US3821074A - Paper from pitch based organic fibers - Google Patents

Paper from pitch based organic fibers Download PDF

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Publication number
US3821074A
US3821074A US00313007A US31300772A US3821074A US 3821074 A US3821074 A US 3821074A US 00313007 A US00313007 A US 00313007A US 31300772 A US31300772 A US 31300772A US 3821074 A US3821074 A US 3821074A
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Prior art keywords
fibers
novolac
fusible
percent
mixture
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US00313007A
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R Lin
H Murty
A Pietrantuone
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Stemcor Corp
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Carborundum Co
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Priority to US00313007A priority Critical patent/US3821074A/en
Priority to JP13545173A priority patent/JPS5650030B2/ja
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Assigned to KENNECOTT CORPORATION reassignment KENNECOTT CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). EFFECTIVE DEC. 31, 1980 NORTH DAKOTA Assignors: BEAR CREEK MINING COMPANY, BEAR TOOTH MINING COMPANY, CARBORUNDUM COMPANY THE, CHASE BRASS & COPPER CO. INCORPORATED, KENNECOTT EXPLORATION, INC., KENNECOTT REFINING CORPORATION, KENNECOTT SALES CORPORATION, OZARK LEAD COMPANY, PLAMBEAU MINING CORPORATION, RIDGE MINING CORPORATION (ALL MERGED INTO)
Assigned to STEMCOR CORPORATION, 200 PUBLIC SQUARE, CLEVELAND, OHIO 44114 A DE. CORP. reassignment STEMCOR CORPORATION, 200 PUBLIC SQUARE, CLEVELAND, OHIO 44114 A DE. CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KENNECOTT MINING CORPORATION
Assigned to KENNECOTT MINING CORPORATION reassignment KENNECOTT MINING CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE DEC. 31, 1986. (SEE DOCUMENT FOR DETAILS) Assignors: KENNECOTT CORPORATION
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • H01B3/485Other fibrous materials fabric
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/22Condensation polymers of aldehydes or ketones

Definitions

  • the present invention relates to fibrous articles made from fibers comprising novolacs, as well as fibers comprising pyrogenous residues, such as pitch, combined with appropriate novolacs.
  • the fibers may be either fusible or infusible, depending on the method of production and the fibrous articles made therefrom may take the form of mats or sheet-like products.
  • Bonded fibrous articles are made from a mixture of fusible and infusible synthetic fibers, the fibers being synthesized either from novolacs or from a pyrogenous residue, such as pitch, combined with a novolac.
  • the process comprises suspending the fibrous mixture in a fluid, depositing the fibers upon a permeable support, removing the fiuid and adding a curing agent to the fibers, and then compresssing the fibers and heating to form the bonded article.
  • the fiber mixture may comprise about to 40 wt. percent of fusible fibers combined with about 60 to 90 wt. percent of infusible fibers, the curing agent being an aldehyde or an amine combined with a catalyst.
  • the pressure applied during curing may vary from about 0 to 5 psi, depending on the density desired in the bonded article, while the curing temperature may range from about to 200 C. Heating may be continued in the range of about 200 to 400 C, if an article of improvedthermal stability is desired.
  • a preferred fiber mixture comprises about 20 wt. percent fusible fibers and 80 wt. percent infusible fibers, the mixture then deposited on a screen as a flat sheet and cured with hexamethylenetetramine at temperatures ranging from about to 400 C to form a bonded fibrous sheet. Fibrous articles made by this method are firmly bonded during the curing reaction of the fusible fibers.
  • the articles may be porous with average pore diameters in the range of l to 50 microns and may be in the form of flat sheets with a sheet thickness which may range from about 1 to 250 mils but preferably is from I to 10 mils. Since the method of curing gives a strong bond between fibers and allows the ready control of pore size and product dimensions, the process of the invention overcomes the deficiencies found in prior art processes andproduces a product having superior mechanical strength, combined with outstanding thermal andchemical resistance. Porosity of the product may be readily controlled, since the uncured fibers are the'binders and bonding takes place only at the contact points between the cured and uncured fibers. Since both types of fibers are produced from the same batch,the resulting bonds are chemically compatible, even when the fibers are produced from'an initial mixture of resins.
  • the startingpyrogenous residues that may be used in the present invention include a variety of pitches such as coal tar pitches, pitches obtained by distillation of oils, petroleum pitches, pyrogenous asphalts, and a va riety of pitch-like substances produced as by-products of various industrial processes such as distillation residues.
  • the starting pyrogenous residue has a softening point of about 80 C to about 200 C, more preferably from about 100 C to about C.
  • the pyrogenous residue has a carbon to hydrogen ratio based on weight percent from about 18 to about 25.
  • the content of aromatic and unsaturated components may vary depending on the source of the raw material pyrogenous residue.
  • pyrogenous residues used as starting materials have a beta-resin content greater than about 5 percent and preferably greater than 10 percent by weight.
  • the beta-resin is the benzene insoluble content of the pyrogenous residue minus the quinoline insoluble content.
  • the beta-resin portion of the pyrogenous residue is believed to enhance the binding and adhesive qualities thereof. It is believed that a suitable amount of beta-resin contributes to rendering the fusible fiber infusible by a short curing process.
  • the upper limit of the weight percent of beta-resin in the starting pyrogenous residue is not. critical but is gener ally limited by the type of pitch used and process conditions. Most commercially available pitches have a betaresin content less than about 30 percent but pitches with a beta-resin content higher than 45 percent may be used in the present invention.
  • coal tar pitch has a benzene insoluble content of about 20 to about 50 percent by weight and a quinoline insoluble content of about 10 to about 20 percent by weight with a resulting beta-resin content in the range of about 10 to 30 percent.
  • pitches are suited for using as a starting material in the present invention without further modificatron.
  • Petroleum pitches and pyrogenous asphalts often have beta-resin contents less than about 5 percent. This is generaly due to a low percentage of benzene insolubles which is generally less than about percent. In such a case, while the fusible fiber of pyrogenous residue and novolac can be rendered infusible by reacting with formaldehyde, the curing process is comparatively slow.
  • Such upgrading can be done by reacting the pitch or asphalt with an aldehyde and phenolic compound in the presence of an acid catalyst at a temperature sufficiently high to effect condensation between the pitch or asphalt, aldehyde and phenolic compound. Such a method'is described in U.S. Pat. No.
  • the amount of aldehyde and phenolic compound that is employed can vary widely depending on the degree of upgrading necessary.
  • the reaction is carried out at a temperature from about 150 F to about 600 F for a suitable period of time.
  • the amount of quinoline insolubles in the starting pyrogenous residue should be less than about percent by weight and preferably less than about 10 percent. As the percentage of quinoline insolubles in the starting pyrogenous residue is decreased, the ease of fiberization of the melt is increased and the uniformity of the fibers is enhanced.
  • the most preferred starting pyrogenous residue contains zero or a very low percentage of quinoline insolubles.
  • the quinoline insolubles represent material which is not soluble in the pyrogenous residue at the spinning temperature and which forms an undesirable second phase. Removal of the quinoline insolubles can be accomplished by diluting the pitch in an appropriate solvent and filtering or centrifuging to remove the insolubles. Such a method is described in U.S. Pat. No. 3,595,946. 7
  • novolac resins may be used as starting materials in the present invention.
  • the term novolac refers to a condensation product of the phenolic compound with formaldehyde, the condensation being carried out in the presence of a catalyst to form a novolac resin wherein there are virtually no methylol groups such as present in resoles and wherein the molecules of the phenolic compounds are linked together by a methylene group.
  • the phenolic compound may be phenol, or phenol wherein one or more of the non-hydroxylic hydrogens are replaced by any of various substituents attached to the benzene ring, a few examples of which are the cresoles, phenyl phenols, 3-5 dialkyl-phenols, chorophenols, resorcinol, hydroquinone, chloroglucinol and the like.
  • the phenolic compound may instead be naphthyl or hydroxyphenathrene or another hydroxyl derivative of a compound having a condensed ring system.
  • any fusible novolac which is capable of further polymerization with a suitable aldehyde or amine may be employed for the production of fibers.
  • the novolac molecules must have two or more available sites for 4 further polymerization.
  • any novolac might be employed, including modified novolacs, i.e., those in which a non-phenolic compound is also included in the molecules, such as the diphenyl oxide or bisphenol-A modified phenol formaldehyde novolac. Mixtures of novolacs may be employed or novolacs containing more than one species of phenolic compounds may be employed.
  • Novolacs generally have a number-average molecular weight in the range from about500 to about 1,200, although an exceptional case in which the molecular weight may be as low as 300 or as high as 2,000 or more may occur.
  • Unmodified phenol formaldehyde novolacs usually have a number-average weight in the. range from about 500 to about 900, most of the commercially available materials falling within this range.
  • novolacs with a molecular weight from about 500 to about 1,200 are employed in the method of the present invention.
  • the temperature at which such novolacs soften and become tacky is usually comparatively low. Therefore, it is necessary to cure the fiberized novolac at a very low temperature to avoid adherence and/or deformation of the fibers. It is usually undesirable to employ such low curing temperatures since the curing rate increases dramatically with the increase in temperature and low curing entails the practical disadvantage of a prolonged curing cycle.
  • novolac having a moderately high molecular weight for the type of novolac under consideration to permit curing in a reasonable time without adherence and/or deformation, but to avoid the extreme upper end of the molecular weight range to minimize problems in fiberizing due to gelling.
  • a mixture of pyrogenous residue and novolac may be formed by any convenient technique such as dry blending or melting the pyrogenous residue and novolac by heating together to form a homogenous mixture.
  • Mixtures containing from about 5 to about 40 percent by weight novolac may be used for preparing the fibers of the present invention. Since the pyrogenous residue is the most economically available component of the mixture, it is preferred to employ less than about 35 percent novolac by weight. It is preferable that the novolac content be at least about 10 percent'and more preferably that it be at least about 25 percent in the mixture so that the spinnability of the fiber is enhanced and the curing time can be sufficiently reduced.
  • the mixture consists essentially of the pyrogenous residue and novolac.
  • the fiberization may be performed by any convenient method such as drawing a continuous filament downwardly from an orifice in the bottom of the vessel containing a molten mixture of pitch and novolac.
  • the filament is wound and collected on a revolving take-up spool mounted below the orifice.
  • the take-up spool also serves to attenuate the filament as it is drawn from the orifice before it cools and solidifies upon contacting the atmosphere between the orifice and the spool.
  • the melt may also be formed into short staple fibers by methods known in the prior art such as blowing the melt through a fiberizing nozzle and collecting the cooled fibers or blowing a thin stream of melt into the path of a hot blast of gas. These methods produce a staple consisting of a multiplicity of fusible uncured pitchnovolac fibers of variable length and diameter.
  • the diameter of the fibers can vary from 0.1 micron to about 300 microns.
  • the fibers When producing a continuous filament having a uniform diameter by melt spinning, preferably the fibers have diameters from about to about 30 microns.
  • the filament diameter depends primarily upon two factors, the drawing rate and the flow rate of the melt through the orifice.
  • the fiber diameter decreases as the drawing is increased and increases as the flow rate of the melt is increased.
  • the flow rate of the melt depends primarily upon the diameter and length of the orifice and the viscosity of the melt, increasing as the orifice diameter is increased, decreasing as the length of the orifice is increased, and increasing as the viscosity of the melt is decreased.
  • An increase of flow rate may also be effected, is desired, by applying pressure to the melt to force it through the orifice.
  • Curing of the fusible fiber to render it infusible is effected by heating the uncured fusible fiber in a liquid or gaseous formaldehyde environment. It appears that the curing mechanism involves the diffusion of the formaldehyde into the fiber and reaction of the novolac and formaldehyde to bring about polymerization of the novolac and pyrogenous residue mixture. It is preferred to effect curing by heating the uncured fusible fibers in an environment containing paraformaldehyde in the presence of a catalyst. The environment may be gaseous, but is preferably liquid as in a solution of the catalyst and formaldehyde.
  • Liquid is preferred because of the greater rapidity of heat and material transport to the fibers, especially the fibers in the interior portions of a bundle of fibers being cured, and also because higher concentrations of formaldehyde and catalysts may be achieved by employing a solution thereof.
  • Any of a wide variety of acids or bases may be used as the catalysts, any of the mineral acids or bases such as hydrochloric, sulfuric, phosphoric, ammonia hydroxide, potassium hydroxide, sodium hydroxide and organic acids or bases such as oxalic acid, or dimethylamine being particularly suitable.
  • the solution is the choice of solvent although other liquids may be employed provided that they do not adversely affect the fiber and are capable of dissolving the formaldehyde in a solution containing the catalyst.
  • the solution contains from about. 12 to about 18 percent formaldehyde.
  • an acid catalyst it is preferred that the solution contain from about 12 to about 18 percent acid, and when a base catalyst is used, from about 1 to about 10 percent base.
  • Lower concentrations of catalysts or formaldehyde in the solution generally require longer curing times. Higher concentrations of formaldehyde or catalysts do not appear to offer any advantage.
  • any gaseous catalyst such as hydrogen chloride or ammonia may be employed.
  • the formaldehyde may conveniently be generated by heating paraformaldehyde.
  • the gaseous atmosphere maycontain as little as about 10 percent formaldehyde up to as much as 99 percent, by volume, and from about 1 percent to about 90 percent, by volume, of the acid.
  • the atmosphere may also contain a diluent such as nitrogen or other inert gas, but air should be excluded to minimize the possibility of side reactions taking place.
  • the rate of curing increases with increasing temperature.
  • a temperature is employed at which adherence and/or deformation does not occur.
  • the outer portion of the fiber begins to cure, forming a shell, and thereupon, the temperature may be raised as necessary to complete the cure, the shell eliminating problems due to fusion which might otherwise occur.
  • the curing time must be sufficiently long to render the uncured fiber infusible. Once such infusibility has been achieved, further curing is unnecessary for purposes of this invention. At a temperature of C, the time is about 10 hours, while at a temperature of about C, the time is about 3 hours.
  • the curing it is generally preferred to carry out the curing be employingan initial room temperature and increasing the temperature to a final curing temperature of about 80 to about 100 C over a period of from about 1 to 3 hours and maintaining the temperature of a final curing temperature for a residence time of about 2 to about 4 hours for a total curing time of from about 3 to about 10 hours.
  • a low weight percent of novolac is employed in the pitch-novolac mixture, such as below about 10 percent novolac, it may be desirable to oxidize the fibers after curing.
  • the curing step renders the fibers infusible, if a low weight percent of novolac is employed or if the diameter of the fiber is greater than about 20 microns, the fiber will smoke when subjected to a flame. It is believed that the additional steps of oxidizing promotes the formation of cross links whereby high polymer carbon material of insoluble and unmeltable characteristics is further produced.
  • the oxidizing of the pitch-novolac fibers is performed by heating the cured fiber in air or other oxidizing atmosphere at a temperature of about 200 C to about 300 C.
  • the fibers are heated in air from about room temperature (25 C) up to a final temperature in the range of from about 200 C to about 300 C, the temperature being continually increased at the rate of from about 25 C per hour to about 100 C per hour, and continuing to heat in the air atmosphere at the final temperature for about 5 to about 60 minutes or longer.
  • the processes of fiber formation both fusible and infusible, have been described at considerable length, since the mechanism of curing the fusible fiber is essential to the proper bonding of the fibrous articles of the invention.
  • the process for making these articles comprises the steps of preparing a mixture of fusible and infusible fibers and suspending this mixture in a suitable fluid. The mixture is then deposited upon a permeable support and the fluid removed, followed by the addition of a curing agent to the fibrous mass. This mass is then compressed and heated, during which time the fusible fibers are cured and become infusible. During the curing step, the fusible fibers bond securely to the infusible fibers which are already present in the fibrous mass, thereby forming strong infusible interfiber bonds throughout the mass.
  • composition of the fibrous articles of the invention may be varied over a wide range, depending on the proportions of fusible and infusible fibers used.
  • the mixture of fibers may comprise from about 10 to about 40 percent of fusible fibers and from about 60 to about 90 percent of infusible fibers. Throughout the following description and claims, percentages will be given by weight, unless otherwise specified.
  • a preferred fibrous mixture comprises about 20 percent fusible fibers and about 80 percent infusible fibers.
  • the fibrous mixture may be suspended in any suitable fluid, either gaseous or liquid. Water is the preferred liquid, but others such as alcohols, esters, or hydrocarbon solvents may be used.
  • the liquid may contain small amounts of wetting agents or binders such as polyvinyl alcohol or other organic wetting agents or binders which are soluble in the liquid, to promote the proper dispersion of the fibers and to hold them temporarily in place while the fibrous mass is being formed.
  • wetting agents or binders such as polyvinyl alcohol or other organic wetting agents or binders which are soluble in the liquid, to promote the proper dispersion of the fibers and to hold them temporarily in place while the fibrous mass is being formed.
  • the fibers may be suspended in a current of gas such as air or nitrogen. The fibrous mixture is then deposited upon a permeable support, such as a screen or perforated plate, and the suspending fluid removed to leave a mat or sheet-like deposit of the mixed fibers.
  • a preferred method for depositing the fibers is to feed the aqueous slurry to a screen such as used in a Fourdrinier papermaking machine, removing the water by suction to form a sheet-like deposit of the fibers, and removing the damp fibrous sheet for further processing.
  • a curing agent is 'added to it, which may be any of those previously described and may be liquid or gaseous; a preferred curing agent is hexamethylene tetramine.
  • the amount of curing agent may vary,'depending on the proportion of fusible fibers present in the fibrous mixture.
  • the fibrous mat is compressed and heated to cure and simultaneously bond the fusible fibers to the infusible fibers at their cross over points. Only moderate pressures in the range of about to psi are required at this step, with curing temperatures in the range of about 90 to 200 C, as previously described. The pressures described are comparable to those applied to the sheet on the drying rolls of a Fourdrinier paper machine.
  • the fibrous article, as bonded by the curing process described is infusible and has excellent dimensional stability, combined with good chemical and thermal resistance. Thermal resistance may be enhanced by further heating the article in air in a range of about 200 to 400 C, as previously described.
  • the bonded fibrous articles of the invention may be impermeable, depending on fiber composition and pressures applied during curing, the preferred type of article is one which is porous, the pores having average diameters in the range of about 1 to 50 microns.
  • the articles may be formed in any shape; however a mat or flat sheet-like articles is preferred, the article having a thickness ranging from about 1 to 250 mils.
  • a paper or sheet-like article can be made with a thickness ranging from about 1 to about mils. This paper can be made either impermeable or porous, as desired, the pores being in the range of l to 50 microns average diameter, as previously described.
  • paper may be passed through calender rolls to give it a hard surface finish and increased mechanical strength.
  • composition of the fibrous articles of the invention may be varied by changing the relative proportions of fusible and infusible fibers used in the fiber mixture.
  • Mixtures of fusible and infusible novolac fibers may be employed, as well as mixtures of fusible and infusible fibers made from a pyrogenous mixture (or pitch) combined with a novolac.
  • fiber mixtures may be made in which infusible fibers of a pyrogenous mixture combined with a novolac are mixed with fusible novolac fibers.
  • the relative proportions of fusible and infusible fibers in these three types of combinations, as well as the curing conditions are all in the ranges as previously described. Experimental details for the preparation of fibrous articles,"using the three combinations described above, are shown in the following examples.
  • a standard funnel (approximately 5 in. diameter) was cemented at the wide end with a fine 325 or 400 mesh screen. After the cement was dry, the small end of the funnel was connected to a vacuum pump, the funnel then put into the slurry and a layer of fibers collected on the screen mesh. Vacuum was applied for a period of 5 to 15 seconds to obtain a sheet or paper of appropriate thickness and density.
  • the thickness and density of the sheet is defined mainly by l fiber diameter; (2) concentration of fiber in the slurry; and (3) extent of time for which vacuum is applied.
  • the sheet thus obtained was placed between two glass plates and heated on a hot plate (while occasionally reversing the sheet and glass plates on the hot plate) to about to C in 1 hour.
  • the paper mat was then removed, put between two stainless steel plates, and heated from room temperature to about 370 C in 4 to hours.
  • a load of 0.05 to 0.2 psi was applied to keep the paper uniformly flat. The paper when removed and tested in a flame produced no detectable odor or smoke.
  • the paper or mat prepared in the above fashion had a thickness in the range of 5 to 15 mils.
  • papers with areal densities in the range of 0.035 to 0.060 gms/sq in. with thicknesses of 5 to 15 mils were obtained.
  • Areal density was obtained from the relation: Area density of Paper weight of paper/area of the paper The porosity of the papers was in the range of 80 to 85 percent.
  • the porosity was computedas: percent porosity (lactual weight of material/theoretical weight of material) X 100 EXAMPLE 2
  • Cured pitch-novolac fibers of to microns average diameter obtained from methods described earlier were mixed with uncured fusible pitch-novolac fibers, preferably produced from the same batch.
  • the fiber mixture was used to prepare a sheet or mat of paper as described in Example 1.
  • The'paper prepared from the above fiber had a thickness in the range of l to 25 mils and the areal densities were in the range of 0.040 to 0.090 gms/sq in. when areal density was computed as in Example 1.
  • the porosity values of the papers were in the range of 78 to 83 percent when the porosity was computed as in Example 1.
  • EXAMPLE 3 Cured pitch-novolac fibers of 10 to 15 microns diameter or 1 to 2 microns diameter, obtained from methods described earlier, were mixed with uncured fusible novolac fibers of similar diameter.
  • the fiber mixture was used to prepare a sheet or mat of paper as described in Example 1.
  • the paper prepared from the above fibers had a thickness in the range of 10 to 25 mils when the 10 to 15 micron diameter fibers were used or 5 to 15 mils with the 1 to 2 micron diameter fibers.
  • the areal densities of the paper when computed as in Example. I were in the range of 0.03 to 0.06 gms/sq in. with l to 2 micron diameter fibers, and 0.04 to 0.09 gms/sq in. with 10 to 15 micron diameter fibers, while the porosity was uniform and in the. range of 75 to 85 percent for papers obtained from either the large or small diameter fibers.
  • the paper thus prepared had a thickness in the range of 5 to 15 mils, and had a uniform porosity in the range of 80 to 85 percent with an areal density of 0.04 to 0.08 gms/sq in.
  • the fibrous articles of the invention may be used as filters for solutions of acids and alkalis, since the fibers are resistant to these reagents. When made in paperlike sheets, these articles may be employed as separators in acid or alkaline batteries or as diaphragms in fuel cells.
  • the fibers are electrically non-conductive and thus may be used in applications which require electrically insulative materials, the flexibility and mechanical strength of the fibrous sheet-like materials making them especially suited for this purpose.
  • the thermal resistance of the fibrous articles of the invention allow them to function as thermal insulators at temperatures up to 500 C.
  • the fiber mixture of the invention can be molded or otherwise formed in place around an object, the fiber mixture then being cured in place to give a bonded fibrous coating surrounding the object and protecting it against thermal and/or mechanical shock. If the fibrous covering was impervious, it could function as a safety envelope around a frangible container to prevent spillage of liquids held therein if the container was damaged or broken. It is apparent, therefore, that the fibrous articles of the invention fulfil the need for a flexible, po-
  • a process according to claim 1 wherein said fusible fiber comprises said mixture of pyrogenous residue and novolac.
  • a process according to claim 1 wherein said mixture comprises about 20 percent fusible novolac fibers and about percent infusible fibers of said mixture of pyrogenous residue and novolac.
  • the fiber mixture comprises about 20 percent fusible fibers and 80 percent infusible fibers, the mixture is suspended in water and deposited in a flat sheet upon a screen with the removal of water, followed by the addition of hexamethylenetetramine as a curing agent, the fibers being simultaneously compressed and heated at a temperature of from about 150 to 180 C, the pressure released and a second heating period continued at a temperature of from 200 to 370 C to form a bonded fibrous sheet.
  • a process for making an infusible fibrous sheet comprising the steps of:
  • a Preparing a mixture of from 10 to 40 percent of fusible fibers and from 60 to 90 percent of infusible fibers, said fusible and infusible fibers selected from novolacs and pyrogenous residues combined with from 5 to 40 wt percent of a novolac, said novolac in each instance having two or more available sites for polymerization, said fibers being from about 0.1 micron to about 300 microns in diameter;
  • a process according to claim 10 wherein said mixture comprises about 20 percent fusible novolac fibers and about percent infusible fibers of said mixture of pyrogenous residue and novolac.
  • a bonded fibrous article comprising infusible fibers selected from the group consisting of novolac fibers, fibers of a pyrogenous residue combined from 5-40 wt percent of a novolac, and mixtures thereof, said article prepared by suspending, in a fluid a mixture comprising from 10 to 40 percent fusible fibers and from 60 to percent infusible fibers, said fusible and infusible fibers each selected from the group consisting of novolac fibers and fibers of a pyrogenous residue combined with a novolac; depositing said mixture upon a substrate and removing said fluid; contacting said fibers with a catalyst and a curing agent selected from the group consisting of aldehydes and amines; and heating said fibers to a temperature of from 90 to 200 C under a pressure of less than 5 psi to cure said fusible fibers to an infusible state and to thereby bind said infusible fibers;

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonwoven Fabrics (AREA)
  • Inorganic Fibers (AREA)
US00313007A 1972-12-07 1972-12-07 Paper from pitch based organic fibers Expired - Lifetime US3821074A (en)

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US00313007A US3821074A (en) 1972-12-07 1972-12-07 Paper from pitch based organic fibers
JP13545173A JPS5650030B2 (da) 1972-12-07 1973-12-05

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US00313007A Expired - Lifetime US3821074A (en) 1972-12-07 1972-12-07 Paper from pitch based organic fibers

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US (1) US3821074A (da)
JP (1) JPS5650030B2 (da)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953236A (en) * 1973-09-05 1976-04-27 Kanebo Kabushiki Kaisha Lead storage battery
EP0014026A1 (en) * 1979-01-19 1980-08-06 Imperial Chemical Industries Plc Paper containing partially cured amino/aldehyde fibres and process for making it
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
US9403936B2 (en) * 2014-09-30 2016-08-02 Gs Caltex Corporation Method for preparing a pitch for carbon fibers and a pitch for carbon fibers prepared by the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5894721A (ja) * 1981-11-30 1983-06-06 松下電工株式会社 スイツチ器具

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953236A (en) * 1973-09-05 1976-04-27 Kanebo Kabushiki Kaisha Lead storage battery
EP0014026A1 (en) * 1979-01-19 1980-08-06 Imperial Chemical Industries Plc Paper containing partially cured amino/aldehyde fibres and process for making it
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
US9403936B2 (en) * 2014-09-30 2016-08-02 Gs Caltex Corporation Method for preparing a pitch for carbon fibers and a pitch for carbon fibers prepared by the same

Also Published As

Publication number Publication date
JPS4986675A (da) 1974-08-20
JPS5650030B2 (da) 1981-11-26

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