Improved batting thermal insulation with fire resistant properties

Abstract: Fibrous thermal insulation comprises an intimate blend of A) non-graphitic carbonized fibers having an LOI value greater than 40, a percentage char value greater than 65, and a thermal conductivity less than 1.7 W/(m. o K) (1.7 W/m. o C)), and B) hollow thermoplastic fibers.

Description: The present invention relates to lightweight structures that have a high degree of thermal insulation, are non-wetting and/or buoyant and have good fire resistance. More particularly, the invention provides a lightweight insulation through the use of hollow styrenic fibers intimately blended with carbonized polymeric fibers, which provide synergistic ignition and fire resistance. It is desirous to have lightweight structures that have a high degree of thermal insulation that can be washed and dried without retention of a great amount of water. Fiberglass containing structures are presently being used to provide fiber battings for use in insulating spaces in buildings and airplanes. In addition, fiberglass battings are being used as insulation in industrial apparel, blankets and curtains. The problems with fiberglass is that it is difficult to handle and can cause dermal irritation. Moreover, fiberglass does not have a high insulation compact value and can pick up moisture so as to cause it to settle down after installation with a loss in insulation value. Styrenic fibers are well-known. Moreover, styrenic fibers are low in cost, are non-irritating, have good insulation value and can be blended with other fibers utilizing conventional processes. The main disadvantage of styrenic fibers is that they are highly flammable. Hollow styrenic fibers are even more flammable because they provide a greater surface area for combustion. US-A-4,879,168 discloses fire retarding and fire blocking structures comprising an intimate blend of non-carbonaceous fibers and at least 7.5 weight percent of heat-set carbonaceous fibers having a limited oxygen index ("LOI") value greater than 40 and derived from heat stabilized acrylic fibers or pitch based fibers. Specified non-carbonaceous fibers include cotton, wool, flax, silk, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polyesters, polyacrylonitrile, polyacrylates, polycarbonate, cellulosic products, ionomers, DACRON™ and KEVLAR™ but there is no reference to styrenic polymers other than to exemplify LOI values of known fibers. It has been discovered that carbonized fibers can provide an improvement in fire resistance when blended with hollow styrenic fibers. According to a first aspect of the present invention, there is provided a fire resistant fibrous thermal insulation comprising a blend of thermoplastic fibers and non-graphitic, carbonized polymeric fibers derived from a polymeric precursor material selected from aromatic polyamides, polybenzimidazoles, and polyacrylonitrile, wherein said carbonized fibers are present in an amount of from 20 to 75 percent by weight (based upon the combined weight of the thermoplastic and carbonized fibers), and have a carbon content of less than 85 percent, an LOI value (as determined by ASTM D 2863-77) of greater than 40, a percentage char value greater than 65, and a thermal conductivity of less than 1.7 W/(m.°C) (1.7 W/(m.°K)), characterized in that the thermoplastic fibers are hollow styrenic fibers. In a second aspect, the invention provides the use to enhance the fire resistance of hollow, styrenic fibers of non-graphitic, carbonized polymeric fibers derived from a polymeric precursor material selected from aromatic polyamides, polybenzimidazoles, and polyacrylonitrile, wherein said carbonized fibers have a carbon content of less than 85 percent, an LOI value (as determined by ASTM D 2863-77) of greater than 40, a percentage char value greater than 65, and a thermal conductivity of less than 1.7 W/(m.°C) (1.7 W/(m.°K)). For the purpose of rendering various terms employed herein clear and readily understandable, the following definitions are provided hereinafter. The term "stabilized" herein applies to fibers which have been stabilized against thermoplasticity to prevent them from fusing during heat-setting or carbonization by, for example, oxidation at a specific temperature, typically less than 250°C for acrylic fibers. It will be understood that in some instances the fibers are oxidized by chemical oxidants at lower temperatures. The procedure is more clearly described in US-A-4,837,076 or EP-A-0199567. The term "reversible deflection" is used herein as it applies to a helical or sinusoidal compression spring. Particular reference is made to the publication, "Mechanical Design - Theory and Practice," MacMillan Publishing Co., 1975, pp 748, particularly Section 14-2, pp 721 to 724 as well as EP-A-0199567. The term "polymer" or "polymeric material" used herein applies to organic polymers as defined in Hawley's Condensed Chemical Dictionary, Eleventh Edition, Published by Van Nostrand Rheinhold Company. The organic polymers generally include: 1) natural polymers, such as cellulose; 2) synthetic polymers, such as thermoplastic or thermosetting elastomers; and 3) semisynthetic cellulosics. Polymers included herein are also low melting polymeric binders as well as polymeric fibers. The term "fibers" as used herein is intended to include linear or nonlinear fibers, or mixtures of such fibers. The term "carbonized fiber" as used herein relates to polymeric carbonaceous fibers whose carbon content has been irreversibly increased as a result of a chemical reaction such as a heat treatment, as disclosed in US-A-4,837,076 or EP-A-0199567, and is at least 65 percent carbon and preferably less than 85 percent carbon. The term "non-graphitic" as used herein relates to those materials which are substantially free of oriented carbon or graphite microcrystals of a three dimensional order, typically have an elemental carbon content less than 98 percent and, for example, are as further defined in US-A-4,005,183. The term "ignition resistant" as used herein generally applies to any one of the characteristics that are referred to as flame arresting, flame retarding, fire shielding and fire barrier, as defined in 14 CFR 25.853(b). An article is considered to be "flame retarding" to the extent that, once an igniting flame has ceased to contact unburned parts of a textile article, the article has the inherent ability to resist further propagation of the flame along its unburned portion, thereby stopping the internal burning process. Recognized tests to determine whether an article is flame retarding are, inter alia, the American Association of Textile Chemists and Colorist Test Method 34-1966 and the National Bureau of Standards described in DOC FF 3-71. An article is considered to be "flame arresting" if it has the ability to block or prevent flames from contacting unburned parts of a flammable substance for at least five (5) minutes. An article is considered to be "fire shielding" if it is capable of deflecting flames and the radiation therefrom in a similar manner as aluminum coated protective garments, which are known in the art. Fire barriers have the characteristic of being nonflammable and flame retarding and also provide thermal insulation characteristics. The term "polymeric" or "polymeric resin" used herein includes natural polymers as well as other organic polymeric resins including organosilicone polymers. The nonlinear carbonized fibers preferably used in the invention are resilient, shape reforming and have a reversible deflection greater than 1.2:1. Usually, they have a multicurvilinear structural configuration with no sharp bends such as, for example, sinusoidal and/or coil-like. It should be understood that the reversible fiber deflection comprises two components, pseudoelongation and fiber elongation. Pseudoelongation results from the nonlinear configuration and/or false twist imposed on the fiber. Fiber elongation is the elongation to fiber break after the fiber has been made linear. The carbonaceous materials that are suitably employed in the present invention have an LOI value of greater than 40 as measured according to test method ASTM D 2863-77. The method is also known as the "oxygen index" or "limiting oxygen index" (LOI) test. With this procedure the concentration of oxygen in 0 2 /N 2 mixtures is determined at which a vertically mounted specimen is ignited at its lower end and just continues to burn. The size of the specimen is 0.65 x 0.3 cm with a length of from 7 to 15 cm. The LOI values of different materials are calculated according to the following equation: LOI = O 2 O 2 +N 2 x 100 The carbonaceous materials of the invention are characterized as having a percentage char value greater than 65 and thermal conductivity of less than 1.7 W/(m.°K) (1.7 w/(m.°C)). The measurement of char formation is made by using a standard thermogravimetric analysis apparatus that is adapted to perform the analysis in a nitrogen atmosphere. The apparatus is described in Encyclopedia of Polymer Science, Vol. 14, p. 21, John Wiley & Son, 1971. The measurement is performed by loading a sample onto a sample pan of the thermogravimetric analysis apparatus. The sample is then heated in an nitrogen atmosphere at a rate of 10°C/min from ambient temperature to 900°C. The thermogravimetric apparatus records the sample weight remaining versus temperature. The percent of original weight remaining at 800°C is taken as the char percentage. The carbonized fibers may be solid, expanded (eg. cellular, hollow, or porous), linear or non-linear in configuration. Preferably, the carbonized fibers contain at least 5 percent voids derived from aromatic polyamides, polybenzimidazole, and polyacrylonitrile based fibers as described in co-pending European Patent Application No. 91306525.6 (EP-A-0471452) corresponding to US Patent Application No. 554778. The hollow fibers used in the invention preferably are crazed or cracked for improved insulation value. They can be obtained by drawing and aspirating or fibrillating the hollow fibers during preparation. Also, cracked hollow styrenic fibers provide the structure a layer volume coverage at lower weight. The cracked or crazed hollow fibers of the invention are believed to be characterized by the following equation: W = D o sin 180 n µm wherein W is the width of the fiber; D o is the outside diameter of the fiber, and n is the number of crazes or cracks, whereby when for a given D o = 30 µm n = 4, W is 21.4 µm; n = 6, W is 15 µm; n = 12, W is 7.8 µm. It has been found that the larger the number of crazes or cracks, the smaller the fiber width and a reduction in K-factor. Preferred hollow fibers are those having a fiber width of 6 µm to 30 µm and at least 6 cracks or crazes, preferably 12. In accordance with one embodiment of the invention there is provided a lightweight batting having a high degree of thermal insulation and good fire resistance by blending (A) 20 to 75% by weight, preferably 20 to 50% by weight, of the non-graphitic carbonized fibers, and (B) the hollow styrenic fibers. A preferred minimum amount of carbonized fibers is that which provides or imparts a sufficient degree of fire resistance to enable the insulation to pass the requirements of 14 FAR 25.853(b) (also referred to as 14 CFR 25.853(b) or FAR. 25.853) for non-flammability. The combination also has improved ignition resistance. The invention is surprising and synergistic in that a relatively small proportion (-20% by weight) of the carbonized fibers is typically sufficient to impart the desired degree of fire resistance to hollow thermoplastic fibers, which are typically highly flammable. In accordance with another embodiment, the structure of the invention can comprise a lightweight structural panel of a compression formed composite of a thermoplastic or thermosetting resin matrix containing from 10 to 95 percent by weight of the fibrous blend of the invention. The panel can be used alone or in combination with a nonflammable reinforcement scrim comprising, for example, a woven, nonwoven, or knitted fabric, web, foam or a metallic screen or glass screen. The structures of the present invention provide an improvement over fiberglass structures which utilize phenolic binders. The improvement includes an advantage in weight as well as in smoke characteristics. The styrenic resins used to form the hollow fibers of the invention may contain plasticizer (eg mineral oil or dioctyl phthalate), flame retardant (eg hexabromocyclododecane, decabromodiphenyl oxide, or alumina trihydrate), acid scavengers (eg MgO), and extrusion aid or lubricant (eg calcium stearate). The hollow fibers of the invention can be in any form. The fibers can be fibrillated or aspirated hollow fibers, stretched hollow fibers or curly hollow fibers. A first group of carbonized fibers that can be used in the invention are classified as being electrically nonconductive and to possess no antistatic characteristics, i.e., they do not have the ability to dissipate an electrostatic charge. The term "electrically nonconductive" as utilized in the present invention relates to fibers having an electrical resistance of greater than 4 x 10 6 ohms/cm when measured on a 6K tow (6000 filaments) formed from precursor fibers having a diameter of from 4 to 25 micrometers. Such fibers have a specific resistivity of greater than 10 -1 ohms/cm. The specific resistivity is calculated from measurements as described in EP-A-0199567. When the precursor fiber is an acrylic fiber it has been found that a nitrogen content of greater than 18 percent results in a nonconductive fiber. In a second group, the carbonized fibers are classified as being partially electrically conductive (i.e., having low conductivity) and having a carbon content of less than 85 percent. Low conductivity means that the fibers have a resistance of from 4 x 10 2 to 4 x 10 6 ohms/cm, as determined by the measurements hereinbefore specified. Preferably, the carbonized fibers are derived from stabilized acrylic fibers and possess a percentage nitrogen content of from 16 to 20 percent for the case of a copolymer acrylic fiber, more preferably from 18 to 20 percent. The structures formed therefrom are lightweight, have low moisture absorbency, good abrasive strength together with good appearance and handle. The following examples are provided for purposes of illustrating the present invention, and are not to be construed as limiting. All percentages are by weight unless otherwise indicated. Example 1 Following the procedure of US-A-4,882,223, which is herein incorporated by reference, polystyrene with a 300,000 weight average molecular weight was introduced into a 1.9 cm extruder. The polymer was melted at about 232 o C and passed through a Zenith gear pump at about 246 o C. The molten polymer was pumped to the pack well and then to a pack assembly consisting of a screen and spinneret with low pressure air passing through the inner hole to produce a hollow fiber. The spinneret had a temperature of 200 o C and an operating pressure of 2758 kPa. The fiber was then passed through draw rolls and was wound around Leesona take-up rolls with an aspirator device at 122 m/min. The aspirator was normally used to "suck" off the fibers while a full roll was taken off and an empty roll loaded on. Some of the fibers were collected by passing through the aspirator and into a plastic bag. In entering the aspirator, the fibers went around a fairly sharp right angle bend. Once entering into the air stream of the aspirator, the fiber appeared to go through a twisting motion. The fibers were cottony soft and somewhat like a loose thread instead of brittle fibers produced without passing it through the aspirator. The individual fibers had a 25-30 µm outside diameter with a wall thickness of 2-5 µm. The aspirated fibers had crazes or cracks along the axial direction of the hollow fibers probably due to the twisting motion of individual fibers when passing through the aspirator. The hollow fibers were then hand cut into two inch (5 cm) length and hand blended with carbonized fibers and polyester binder fibers. After hand blending, the fiber blend was fed into a Rando Mizer Card to further blend and open the fibers. The Rando Mizer Product was processed into a non-woven batting on a Rando-B machine. The batting was thermobonded at 107 o C for 60 seconds. Table I shows the K-factors as a function of density and carbonized fiber concentration. As a comparison, the fiberglass batt with a density of 10 kg/m 3 has a K-factor of 0.315. Example 2 Example 1 was repeated using a carbonized fiber derived from a special acrylic fiber (SAF) from Courtaulds Ltd. dissolved in N-methyl pyrrolidone to obtain a 15-45 vol. % solution. The polymer was then spun at a temperature between 160° to 200°C using a 16 hole fiber spinneret and nitrogen as a core gas. The spun hollow fibers were then quenched in a water bath at about 10°C for about 2 seconds to coagulate or phase separate the denser polymer at the surface of hollow fibers squeezing more solvent toward the inner surface. These hollow fibers were then passed through a water bath at about 30°C to leach out the solvent and to obtain an asymmetric porous structure with greater porosity toward the inside of the hollow fibers (200 µ O.D./20 µ I.D.). These asymmetric porous hollow fibers were dried and then heat treated in a forced air oven at 200°C for 30 minutes to promote the oxidation and crosslinking reactions of the SAF. This was followed by a heat treatment in an inert atmosphere of nitrogen at 500°C until an 85% loss of initial polymer sample weight is achieved. The result is an asymmetric porous carbonized fiber. In lieu of N-methyl pyrrolidone there may be utilized as a solvent sulfolane, dimethylformamide, polyethylene glycol, polyethylene glycerol or mixtures thereof, for example, 25% polyethylene glycol/75% sulfolane. In lieu of SAF there may be utilized polyacrylonitrile or its copolymers. Example 3 - Nonflammability Test The nonflammability of the various blends of the invention were determined following the test procedure set forth in 14 CFR 25.853(b). The tests were performed as follows: A minimum of three 2.5 cm x 15 cm x 30 cm specimens of each blend were conditioned by maintaining the specimens in a conditioning room maintained at a temperature of 21°C ± 5° and 50 percent ± 5 percent relative humidity for 24 hours preceding the test. Each specimen was supported vertically and exposed to a Bunsen or Turill burner with a nominal I.D. tube adjusted to give a flame of 3.8 cm in height. The minimum flame temperature measured by a calibrated thermocouple pyrometer in the center of the flame was 843°C. The lower edge of the specimen was 1.9 cm above the top edge of the burner. The flame was applied to the center line of the lower edge of the specimen for 12 seconds and then removed. The results of the test are shown in Table II. Flammability Test According to FAR.25.853 Sample No. Sample Composition Burn Length (cm) Flame Time (sec) Drip Time (sec) Pass or Fail 1 30% NCF 7.5 <5 0 Pass 20% Polyester 50% Polystyrene hollow fiber 2 20% NCF 14 <15 0 Pass 20% Polyester 60% Polystyrene hollow fiber 3 12% NCF 25 25 0 Fail 20% Polyester 68% Polystyrene hollow fiber 4 30% NCF 3.8 <5 0 Pass 20% Polyester 50% Nylon 8207F hollow fiber 5 20% NCF 5.0 <5 0 Pass 20% Polyester 60% Nylon 8207F hollow fiber 6 10% NCF 7.5 <5 0 Pass 20% Polyester 70% Nylon 8207F hollow fiber 7 30% NCF 3.8 <10 0 Pass 20% Polyester 50% PET recycled hollow fiber 8 20% NCF 2.5 0 0 Pass 20% Polyester 60% PET recycled hollow fiber Example 4 Example 1 was repeated using crimped expanded carbonized fibers prepared as follows:- A copolymer comprising 95% acrylonitrile and 5% vinyl chloride was dissolved in acetone. To this copolymer solution, 40% of 1,1,2-trichloro-1,2,2-trifluoroethane and 0.2% titanium dioxide were added to have the final polymer concentration adjusted to 35%; and the solution was stirred at 40°C to yield a spinning solution. This solution was then discharged into a 20% aqueous solution of acetone at 35° through a spinneret with 10000.10 mm Φ slits. After immersion therein for 9 seconds at a take-up rate of 4.5 m/min., the spun mix was immersed for 6 sec. in a 25% aqueous acetone solution at 30°C while drawing it 1.8 times, and thereafter, crimped and heat treated at 525°C without any tension or stress in an apparatus described in US-A-4,979,274. The fiber when carbonized had low electrical conductivity, an expansion of about 10%, a reversible deflection ratio greater than 2:1 and an LOI greater than 40. To prepare linear fibers, the crimping step may be omitted. Similarly, there may be prepared expanded carbonized polybenzimidazole fibers. Example 5 Example 1 was repeated using expanded KEVLAR polyamide continuous 3K tow prepared according to US-A-4,752,514 having nominal single fiber diameters of 15 micrometer. The tow was knit on a circular knitting machine into a cloth having from 3 to 4 loops per centimeter. The cloth was heat set at 525°C for two minutes. When the cloth was deknitted, it produced a tow which had an elongation or reversible deflection ratio of greater than 2:1. The deknitted tow was cut into various lengths of from 5 to 25 cm, and fed into a Platt Shirley Analyzer. The fibers of the tow were separated by a carding treatment and blended with hollow styrenic fibers to produce a light weight insulation. Example 6 Example 1 was repeated using carbonized fibers derived from a 3K tow of expanded p-aramid knit on a circular knitting machine at a rate of 4 stitches/cm and was then heat treated at a temperature of 425°C without stabilizing for ten minutes. The cloth was deknitted and the tow (which had an elongation or reversible deflection ratio of greater than 2:1) was cut into 7.5 cm lengths. The cut tow was then carded on a Platt Miniature carding machine together with the fibers of Example 1 to produce a resilient compressible fluff. The fluff can be densified by needle punching, treated with thermoplastic binder such as a polyester binder, or the like, to form a mat or felt-like structure. Example 7 Example 1 was repeated using a hollow fiber with about 6-12 cracks obtained from polystyrene (Dow Chemical Company) using a spinneret temperature of 290-295°C, a spinneret pressure of 2620-3030 kPa and a take-up speed of 980-1530 m/min to provide a fiber ID of 45-55 µm and a wall thickness of 5-7 µm. The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention however, is defined by the following claims and not limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive.

Claims: A fire resistant fibrous thermal insulation comprising a blend of thermoplastic fibers and non-graphitic, carbonized polymeric fibers derived from a polymeric precursor material selected from aromatic polyamides, polybenzimidazoles, and polyacrylonitrile, wherein said carbonized fibers are present in an amount of from 20 to 75 percent by weight (based upon the combined weight of the thermoplastic and carbonized fibers), and have a carbon content of less than 85 percent, an LOI value (as determined by ASTM D 2863-77) of greater than 40, a percentage char value greater than 65, and a thermal conductivity of less than 1.7 W/(m.°C) (1.7 W/(m.°K)), characterized in that the thermoplastic fibers are hollow styrenic fibers. An insulation as claimed in Claim 1, wherein said carbonized fibers are present in an amount of from 20 to 50 weight percent (based on the weight of the hollow, thermoplastic fibers and the carbonized fibers). An insulation as claimed in Claim 1 or Claim 2, wherein the amount of said carbonized fibers is sufficient to enable the fibrous insulation to conform to the nonflammability standards of 14 CFR 25. 853(b). An insulation as claimed in any one of the preceding claims, wherein the hollow, styrenic fibers are crazed or cracked. An insulation as claimed in Claim 4, wherein the hollow, styrenic fibers have a fiber width of 6 to 30 micrometers and at least 6 cracks or crazes. An insulation as claimed in any one of the preceding claims, wherein said carbonized fibers contain at least 5 percent voids. An insulation as claimed in Claim 6, wherein the carbonized fibers are porous or hollow. An insulation as claimed in Claim 7, wherein the carbonized fibers are asymmetrically porous. An insulation as claimed in any one of the preceding claims, wherein the carbonized fibers are nonlinear. An insulation as claimed in Claim 9, wherein the carbonized fibers have a permanently set multicurvilinear structural configuration with no sharp bends and a reversible deflection ratio greater than 1.2:1. A lightweight structural panel of a compression formed composite of a resin matrix containing 10 to 95 weight percent of a blend as defined in any one of the preceding claims. The use to enhance the fire resistance of hollow, styrenic fibers of non-graphitic, carbonized polymeric fibers derived from a polymeric precursor material selected from aromatic polyamides, polybenzimidazoles, and polyacrylonitrile, wherein said carbonized fibers have a carbon content of less than 85 percent, an LOI value (as determined by ASTM D 2863-77) of greater than 40, a percentage char value greater than 65, and a thermal conductivity of less than 1.7 W/(m.°C) (1.7 W/(m.°K)). A use as claimed in Claim 12, wherein the amount of said carbonized fibers is as defined in any one of Claims 1 to 3. A use as claimed in Claim 12 or Claim 13, wherein said carbonized fibers are as defined in any one of Claims 6 to 10. A use as claimed in any of Claims 12 to 14, wherein said styrenic fibers are as defined in Claim 4 or Claim 5.

Inventors: BRUBAKER BURTON D, MCCULLOGH FRANCIS P, SNELGROVE R VERNON, STOBBY WILLIAM G, SUH KYUNG W, BRUBAKER, BURTON D., MCCULLOGH, FRANCIS P., SNELGROVE, R. VERNON, STOBBY, WILLIAM G., SUH, KYUNG W.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1991
Main classification: D04H1
IPC codes: C04B14, C04B16, D02G3, D01F9, D04B1, D01F6, C04B30, D04H1