Account Options

  1. Sign in
    Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

    Patents

    1. Advanced Patent Search
    Publication numberUS20100264559 A1
    Publication typeApplication
    Application numberUS 12/727,365
    Publication dateOct 21, 2010
    Filing dateMar 19, 2010
    Priority dateJan 23, 2004
    Also published asCN1926282A, EP1716283A2, EP1716283A4, EP2360198A1, US7763341, US7794817, US7993552, US7993553, US20050163969, US20060105145, US20060115625, US20060186571, US20060186572, US20080029925, US20100292397, US20120161351, US20130075945, WO2005072188A2, WO2005072188A3
    Publication number12727365, 727365, US 2010/0264559 A1, US 2010/264559 A1, US 20100264559 A1, US 20100264559A1, US 2010264559 A1, US 2010264559A1, US-A1-20100264559, US-A1-2010264559, US2010/0264559A1, US2010/264559A1, US20100264559 A1, US20100264559A1, US2010264559 A1, US2010264559A1
    InventorsWade H. Brown
    Original AssigneeCentury-Board Usa, Llc
    Export CitationBiBTeX, EndNote, RefMan
    External Links: USPTO, USPTO Assignment, Espacenet
    Filled polymer composite and synthetic building material compositions
    US 20100264559 A1
    Abstract
    The invention relates to composite compositions having a matrix of polymer networks and dispersed phases of particulate or fibrous materials. The polymer matrix contains a polyurethane network formed by the reaction of a poly- or di-isocyanate and one or more saturated polyether or polyester polyols, and an optional polyisocyanurate network formed by the reaction of optionally added water and isocyanate. The matrix is filled with a particulate phase, which can be selected from one or more of a variety of components, such as fly ash particles, axially oriented fibers, fabrics, chopped random fibers, mineral fibers, ground waste glass, granite dust, or other solid waste materials. The addition of water can also serve to provide a blowing agent to the reaction mixture, resulting in a foamed structure, if such is desired.
    Images(7)
    Previous page
    Next page
    Claims(13)
    1. A method of producing a polymer matrix composite, comprising:
    (1) mixing a first poly ether polyol having a first molecular weight and a second poly ether polyol having a second molecular weight higher than the first molecular weight with one or more catalysts, water, and optional surfactant;
    (2) optionally introducing reinforcing fibrous materials into the mixture;
    (3) introducing inorganic filler into the mixture;
    (4) introducing poly- or di-isocyanate into the mixture; and
    (5) allowing the exothermic reaction to proceed without forced cooling except to control runaway exotherm, thereby forming a polymer matrix composite.
    2. The method of claim 1, further comprising extruding the mixture or the polymer matrix composite through a die.
    3. The method of claim 2, wherein at least a portion of the mixing or reaction, or both occurs in an extruder.
    4. The method of claim 1, further comprising molding the polymer matrix composite into a desired shape.
    5. The method of claim 2, further comprising forming the polymer matrix composite into a synthetic lumber.
    6. The method of claim 5, wherein the forming comprises shaping the polymer matrix composite into a size and shape suitable for synthetic lumber.
    7. The method of claim 6, wherein the forming further comprises embossing or impressing at least one surface of the polymer matrix composite with a pattern.
    8. The method of claim 1, wherein the one or more catalysts comprise a skin-forming catalyst.
    9. The method of claim 8, wherein the skin-forming catalyst comprises an organic tin compound.
    10. The method of claim 1, wherein the one or more catalysts comprise a gelation catalyst.
    11. The method of claim 10, wherein the gelation catalyst comprises an amine.
    12. The method of claim 1, further comprising introducing axially oriented fiber rovings into the polymer matrix composite.
    13. The method of claim 12, wherein the fiber rovings are introduced on, in, or beneath the surface of the composite.
    Description
      CROSS-REFERENCE TO RELATED APPLICATIONS
    • [0001]
      This application is a continuation of Ser. No. 11/317,958, filed Dec. 22, 2005, which is a divisional of Ser. No. 10/764,012, filed Jan. 23, 2004, both of which are incorporated by reference herein in their entirety.
    • BACKGROUND OF THE INVENTION
    • [0002]
      1. Field of the Invention
    • [0003]
      The invention relates to composite compositions having matrices of polymer networks and dispersed phases of particulate and/or fibrous materials, which have excellent mechanical properties, rendering them suitable for use in load bearing applications, such as in building materials. The composites are stable to weathering, can be molded and colored to desired functional and aesthetic characteristics, and are environmentally friendly, since they can make use of recycled particulate or fibrous materials as the dispersed phase.
    • [0004]
      2. Description of the Related Art
    • [0005]
      Polymeric composite materials that contain organic or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties, weathering stability, and environmental friendliness.
    • [0006]
      These materials can be are relatively low density, due to their foaming, or high density when unfoamed, but are extremely strong, due to the reinforcing particles or fibers used throughout. Their polymer content also gives them good toughness (i.e., resistance to brittle fracture), and good resistance to degradation from weathering when they are exposed to the environment. This combination of properties renders some polymeric composite materials very desirable for use in building materials, such as roofing materials, decorative or architectural products, outdoor products, insulation panels, and the like.
    • [0007]
      In addition, the filler materials used need not be virgin materials, and can desirably be recycled fibers or particulates formed as waste or by-product from industrial processes. Polymeric composites allow these materials to be advantageously reused, rather than present disposal problems.
    • [0008]
      Filled composite polymeric materials have been described in U.S. Pat. Nos. 5,302,634; 5,369,147; 5,548,315; and 5,604,260, the contents of each of which is incorporated herein by reference. However, the materials disclosed in these patents all use polyester polyurethane resins that are formed as the reaction products of unsaturated polyester polyols, saturated polyols, poly- or di-isocyanates, and a reactive monomer, such as styrene. The number of different reactants, and the complexity of the resulting process chemistry, adds increased cost to the preparation of these materials, both through added costs for materials inputs and through added capital costs for additional process equipment.
    • [0009]
      A filled closed cell foam material is disclosed in U.S. Pat. No. 4,661,533 (Stobby), but provides much lower densities than are desirable for structural building products. Moreover, Stobby does not disclose or suggest a composite material that is “self-skinning,” i.e., that forms a continuous skin on the surface of the material that covers and protects the material underneath, which is porous, and subject to visible scratching.
    • SUMMARY OF THE INVENTION
    • [0010]
      It has been found, however, that a highly filled, foamed or unfoamed composite polymeric material having good mechanical properties can be obtained without the need for all of the components required in the patents cited above. This results in a substantial decrease in cost, because of decreased materials cost, and because of decreased complexity of the process chemistry, leading to decreased capital investment in process equipment.
    • [0011]
      In one embodiment, the invention relates to composite compositions having a matrix of polymer networks and dispersed phases of particulate or fibrous materials. The polymer matrix contains a polyurethane network formed by the reaction of a poly- or di-isocyanate and one or more saturated poly ether or polyester polyols, and an optional polyisocyanurate network formed by the reaction of optionally added water and isocyanate. The matrix is filled with a particulate phase, which can be selected from one or more of a variety of components, such as fly ash particles, axially oriented fibers, fabrics, chopped random fibers, mineral fibers, ground waste glass, granite dust, or other solid waste materials. The addition of water can also serve to provide a blowing agent to the reaction mixture, resulting in a foamed structure, if such is desired.
    • [0012]
      The composite material of the invention is advantageously used as structural building material, and in particular as synthetic lumber, for several reasons. First, it has the desired density, even when foamed, to provide structural stability and strength. Second, the composition of the material can be easily tuned to modify its properties by, e.g., adding oriented fibers to increase flexural stiffness, or by adding pigment or dyes to hide the effects of scratches. This can be done even after the material has been extruded. Third, the material is self-skinning, forming a tough, slightly porous layer that covers and protects the more porous material beneath. This tough, continuous, highly adherent skin provides excellent water and scratch resistance. In addition, as the skin is forming, an ornamental pattern (e.g., a simulated wood grain) can be impressed on it, increasing the commercial acceptability of products made from the composite.
    • [0013]
      In a more specific embodiment, the invention relates to a polymer matrix composite material, comprising:
    • [0014]
      (1) a polyurethane formed by reaction of
        • (a) one or more monomeric or oligomeric poly- or di-isocyanates;
        • (b) a first polyether polyol having a first molecular weight; and
        • (c) an optional second polyether polyol having a second molecular weight lower than the first molecular weight; and
    • [0018]
      (2) optionally, a polyisocyanurate formed by reaction of a monomeric or oligomeric poly- or di-isocyanate with water or other blowing agents;
    • [0019]
      (3) a particulate inorganic filler.
    • [0020]
      As indicated above, the polymer matrix composite material of the invention can have a variety of different uses. However, it is particularly suitable in structural applications, and in particular as an synthetic lumber. Accordingly, another specific embodiment of the invention relates to an synthetic lumber, comprising the polymer matrix composite material described above, and having a relatively porous material and a relatively non-porous toughening layer disposed on and adhered to the porous material.
    • [0021]
      It has been found that the process used to manufacture the polymer matrix composite material and the synthetic lumber formed therefrom can have an important impact on the appearance and properties of the resulting material, and thus on its commercial acceptability. Accordingly, another particular embodiment of the invention relates to a method of producing a polymer matrix composite, by:
    • [0022]
      (1) mixing a first polyether polyol having a first molecular weight and a second polyether polyol having a second molecular weight higher than the first molecular weight with a catalyst, optional water, and optional surfactant;
    • [0023]
      (2) optionally introducing reinforcing fibrous materials into the mixture;
    • [0024]
      (3) introducing inorganic filler into the mixture;
    • [0025]
      (4) introducing poly- or di-isocyanate into the mixture; and
    • [0026]
      (5) allowing the exothermic reaction to proceed without forced cooling except to control runaway exotherm.
    • [0027]
      The materials of the invention, and the process for their preparation, are environmentally friendly. They provide a mechanism for reuse of particulate waste in a higher valued use, as described above. In addition, the process for making them optionally uses water in the formation of polyisocyanurate, which releases carbon dioxide as the blowing agent. The process thus avoids the use of environmentally harmful blowing agents, such as halogenated hydrocarbons.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
    • [0028]
      As described above, one embodiment of the invention relates to a composite composition containing a polymeric matrix phase and a dispersed inorganic particulate phase, and which can contain other materials, such as reinforcing fibers, pigments and dyes, and the like. One of the desirable properties of the material is its self-skinning nature.
    • [0029]
      The polymeric phase desirably contains at least a polyurethane, generally considered to be a 2-part or thermosetting polyurethane. The polyurethane is formed by reacting a poly- or di-isocyanate (hereinafter “isocyanate”), particularly an aromatic diisocyanate, more particularly, a methylene diphenyl diisocyanate (MDI), with one or more poly ether polyols, described in more detail below.
    • [0030]
      The MDI used in the invention can be MDI monomer, MDI oligomer, or a mixture thereof. The particular MDI used can be selected based on the desired overall properties, such as the amount of foaming, strength of bonding to the inorganic particulates, wetting of the inorganic particulates in the reaction mixture, strength of the resulting composite material, and stiffness (elastic modulus). Although toluene diisocyanate can be used, MDI is generally preferable due to its lower volatility and lower toxicity. Other factors that influence the particular MDI or MDI mixture used in the invention are viscosity (a low viscosity is desirable from an ease of handling standpoint), cost, volatility, reactivity, and content of 2,4 isomer. Color may be a significant factor for some applications, but does not generally affect selection of an MDI for preparing synthetic lumber.
    • [0031]
      Light stability is also not a particular concern for selecting MDI for use in the composite of the invention. In fact, the composite of the invention allows the use of isocyanate mixtures not generally regarded as suitable for outdoor use, because of their limited light stability. When used in the composite of the invention, these materials surprisingly exhibit excellent light stability, with little or no yellowing or chalking. Since isocyanate mixtures normally regarded as suitable for outdoor use (generally aliphatic isocyanates) are considerably more expensive than those used in this invention, the ability of the invention to use MDI mixtures represents a significant cost advantage.
    • [0032]
      Suitable MDI compositions for use in the invention include those having viscosities ranging from about 25 to about 200 cp at 25° C. and NCO contents ranging from about 30% to about 35%. Generally, isocyanates are used that provide at least 1 equivalent NCO group to 1 equivalent OH group from the polyols, desirably with about 5% to about 10% excess NCO groups. Suitable isocyanates include Bayer MRS-4, Bayer MR Light, Dow PAPI 27, Bayer MR5, Bayer MRS-2, and Rubinate 9415.
    • [0033]
      As indicated above, the isocyanate used in the invention is reacted with one or more polyols. In general, the ratio of isocyanate to polyol, based on equivalent weights (OH groups for polyols and NCO groups for isocyanates) is generally in the range of about 0.5:1 to about 1.5:1, more particularly from about 0.8:1 to about 1.1:1. Ratios in these ranges provide good foaming and bonding to inorganic particulates, and yields low water pickup, fiber bonding, heat distortion resistance, and creep resistance properties. However, precise selection of the desired ratio will be affected by the amount of water in the system, including water added per se as a foaming agent, and water introduced with other components as an “impurity.”
    • [0034]
      The polyol or polyols used may be single monomers, oligomers, or blends. Mixtures of polyols can be used to influence or control the properties of the resulting polymer network. For example, mixtures of two polyols, one a low molecular weight, rubbery (relative to the second) polyol and the other a higher molecular weight, more rigid (relative to the first) polyol. The amount of rigid polyol is carefully controlled in order to avoid making the composite too brittle (a ratio of flexible polyol to rigid polyol of between about 5 wt % and about 20 wt %, more particularly around 15 wt % has generally been found to be suitable. It is generally desirable to use polyols in liquid form, and generally in the lowest viscosity liquid form available, as these can be more easily mixed with the inorganic particulate material. So-called “EO” tipped polyols can be used; however their use is generally avoided where it is desired to avoid “frosting” of the polymer material when exposed to water.
    • [0035]
      In general, desirable polyols include polyether polyols, such as MULTRANOL (Bayer), including MULTRANOL 3400 or MULTRANOL 4035, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 2-butyn-1,4-diol, neopentyl glycol, 1,2-propanediol, pentaerythritol, mannitol, 1,6-hexanediol, 1,3-buytylene glycol, hydrogenated bisphenol A, polytetramethyleneglycolethers, polythioethers, and other di- and multifunctional poly ethers and polyester polyethers, and mixtures thereof. The polyols need not be miscible, but should not cause compatibility problems in the polymeric composite.
    • [0036]
      As indicated above, the composite of the invention can desirably be prepared by mixing the polyols together (if multiple polyols are used), and then mixing them with various additives, such as catalysts, surfactants, and foaming agent, and then adding the inorganic particulate phase, then any reinforcing fiber, and finally the isocyanate.
    • [0037]
      One or more catalysts are generally added to control the curing time of the polymer matrix (upon addition of the isocyanate), and these may be selected from among those known to initiate reaction between isocyanates and polyols, such as amine-containing catalysts, such as DABCO and tetramethylbutanediamine, tin-, mercury- and bismuth-containing catalysts. To increase uniformity and rapidity of cure, it may be desirable to add multiple catalysts, including a catalyst that provides overall curing via gelation, and another that provides rapid surface curing to form a skin and eliminate tackiness. For example, a liquid mixture of 1 part tin-containing catalyst to 10 parts amine-containing catalyst can be added in an amount greater than 0 wt % and below about 0.10 wt % (based on the total reaction mixture) or less, depending on the length of curing time desired. Too much catalyst can result in overcuring, which could cause buildup of cured material on the processing equipment, or too stiff a material which cannot be properly shaped, or scorching; in severe cases, this can lead to unsaleable product or fire. Curing times generally range from about 5 seconds to about 2 hours.
    • [0038]
      A surfactant may optionally be added to the polyol mixture to function as a wetting agent and assist in mixing of the inorganic particulate material. The surfactant also stabilizes bubbles formed during foaming (if a foamed product is desired) and passivates the surface of the inorganic particulates, so that the polymeric matrix covers and bonds to a higher surface area. Surfactants can be used in amounts below about 0.5 wt %, desirably about 0.3 wt %, based on the total weight of the mixture. Excess amount of surfactant can lead to excess water absorption, which can lead to freeze/thaw damage to the composite material. Silicone surfactants have been found to be suitable for use in the invention. Examples include DC-197 and DC-193 (silicone-based, Air Products), and other nonpolar and polar (anionic and cationic) products.
    • [0039]
      Foaming agent may also be added to the polyol mixture if a foamed product is desired. While these may include organic blowing agents, such as halogenated hydrocarbons, hexanes, and other materials that vaporize when heated by the polyol-isocyanate reaction, it has been found that water is much less expensive, and reacts with isocyanate to yield CO2, which is inert, safe, and need not be scrubbed from the process. Equally as important, CO2 provides the type of polyurethane cells desirable in a foamed product (i.e., mostly open, but some closed cells), is highly compatible with the use of most inorganic particulate fillers, particularly at high filler levels, and is compatible with the use of reinforcing fibers. Other foaming agents will not produce the same foam structure as is obtained with water.
    • [0040]
      If water is not added to the composition, some foaming may still occur due to the presence of small quantities of water (around 0.2 wt %, based on the total weight of the reaction mixture) introduced with the other components as an “impurity.” On the other hand, excessive foaming resulting from the addition of too much water (either directly or through the introduction of “wet” reactants or inorganic particulate materials) can be controlled by addition of an absorbent, such as UOP “T” powder.
    • [0041]
      The amount of water present in the system will have an important effect on the density of the resulting composite material. This amount generally ranges from about 0.10 wt % to about 0.40 wt %, based on the weight of polyol added, for composite densities ranging from about 20 lb/ft3 to about 90 lb/ft3.
    • [0042]
      Reinforcing fibers can also be introduced into the polyol mixture prior to introduction of the isocyanate. These can include fibers per se, such as chopped fiberglass, or fabrics or portions of fabrics, such as rovings or linear tows, or combinations of these. Typically, the reinforcing fibers range from about 0.125 in. to about 1 in, more particularly from about 0.25 in to about 0.5 in. The reinforcing fibers give the material added strength (flexural, tensile, and compressive), increase its stiffness, and provide increased toughness (impact strength or resistance to brittle fracture). Fabrics, rovings, or tows increase flexural stiffness and creep resistance. The inclusion of the particular polyurethane networks of the invention, together with the optional surfactants, and the inorganic particulate sizes used make the composite of the invention particularly and surprisingly well suited for inclusion of reinforcing fibers in foamed material, which normally would be expected to rupture or distort the foam bubbles and decrease the strength of the composite system.
    • [0043]
      In addition to inclusion of reinforcing fibers into the polyol mixture prior to polymerization, oriented axial fibers can also be introduced into the composite after extrusion, as the polymer exits the extruder and prior to any molding. The fibers (e.g., glass strings) can desirably be wetted with a mixture of polyol (typically a higher molecular weight, rigid polyol) and isocyanate, but without catalyst or with a slow cure catalyst, or with other rigid or thermosetting resins, such as epoxies. This allows the wetted fiber to be incorporated into the composite before the newly added materials can cure, and allows this curing to be driven by the exotherm of the already curing polymer in the bulk material.
    • [0044]
      Whether added before or after polymerization and extrusion, the composite material of the invention contains a polymeric matrix phase that is strongly bonded to the dispersed reinforcing fibers, increasing the strength and stiffness of the resulting material. This enables the material to be used as a structural synthetic lumber, even at relatively low densities (e.g., about 20 to about 60 lb/ft3).
    • [0045]
      Pigment or dye can be added to the polyol mixture or can be added at other points in the process. The pigment is optional, but can help make the composite material more commercially acceptable, more distinctive, and help to hide any scratches that might form in the surface of the material. Typical examples of pigments include iron oxide, typically added in amounts ranging from about 2 wt % to about 7 wt %, based on the total weight of the reaction mixture.
    • [0046]
      The inorganic particulate phase is an important feature of the invention, and is typically present in amounts ranging between about 45 wt % to about 85 wt % of the total composition. Increasing the proportion of inorganic particulate can lead to increased difficulty in mixing, making the inclusion of a surfactant more desirable. The inorganic particulate material should have less than about 0.5 wt % water (based on the weight of the particulate material) in order to avoid excessive or uncontrolled foaming.
    • [0047]
      It is generally desirable to use particulate materials with a broad particle size distribution, because this provides better particulate packing, leading to increased density and decreased resin level per unit weight of composite. Since the inorganic particulate is typically some form of waste or scrap material, this leads to decreased raw material cost as well. Particles having size distributions ranging from about 0.0625 in to below 325 mesh have been found to be particularly suitable.
    • [0048]
      Suitable inorganic particulates can include ground glass particles, fly ash, bottom ash, sand, granite dust, and the like, as well as mixtures of these. Fly ash is desirable because it is uniform in consistency, contains some carbon (which can provide some desirable weathering properties to the product due to the inclusion of fine carbon particles which are known to provide weathering protection to plastics, and the effect of opaque ash particles which block UV light, and contains some metallic species, such as metal oxides, which are believed to provide additional catalysis of the polymerization reactions. Ground glass (such as window or bottle glass) absorbs less resin, decreasing the cost of the composite. A 1:1 mixture of coal fly ash and bottom ash has also been found to be suitable as the inorganic particulate composition. In general, fly ash having very low bulk density (e.g., less than about 40 lb/ft3) and/or high carbon contents (e.g., around 20 wt % or higher) are less suitable, since they are more difficult to incorporate into the resin system, and may require additional inorganic fillers that have much less carbon, such as foundry sand, to be added. Fly ash produced by coal-fueled power plants, including Houston Lighting and Power power plants, fly and bottom ash from Southern California Edison plants (Navajo or Mohave), fly ash from Scottish Power/Jim Bridger power plant in Wyoming, and fly ash from Central Hudson Power plant have been found to be suitable for use in the invention.
    • [0049]
      The process for producing the composite material may be operated in a batch, semibatch, or continuous manner. Mixing may be conducted using conventional mixers, such as Banbury type mixers, stirred tanks, and the like, or may be conducted in an extruder, such as a twin screw, co-rotating extruder. When an extruder is used, additional heating is generally not necessary, especially if liquid polyols are used. In addition, forced cooling is not generally required, except for minimal cooling to control excessive or runaway exotherms.
    • [0050]
      For example, a multi-zone extruder can be used, with polyols and additives introduced into the first zone, inorganic particulates introduced in the second zone, and chopped fibers, isocyanate, and pigments introduced in the fifth zone. A twin screw, co-rotating, extruder (e.g. 100 mm diameter, although the diameter can be varied substantially) can be used, with only water cooling (to maintain room temperature), and without extruder vacuum (except for ash dust). Liquid materials can be pumped into the extruder, while solids can be added by suitable hopper/screw feeder arrangements. Internal pressure build up in such an exemplary arrangement is not significant.
    • [0051]
      Although gelation occurs essentially immediately, complete curing can take as long as 48 hours, and it is therefore desirable to wait at least that long before assessing the mechanical properties of the composite, in order to allow both the composition and the properties to stabilize.
    • [0052]
      As explained above, the composite material of the invention is advantageously used in structural products, including synthetic lumber. The synthetic lumber may be formed in a batch, semibatch, or continuous fashion. For example, in continuous operation, polymerized (and polymerizing) material leaving the extruder (after optional incorporation of post-extruder fibers, tows, or rovings) is supplied to a forming system, which provides dimensional constraint to the material, and can be used to pattern the surfaces of the resulting synthetic lumber with simulated woodgrain or other designs, in order to make the material more commercially desirable. For example, a conveyor belt system comprising 2, 4, or 6 belts made from a flexible resin having wood grain or other design molded therein can be used. One such suitable system is described in copending U.S. patent application Ser. No. ______ (Attorney Docket No. ______) filed on even date herewith, the entire contents of which are incorporated herein by reference. Desirably, the belts are formed from a self-releasing rubber or elastomeric material so that it will not adhere to the polymer composite. Suitable belt materials include silicone rubber, oil impregnated polyurethane, or synthetic or natural rubbers, if necessary coated with a release agent, such as waxes, silicones, or fluoropolymers.
    • [0053]
      Representative suitable compositional ranges for synthetic lumber, in percent based on the total composite composition, are provided below:
    • [0000]
      Rigid polyol about 6 to about 18 wt %
      Flexible polyol 0 to about 10 wt %
      Surfactant about 0.2 to about 0.5 wt %
      Skin forming catalyst about 0.002 to about 0.01 wt %
      Gelation catalyst about 0.02 to about 0.1 wt %
      Water 0 to about 0.5 wt %
      Chopped fiberglass 0 to about 10 wt %
      Pigments 0 to about 6 wt %
      Inorganic particulates about 60 to about 85 wt %
      Isocyanate about 6 to about 20 wt %
      Axial tows 0 to about 6 wt %.
    • [0054]
      The invention can be further understood by reference to the following non-limiting examples.
    • Example 1
    • [0055]
      A polymer composite composition was prepared by introducing 9.5 wt % rigid polyol (MULTRANOL 4035, Bayer), 0.3 wt % rubber polyol (ARCOL LG-56, Bayer), 0.3 wt % surfactant/wetting agent (DC-197, Air Products), 0.005 wt % film forming organic tin catalyst (UL-28/22, Air Products), 0.03 wt % amine gelation catalyst (33LV, Air Products), and 0.05 wt % water as foaming agent to the drive end of a 100 mm diameter twin screw co-rotating extruder with water cooling to maintain room temperature. At a point around 60% of the length of the extruder, 4.2 wt % chopped glass fibers (Owens Corning) with ¼ to ½ inch lengths were added, along with 4.0 wt % brown pigment (Interstar), 74 wt % fly ash (ISG), and 9.6 wt % isocyanate (MONDUR MR Light, Bayer). The extruder was operated at room temperature (75° F.), at 200 rpm for one hour. Following extrusion, 0.4 wt % of a resin mixture of rubbery polyol (ARCOL LG-56, Bayer), and isocyanate (MONDUR MR Light, Bayer) were added to the surface of the extruded material to provide a bonding adhesive for glass tows. The glass tows (Owens Corning) ¼ to ½ inch length were added in an amount of around 2 wt % to provide added rigidity, and were added just below the surface of the material produced by the extruder.
    • [0056]
      The resulting composite material was particularly useful as synthetic decking material.
    • Example 2
    • [0057]
      In a batch reactor, 16.4 wt % rigid polyol (Bayer 4035) was combined with 1.9 wt % flexible polyol (Bayer 3900), 0.2 wt % surfactant (DC-197), water, 3.2 wt % pigments, 0.0001 wt % UL-28 organic tin catalyst, and 0.1 wt % 33LV amine catalyst, and thoroughly mixed for 1 minute. 31.5 wt % Wyoming fly ash was then added and mixed for an additional 1 minute. Finally, 17.3 wt % isocyanate (1468A, Hehr), 0.9 wt % chopped brown fiber, 3.5 wt % chopped glass (0.25 in. diameter), and an additional 25.2 wt % Wyoming fly ash were added and mixed for 30 seconds. The resulting material had a resin content of 36%, a ratio of rigid to rubbery polyol of 90%, a solids content of 64%, a 10% excess isocyanate content, and a fiber content of 4.4%, all by weight based on the total composition unless noted otherwise. The resulting material was suitable for forming synthetic lumber boards.
    • Example 3
    • [0058]
      In a batch reactor, 16.4 wt % rigid polyol (Bayer 4035) was combined with 1.9 wt % flexible polyol (Bayer 3900), 0.2 wt % surfactant (DC-197), water, 3.2 wt % pigments, 3.5 wt % chopped glass (0.25 in. diameter), around 0.4 wt % Mohave bottom ash, 0.0001 wt % UL-28 organic tin catalyst, and 0.1 wt % 33LV amine catalyst, and thoroughly mixed for 1 minute. 31.5 wt % Wyoming fly ash was then added and mixed for an additional 1 minute. Finally, 17.3 wt % isocyanate (1468A, Hehr), 0.9 wt % chopped brown fiber, and an additional 25.2 wt % Wyoming fly ash were added and mixed for 30 seconds. The resulting material had a resin content of 36%, a ratio of rigid to rubbery polyol of 90%, a solids content of 64%, a 10% excess isocyanate content, and a fiber content of 4.4%, all by weight based on the total composition unless noted otherwise. The resulting material was suitable for forming synthetic lumber boards.
    • [0059]
      For each of Examples 2 and 3, water was added in amounts shown below (in percent based on total polyol added); physical properties of the resulting material were tested, and the results provided below. The 200 lb impact test was conducted by having a 200 lb man jump on an 18 inch span of synthetic lumber board, 2×6 inches. supported above the ground from a height of about 1 ft in the air, and evaluating whether the board breaks.
    • [0000]
      H20 Break 100 psi Hardness Flexural Flexural 200 lb
      (% of Density Strength Deflection (Durometer Strength Modulus impact test
      Example polyol) (lb/ft3) (psi) (in) C) (psi) (psi) (P/F)
      2 0.10 63 730 0.15 62 3129 118,331 P
      2 0.23 59 650 0.15 57 2786 118,331 P
      2 0.40 47 450 0.15 52 1929 118,331 F
      3 0.10 63 810 0.15 62 3472 118,331 P
    • Example 4
    • [0060]
      Fiberglass rovings (Ahlstrom, 0.755 gift) or brown basalt rovings (0.193 gift) were positioned in a 24 inch mold for 2×4 inch synthetic lumber, and stabilized to limit movement relative to the mold surface (about 0.125 in. in from the mold surface) and to keep them taut. The rovings were applied dry, coated and pre-cured with the synthetic lumber composition (minus ash and chopped glass), and wet with a mixture of 49 wt % rigid polyol (MULTRANOL 4035), 0.098 wt % surfactant (DC-197), 0.20 wt % amine catalyst (33LV), and 49.59 wt % isocyanate (Hehr 1468A).
    • [0061]
      To the mold was added a synthetic lumber mixture, formed by combining 16.6 wt % rigid polyol (MULTRANOL 4035), 5.5 wt % flexible polyol (MULTRANOL 3900), 0.16 wt % surfactant (DC-197), 0.07 wt % water, 3.7 wt % pigments, 0.003 wt % organic tin catalyst (UL-28, Air Products), and 0.1 wt % amine catalyst (33LV), and mixing for 1 minute, then adding 26.4 wt % Wyoming fly ash, mixing for 1 minute, and finally adding 20.4 wt % isocyanate (MRS4, Bayer), 1.1 wt % chopped brown fiber, 3.4 wt % chopped 0.25 in. fiberglass, and 22.5 wt % Wyoming fly ash, and mixing for 30 seconds.
    • [0062]
      The physical properties of the resulting boards were assessed, and are indicated below. Control boards were also prepared to different densities, and their physical properties evaluated as well. The axially oriented rovings greatly increased flexural strength, with little added weight. The rovings tend to have a more pronounced strengthening effect as the load on the material is increased.
    • [0000]
      Number Flexural Flexural Flexural
      of Density strength Modulus @ 100 psi Modulus @ 200 psi
      Roving Type rovings Roving Coating (lb/ft3) (psi) (Ksi) (Ksi)
      Basalt 10 Dry 41 1191 73 53
      Fiberglass 10 Pre-cured resin 58 4000 188 135
      Fiberglass 10 Dry 62 5714 339 169
      Basalt 40 Dry 49 2465 96 101
      Basalt 40 Dry 31 1650 62 165
      Fiberglass 10 Dry 32 2717 37 57
      Fiberglass 10 Wet 36 3533 77 93
      Fiberglass 5 Wet 36 2410 64 71
      Fiberglass 15 Wet 38 4594 171 80
      Fiberglass 20 Wet 35 4356 84 80
      None 55 1808 147 98
      None 66 4724 121 100
      None 68 169 135
      None 59 2568 70 84
      None 45 1319 82 62
      None 35 1174 56 63
      None 41  746 59 0
    • [0063]
      The synthetic lumber produced by the invention was found to have good fire retardant properties, achieving a flame spread index of 25, and to produce only small quantities of respirable particles of size less than 10 μm when sawn. It provides excellent compressive strength, screw and nail holding properties, and density. Extruded composite of the invention generally provides mechanical properties that are even better than those provided by molded composite.
    Patent Citations
    Cited PatentFiling datePublication dateApplicantTitle
    US3071297 *Sep 14, 1961Jan 1, 1963Yee LeeHyperbolic hopper outlet means
    US3078512 *Sep 30, 1960Feb 26, 1963Phillips Petroleum CoExtruder vent cleaner
    US3308218 *May 24, 1961Mar 7, 1967Wood Conversion CoMethod for producing bonded fibrous products
    US3566448 *Jul 16, 1968Mar 2, 1971Hennecke Gmbh MaschfApparatus for the continuous production of sections of foamed materials,particularly on a polyurethane base
    US3644168 *Jun 12, 1970Feb 22, 1972Upjohn CoVaried density polyisocyanurate foam structure
    US3726624 *Feb 27, 1970Apr 10, 1973I SchwarzFoam sheet material means
    US3802582 *Sep 28, 1971Apr 9, 1974Cmi CorpMass flow asphalt storage and dispensing system and method
    US3867494 *Mar 6, 1973Feb 18, 1975Owens Corning Fiberglass CorpMethod and apparatus for producing fiber reinforced organic foam
    US3878027 *Jan 4, 1973Apr 15, 1975Trus Joist CorpContinuous, laminated-platen press for pressing glue-coated press charges
    US4005035 *Dec 24, 1974Jan 25, 1977Tecnik International CorporationComposition for reinforced and filled high density rigid polyurethane foam products and method of making same
    US4073840 *Apr 7, 1975Feb 14, 1978Exxon Research & Engineering Co.Method for forming a fiber reinforced foam article
    US4078032 *May 2, 1977Mar 7, 1978Wenner Ralph BMethod and apparatus for fabricating a continuous length of cleated belting
    US4137200 *Jun 10, 1977Jan 30, 1979W. R. Grace & Co.Crosslinked hydrophilic foams and method
    US4141862 *Oct 25, 1977Feb 27, 1979Abbott LaboratoriesCatalyst combination for polyurethanes
    US4143759 *Apr 8, 1977Mar 13, 1979Paradis Joseph RPositionable cleats and associated conveyors
    US4149840 *Nov 8, 1977Apr 17, 1979Tippmann Eugene RApparatus for producing rigid foam plastic insulating panels
    US4243755 *Nov 13, 1979Jan 6, 1981Basf AktiengesellschaftProcess for the manufacture of reinforced polyurethane foams
    US4247656 *Mar 14, 1979Jan 27, 1981Minnesota Mining And Manufacturing CompanyPoly(urethane-isocyanurate) foams
    US4248975 *Mar 22, 1978Feb 3, 1981Witco Chemical CorporationRigid shrink stable polyurethane foam derived from an adduct of an alkylene oxide having at least three carbon atoms and a polyol having at least four hydroxy groups and blown with a fluorinated-chlorinated alkane
    US4251428 *Sep 24, 1979Feb 17, 1981Bayer AktiengesellschaftThermosetting molding compositions containing polyurethane and a fibrous material, and a process for the production of moldings
    US4254002 *Feb 21, 1979Mar 3, 1981Sperling L HTough plastics based on castor oil elastomer-reinforced vinyl polymers
    US4254176 *Sep 29, 1978Mar 3, 1981Bayer AktiengesellschaftNovel transparent polyurethane polyurea films for lamination of glazing materials and their method of production
    US4256846 *Jul 20, 1979Mar 17, 1981Bridgestone Tire Co., Ltd.Method of producing flameproof polyisocyanurate foams
    US4260538 *Sep 27, 1979Apr 7, 1981The Budd CompanyMatured moldable thermosetting dual polyester resin system
    US4261946 *Dec 13, 1979Apr 14, 1981Bayer AktiengesellschaftProcess for the production of thermoplastic polymer by introducing thermoplastic polymer into an extruder and adding organic polyisocyanate and chain lengthening agent
    US4367259 *Jul 27, 1981Jan 4, 1983W. R. Grace & Co.Sound deadening material
    US4376171 *May 13, 1982Mar 8, 1983Blount David HProcess for the production of polyester resins
    US4381352 *Aug 12, 1981Apr 26, 1983Basf Wyandotte CorporationProcess for reinforced reaction injection molding of polyurethanes
    US4439548 *Sep 3, 1982Mar 27, 1984Morey WeismanModified polyurethane product having improved load-bearing characteristics
    US4512942 *Jun 13, 1983Apr 23, 1985B. F. Goodrich CompanyMethod and apparatus for vulcanizing hose
    US4514162 *Jan 21, 1983Apr 30, 1985Sicowa Verfahrenstechnik Fur Baustoffee Gmbh & Co. KgAppliance for heating an electroconductive material in the form of a continuous strand
    US4568702 *Apr 15, 1985Feb 4, 1986Atlantic Richfield CompanyMethod for the preparation of semi-rigid polyurethane modified polyurea foam compositions
    US4576718 *Nov 16, 1984Mar 18, 1986Bayer AktiengesellschaftUse of water-absorbing, highly-filled polyurethane (urea) compositions for biological treatment of waste-containing liquids
    US4581186 *Jul 30, 1984Apr 8, 1986Larson Roger EMethod of making foam core building panels in a continuous operation
    US4649162 *Jan 23, 1986Mar 10, 1987Basf AktiengesellschaftProcess for the preparation of cellular or noncellular plastics from at least two components which react with one another
    US4661533 *Oct 28, 1985Apr 28, 1987The Dow Chemical CompanyRigid polyurethane modified polyisocyanurate containing fly ash as an inorganic filler
    US4717027 *Mar 28, 1986Jan 5, 1988Laros Equipment Company, Inc.Vibratory belt separator for blow-molded parts
    US4717778 *Oct 1, 1985Jan 5, 1988Uop Inc.Process for separating the minor isomers of dinitrotoluene
    US4795763 *Apr 18, 1988Jan 3, 1989The Celotex CorporationCarbon black-filled foam
    US4802769 *Dec 29, 1986Feb 7, 1989Veb Kombinat Polygraph "Werner Lamberz" LeipzigApparatus for treating thermoplastic resin
    US4892891 *Dec 2, 1988Jan 9, 1990Syn-Coat EnterprisesNovel foam compositions
    US4895352 *Jan 9, 1989Jan 23, 1990Simmons CompanyMattress or cushion spring array
    US4995801 *Jul 19, 1989Feb 26, 1991Karl HehlInjection molding machine provided with a conveyor for delivering molding from the machine
    US5001165 *May 17, 1989Mar 19, 1991Sloss Industries CorporationPolyoxyalkylene solubilizers for polyol blends
    US5010112 *Dec 1, 1989Apr 23, 1991Massachusetts Institute Of TechnologyMethod and apparatus for improving the insulating properties of closed cell foam
    US5091436 *Feb 20, 1990Feb 25, 1992Frisch Kurt CReinforced foam composites comprising hydroxy-containing vinyl ester resin
    US5094798 *Sep 19, 1990Mar 10, 1992Hewitt Michael JohnManufacture of lightweight structural profile
    US5096993 *Nov 2, 1990Mar 17, 1992Olin CorporationThermoplastic polyurethane elastomers and polyurea elastomers made using low unsaturation level polyols prepared with double metal cyanide catalysts
    US5102918 *May 16, 1990Apr 7, 1992Nippon Polyurethane Industry Co., Ltd.Process for producing modified organic polyisocyanate
    US5185420 *Mar 16, 1992Feb 9, 1993Olin CorporationThermoplastic polyurethane elastomers and polyurea elastomers made using low unsaturation level polyols prepared with double metal cyanide catalysts
    US5296545 *Jul 14, 1992Mar 22, 1994Cook Composites And PolymersSurface appearance and processing characteristics for urethane-catalyzed low profile-modified polyester-polyurethane hybrid resins
    US5491174 *Apr 7, 1995Feb 13, 1996The Dow Chemical CompanyProcess for preparation of polyurethanes utilizing novel catalysts
    US5495640 *Apr 18, 1995Mar 5, 1996Wayne-Dalton Corp.Sectional overhead door
    US5604266 *Apr 15, 1996Feb 18, 1997Ecomat, Inc.Cured unsaturated polyest-polyurethane highly filled resin materials and process for preparing them
    US5611976 *May 22, 1995Mar 18, 1997Bayer AktiengesellschaftProcess for the production of moldings from two-component reactive systems having a high filler content
    US5710231 *Feb 20, 1996Jan 20, 1998Imperial Chemical Industries PlcIsocyanate-reactive compositions containing internal mold release agents
    US5723506 *Nov 1, 1996Mar 3, 1998Apache Products CompanyExtruded polymer foam with filler particles and method
    US5728337 *Jul 18, 1996Mar 17, 1998Toshiba Machine Co., Ltd.Twin screw extruder and an extruding method using the same
    US6019269 *Oct 9, 1998Feb 1, 2000Wayne-Dalton Corp.Conveyor apparatus for the transport of door panels
    US6020387 *Sep 22, 1997Feb 1, 2000Caschem, Inc.Low density polymers and methods of making and using same
    US6040381 *Mar 12, 1999Mar 21, 2000The Dow Chemical CompanyPreparation of filled reactive polyurethane carpet backing formulations using an in-line continuous mixing process
    US6177232 *Jul 14, 1998Jan 23, 2001Vantico Inc.Sedimentation stabilized radiation-curable filled compositions
    US6180192 *Mar 24, 1997Jan 30, 2001Wood Waste Energy, Inc.Solids produced from ash and process for producing the same
    US6180686 *Sep 17, 1998Jan 30, 2001Thomas M. KurthCellular plastic material
    US6204312 *Jul 5, 1996Mar 20, 2001Advance Enterprises Ltd.Process for manufacturing organic and inorganic compositions, moulded flat or extruded to give complex formation, dimensional stability, added strength, biological resistance, using non toxic resin formulations
    US6343924 *Nov 26, 1997Feb 5, 2002Firma Ploytech Klepsch & Co. GmbhArrangement with conveyor belts for the manufacture of molded articles
    US6348514 *Sep 29, 1998Feb 19, 2002Uniroyal Chemical Company, Inc.Stabilized polyether polyol and polyurethane foam obtained therefrom
    US6534617 *Nov 22, 1999Mar 18, 2003Kraton Polymers U.S. LlcExtruder process for making thermoplastic polyurethanes
    US6686435 *Jun 20, 2002Feb 3, 2004Pittsburg State UniversityMethod of making natural oil-based polyols and polyurethanes therefrom
    US6695902 *Nov 14, 2001Feb 24, 2004Boral Material Technologies, Inc.Asphalt composites including fly ash fillers or filler blends, methods of making same, and methods for selecting or modifying a fly ash filler for use in asphalt composites
    US6706774 *Feb 20, 2001Mar 16, 2004Hilti AktiengesellschaftTwo-component on-site foam system and its use for foaming openings for the purpose of fire protection
    US6849676 *Jan 8, 1999Feb 1, 2005Matsumoto Yushi-Seiyaku Co., Ltd.Antistatic polyurethane elastic fiber and material for producing the same
    US6864296 *Aug 4, 2003Mar 8, 2005Urethane Soy Systems CompanyPlastic material
    US6867239 *Aug 12, 2003Mar 15, 2005Urethane Soy Systems CompanyPlastic material
    US6871457 *May 30, 2002Mar 29, 2005Hylsa, S.A. De C.V.Vessel for enabling a uniform gravity driven flow of particulate bulk material therethrough, and direct reduction reactor incorporating same
    US6989123 *Feb 18, 2005Jan 24, 2006Aspen Aerogels, Inc.Methods to produce gel sheets
    US6997346 *Dec 8, 2003Feb 14, 2006Process Control CorporationApparatus and method for reducing buildup of particulate matter in particulate-matter-delivery systems
    US7160976 *Apr 1, 2004Jan 9, 2007Tesa AktiengesellschaftPolyurethane PSA
    US7188992 *Jul 30, 2003Mar 13, 2007Americhem, Inc.Kneading element and related articles
    US7196124 *Jan 8, 2004Mar 27, 2007Texas Tech UniversityElastomeric material compositions obtained from castor oil and epoxidized soybean oil
    US7316559 *Jun 23, 2005Jan 8, 2008Century-Board Usa, LlcContinuous forming apparatus for three-dimensional foam products
    US7491351 *May 4, 2006Feb 17, 2009Century-Board Usa LlcContinuous forming system utilizing up to six endless belts
    US20020034598 *Sep 27, 2001Mar 21, 2002Bonk Henry W.Membranes of polyurethane based materials including polyester polyols
    US20030004232 *Jun 28, 2001Jan 2, 2003Certainteed CorporationNon-staining polymer composite product
    US20030021915 *Jun 14, 2002Jan 30, 2003Vivek RohatgiCellulose - polymer composites and related manufacturing methods
    US20040048055 *Sep 11, 2002Mar 11, 2004Alfonso BrancaContinuous fiber composite reinforced synthetic wood elements
    US20040049002 *Jul 30, 2001Mar 11, 2004Geoffrey AndrewsPrecision polyurethane manufacture
    US20050031578 *Mar 24, 2004Feb 10, 2005Doctor's Research Group, Inc.Methods of performing medical procedures which promote bone growth, compositions which promote bone growth, and methods of making such compositions
    US20060014891 *May 10, 2005Jan 19, 2006Reichhold, Inc.Low volatile organic compound stable solvent-based polyurethane compositions for coatings
    US20060041155 *Aug 23, 2004Feb 23, 2006Biobased ChemicalMethod of preparing a hydroxy functional vegetable oil
    US20060041156 *Jul 28, 2005Feb 23, 2006Casper David MMethods of preparing hydroxy functional vegetable oils
    US20060045899 *Mar 1, 2005Mar 2, 2006Shantha SarangapaniAntimicrobial composition for medical articles
    US20070027227 *Jul 27, 2005Feb 1, 2007Shutov Fyodor AComposite material including rigid foam with inorganic fillers
    US20070037953 *Mar 3, 2006Feb 15, 2007Geiger Eric JNovel polyols derived from a vegetable oil using an oxidation process
    US20070052128 *Nov 6, 2006Mar 8, 2007Taylor Zachary RMethod for molding three-dimensional foam products using a continuous forming apparatus
    US20070066697 *Aug 31, 2006Mar 22, 2007Gilder Stephen DStrut-reinforced polyurethane foam
    US20080029925 *Aug 20, 2007Feb 7, 2008Wade BrownFilled polymer composite and synthetic building material compositions
    US20100025882 *Jan 28, 2009Feb 4, 2010Century-Board Usa, LlcContinuous forming system utilizing up to six endless belts
    USRE37095 *May 4, 1999Mar 13, 2001Apache Products CompanyExtruded polymer foam with filler particles and method
    Referenced by
    Citing PatentFiling datePublication dateApplicantTitle
    US8138234Mar 26, 2007Mar 20, 2012Century-Board Usa, LlcPolyurethane composite materials
    US8299136Mar 26, 2007Oct 30, 2012Century-Board Usa, LlcPolyurethane composite materials
    US8846776Aug 12, 2010Sep 30, 2014Boral Ip Holdings LlcFilled polyurethane composites and methods of making same
    US9139708Feb 14, 2014Sep 22, 2015Boral Ip Holdings LlcExtrusion of polyurethane composite materials
    US9481759Aug 12, 2010Nov 1, 2016Boral Ip Holdings LlcPolyurethanes derived from highly reactive reactants and coal ash
    US9512288Feb 14, 2014Dec 6, 2016Boral Ip Holdings LlcPolyurethane composite materials
    US20100201014 *Jan 22, 2010Aug 12, 2010Taylor Zachary RMethod for molding three-dimensional foam products using a continuous forming apparatus
    US20110002190 *Jul 6, 2010Jan 6, 2011Boral Material Technologies Inc.Fiber Feed System For Extruder For Use In Filled Polymeric Products
    Classifications
    U.S. Classification264/210.1, 524/590
    International ClassificationB29C47/00, B32B1/00, C08G18/48
    Cooperative ClassificationY02W30/92, C04B26/16, Y10T428/24479, Y10T428/24438, C08G18/0895, C08J5/04, C08K3/22, C08G2101/0066, C08J2375/08, C08L2203/14, B29C39/16, C08G18/4816, C08J5/043, C08G2101/0083
    European ClassificationC08J5/04G, C08J5/04, C08G18/48A6, C08G18/08R