Abstract:
A thermosetting foam, preferably polyisocyanurate or polyurethane foam, is prepared in an extruder which permits the incorporation of high levels of filler particles. The method includes introducing polyol, isocyanate and filler particles to an extruder screw for mixing. In conjunction with extruding, a catalyst is added. The catalyst may be added either in a last extruder barrel or with the extruder head. Foam with filler particle content in excess of 12% made be readily made. Filler particles, such as aluminum trihydrate, perlite, carbon black, diatomaceous earth, polyiso powders, ammonium phosphate, fly ash, barium sulfate, calcium silicate, and calcium carbonate, may be used. The process described is preferably used for making foam boards or bunstock.

Description:
This application is a continuation-in-part of application Ser. No. 08/369,400, filed on Jan. 6, 1995, which is a continuation-in-part of U.S. application Ser. No. 08/144,621, filed Nov. 1, 1993, which issued as U.S. Pat. No. 5,424,014 on Jun. 13, 1995, which is a file wrapper continuation of Ser. No. 07/946,738, filed Sep. 18, 1992, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention relates to foamed polymer material, methods for producing polymer foams, and, particularly, to a method for extruding polymer foam material, such as polyisocyanurate and polyurethane foams, using a screw-type extruder. The extruded polymer foams contain substantial amounts of filler particles. 
     2. Description of the Prior Art 
     Polymer foams, such as polyisocyanurate and polyurethane foams, have not previously been able to be produced using an extruder. The foaming material “firms” in the extruder and blocks the equipment. Additionally, use of filler materials has been limited using conventional methods to produce foam sheets. 
     U.S. Pat. No. 3,466,705, (Richie) describes an apparatus for extruding foamable thermoplastic material, such as polystyrene, preferably in tubular form. Richie discloses that the apparatus can be used for thermosetting materials, such as polyurethanes, but that steam or hot water would have a damaging effect and therefore are not used. A foam-augmenting gas such as Freon is used as the foaming agent. Richie uses an expansion space of transverse cross-sectional area which increases in size gradually in the direction of travel of the extruded product. 
     U.S. Pat. No. 5,149,722 (Soukup) and U.S. Pat. No. 4,795,763 (Gluck) describe the use of about 1-10% by weight of carbon black as a filler material. Gluck specifically recites the problem of cell rupture which can occur with the addition of too much filler materials. The Soukup and Gluck patents are incorporated herein by reference as if fully set forth. 
     SUMMARY OF THE INVENTION 
     Polymer foam board is disclosed which includes high levels of filler material, such as 15%-20% by weight filler particles, or higher. Polyisocyanurate or polyurethane foam is made using a screw-type extruder for mixing the components of the composition. Isocyanate and polyol are introduced into a screw of an extruder. Filler particles are also introduced in the extruder screw. The isocyanate, polyol, and filler particles are mixed together with a foaming agent and, optionally, a surfactant with the extruder to produce a high quality dispersion. The mixture is cooled via a cooling manifold of the screw extruder and the addition of the various components in the mixture. Cooling inhibits reaction of the mixed components within the screw. 
     Catalyst is added and mixed with the polyol/isocyanate/filler particle mixture in conjunction with extrusion proximate the extruder head, either in the last extruder barrel or the extruder head itself as a final mixing step. After the catalyst is introduced, the mixture immediately exits the extruder onto a conveyor so that the foaming and firming occurs outside of the extruder to avoid clogging. The mixture is foamed and firmed on the conveyor in a conventional manner and, preferably, formed into a continuous flat sheet which is thereafter cut to produce boards of standard sizes. Paper liners may be applied to both sides of the foam as it travels on the conveyor. 
     The filler particles included in the thermoset foams produced in accordance with the invention maintain the mechanical or insulative characteristics of the resultant extruded foam as compared to the properties of the extruded foam without filler particles. However, with some fillers improved characteristics result. For example, carbon black can improve the insulation properties of the foam as set forth in the Soukup and Gluck patents, supra. Ammonium phosphate can improve flame-retardant properties. Overall, the addition of filler particles makes the resultant foam more economical to produce and the process enables the use of more filler materials in the production of suitable foam board insulation. 
     Different filler particles can be used in the same foam. For example, carbon black and another type filler particle, which is less expensive, can be used to gain the insulative effect of the carbon black while increasing costs savings. Aluminum trihydrate, perlite, ammonium phosphate and calcium carbonate are preferred filler materials, used either as the sole filler material or with carbon black. Other filler materials include carbon black, fly ash, diatomaceous earth, polyiso powder, barium sulfate, melamine and calcium silicate. The filler particles added to the polyol/isocyanate mixture in the extruder reduce the cost of the resultant extruded thermoset foam, since the filler particles are lower in cost than polyol and/or polyisocyanate. 
     Ammonium phosphate is also useful as a filler particle. This includes ammonium phosphate and ammonium polyphosphate compounds, including ammonium phosphate, primary ammonium phosphate, secondary ammonium phosphate and other like phosphate compounds. Monobasic ammonium phosphate has been found especially useful as a filler particle. 
     The filler particles and/or dispersant and/or foaming agent and/or surfactant may be mixed with the isocyanate or with the polyol before introduction thereof to the extruder screw. If multiple fillers are used, they can be mixed prior to entering the extruder screw or can be introduced, simultaneously or separately, into the extruder screw and mixed therein. Entry of the filler particles, or a filler particle mixture can occur simultaneously or separately from entry of dispersing agent and/or surfactant and/or the polyol and/or the isocyanate. Preferably, the filler particles have a Tyler Mesh size of 20 or smaller where only about 4% of the filler is 20 mesh. More preferably, the size of the filler particles are between 50-300 mesh, and most preferably 80-300 mesh. 
     The foaming agent, which is preferably a hydrochlorofluorocarbon (HCFC) or water, is preferably introduced directly into the extruder or may be mixed with one of the components, preferably the polyol, before introduction thereof to the extruder screw. If water is the foaming agent, the water reacts with the isocyanate to form carbon dioxide, which further foams the mixture. Other foaming agents may alternatively be used. 
     Foam cell size is generally decreased when extruder speed is increased. 
     A filler particle dispersion may be made in the extruder using filler particles, dispersant, optional surfactant, and isocyanate or polyol. Preferably, a catalyst is added to this dispersion for immediate extrusion and foaming. Alternatively the dispersion can be stored for future use. An extruder provides better quality dispersion, measuring 7 or more on the Hegman scale, than a dispersion made in a Kady (kinetic dispersion) mill. 
     It is an object of the invention to provide an improved method for making polymer foams containing filler particles. 
     It is another object of the invention to provide a method for extruding filler particle-containing thermosetting foams, such as polyisocyanurate and polyurethane foams, using a screw-type extruder, such as a single-screw or twin-screw extruder. 
     It is yet another object of the invention to provide a method for making a filler particle dispersion in an extruder. 
     It is a further object of the invention to combine preparation of a filler particle dispersion and production of a foam using the filler particle dispersion, in a single operation. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a schematic illustration of an apparatus for extruding polymer foam onto a conveyor. 
     FIG. 2 is a schematic illustration of an extruder for an integrated process including preparation of a polymer premix before extruding the polymer mixture for foaming. 
     FIG. 3 is a cross-sectional view of a preferred extruder head. 
     FIG. 4 is a front elevational view of the extruder head shown in FIG.  3 . 
     FIG. 5 is a schematic illustration of an apparatus for polymer foam. 
     FIG. 6 is a cross-sectional side view of the extruder head for mixing catalyst with the extruding polymer foam. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Thermosetting foams, such as polyisocyanurate or polyurethane foams, are made using an extruder for mixing the foamable mixture before extruding onto a belt conveyor. Through such a continuous process, thermosetting foams are made much faster than previously possible without any decrease in quality. Additionally, the process enables the dispersion of filler particles with the polymer mixture to produce foams which include greater than 12% by weight of filler particles thereby reducing the production cost of the thermoset foams. Preferable range of filler particles is 12-50% by weight, more preferably 15-50% by weight. 
     The extruder enhances the dispersion of the polymer mixture. A twin-screw extruder is preferred. However, a single screw extruder with multiple mixing sections can also be used. The extruder can process materials for making a thermosetting polymer, such as an isocyanate polymer, in a controlled manner with independent catalyst addition and variable reactivity. High quality filler particle dispersions in isocyanate or polyol media are obtained. These dispersions exceed 7 on the Hegman scale. Moreover, higher levels of filler particles can be handled than on conventional foam mixing equipment. 
     The foams may be blown with blowing agents such as hydrochlorofluorocarbons (HCFC), CFC, HFC, HC, liquid CO 2  and/or water which produces CO 2 . Typical examples of hydrochlorofluorocarbon blowing agents are HCFC 141b and HCFC 22 which can be advantageously combined in preferred proportions. High viscosity isocyanates and polymer premix, which cannot be processed using a conventional Kady mill and conventional foam mixing equipment, may be used in the process described. 
     The extruder is cooled downstream of the dispersion section of the extruder to prevent premature reaction of the foam ingredient. The low torque requirements permits use of virtually any size extruder. Flocculation of filler particle/polyol dispersions can be avoided by maintaining a high shear rate on the dispersion, through the foaming section, producing a foam with excellent filler particle dispersion. 
     In general, the quality of the dispersion increases with a decrease in filler particle size and with increased viscosity of the starting medium. Decreasing the particle size enables the use of higher loading of filler material without detriment to dispersion quality. Addition of the polyol or isocyanate in the dispersion section may be accomplished in several staged injections. This is preferred for keeping the viscosity and shear high enough to ensure a high quality dispersion. 
     The preferred dispersions were obtained when the charge of filler particles was added with the first injection of the dispersion medium to form a mixture. The final preferred filler percentage of 12% to 20% was then obtained by subsequent liquid injections in the dispersion section of the extruder. Maximum temperatures of about 50° C. in the dispersion section do not present an operational problem. The dispersion is actively cooled by cold water circulating in the barrel jackets and screws and passively cooled by injection of the remaining foam ingredients into the dispersion. 
     A preferred extruder screw speed to provide a good foam mix is about 300-900 rpm. with 600-800 rpm typical. Speeds may range to 1000 rpm or higher. For extended use at high speed, a special hardening treatment is advantageously used on the screw element in the dispersion section due to the abrasiveness of the filler particles. Throughput is a function of both screw speed and extruder size. A desired throughput for a 30-40 mm extruder is about 450-600 lb./hr. 
     One method of extruding polyisocyanurate foam includes adding a blend of isocyanate, and filler particles at a first position of the extruder, adding polyol blend to mix with the isocyanate blend at a second position of the extruder closer to the extrusion position than the first position, adding catalyst blend to the mixed polyol and isocyanate blend at a third position of the extruder proximate the extrusion position, and extruding the catalyzed mixture onto a belt conveyor for foaming. 
     With reference to FIG. 1, an extruder apparatus  2  suitable for practicing the invention is illustrated. The apparatus  2  includes an extruder  4  which has barrels, B 1 -B 9 . A single or twin screw extruder may be used. A twin screw extruder provides better mixing and is preferred. The barrels of the extruder are preferably separated by sheets of Graphoil paper, which aids in taking down the apparatus. 
     Isocyanate solution is mixed and provided to reservoir  6  having a large capacity, preferably a 30 gallon capacity. A suspension of filler particles in the isocyanate may be fed to reservoir  6  or the filler particles can be fed into barrel B 1  via a hopper  8 . Solution from reservoir  6  is fed, in a non-limiting example, to barrel B 7  of extruder  4 . Polyol is mixed with water (foaming agent), for example in Lightening mixer  10 , and fed to extruder  4  at location  12 , between barrels B 7  and B 8 . Alternatively, the isocyanate and the filler particles may be fed, for example, to hopper  8  feeding into barrel B 1 , and the isocyanate and/or filler particles mixed together in the extruder before the polyol is added. 
     The polyol and isocyanate containing filler particles and/or carbon black are mixed in the extruder. Thereafter catalyst is fed from a reservoir  14  to barrel B 9  and mixed therewith. The catalyzed mixture is fed through the discharge end of the extruder onto a belt conveyor. The discharge end  16  of the extruder  4  suitably has an inclined discharge piece  18  or a flat discharge piece (FIG.  4 ), for directing the foam downward onto a conveying/forming apparatus  11 . 
     The temperature in the extruder is controlled by cooling the barrels and screws, as known in the art. Barrels B 7  through B 9  (at least) are cooled, generally by water cooling, to facilitate mixing the components of the reaction mixture without clogging the extruder. 
     The conveying/forming apparatus  11  includes a conveyor  20 , onto which the foam is discharged from end  16  of extruder  4 . The foam, passes between a pair of rolls  23  which rotate in opposite directions and then onto a slat conveyor  24 ,  26  through a heated area  28  in which the foam rises. 
     Optionally the foam is introduced between upper and lower paper liners. Appropriate location of the lining paper rolls (not shown) is apparent to one skilled in the art. The resultant product is a laminated insulation sheet. 
     Slat conveyors typically vary from 20-100 feet in length. The slat conveyor  24  is heated to about 150° F. This portion of the conveyor is substantially closed in by enclosure  28  to conserve heat. Doors (not shown) are placed about every 10 ft. along the enclosure to allow access to the equipment. The mixture foams and firms as it passes at about 30 to 250 ft./min. along the conveyor. The foam passes onto a roller conveyor  30  about 20 to 100 ft. in length, substantially at room temperature for curing before being cut into panels for use. A typical apparatus of this type is shown in Gluck, U.S. Pat. No. 4,795,763, discussed above. 
     In another example, shown in FIG. 2, an extruder  32  having 12 barrels A 1 -A 12  is used. Filler particles are fed to barrel A 1  from hopper  34 , a premix of polyol and surfactant is fed from mixer  36  between barrels A 1  and A 2  and mixed together with the filler particles in the extruder screw. The remainder of the polyol is added from a reservoir  38  to barrel A 6  and mixed with the filler particle and optional carbon black and polyol premix. Isocyanate is fed from a reservoir  40  to barrel A 9  and mixed with the ingredients already in the screw of the extruder. In this example, hydrochlorofluorocarbon blowing agent (HCFC-141b) is used, and is added from a reservoir  42  to barrel A 11 . Catalyst, such as potassium octoate, is added from a reservoir  44  to barrel A 12  of the extruder, and mixed into the reaction mix immediately before extrusion. The mixture is extruded from extruder head  46  onto a conveying/forming apparatus, such as illustrated in FIG.  1 . 
     Where more than one type of filler material is to be used, separate feed bins  48  for each type of material are provided. The amount of filler fed to the hopper  34  from each bin is controlled to provide a desired proportion. A preferred combination of filler materials is carbon black and aluminum trihydrate, relative proportions are dependent upon the R value and physical properties desired. For making dispersions without foaming, the fillers are added via hopper  34  and the isocyanate is added from mixer  36  and reservoir  38 . 
     It is well known in the art of thermosetting foams that, in the process of making polyisocyanurate or polyurethane foams, when the mixture is prepared, there is an exothermic foaming reaction. The speed of this reaction is controllable according to the temperature at which the reaction takes place. The foaming action is described as having a “cream time”, during which foaming is initiated and the material reaches a consistency of a soft creamy foam, and a “firm time” at which the foam sets up and hardens. In a typical non-limiting example, the cream time may be 7 to 12 seconds and the firm time may be 35 to 60 seconds. The properties of the product may be changed by adjusting the concentration of the materials, temperatures of the barrels, etc. 
     In prior attempts to extrude thermosetting resins of this type, extrusion has not been successful because the reaction mechanism has not been controlled within the extruder and the mixture has creamed and/or foamed within the extruder and blocked the extruder, preventing extrusion. 
     A typical extruder head which is useful in avoiding excessive build-up of foam on the head is shown in FIGS. 3 and 4. Discharge plate  50  of extruder  52  is attached to barrel  54 . Screw  56  has a flat tip  58  and discharged material  60  falls directly between rolls  62 ,  64  carrying lining paper  66 ,  68  for the conveyor (as shown in FIG. 1) on which the isocyanate polymer is foamed. 
     With reference to FIG. 5, a second embodiment of an extrusion system  102  which is also suitable for practicing the invention is illustrated. Extrusion system  102  includes a single or twin screw extruder  104  and an associated reservoir system  106 . The extruder  104  includes a series of barrels C 1 -C 12  and an extruder head  120 . The reservoir system  106  includes a plurality of reservoirs  150 - 156  from which the foam components are supplied. 
     The reservoirs  150 - 156  feed the foam component materials to the barrels C 1 -C 12  and head  120  of the extruder  104  via a network of feed lines and valves as illustrated. 
     In manufacturing foam using the extrusion system of FIG. 5, filler material is preferably provided to the extruder  104  at barrels C 1  and C 4  from reservoirs  150  and  152 . Isocyanate solution is mixed and fed to barrels C 2  and C 6  of the extruder  104  from reservoirs  151  and  153 . The isocyanate solution may be optionally mixed with a dispersing agent and/or surfactant. Surfactant may be mixed at reservoirs  151  and  153  with the isocyanate and dispersing agent and provided to the extruder  104  with the isocyanate and dispersing agent at barrels C 2  and C 6 . 
     Polyol is preferably provided from a reservoir  155  and fed to the extruder  104  at barrel C 9 . The surfactant, curing agent and foaming agent may be mixed with the polyol at reservoir  155  and fed to the extruder  104  at barrel C 9 . 
     Foaming agent is provided to the extruder  104  at barrel C 8  without previous mixing with other components. Additionally, foaming agent may be mixed with polyol at reservoir  155  prior to entry to the extruder  104  at barrel C 9 . For example, foaming agent is provided to extruder  104  at barrel C 9  after the foaming agent is first mixed with polyol/surfactant mixture. Catalyst is introduced into the extruder  104  via an extruder head  120  from reservoir  156 . 
     A cross-sectional side view of the extruder head  120  in the extrusion system is shown in FIG.  6 . The mixture of the component parts of the filler, isocyanate, polyol, and additional agents, without the catalyst, arrives via a hose  200  (shown in FIG. 5) to entry port  202  in a mixing block  204  of the extruder head  120 . At mixing block  204 , the component mixture travels via a worm gear  206  to agitator  208  located in a cavity area  210 . Concurrently, catalyst enters at a catalyst port  214  and travels along a duct  215  to arrive in the cavity area  210  via a catalyst entry port  216 . The mixture of the component parts of the filler isocyanate, polyol and additional agents and catalyst are mixed together by agitator  208  in the cavity area  210  and continues out of the cavity area  210 , preferably onto a conveyor system such as the conveyor forming system  11  illustrated in FIG.  1 . Preferably, the cavity  210  is 2 to 3 inches wide and the agitator is rotated at approximately 3500 to 5500 rpm. 
     A preferred method of manufacturing foam using the extruder of FIG. 5 includes feeding a first filler from source  150  to the extruder  104  at barrel C 1 . A mixture of isocyanate, dispersing agent and surfactant is fed to the extruder  104  at barrel C 2  from reservoir  151 . Additional filler is added from source  152  and fed to the extruder  104  at barrel C 4 . An additional mixture of isocyanate, dispersing agent and surfactant is then added to the extruder  104  at barrel C 6  from reservoir  153 . Foaming agent is provided to the extruder  104  at barrel C 8  from reservoir  154 . Polyol, foaming agent, surfactant and curing agent are fed to the extruder  104  at barrel C 9  from reservoir  155 . Finally, a catalyst or catalyst mixture is provided to the extruder head  120  from reservoir  156 . 
     In making insulation boards, the extrusion processes described herein allow fast, economical production. The use of filler particles additionally reduces the cost of the insulation boards. 
     The thermal conductivity of insulation board is reduced by adding carbon black. This advantageously reduces board thickness. The thermal conductivity of polyisocyanurate foams, based on different foaming agents, in BTU per cu. ft., per hr., per °F., are as follows: 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 isocyanurate/HCFC 
                 0.12 
               
               
                   
                 isocyanurate/carbon black/HCFC 
                 0.09-0.1 
               
               
                   
                 isocyanurate/water 
                  0.14-0.19 
               
               
                   
                 isocyanurate/carbon black/water 
                 0.135-0.17 
               
               
                   
                 isocyanurate/carbon black/HCFC/water 
                  0.09-0.135 
               
               
                   
                   
               
             
          
         
       
     
     Use of HCFC (hydrochlorofluorocarbon) foaming agent advantageously reduces the foam&#39;s thermal conductivity. Carbon black also reduces the thermal conductivity, compensating for increased thermal conductivity when water is the foaming agent. The formulation may also include inorganic flame retardants. Inorganic flame retardants increase the isocyanurate and polyol components&#39; viscosities. A screw extruder allows thorough mixing of higher viscosity components with better dispersion for use of higher percentage of filler materials. The mix is discharged from the extruder prior to the start of the firming reaction. 
     A filler particle dispersion may be made in the extruder using the filler particles, carbon black, optional surfactant and isocyanate or polyol. Dispersions may be used immediately or stored for future use. Isocyanate dispersions are preferred where storage is intended since polyol dispersions tend to become less disperse when stored. 
     EXAMPLES 
     The following Examples 1-48 were made in accordance with the process described in conjunction with FIGS. 1-4. Examples 49-60 were made using the alternate embodiment of the process as described in conjunction with FIGS. 5-6. 
     Examples 1 to 33 
     Carbon Black Dispersion Made in the Extruder Screw 
     Table 1 shows the composition used for each formulation and Table 2 shows the composition of each polyol premix, used as indicated in Table 1. Pelron P-344 dispersant and Cabot Black Pearls 280 carbon black were used in all the examples. The catalyst was a 3:1 blend, by weight, of potassium octoate and DMP-30. A catalyst blend of 3:1 to 6:1 may be used. The ratio of the catalyst blend is dependent upon how close the catalyst is added to the extruder outlet. The average equivalent weight of BASF 226 prepolymer (polymer/isocyanate mix) and ICI high viscosity isocyanate is about 152. 
     
       
         
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                 Parts by 
                   
                   
                 % 
               
               
                 Formulation 
                 Component 
                 Weight 
                 % 
                 Index 
                 Trimer 
               
               
                   
               
             
             
               
                 I 
                 Premix I 
                 40.6 
                 11.8 
                 2.74 
                 12.4 
               
               
                   
                 2852E Polyol 
                 59.4 
                 17.2 
               
               
                   
                 MR-200 Isocyanate 
                 192.0 
                 55.7 
               
               
                   
                 Catalyst 
                 7.5 
                 2.2 
               
               
                   
                 HCFC - 14 lb 
                 45.0 
                 13.1 
               
               
                 II 
                 Premix II 
                 40.6 
                 11.2 
                 2.93 
                 12.8 
               
               
                   
                 Carbon Black (C/B) 
                 17.4 
                 4.8 
               
               
                   
                 2852E Polyol 
                 59.4 
                 16.4 
               
               
                   
                 MR-200 Isocyanate 
                 192.0 
                 53.0 
               
               
                   
                 Catalyst 
                 7.5 
                 2.1 
               
               
                   
                 HCFC - 14 lb 
                 45.0 
                 12.4 
               
               
                 III 
                 Premix III 
                 63.5 
                 17.0 
                 3.00 
                 12.9 
               
               
                   
                 Carbon Black (C/B) 
                 27.2 
                 7.3 
               
               
                   
                 2852E Polyol 
                 36.5 
                 9.8 
               
               
                   
                 MR-200 Isocyanate 
                 192.0 
                 51.5 
               
               
                   
                 Catalyst 
                 7.5 
                 2.0 
               
               
                   
                 HCFC - 14 lb 
                 46.3 
                 12.4 
               
               
                 IV 
                 Premix IV 
                 40.6 
                 11.5 
                 2.97 
                 12.7 
               
               
                   
                 Carbon Black (C/B) 
                 17.4 
                 4.9 
               
               
                   
                 2852E Polyol 
                 50.0 
                 14.2 
               
               
                   
                 Isocyanate (ICI, 
                 192.0 
                 54.5 
               
               
                   
                 or BASF 226 
               
               
                   
                 Prepolymer) 
               
               
                   
                 Catalyst 
                 7.5 
                 2.1 
               
               
                   
                 HCFC - 14 lb 
                 45.0 
                 12.8 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                 I 
                 II 
                 III 
                 IV 
               
             
          
           
               
                 Polyol Premix 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 %  
               
               
                   
               
               
                 2852E Polyol 
                 37.1 
                 91.4 
                 33.9 
                 83.5 
                 55.0 
                 86.6 
                 33.9 
                 83.5 
               
               
                 Y10222 
                 3.5 
                 8.6 
                 3.5 
                 8.6 
                 3.5 
                 5.5 
                 3.5 
                 8.6 
               
               
                 Surfactant 
               
               
                 P-344 
                 — 
                 — 
                 3.2 
                 7.9 
                 5.0 
                 7.9 
                 3.2 
                 7.9 
               
               
                 Dispersant  
               
               
                   
               
             
          
         
       
     
     The operating run schedule is shown in Table 3 and operating parameters of the extruder are shown in Table 4. The torque developed was higher for the carbon black dispersions when compared with the white controls, but was still very low relative to the capabilities of the extruder, and is not a limiting factor. Exit temperatures of the foam mix are shown to be a function of the level of carbon black and the original viscosity of the dispersion medium. The preferred exit temperature is about 25° to 32° C. 
     Table 5 shows properties of selected test foams. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 RUN SCHEDULE 
               
             
          
           
               
                 Run No. 
                 Formation 
                 Foam Type 
                 Key Variable 
               
               
                   
               
               
                  1 
                 I 
                 White Control 
                 Density Check 1.65 
               
               
                  2 
                 I 
                 White Control 
                 Lower 14 lb 1.67 
               
               
                  3 
                 I 
                 White Control 
                 Higher 14 lb 1.51 
               
               
                  4 
                 II 
                 Black Control 
                 Hegman 7 
               
               
                  5 
                 II 
                 Black Control 
                 Lower 14 lb 
               
               
                  6 
                 II 
                 Black Control 
                 ISO Adjustment 
               
               
                  7 
                 II 
                 Black Control 
                 Mix/Rate Study @ 600 RPM 
               
               
                  8 
                 II 
                 Black Control 
                 Mix/Rate Study @ 500 RPM 
               
               
                  9 
                 II 
                 Black Control 
                 Mix/Rate Study @ 600 RPM 
               
               
                 10 
                 III 
                 Black Control 
                 Mix/Rate Study @ 600 RPM 
               
               
                 11 
                 III 
                 Black Control 
                 Mix/Rate Study @ 500 RPM 
               
               
                 12 
                 III 
                 Black Control 
                 Mix/Rate Study @ 500 RPM 
               
               
                 13, 13A 
                 IV 
                 Black, Prepol. 
                 Mix @ 500 RPM, 13A Higher 
               
               
                   
                   
                   
                 ISO 
               
               
                 14 
                 IV 
                 Black, Prepol. 
                 Mix @ 600 RPM 
               
               
                 15 
                 IV 
                 Black, Prepol. 
                 Mix/Rate Study @ 600 RPM 
               
               
                 16 
                 IV 
                 Black, Prepol. 
                 Mix/Rate Study @ 500 RPM 
               
               
                 17 
                 IV 
                 Black, Prepol. 
                 Mix/Rate Study @ 500 RPM 
               
               
                 18 
                 IV 
                 Black, ICI 
                 Mix @ 500 RPM 
               
               
                 19 
                 IV 
                 Black, ICI 
                 Mix @ 600 RPM 
               
               
                 20 
                 IV 
                 Black, ICI 
                 Catalyst Adjustment 
               
               
                 21 
                 IV 
                 Black, ICI 
                 14 lb Adjustment 
               
               
                 22 
                 IV 
                 Black, ICI 
                 14 lb Adjustment 
               
               
                 23 
                 IV 
                 White, Prepol. 
                 Control 
               
               
                 24 
                 IV 
                 Black, Prepol. 
                 Prepol + C/B 
               
               
                 25 
                 IV 
                 Black, Prepol. 
                 Higher C/B @ 500 RPM 
               
               
                 26 
                 IV 
                 Black, Prepol. 
                 Higher C/B @ 600 RPM 
               
               
                 27 
                 IV 
                 Black, Prepol. 
                 Low Rate, Low on Matl. 
               
               
                 28 
                 IV 
                 White Control 
                 ICI High Visc. ISO 
               
               
                 29 
                 IV 
                 Black Control 
                 Std. % C/B 
               
               
                 30 
                 IV 
                 Black Control 
                 Higher C/B 
               
               
                 31 
                 IV 
                 Black Control 
                 Higher C/B 
               
               
                 32 
                 IV 
                 Black Control 
                 Higher C/B 
               
               
                 33 
                 IV 
                 White Control 
                 R-22 Froth 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 OPERATING PARAMETERS 
               
             
          
           
               
                 Run 
                   
                   
                   
                 Exit 
                   
                 Foam 
               
               
                 No. 
                 RPM 
                 % Torque 
                 lbs/hr 
                 Temp. ° C. 
                 % C/B 
                 Quality  
               
               
                   
               
               
                 1 
                 500 
                 5.1 
                 300 
                 28 
                 0 
                 Good 
               
               
                 2 
                 500 
                 5 
                 300 
                 27 
                 0 
                 Good 
               
               
                 3 
                 500 
                 4.9 
                 300 
                 28 
                 0 
                 Good 
               
               
                 4 
                 500 
                 16 
                 300 
                 27 
                 4.8 
                 Good 
               
               
                 5 
                 500 
                 15.9 
                 300 
                 28 
                 4.8 
                 Good 
               
               
                 6 
                 500 
                 15.8 
                 300 
                 28 
                 4.8 
                 Good 
               
               
                 7 
                 600 
                 15.2 
                 300 
                 29 
                 4.8 
                 Good 
               
               
                 8 
                 500 
                 17.7 
                 400 
                 29 
                 4.8 
                 Good 
               
               
                 9 
                 600 
                 16.4 
                 400 
                 29 
                 4.8 
                 Good 
               
               
                 10 
                 600 
                 16.7 
                 450 
                 29 
                 7.3 
                 Good 
               
               
                 11 
                 500 
                 22 
                 450 
                 29 
                 7.3 
                 Good 
               
               
                 12 
                 500 
                 24 
                 400 
                 29 
                 7.3 
                 Good 
               
               
                 13 
                 500 
                 14.3 
                 300 
                 30, 31 
                 4.8 
                 Good, Sl. Soft 
               
               
                 14 
                 600 
                 13.7 
                 300 
                 33 
                 4.8 
                 Fair 
               
               
                 15 
                 600 
                 16.1 
                 450 
                 35 
                 4.8 
                 Fair 
               
               
                 16 
                 500 
                 16.8 
                 450 
                 34 
                 4.8 
                 Fair 
               
               
                 17 
                 500 
                 21.0 
                 600 
                 32 
                 4.8 
                 Fair 
               
               
                 18 
                 500 
                 20.6 
                 300 
                 31 
                 4.8 
                 V. Good 
               
               
                 19 
                 600 
                 19.8 
                 300 
                 32 
                 4.8 
                 V. Good 
               
               
                 20 
                 600 
                 18.0 
                 300 
                 32 
                 4.8 
                 V. Good 
               
               
                 21 
                 600 
                 17.6 
                 300 
                 33 
                 4.8 
                 V. Good 
               
               
                 22 
                 600 
                 17.4 
                 300 
                 32 
                 4.8 
                 V. Good 
               
               
                 23 
                 500 
                 7.0 
                 300 
                  7 
                 4.8 
                 V. Good 
               
               
                 24 
                 500 
                 14.0 
                 300 
                 14 
                 4.7 
                 V. Good 
               
               
                 25 
                 500 
                 27.0 
                 300 
                 27 
                 7 
                 V. Good 
               
               
                 26 
                 600 
                 24.8 
                 300 
                 25 
                 7 
                 V. Good 
               
               
                 27 
                 600 
                 24.0 
                 190 
                 24 
                 7 
                 V. Good 
               
               
                 28 
                 500 
                 6.4 
                 300 
                 34 
                 0 
                 V. Good 
               
               
                 29 
                 600 
                 13.5 
                 300 
                 37 
                 4.7 
                 V. Good 
               
               
                 30 
                 600 
                 14.7 
                 450 
                 34 
                 7 
                 V. Good 
               
               
                 31 
                 600 
                 29.0 
                 300 
                 39 
                 7 
                 V. Good 
               
               
                 32 
                 600 
                 27.6 
                 300 
                 40 
                 7 
                 V. Good 
               
               
                 33 
                 600 
                 26 
                 300 
                 33 
                 0 
                 V. Good  
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                   
                   
                   
                 % Closed 
                 % 
                   
               
               
                 Run No. 
                 k-Init. 
                 k-Aged 
                 Cell 
                 Friability 
                 Density  
               
               
                   
               
             
             
               
                  1 
                 .136 
                 — 
                 — 
                 — 
                 1.62 
               
               
                  2 
                 .140 
                 — 
                 — 
                 — 
                 1.69 
               
               
                  4 
                 — 
                 .167 
                 79 
                 29 
               
               
                  7 
                 .128 
                 — 
                 — 
                 — 
               
               
                  9 
                 .124 
                 — 
                 — 
                 — 
               
               
                 10 
                 .131 
                 — 
                 — 
                 — 
               
               
                 12 
                 .134 
                 — 
                 — 
                 — 
               
               
                 13 
                 — 
                 .141 
                 81 
                  8 
               
               
                 13A 
                 — 
                 .136 
                 81 
                 13 
               
               
                 14 
                 .123 
                 — 
                 — 
                 — 
               
               
                 15 
                 .121 
                 .145 
                 86 
                 12 
               
               
                 16 
                 — 
                 .138 
                 85 
                 13 
               
               
                 17 
                 — 
                 .148 
                 87 
                 35 
               
               
                 18 
                 — 
                 .155 
                 85 
                 18 
               
               
                 19 
                 .123 
                 .146 
                 — 
                 — 
               
               
                 20 
                 — 
                 .146 
                 86 
                 20 
               
               
                 21 
                 .128 
                 — 
                 — 
                 — 
               
               
                 22 
                 .139 
                 — 
                 — 
                 — 
               
               
                 23 
                 .132 
                 .139 
                 84 
                  8 
               
               
                 28 
                 — 
                 .149 
                 90 
                 20 
               
               
                 29 
                 — 
                 .132 
                 — 
                 — 
               
               
                 33 
                 — 
                 .177 
                 81 
                 12  
               
               
                   
               
             
          
         
       
     
     Example 34 
     Foam with Pre-Mixed Carbon Black Dispersion 
     Component A: 
     Polymeric methyldiisocyanate (MDI) 91% 
     carbon black 9% 
     (viscosity: 20,000 cps) 
     (dispersion quality: Hegman bar—50 microns) 
     Component B: 
     polyol 91% 
     silicone surfactant 5% 
     water 4% 
     Component C: 
     preblended catalyst (potassium octoate) 2% 
     Components A, B and C were mixed in the percentage ratio A:B:C of 74:24:2, by weight. 
     Using the apparatus of FIG. 1, the process was started by injecting component A into barrel B 7  until it was observed exiting the extruder. Component B was then injected to the spacer between barrels B 7  and B 8 , followed by injection of catalyst to barrel B 9 . Shutdown was performed in reverse order. The machine was purged with methylene chloride. 
     The product had a compression strength of 26 psi, a density of 2.3 lb./cu. ft. and a K factor (thermal conductivity) of 0.168 BTU/sq. ft./°F. 
     When the machine was taken apart, it was easy to remove the barrels separated by Graphoil paper. The internal surfaces of the barrel in the process section were coated with a thin hard layer of cured material but this was readily removable. 
     Substantially higher concentration of isocyanate (component A) leads to hard and brittle foam. Substantially higher concentration of polyol (component B) leads to rubbery, soft foam and increased exotherm of reaction. 
     As the speed of the machine is increased, the cell size of the foam is decreased. Variation of these parameters to provide foam having certain characteristics will be apparent to one skilled in the art. 
     Example 35 
     Carbon Black Dispersion Made in the Extruder Screw 
     
       
         
               
               
               
             
           
               
                   
               
             
             
               
                 Component A: 
                 polymeric methyldiisocyanate (MDI) 
                 100.00 parts 
               
               
                   
                 carbon black 
                  9.29 parts 
               
               
                   
                 dispersant 
                  1.93 parts 
               
               
                   
                 surfactant 
                   1.7 parts 
               
               
                   
               
             
          
         
       
     
     Using apparatus of FIG. 1, the process was started by injecting the ingredients for component A into barrel B 7  until it was observed exiting the extruder. The dispersion produced was of better quality than that produced in a Kady mill and registered more than 8 on the Hegman scale. 
     In a further embodiment of the invention, polyisocyanurate bunstock may be made using an extruder. The bun is cut from an extrudate which is passed from the die of the extruder to a conveyor belt having release-coated paper liners on the top, bottom and sides. A kraft paper liner having a polymer coating is suitable for use as a release paper. A 20 ft. conveyor may be used, moving at about 9 to 10 ft/min. The bunstock may be from 4 in. to 2 ft. or more in thickness. The foam is warm as it exits the extruder and is allowed to cure for 4 to 6 days. In a typical example of making bunstock on an extruder, the following formulation was used: 
     Example 36 
     Bunstock Made in the Extruder 
     
       
         
               
               
               
             
           
               
                   
                   
               
               
                   
                 Material 
                 ppm 
               
               
                   
                   
               
             
             
               
                   
                 Isocyanate (Miles - Mondur MR) 
                 101 
               
               
                   
                 Polymer resin (Iso-Shield - P101) 
                 78 
               
               
                   
                 R-11 (Atochem - Isotron 11 or 141B) 
                 13.81 
               
               
                   
                 Catalyst #1 (Air Products - TMR-3) 
                 1.17 
               
               
                   
                 Catalyst #2a (Air Products - DMEA) 
                 .312 
               
               
                   
                 Catalyst #2b (Ashland - DEG) 
                 .312 
               
               
                   
                   
               
             
          
         
       
     
     The foam was extruded from a die of an extruder, having a large cross-section, as shown in FIGS. 3 and 4, onto a conveyor lined with paper on the top, bottom and sides, to form bunstock having dimensions of about 27″ high×51½″ wide. The cream time was 28 sec., the gel time was 2 min. 34 sec., the rise time was 3 min. 55 sec. and the tack free time was 4 min. 31 sec. The conveyor speed was about 9 to 10 ft./min. Bunstock may be extruded at a speed of about 200 lb./min. A typical bun may be about 27″×51½″×10 ft. in size and may be cut to smaller blocks, as required. Different levels of carbon black may be used, providing different K-values. 
     The extruder may alternatively be used to make the filler particle dispersion only, which is then fed to a tank for storage and later use. 
     When the extruder is used for making both the dispersion and the foam, the cream time and gel time are relatively slow due to the size of the bunstock. The bunstock which is liquid at extrusion onto the conveyor, is firm after reaching the end of the conveyor and being released from the paper liners. The process described allows for large volume bunstock to be made, of very high quality. 
     Examples 37-48 
     High Filler Particle Content Foam 
     A number of examples of foams having a high filler particle content were produced using the process explained in conjunction with FIG. 2 above. 
     Table 6 presents the various formulations of materials which were used in the examples and Tables 7a and 7b provide a tabulation of the characteristics of the resultant thermoset foam. The examples illustrate how polymer foams can be made using the extrusion process which can contain in excess of 15% filler material. 
     Test runs were conducted using a ZSK-40 extruder having a 40 mm wide extruder. Depending upon the type and size of the sheet to be produced, larger capacity extruders are used for commercial production such as extruders having diameters 50 mm, 70 mm, 92 mm, or 120 mm. Table 8 provides ranges of preferred ranges of preferred processing rates for the various size extruders. 
     
       
         
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
             
             
               
                   
                   
               
               
                   
                 FORMULATION 
               
             
          
           
               
                   
                 A 
                 B 
                 C 
                 D 
                 E 
               
             
          
           
               
                   
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 %  
               
               
                   
                   
               
             
          
           
               
                 Polyol 
                 Cape 254C 
                 100 
                 24.8 
                 100 
                 26 
                 100 
                 22.8 
                 100 
                 22.6 
                 100 
                 22.7 
               
               
                 Surfactant 
                 D.C. 9342 
                 3 
                 0.8 
                 3 
                 .78 
                 2 
                 .5 
                 2 
                 .5 
                 2 
                 .5 
               
               
                 Blowing 
                 Water 
                 0.5 
                 0.1 
                 0.5 
                 .13 
                 1.40 
                 .3 
                 1.40 
                 .3 
                 1.40 
                 .3 
               
               
                 Agent 
                 Forane 
                 47.5 
                 11.8 
                 38 
                 9.9 
                 43 
                 9.8 
                 47 
                 10.6 
                 40 
                 9.1 
               
               
                   
                 141b 
               
               
                   
                 HCFC 22 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 6 
                 1.4 
               
               
                 Catalyst 
                 TMR-30 
                 0.84 
                 .2 
                 0.45 
                 .12 
                 0.96 
                 .2 
                 1.25 
                 .3 
                 1.25 
                 .3 
               
               
                   
                 OMG 977 
                 2.51 
                 0.6 
                 2.2 
                 .58 
                 2.65 
                 .6 
                 3.40 
                 .8 
                 3.40 
                 .8 
               
               
                   
                 Polycat 46 
                 0.54 
                 0.1 
                 0.39 
                 .11 
                 0.57 
                 .1 
                 0.65 
                 .2 
                 0.65 
                 .2 
               
               
                 Filler 
                 Alumina 
                 76 
                 19 
                 72.27 
                 18.7 
                 0 
                 0 
                 0 
                 0 
                 77.40 
                 17.6 
               
               
                   
                 Trihydrate 
               
               
                   
                 Calcium 
                 0 
                 0 
                 0 
                 0 
                 73.80 
                 16.8 
                 0 
                 0 
                 0 
                 0 
               
               
                   
                 Carbonate 
               
               
                   
                 Non-expanded 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 77.80 
                 17.6 
                 0 
                 0 
               
               
                   
                 Perlite 
               
               
                 ISOCYANATE 
                   
                 171.84 
                 42.7 
                 168.4 
                 44 
                 214.19 
                 48.8 
                 208.45 
                 47.2 
                 208.45 
                 47.3  
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
               
             
           
               
                 TABLE 7a 
               
               
                   
               
               
                 EXAMPLE 
                 37 
                 38 
                 39 
                 40 
                 41 
                 42 
               
               
                   
               
             
             
               
                 Formulation 
                 A 
                 A 
                 A 
                 A 
                 B 
                 B 
               
               
                 Type 
               
               
                 Iso. Index 
                 2.30 
                 2.50 
                 2.50 
                 2.50 
                 2.50 
                 2.20 
               
               
                 Avg. Thickness 
                 1.53″ 
                 1.56″ 
                 1.56″ 
                 2.12″ 
                 1.28″ 
                 1.44″ 
               
               
                 Board Density 
                 2.29 
                 2.45 
                 2.54 
                 2.09 
                 2.83 
                 2.48 
               
               
                 Core Density 
                 2.10 
                 2.39 
                 2.39 
                 1.86 
                 2.61 
                 2.17 
               
               
                 K-Value 
                 0.138 
                 0.136 
                 0.138 
                 0.135 
                 0.133 
                 0.13 
               
               
                 Compressive 
                 22.41 
                 19.6 
                 26.44 
                 19.34 
                 32.62 
                 30.4 
               
               
                 (psi) 
               
               
                 % Closed Cell 
                 82.00% 
                 84.20% 
                 83.30% 
                 83.30% 
                 81.00% 
                 77.30% 
               
               
                 Hot Dip 
                 good 
                 good 
                 good 
                 good 
                 good 
                 good 
               
               
                 Cold Aging 
                 0.00%/ 
                 0.58%/ 
                 0.42%/ 
                 0.00%/ 
                 0.00%/ 
                 0.00%/ 
               
               
                 (% shrink) 
                 0.42% 
                 0.00% 
                 0.00% 
                 0.00% 
                 0.00% 
                 0.00% 
               
               
                 machine/ 
               
               
                 crosscut 
               
               
                 Humid Aging 
                 0.93%/ 
                 0.37%/ 
                 0.37%/ 
                 0.56%/ 
                 0.37%/ 
                 0.37%/ 
               
               
                 (% growth) 
                 0.45% 
                 0.69% 
                 0.45% 
                 0.00% 
                 0.34% 
                 0.34% 
               
               
                 machine/ 
               
               
                 crosscut 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
               
             
           
               
                 TABLE 7b 
               
               
                   
               
               
                 EXAMPLE 
                 43 
                 44 
                 45 
                 46 
                 47 
                 48 
               
               
                   
               
             
             
               
                 Formulation 
                 C 
                 C 
                 D 
                 D 
                 E 
                 E 
               
               
                 Type 
               
               
                 Iso. Index 
                 2.60 
                 2.60 
                 2.50 
                 2.50 
                 2.50 
                 2.50 
               
               
                 Avg. Thickness 
                 1.33 
                 2.50 
                 1.44 
                 2.43 
                 1.44 
                 2.44 
               
               
                 Board Density 
                 2.42 
                 2.33 
                 2.38 
                 2.33 
                 2.89 
                 1.99 
               
               
                 Core Density 
                 2.28 
                 2.28 
                 2.14 
                 2.14 
                 2.59 
                 1.86 
               
               
                 K-Value 
                 0.141 
                 0.141 
                 0.138 
                 0.135 
                 0.138 
                 0.134 
               
               
                 Compressive 
                 14.6 
                 18.0 
                 22.04 
                 21.82 
                 22.50 
                 20.66 
               
               
                 (psi) 
               
               
                 % Closed Cell 
                 81.13% 
                 82.17% 
                 83.37% 
                 82.00% 
                 84.19% 
                 82.63% 
               
               
                 Hot Dip 
                 good 
                 good 
                 good 
                 good 
                 good 
                 good 
               
               
                 Cold Aging 
                 0.00%/ 
                 0.09%/ 
                 0.17%/ 
                 0.11%/ 
                 0.00%/ 
                 0.08%/ 
               
               
                 (% shrink) 
                 0.00% 
                 0.12% 
                 0.00% 
                 0.08% 
                 0.00% 
                 0.00% 
               
               
                 machine/ 
               
               
                 cross cut 
               
               
                 Humid Aging 
                 0.06%/ 
                 0.12%/ 
                 0.06%/ 
                 0.13%/ 
                 0.00%/ 
                 0.06%/ 
               
               
                 (% growth) 
                 0.17% 
                 0.11% 
                 0.12% 
                 0.17% 
                 0.00% 
                 0.17% 
               
               
                 machine/ 
               
               
                 cross cut 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Extruder Output Ranges 1   
               
             
          
           
               
                 Extruder 
                 ZSK-40 
                 ZSK-58 
                 ZSK-70 
                 ZSK-92 
                 C-120  
               
               
                   
               
             
          
           
               
                 High Range 
               
             
          
           
               
                 lbs/hr 
                 450 
                 1350 
                 2411 
                 5500 
                 12150 
               
               
                 lbs/min 
                 7.5 
                 22.5 
                 40 
                 92 
                 202.5 
               
             
          
           
               
                 Low Range 
               
             
          
           
               
                 lbs/hr 
                 600 
                 1800 
                 3215 
                 7300 
                 16200 
               
               
                 lbs/min 
                  10 
                  30 
                  54 
                  122 
                  270 
               
               
                 ft/min 
                 — 
                 33-44 
                 58-78 
                 134-177 
                 276-391  
               
               
                   
               
               
                   1 Calculated for 1″ thick foam product 49″ wide and 2.0 lbs/cu. ft. in-place density.  
               
             
          
         
       
     
     Examples 49-60 
     Tables 9a, 9b and 9c present the various relations of materials used in Examples 49-60. Tables 10a and 10b provide a tabulation of characteristics of the resultant thermoset foam examples. The examples illustrate how polymer foams can be made using the extrusion process while using ammonium phosphate and/or fly ash, with and without carbon black or alumina as fillers. 
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 9a 
               
             
             
               
                   
                   
               
               
                   
                 FORMULATION 
               
             
          
           
               
                   
                 49 
                 50 
                 51 
                 52 
               
             
          
           
               
                   
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
               
               
                   
                   
               
             
          
           
               
                 Polyol 
                 Cape 254C 
                 100 
                 26.6 
                 100 
                 25.2 
                 100 
                 23.7 
                 100 
                 26.6 
               
               
                 Surfactant 
                 D.C. 9342 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
               
               
                 Blowing 
                 Water 
                 0.6 
                 0.2 
                 0.6 
                 0.2 
                 0.6 
                 0.1 
                 0.6 
                 0.2 
               
               
                 Agent 
                 Forane 
                 41.5 
                 11.0 
                 41.5 
                 10.4 
                 41.5 
                 9.9 
                 41.5 
                 11.0 
               
               
                   
                 141b 
               
               
                   
                 HCFC 22 
                 5 
                 1.5 
                 5 
                 1.3 
                 5 
                 1.2 
                 5 
                 1.5 
               
               
                 Catalyst 
                 Octoate 
                 8 
                 2.0 
                 8 
                 2.0 
                 8 
                 1.9 
                 8 
                 2.0 
               
               
                   
                 P-5 
               
               
                   
                 Polycat 46 
               
               
                 Filler 
                 Ammonium 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 19 
                 5 
               
               
                   
                 Phosphate 
               
               
                   
                 Alumina 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Flyash 
                 19 
                 5 
                 29.8 
                 7.5 
                 42.2 
                 10 
                 19 
                 5 
               
               
                   
                 Carbon 
                 19 
                 5 
                 29.8 
                 7.5 
                 42.2 
                 10 
                 — 
                 — 
               
               
                   
                 Black 
               
               
                 Isocyanate 
                   
                 175 
                 46.6 
                 175 
                 44.0 
                 175 
                 41.4 
                 175 
                 46.6 
               
               
                 Dispensing Agent 
                   
                 1.75 
                 0.5 
                 1.75 
                 0.4 
                 1.75 
                 0.4 
                 1.75 
                 0.5 
               
               
                 Curing Agent 828 
                   
                 4.0 
                 1.1 
                 4.0 
                 1.0 
                 4.0 
                 0.9 
                 4.0 
                 1.1 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 9b 
               
             
             
               
                   
                   
               
               
                   
                 FORMULATION 
               
             
          
           
               
                   
                 53 
                 54 
                 55 
                 56 
               
             
          
           
               
                   
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
               
               
                   
                   
               
             
          
           
               
                 Polyol 
                 Cape 254C 
                 100 
                 25.2 
                 100 
                 23.7 
                 100 
                 26.6 
                 100 
                 25.2 
               
               
                 Surfactant 
                 D.C. 9342 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
               
               
                 Blowing 
                 Water 
                 0.6 
                 0.2 
                 0.6 
                 0.1 
                 0.6 
                 0.2 
                 0.6 
                 0.2 
               
               
                 Agent 
                 Forane 
                 41.5 
                 10.4 
                 41.5 
                 9.9 
                 41.5 
                 11.0 
                 41.5 
                 10.4 
               
               
                   
                 141b 
               
               
                   
                 HCFC 22 
                 5 
                 1.3 
                 5 
                 1.2 
                 5 
                 1.5 
                 5 
                 1.3 
               
               
                 Catalyst 
                 Octoate 
                 8 
                 2.0 
                 8 
                 1.9 
                 8 
                 2.0 
                 8 
                 2.0 
               
               
                   
                 P-5 
               
               
                   
                 Polycat 46 
               
               
                 Filler 
                 Ammonium 
                 29.8 
                 7.5 
                 42.2 
                 10 
                 19 
                 5 
                 29.8 
                 7.5 
               
               
                   
                 Phosphate 
               
               
                   
                 Alumina 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Flyash 
                 29.8 
                 7.5 
                 42.2 
                 10 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Carbon 
                 — 
                 — 
                 — 
                 — 
                 19 
                 5 
                 29.8 
                 7.5 
               
               
                   
                 Black 
               
               
                 Isocyanate 
                   
                 175 
                 44.0 
                 175 
                 41.4 
                 175 
                 46.6 
                 175 
                 44.0 
               
               
                 Dispersing Agent 
                   
                 1.75 
                 0.4 
                 1.75 
                 0.4 
                 1.75 
                 0.5 
                 1.75 
                 0.4 
               
               
                 Curing Agent 828 
                   
                 4.0 
                 1.1 
                 4.0 
                 0.9 
                 4.0 
                 1.1 
                 4.0 
                 1.1 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 9c 
               
             
             
               
                   
                   
               
               
                   
                 FORMULATION 
               
             
          
           
               
                   
                 57 
                 58 
                 59 
                 60 
               
             
          
           
               
                   
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
                 pbw 
                 % 
               
               
                   
                   
               
             
          
           
               
                 Polyol 
                 Cape 254C 
                 100 
                 23.7 
                 100 
                 26.6 
                 100 
                 26.6 
                 100 
                 29.6 
               
               
                 Surfactant 
                 D.C. 9342 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.5 
                 2.0 
                 0.6 
               
               
                 Blowing 
                 Water 
                 0.6 
                 0.1 
                 0.6 
                 0.2 
                 0.6 
                 0.2 
                 0.6 
                 0.2 
               
               
                 Agent 
                 Forane 
                 41.5 
                 9.9 
                 41.5 
                 11.0 
                 41.5 
                 11.0 
                 41.5 
                 12.2 
               
               
                   
                 141b 
               
               
                   
                 HCFC 22 
                 5 
                 1.2 
                 5 
                 1.5 
                 5 
                 1.5 
                 5 
                 1.5 
               
               
                 Catalyst 
                 Octoate 
                 100 
                 1.9 
                 8 
                 2.0 
                 8 
                 2.0 
                 8 
                 2.4 
               
               
                   
                 P-5 
               
               
                   
                 Polycat 46 
               
               
                 Filler 
                 Ammonium 
                 42.2 
                 10 
                 38 
                 10 
                 19 
                 5 
                 — 
                 — 
               
               
                   
                 Phosphate 
               
               
                   
                 Alumina 
                 — 
                 — 
                 — 
                 — 
                 19 
                 5 
                 — 
                 — 
               
               
                   
                 Flyash 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Carbon 
                 42.2 
                 10 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Black 
               
               
                 Isocyanate 
                   
                 175 
                 41.4 
                 175 
                 46.6 
                 175 
                 46.6 
                 175 
                 51.8 
               
               
                 Dispersing Agent 
                   
                 1.75 
                 0.4 
                 1.75 
                 0.5 
                 1.75 
                 0.5 
                 1.75 
                 0.5 
               
               
                 Curing Agent 828 
                   
                 4.0 
                 0.9 
                 4.0 
                 1.1 
                 4.0 
                 1.1 
                 4.0 
                 1.2 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
               
             
           
               
                 TABLE 10a 
               
               
                   
               
               
                 EXAMPLE 
                 49 
                 50 
                 51 
                 52 
                 53 
                 54 
               
               
                   
               
             
             
               
                 Avg. Thickness 
                 1.49″ 
                 1.48″ 
                 1.56″ 
                 1.48″ 
                 1.51″ 
                 1.51″ 
               
               
                 Board Density 
                 1.98 
                 2.06 
                 2.27 
                 1.96 
                 2.14 
                 2.14 
               
               
                 Core Density 
                 1.82 
                 1.91 
                 2.04 
                 1.83 
                 1.98 
                 1.87 
               
               
                 K-Value 
                 0.134 
                 0.133 
                 0.141 
                 0.136 
                 0.138 
                 0.137 
               
               
                 Comprehensive 
                 26.18 
                 28.02 
                 26.19 
                 27.99 
                 29.88 
                 26.68 
               
               
                 Hot Dip 
                 good 
                 good 
                 good 
                 good 
                 good 
                 good 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
               
             
           
               
                 TABLE 10b 
               
               
                   
               
               
                 EXAMPLE 
                 55 
                 56 
                 57 
                 58 
                 59 
                 60 
               
               
                   
               
             
             
               
                 Avg. Thickness 
                 1.49″ 
                 1.51″ 
                 1.54″ 
                 — 
                 — 
                 — 
               
               
                 Board Density 
                 1.83 
                 1.91 
                 2.06 
                 1.88 
                 1.91 
                 1.96 
               
               
                 Core Density 
                 1.69 
                 1.80 
                 1.84 
                 1.77 
                 1.74 
                 1.81 
               
               
                 K-Value 
                 0.130 
                 0.137 
                 0.133 
                 0.127 
                 — 
                 0.135 
               
               
                 Comprehensive 
                 27.51 
                 28.01 
                 26.46 
                 32.61 
                 29.79 
                 — 
               
               
                 Hot Dip 
                 good 
                 good 
                 good 
                 good 
                 good 
                 — 
               
               
                   
               
             
          
         
       
     
     The extruded examples contain various amounts of filler, which include examples at greater than 12% filler material. Polyol was premixed with foaming agent and curing agent prior to introduction into the extruder. Isocyanate was premixed with surfactant prior to introduction into the extruder. Catalyst was fed at the extruder head as previously described with reference to FIG.  6 . 
     Various properties were maintained within set parameters for Examples 49-60. Cold aging, the percentage of shrinkage, remained less than 2%. Humid aging, the percentage of growth, also remained less than 2%. Percent (%) closed cell was in the range of 89-93% and Hegman Scale readings greater than 7.5 for the dispersions were present for all the examples. 
     While the invention has been described with reference to certain embodiments thereof, it will be appreciated that variations and modifications may be made without departing from the spirit and scope of the invention.