity material that may be used together with or in place of the activated carbon. Similar to activated carbon, bamboo charcoal is a highly porous carbon based material with very high water absorption characteristics.
Where an additional blowing agent besides water is provided (as the method may be carried out with water alone), the blowing agent may be any agent (liquid or gas) effective to provide a foaming action, such as those set forth herein. Preferably, the blowing agent comprises CO2. It is also possible that an example of the method of the present invention may be carried out with a blowing agent alone.
An exemplary embodiment of the present invention includes products made in accordance with any of the variations of the methods disclosed herein.
One exemplary embodiment of the present invention thus produces CO2-containing polymer nanocomposite foams with both mechanical and thermal insulation properties superior to foams produced with either hydrochlorofluorocarbon (HCFC) or hydrofluorocarbon (HFC) blowing agents.
The replacement of the ozone-depleting substances in an exemplary embodiment of the present invention may allow one to retain the insulating R-value and decrease manufacturing costs. The replacement in this exemplary embodiment of the present invention is legally mandated and, in general, maintains the insulating R-value and decreases manufacturing costs.
An exemplary embodiment of the present invention also permits the use of up to 100% recycled plastics, e.g., recycled expanded polystyrene (EPS). Such material may not be biodegradable and are typically taken to a landfill, contributing to environmental issues.
An exemplary embodiment of the present invention provides light-weight and low-cost microcellular, nanocomposite materials with tunable thermal and mechanical properties. These nanocomposite foams may save not only raw materials derived from petrochemicals but also energy consumption through the product's life time.
The technical approach for surmounting the challenges associated with the use of nanomaterials and CO2 as a blowing agent is described below.
Nanoparticle Material Innovations: Polymer nanocomposites have demonstrated impressive improvements in mechanical strength without losing toughness/impact strength. A recent study by NIST and several research groups showed that adding nanoclay to polymers can address fire prevention issues.
Recent work has shown that the different distribution morphology of nano-montmorillonite (MMT) clay particles in polystyrene rigid foams (clay layers become exfoliated, intercalated, or agglomerated) greatly changes the cell density, cell size and orientation, and other cell morphology characteristics.
However, it has also been found that the modifiers currently used in preparing the commercial nanoclay precursor present a fire hazard.
The nanoclay/polystyrene composite foams suffer from a very high ignitability (low oxygen index) due to the presence of a high amount of organic surface modifiers. To achieve truly fire resistant advantages, an exemplary embodiment of the present invention provides for fire retardant modifiers, low modifier content nanoparticles, and/or a special treatment to eliminate the modifier during compounding.
Exemplary embodiments of the present invention may also provide for the development of multi-functional nano-carbon materials including layered graphite, nanoporous activated carbon, carbon nanofibers (CNF), and multi-wall carbon nanotubes (MWCNT), which may not only work as a cell morphology control agent and a gas diffusing barrier, but also as an infrared attenuation agent and a carrier for benign co-blowing agents such as water to enhance the insulation R-value.
Blowing Agent Innovations: The use of traditional chlorofluoromethane blowing agents has been prohibited globally because of their high ozone depletion effect. Among the potential replacements, CO2 is the most favorable, because it is nontoxic and environmentally benign (zero Ozone Depletion Potential, and 100 year Globe Warming Potential only one in comparison with 1300 for HFC-134a, and 2000 for HCFC-142b), and it is inexpensive.
Companies such as Dow Chemical and Owens Corning are very active in research and development related to the use of CO2 as the future blowing agent. For example, Dow has been granted patents (U.S. Pat. Nos. 5,250,577, 5,266,605 and 5,389,694, hereby incorporated herein by reference) for CO2-containing polystyrene foams and Owens Corning has been granted patents (WO 00/15701 and U.S. Pat. No. 6,268,046, hereby incorporated herein by reference) for a process for producing extruded polystyrene with CO2 as a blowing agent. However, the CO2-containing foam products developed to date are intended primarily for use in the packaging market, for which thermal insulation properties and structural strength are not as critical as in the building insulation market.
Thus, an exemplary embodiment of the present invention provides a method of producing CO2-containing polymer foam that has both tunable thermal insulation property and mechanical strength in comparison with existing polymer foam board.
The primary three issues regarding CO2 that may be addressed by an exemplary embodiment of the present invention thus are: (1) the low solubility of CO2 in polymer melts. (The solubility of CO2 in polystyrene is only about 3.5% at elevated temperature and pressure, at 150° C. and 10 Mpa. However, a solubility of about 5 to 6% is required to achieve the necessary cell growth); and (2) CO2 has a high diffusivity in the polymer melt due to its small size. While this ensures a fast mixing process, it also offers a quick escape from the foam after processing. Compared with HCFC's, CO2 has a much greater nucleation ability, which means that nuclei may be created without the aid of nucleation agents; and (3) higher gas thermal conductivity in comparison with that of HFC blowing agents. The challenges of developing CO2 as a foaming agent arise therefore from solubility limitations, high-pressure operation, high thermal conductivity, and rapid gas escape after the foaming process.
An exemplary embodiment of the present invention may provide several alternatives: (1) modifying the structure or composition of the polymer and polymer blends to increase intermolecular interactions with CO2; and (2) adding nanoparticles that have a high affinity for CO2.
The surfactant commonly introduced onto the particle surface to achieve good compatibility between the inorganic nanoparticles and the organic polymer or monomer to achieve good particle dispersion is usually a flammable material.
Using activated carbon to carry nanoclay-water into the polymer matrix may therefore achieve surfactant-free composites with good clay dispersion. In examples, incorporation of a very small amount of nanoclay (typically no more than 0.5% by weight) substantially increased the expansion ratio of PS composites.
Using CO2 as the co-blowing agent in studies, the resultant PS foams exhibited lower bulk density and a cell structure better than the current insulation foams. Together with the lower bulk density, the activated carbon PS foam may be superior to the PS or WEPS foams for thermal insulation applications. CO2-assisted extrusion foaming of water-containing activated carbon-PS foam beads can reach a bulk density of 0.032 g/cc with a thermal conductivity of 20 mW/mK.
Materials produced in accordance with an exemplary embodiment of the present invention may therefore eliminate the need of an expensive vacuum system, and one can realize the complete replacement of HCFC and HFC by CO2 if desired.
The foamable mixtures of an exemplary embodiment of the present invention may be extruded and foamed into foam products, such as foam board, foam sheet, and other foam structures, which are also exemplary embodiments of the present invention.
EXAMPLE 1
53 g of polystyrene, 0.25 g of AlBN, 0.15 g of BPO, and 3 g of activated carbon containing 7.5 g of water were mixed with 47 g of styrene. The mixture was kept overnight at room temperature. The viscous solution (around 100 g) was suspended in water (300 g) with the aid of suspension stabilizers, hydroxyethyl cellulose (HEC) (0.6 wt % based on the suspension water) and PVA (0.005 wt % based on suspension water), at 80° C. at a high stirring rate (800 rpm). During the polymerization, the stirring rate and temperature were kept at 600 rpm and 90° C. respectively. After approximately 5 hours, the suspension was transferred to an autoclave and post-cured at 120° C. under 100 psi for 12 hours to achieve complete reaction. Finally, the suspension was cooled to room temperature. The spherical black beads were washed and stored in water. Water on the surface of PS/AC beads was removed before extrusion.
EXAMPLE 2
53 g of polystyrene, 0.25 g of AlBN, 0.15 g of BPO, 3 g of nanoclays, and 3 g of activated carbon containing 7.5 g of water were mixed with 47 g of styrene. The mixture was kept overnight at room temperature. The viscous solution (around 100 g) was suspended in water (300 g) with the aid of suspension stabilizers, HEC (0.6 wt % based on the suspension water) and PVA (0.005 wt % based on suspension water), at 80° C. at a high stirring rate (800 rpm). During the polymerization, the stirring rate and temperature were kept at 600 rpm and 90° C. respectively. After approximately 5 hours, the suspension was transferred to an autoclave and post-cured at 120° C. under 100 psi for 12 hours to achieve complete reaction. Finally, the suspension was cooled to room temperature. The spherical black beads were washed and stored in water. Water on the surface of PS/AC beads was removed before extrusion.
EXAMPLE 3
53 g of polystyrene, 0.25 g of AlBN, 0.15 g of BPO, 3 g of carbon nanofibers, and 3 g of activated carbon containing 7.5 g of water were mixed with 47 g of styrene. The mixture was kept overnight at room temperature. The viscous solution (around 100 g) was suspended in water (300 g) with the aid of suspension stabilizers, HEC (0.6 wt % based on the suspension water) and PVA (0.005 wt % based on suspension water), at 80° C. at a high stirring rate (800 rpm). During the polymerization, the stirring rate and temperature were kept at 600 rpm and 90° C. respectively. After  ̃5 h, the suspension was transferred to an autoclave and post-cured at 120° C. under 100 psi for 12 h to achieve complete reaction. Finally, the suspension was cooled to room temperature. The spherical black beads were washed and stored in water. Water on the surface of PS/AC beads was removed before extrusion.
EXAMPLE 4
A mixture comprised of 97 g of styrene, 3 g of activated carbon, with 0.25 g of AlBN (initiator) and 0.25 g of BPO, was polymerized at 120° C. at a high stirring rate (800 rpm) for 12 hours. The mixture was suspended in water (300 g) with the aid of suspensions, HEC (0.6 wt % based on the suspension water) and PVA (0.005 wt % based on suspension water), at 80° C. at a high stirring rate (800 rpm). During the polymerization, the stirring rate and temperature were kept at 600 rpm and 90° C. respectively. After  ̃5 h, the suspension was transferred to an autoclave and post-cured at 120° C. under 100 psi for 12 h to achieve complete reaction. Finally, the suspension was cooled to room temperature. The spherical black beads were washed and stored in water. Water on the surface of PS/AC beads was removed before extrusion.
EXAMPLE 5
In examples 1-4, the foaming method may be extrusion foaming or batch foaming or injection molding foaming. The primary blowing agent may be CO2 or N2 or hydrofluorocarbon or fluorocarbon or mixtures thereof. Fluorocarbon and hydrofluorocarbon include CFC11, HCFC 123, or HCFC 141b, etc.
EXAMPLE 6
In this example, water acts as a co-blowing agent to support carbon dioxide (CO2) in the extrusion foaming process of polystyrene (PS) to produce foams with very low density for thermal insulation applications. Herein, we report a simple suspension polymerization method to prepare water expandable polystyrene (W EPS) based on a PS-water containing activated carbon (AC) composite. AC pre-saturated with water was introduced into the styrene monomer to form a water-in-oil inverse emulsion without emulsifiers. Via suspension polymerization, water expandable PS-AC (WEPSAC) beads could be subsequently obtained. Low density PS foams ( ̃0.03 g/cc) were successfully produced in the CO2 extrusion foaming process using WEPSAC. Because of lower foam density and better IR absorption due to the presence of water containing AC, WEPSAC foams provided a lower thermal conductivity than conventional talc reinforced PS foams.
Polymeric foams are widely used in applications such as insulation, cushions, absorbents, and scaffolds for cell attachment and growth [4-6]. Polystyrene (PS) is one of the major foam materials in the market [7, 8]. Currently, hydrogen-containing chlorofluorocarbons (HCFCs) and fluorocarbons (HFCs) are the main blowing agents for PS foaming. However, HCFCs and HFCs have to be replaced soon due to the ozone-depletion and global warming problems. Among various alternative blow agents, carbon dioxide (CO2) is the most promising material because it is nonflammable, inexpensive, environmentally benign, and has relatively high solubility than other inert gases in many polymers [9, 10]. However, the low solubility and high diffusivity of CO2 in polymers make it difficult to produce low density foams necessary for thermal insulation applications.
Water has been used as a co-blowing agent in the batch polymer foaming process for many years. Water expandable polystyrene (WEPS) is a good example. WEPS is generally synthesized by preparing a water-in-oil mixture for styrene suspension polymerization. The first method to produce WEPS was developed by Crevecoeur et al [1]. In that method, water was emulsified in a pre-polymerized styrene/PS mixture in the presence of emulsifiers. Subsequently, the inverse emulsion was suspended in a water medium containing suspension agents. Polymerization was continued until complete conversion. The final products are spherical PS beads with entrapped micrometer-scaled water droplets. The second method was developed by Pallay et al [2]. Instead of using emulsifiers, starch was used as a water-swellable phase. Pre-polymerization of the styrene/starch mixture was carried out to a conversion of approximately 30%. The viscous reaction phase was subsequently transferred to a water medium containing suitable suspension agents. In the last step, polymerization was completed and water was directly absorbed into the starch inclusions.
We recently reported a modified route of suspension polymerization to prepare water expandable polystyrene-clay nanocomposites (WEPSCN) [11]. The presence of nanoclay in the water-in-oil emulsion reduced the amount of emulsifiers used and enhanced the water stability in the PS beads. Although low density ( ̃0.03 g/cc) foams were obtained by using WEPSCN in the CO2 batch foaming process, it is difficult to use WEPS or WEPSCN in the extrusion foaming process because water tends to evaporate away in the early portion of the extruder when the WEPS or WEPSCN pellets are crushed and melted by the rotating screw in the heated barrel. A better water carrying material or process is needed to solve this problem in the extrusion foaming process.
Activated carbon (AC) has an exceptionally high surface area which makes it an excellent water-absorbent. Previously, our group has studied the effect of moisture content in the extrusion foaming process by adding activated carbon particles containing different amounts of water together with PS into a twin screw extruder. However, most of the water was evaporated by the heat generated from the extruder and only a slight decrease in foam density was observed [3]. In this study, AC pre-saturated with water was introduced into a styrene/PS solution. The viscous mixture was subsequently transferred to a water medium containing suspension agents. Via suspension polymerization, PS beads containing AC/water droplets were obtained. Applying these beads into the extrusion foaming process with CO2 as a blowing agent, more water could be trapped. The extruded foams were characterized for cell morphology, IR transmission, and thermal conductivity.
Materials
PS (CX5197; Mn=86,000) from Total Petrochemicals (formerly Nova) was used as received. Foaming agent CO2 (>99.9%) was provided by Praxair. Wood based activated carbon (AC) particles with diameters of 38 μm were provided by MeadWestvaco Corp. Styrene was purchased from Aldrich and distilled before use. The initiators, 2,2′-azobis(isobutyronitrile) (AlBN) and dibenzoyl peroxide e(BPO) with a half-life (t1/2) at 90° C. of 25 and 145 min, respectively, were purchased from Aldrich. The suspension stabilizers, hydroxyethyl cellulose (HEC, Mw=250,000) and polyvinyl alcohol (PVA), were supplied by Aldrich and used as received.
Suspension Polymerization
53 g PS, 0.25 g AlBN, 0.15 g BPO, and 3 g AC absorbed 7.5 g water were mixed with 47 g styrene and the mixture was kept overnight at room temperature. Approximately 100 grams of viscous solution was suspended in 300 grams of water with the aid of suspension stabilizers, HEC (0.6 wt % based on the suspension water) and PVA (0.005 wt % based on suspension water), at 80° C. and a high stirring rate of 800 rpm. During the polymerization, the stirring rate and temperature were kept at 600 rpm and 90° C., respectively. After about 5 hours, the suspension was transferred to an autoclave and post-cured at 120° C. and 0.69 MPa (100 psi) in a nitrogen atmosphere for 12 hours to achieve complete conversion. Finally, the suspension was cooled to room temperature and the final products, WEPSAC pellets, were collected by filtration.
Expansion of WEPSAC Beads
After the suspension polymerization, the moisture content of the beads was determined by drying them in an oven. The average water content was found to be around 13.0%. To control the water content, the beads were dried at 70° C. in a vacuum oven for a specific duration of time. The beads with different moisture contents were expanded in an oil bath at 135° C. for 30 seconds. After that, the expanded beads were quenched by an ice-water mixture.
Batch Foaming of WEPSAC by CO2 
In this study, a two-step batch foaming process was employed. The beads were first saturated with CO2 at 25° C. under a pressure of 13.8 MPa (2002 psi) for 24 hours to reach the equilibrium. After that, the pressure was quickly released and the beads were removed from the high-pressure chamber. The beads were subsequently immersed into an oil bath at a temperature of 135° C. for 15 seconds. The expanded beads were quenched in an ice-water mixture.
Extrusion Foaming
Extrusion foaming was carried out by pumping the blowing agent (CO2) into a twin screw extruder (Leistritz ZSE-27; L/D=40; D=27 mm) using a gas/liquid injection port. For the PS/3.0 wt % AC sample without water, PS containing 5.0 wt % AC was pre-compounded with pure PS to dilute the AC content to 3.0t % via extrusion. For WEPSAC samples, the pre-dried PS beads were directly fed into the hopper by a volumetric feeder. The extruder was outfitted with a slit die, a shaping die, and rollers for foam uptake. During the extrusion foaming process, the screw speeds of the feeder and extruder were both kept at 50 rpm. The pressure of CO2 was kept at 7.58 ̃8.27 MPa (1100 ̃1200 psi). The die temperature was kept at 120° C. and the die pressure was in the range of 8.62 ̃9.31 MPa (1250 ̃1350 psi) depending on different samples. The openings of the slit die and shaping die were kept as a constant. Foam samples were cut and removed before entering the rollers to maintain the cell morphology.
Foam Characterization
The specimens for characterization were prepared by cutting segments out of extruded foams and then sanded on a sandpaper to achieve a thickness about 6.5 mm. During this process the skin of the foam was removed. After sanding, compressed air was blown on the foams to remove residual powders. The morphology of the foam was observed by a scanning electron microscope (SEM, Phillips XL30). Samples were cryo-fractured in liquid nitrogen, and the fracture surface was sputter-coated with gold.
Infrared (IR) transmission of each sample was measured using an in-house IR transmission tester to provide a property relevant for thermal insulation applications. This test provided data at a localized point, so the test was performed at several locations on the specimens and the resulting values were averaged. IR transmission is the ratio of power exiting to that entering the sample. The input power was 0.5 Watts for all samples measured. The distance between the optical fiber output of the laser diode and the power meter was about 5 cm.
The thermal conductivity was measured using a heat flow meter (FOX 200, Laser Comp). The temperature difference between the top and bottom plate was set at 40° C.
Results
For the water expandable PS beads, the uniform distribution of water in PS plays a key role in achieving the foam product with desirable structure and properties. To realize this goal, surfactants such as AOT or water-swellable materials, for example starch, were introduced to facilitate the dispersion of water. However, the existence of surfactants and starch will deteriorate the fire resistance property and mechanical strength of the foam. In our case, AC was used as a water carrier and reinforcement material to avoid the use of surfactants and the loss of mechanical strength. Due to their exceptionally high surface area, almost three times the amount of water can be trapped by AC.
The structures of foamed PS beads in the oil bath at 135° C. with different moisture contents are shown in FIGS. 4(a) through 4(d). In the SEM micrographs, the large cavities and the smaller bubbles were formed during the suspension polymerization and the batch foaming process, respectively. It is obvious that the expansion ratio and the cell density increased with increasing water content. For the dried beads, only large cavities were observed, while the smaller bubbles were formed from the nucleation and growth of water vapor. The WEPSAC beads saturated with CO2 at 25° C. were also foamed in the same oil bath in an attempt to enhance the expansion ratio and to lower the foam density. It was found that the expansion ratio greatly increased due to the combination of two blowing agents, i.e., CO2 and water. The cell morphologies are presented in FIGS. 5(a) through 5(d). Although not well-defined, a bi-model foam structure was observed even in the foam made from dried beads. Since CO2 was the sole blowing agent in dried beads, the large bubbles originated from the cavities shown in FIG. 4(a).
The feasibility of using WEPSAC in CO2 in the extrusion foaming process was tested in the twin-screw extruder. Table 1 shows the bulk densities of different foams produced under the same operating conditions. It is clear that the dry AC did not change the foam density while the WEPSAC foam showed a much lower density (0.032 vs. 0.043 g/cc). This observation demonstrates that some water in WEPSAC was able to survive the harsh environment in the extruder and could serve as a co-blowing agent in foam extrusion. Since both water and CO2 served as blowing agents, they produced a foam with a higher expansion ratio and hence a lower bulk density.







TABLE 1







Bulk density of PS/1.0% talc, PS/3.0% AC and water expendable


PS/3.0% AC foams











PS/1.0%
PS/3.0%
Water expendable



talc
AC
PS/3.0% AC
















Bulk density
0.043
0.043
0.032



(g/cc)










The morphology of extruded foam samples obtained by SEM is shown in FIGS. 6(a) through 6(c). As shown in the images, the PS/3.0 wt % AC foam has the smallest cell size, indicating that AC may act as a nucleating agent. Comparing FIGS. 5(b) and 5(c), the WEPSAC foam shows a larger cell size, which demonstrates that the existence of water helps to enlarge the cell size and reduces the foam density. Cell distribution was analyzed by Scion Image software and a minimum number of 100 cells were counted. The analyzed results are also shown in FIGS. 6(a) through 6(c). It can be seen that the WEPSAC foam has a broader cell distribution and an increased portion of larger cells (>200 um). The large cells are probably created by water.
The thermal conductivity of foams was measured at various temperatures and the results are presented in FIG. 7. It is clear that the addition of AC decreased the thermal conductivity of PS foams and the WEPSAC foam possessed the lowest value. The overall thermal conductivity (λ) of a closed-cell foam comprises three components, conduction through the gas phase (λg), conduction through the cell wall and the solid struts (λs), and thermal radiation (λr). Although the lower density decreases λg, the addition of AC will increase λs. Therefore, the overall thermal conductivity may depend upon λr.
It is well known that carbon is a good IR absorber. FIG. 8 shows the IR transmission of different foams. The foam density is also presented for comparison. The transmission values decreased from 14.6% for pure PS foam to about 6.3% for PS with 3.0 wt % of AC and about 5% for WEPSAC with 3.0 wt % of AC. The difference of IR absorption is further demonstrated in FIGS. 9(a) through 9(c). During the IR measurement, the temperature of samples increases due to IR absorption. When the temperature was higher than glass transition temperature, the foam would collapse and form a cavity. FIGS. 9(a) through 9(c) show that the cavity size, corresponding to the heat produced by the IR absorption, increased with the exposed time. Therefore, the cavity size can qualitatively reflect the IR absorption. Comparing the three images, the existence of a cavity on the PS/AC foams verifies the higher IR absorption caused by AC. The larger cavities on the surface of WEPSAC foam samples may imply a better AC dispersion than that in the PS/AC foam.
Conclusions from Example 6
In summary, water expandable PS/AC beads were successfully synthesized via a modified suspension polymerization process. Using AC as the carrier, water was introduced into the beads without emulsifiers. The synthesized WEPSAC beads trapped more water than just adding water containing AC in the PS extrusion foaming process. Water acted as a co-blowing agent, which enlarged the cell size and decreased the foam density in the CO2 extrusion foaming process. With the addition of water containing AC, IR transmission through the foam decreased substantially. Together, the WEPSAC foam showed the lowest thermal conductivity in this study. This new material may be useful for replacing the ozone-depleting blowing agents in thermal insulation foam applications.
The following references are hereby incorporated herein by reference:

    
    
        (1) Crevecoeur, J. J.; Nelissen, L.; Lemstra P. J. Polymer, 1999, 40, 3685-3689.
        (2) Pallay, J.; Kelemen, P.; Berghmans, H.; Van Dommelen, D.; Macromol Mater Eng, 2000, 275, 18-25.
        (3) Guo, Z. H.; Yang, J. T.; Wingert, M. J.; Shen, J.; Tomasko, D, L.; Lee, L. J. ANTEC, 2007, 3062-3065.
        (4) Martinez-Perez, C. A.; Garcia-Casillas, P. E.; Romero, P.; Juarez, C.; Martinez-Villafane, C. A.; Moller, A. D.; Romero-Garcia, J.; Journal of Advanced Materials 2006, 5-11.
        (5) Li, R. H.; White, M.; Williams, S.; Hazlett, T.; Journal of Biomaterials Science, Polymer Edition 1998, 9, 239-258.
        (6) Wake, M. C.; Gupta, P. K.; Mikos, A. G.; Cell Transplantation 1996, 5, 465-73.
        (7) RP-120X Polymeric Foams-Updated Edition; Business Communications Company, Inc., December 2001.
        (8) Han, X. M.; Shen, J; Huang, H. X.; Tomasko, D. L.; Lee, L. J.; Polymer Engineering and Science, 2007, 47, 103-111.
        (9) Lee L. J.; Zeng C. C.; Cao X.; Han X. M.; Shen J.; Xu G. J.; Composite Science and Technology, 2005, 65, 2344-2363.
        (10) Lee, L. J.; Zeng, C.; Cao, X.; Han, X.; Shen, J.; Xu, G.; Composites Science and Technology 2005, 65, 2344-2363.
        (11) Shen, J.; Zeng, C.; Lee, L. J.; Polymer, 2005, 46, 5218-5224.
    
    


Any embodiment of the present invention may include any of the optional or preferred features of the other embodiments of the present invention. The exemplary embodiments herein disclosed are not intended to be exhaustive or to unnecessarily limit the scope of the invention. The exemplary embodiments were chosen and described in order to explain the principles of the present invention so that others skilled in the art may practice the invention. Having shown and described exemplary embodiments of the present invention, those skilled in the art will realize that many variations and modifications may be made to affect the described invention. Many of those variations and modifications will provide the same result and fall within the spirit of the claimed invention. It is the intention, therefore, to limit the invention only as indicated by the scope of the claims.

## Claims

1. A method of making a foamed polymer, said method comprising:
(a) preparing a foamable polymeric material precursor comprising:
(1) an aqueous suspension polymerization of a mixture comprising:
i. styrene or other monomer;
ii. solid polymeric material selected from the group consisting of polystyrene;
iii. foaming facilitating material having affinity for a suspension liquid, said foaming facilitating material selected from the group consisting of activated carbon, said foaming facilitating material adapted to absorb said suspension liquid in the absence of any surfactant-like molecules or polymers;
iv. selected additional material selected from the group consisting of 1-dimensional nano/micro-materials;
v. a suspension stabilizer selected from the group consisting of hydroxyethyl cellulose; and
vi. said suspension liquid selected from the group consisting of water; and

(2) a blowing agent selected from the group consisting of CO2, N2, hydrofluorocarbons, fluorocarbons, and mixtures thereof; and

(b) preparing a foamed polymer by a method selected from the group consisting of extrusion, injection molding, and batch foaming of said foamable polymeric material precursor.

2. A method according to claim 1 wherein said suspension liquid is absorbed by said foaming facilitating material before mixing with said styrene or other monomer or said polymeric material and starting suspension polymerization.

3. A method according to claim 1 wherein said solid polymeric material is present in an amount less than 65% by weight, based on a total amount of said styrene and said solid polymeric material.

4. A method according to claim 1 wherein said suspension liquid is present in an amount of from 10% to 400% by weight, based on said foaming facilitating material.

5. A method according to claim 1 wherein said foaming facilitating material is present in an amount of from about 20% to about 0.01% by weight, based on a total amount of said styrene and said solid polymeric material.

6. A method according to claim 1 wherein a ratio of said activated carbon to a total amount of said styrene and said polystyrene is in a range of from about 20% to about 0.01% by weight.

7. A method according to claim 1 wherein said foaming facilitating material is selected from the group consisting of activated carbon with an average particle size from 1 micrometer to 40 micrometers.

8. A method according to claim 1 wherein said additional material comprises a 1-dimensional nano/micro-material selected from the group consisting of smectite clays, organoclays, nanographites, graphite, graphene, and graphene oxide.

9. A method according to claim 1 wherein a ratio of said additional material to a total weight of said styrene and said solid polymeric material is in an amount less than 20% by weight.

10. A method of making a foamed polymer, said method comprising:
(a) preparing a foamable polymeric material precursor comprising:
(1) an aqueous suspension polymerization of a mixture comprising:
i. styrene or other monomer;
ii. solid polymeric material selected from the group consisting of polystyrene;
iii. foaming facilitating material having affinity for a suspension liquid, said foaming facilitating material selected from the group consisting of activated carbon, said foaming facilitating material adapted to absorb said suspension liquid in the absence of any surfactant-like molecules or polymers;
iv. selected additional material selected from the group consisting of 1-dimensional nano/micro-materials;
v. a suspension stabilizer selected from the group consisting of hydroxyethyl cellulose; and
vi. said suspension liquid selected from the group consisting of water; and

(2) a blowing agent comprising CO2; and

(b) preparing a foamed polymer by a method selected from the group consisting of extrusion, injection molding, and batch foaming of said foamable polymeric material precursor.

11. A method according to claim 10 wherein said suspension liquid is absorbed by said foaming facilitating material before mixing with said styrene or other monomer or said polymeric material and starting suspension polymerization.

12. A method according to claim 10 wherein said solid polymeric material is present in an amount less than 65% by weight, based on a total amount of said styrene and said solid polymeric material.

13. A method according to claim 10 wherein said suspension liquid is present in an amount of from 10% to 400% by weight, based on said foaming facilitating material.

14. A method according to claim 10 wherein said foaming facilitating material is present in an amount of from about 20% to about 0.01% by weight, based on a total amount of said styrene and said solid polymeric material.

15. A method according to claim 10 wherein a ratio of said activated carbon to a total amount of said styrene and said polystyrene is in a range of from about 20% to about 0.01% by weight.

16. A method according to claim 10 wherein said foaming facilitating material is selected from the group consisting of activated carbon with an average particle size from 1 micrometer to 40 micrometers.

17. A method according to claim 10 wherein said additional material comprises a 1-dimensional nano/micro-material selected from the group consisting of smectite clays, organoclays, nanographites, graphite, graphene, and graphene oxide.

18. A method according to claim 10 wherein a ratio of said additional material to a total weight of said styrene and said solid polymeric material is in an amount less than 20% by weight.