[1]3 1 5 2 3 , 1 5 1 Umeted States Patent Office Patented Aug. 4, 1970 3,523,151 ULT'RA-STABLE POLYMERS OF BBB TYPE, ARTI. CLES SUCH AS FIBERS MADE THEREFROM, AND HIGH TEMPERATURE PROCESS: FOR FORMING SUCH POLYMERS AND ARTICLES 5 Jay M. Steinberg, Plainfield, N.J., assignor to Celanese Corporation, New York, N.Y., a corporation of Delaware Filed Nov. 7, 1967, Ser. No. 681,136 Int. Cl. B29c 25100 U.S. Cl. 264-210 7 Claims 10 ABSTRACT OF THE DISCLOSURE Plastic articles of particularly high thermal stability, 1,5 such as fibers or other extruded shapes, are made from "BBB" type polymers, i.e., polymers of the polyaroylenebenzimidazole type, or more particularly of the polybisbenzimidazobenzophenanthroline type, by heat treatment of sufficiently oriented polymer at an ultra-high teinpera- 20 ture between about 750' and 1500' t. following preheating at an intermediate temperature in the 500' to 700' C. range. As a result of such a high-temperature treatment a new kind of polymer structure is obtained arbonyl 25 which is attributed to the splitting out of the c groups from the BBB polymer molecule. BA CKGROUND OF THE INVENTION In recent years flie use of various shaped, rigid com- 30 po nents, woven fabrics and other articles made from plastic materials capable of resisting high temperatures has attr acted considerable attention in connection with space ve hicle structures or in auxiliary equipment such as reent ry parachutes for such vehicles. Condensation polymers 35 of the benzimidazobenzophenanthroline type, made as descr ibed for instance in an earlier copending patent applicati on Celanese Docket No. 4449, U.S. Ser. No. 657,868, @f iled Aug. 2, 1967, have been among the more attractive 40 mat erials heretofore proposed in this connection. Howev er, while oriented fibers wet spun from this type of polyme r have shown superior tensile properties and strength ret ention ability at temperatures up to about 800' C., and ev en these have tended to degrade at more elevated te mperatures. 45 Th objects of the present invention include the productio n of still more thermally stable polymer compositions, an d particularly the production of fibers, films and the like the refrom. 50 SU MMARY OF INVENTION It has now been discovered that polymers possessing a new kind of molecular structure and particularly good the rmal stability even at temperatures above 800' C. can be prepared by subjecting the previously known kind of 55 BB B type oriented polymers to a special kind of heat tre atment. More particularly, it has been discovered that a new and upgraded product can be obtained by preheating BBB type oriented polymers to a temperature between ab 6ut 500' and 700' C., e.g., 0.2 second at 600' C. and 60 in such preheated condition further treating them for a sm all fraction of a second at between about 750' and 150 0' C., preferably between about 1000' and 1300' C., e.g ., by passing them through a propane flame having a fla me temperature of about 1200' C. at a rate resulting in 65 2 an appropriately limited flame residence time of between about I and 30 or 50 milliseconds. For reasons wbich those skilled in the synthetic fiber art will readily understand, the optimum flame residence time depends somewhat on factors such as the specific temperature and heating environment employed, the thickness and initial strength of the fiber, film or other plastic body being treated, etc. As a result of such heat treatment the molecular structure of the polymer changes from the usual structure represented by Formula I (1) 0 <a>-J@ N to a decarbonylated structure presumably represented by Formula II [N 0 >@N BRIEF DESCRIPTION OF DRAWING The attached drawing is a schematic illustration of an apparatus suitable for preheating a previously hot drawn or oriented BBB type fiber and further heat treating such preheated fiber. DETAILED DESCRIPT'ION The starting polymer The present invention is generally applicable to poly (aroylenebenzimidazoles) or, more particularly, to poly (bisbenzimidazobenzophenanthroline), herein referred to as BBB polymers. As is now otherwise known in the art, these polymers are made by mixing and condensing (1) at least one organic tetraamine having the structural formula NI12 NHZ-RI -N]12 H2 wherein R is a monocyclic or bicyclic aromatic or cycloaliphatic tetravalent hydrocarbon radical and wherein each of the four amino groups is attached directly to a carbon atom of a ring of said aromatic or cycloaliphatic radical in a position which is ortho or peri (in the case of a bicyclic radical) to another carbon atom to which a second amino group is also directly attached; with (2) at least one tetracarboxylic acid (which also may be in the form of the coffesponding dianhydride) having the structural formula 1100C COOH \P@/ / . \ IE[OOC COOH wherein R' is a tetravalent radical containing at least 2 carbon atoms and wherein no more than 2 carboxy or carbonyl groups of said acid or anhydride are attached to any one carbon atom of said tetravalent radical.
[2]'@-3,523,151 3 The reaction involved in the formation of these polymers may be effected in an organic liquid which is a Solvent for at least one of the reactants, and is inert to the reactants, preferably under anhydrous conditions, at a temperature below 125' C., preferably at below 100' C., 5 and for a time sufficient to provide the desired condensation product without gelation. Subsequent high - temperature heating is required to completely cyclize the - polymer. The tetra-amine and tetracarboxy acid or corresponding dianhydride are preferably reacted in substantially equi- 10 molar quantities. Altematively, the polymeri2ation may be,effected in an inorganic solvent such as p olyphosphoric acid by heating at temperatures of 100' to 250' C. for @L @ufficient time to produce the desired molecblar weight. ff an excessive reaction temperature is used, a product 15 which is difficult or impossible to shape is obtained. But the permissible upper temperature limit will vary d4eiiding upon the monomer and solvent system used, the mutual proportions of the monomers, and the concentration in the polymerization mixture and the minimum time that 20 one desires for the reaction. The particular polymerization temperatures that should not be exceeded if a particular system is desired to provide a reaction product composed of a shapable polymer *ill accordingly vary from system to system but can be determined for any given @25 n system by a simple test by any person ordinary skill in the art. It is preferred that the molecular weight of the polymer used herein be such that its inherent viscosity be at least 0.3, preferably 0.5 to 5.0. The inherent viscosi,ty is meas- 30 ured at 25 C. at a concentratioii of 0.4 g. of polymer per 100 ml. of solvent. Ninety-seven percent sulphuric acid (by weight) is a convenient and preferred solvent for the purpose of this invention though other solvents may be used similarly. The viscosity of the polymer solution is 35 measured relative to that of the solvent alone and the inherent viscosity (I.V.) is determined frorn the following equation: V?, 1- n- VI 40 I.V. = C In the above formula, V2 is the viscosity -ofthe solution; V, is the viscosity of the solvent, and C is the concentration expressed in grams of polymer per 100 ml. of solution. As is known in the polymer art, inherent viscosity 45 is monotonically related to the molecular weight of the polymer. Non-limiting examples of the tetra-amine monomers which may be used individually or in mutual, admixture in 50 forming the desired pplymers aie: 3,3'-diam inobenzidine; bis(3,4 - diamino phenyl) methane; 1,2-bi s(3,4-diamino phenyt) ethane; 2,2 - bis(3,4-diamino phenyl) - propane; bis(3,4 - diamino phenyl) ether; bis(3,4 - d iaminophenyl) sulfide; bis(3,4 - diamino phenyl) sulfone; 1 ,21415-tetraamino benzene; 2,3,6,7-tetraamino naphthalene; etc., and 55 the corresponding ring-hydrogenated tetra-amines. . . Non-limitin.- examples of the tetracarboxylic acids include: pyromellitic acid; 60 2,3,6,7-naphthalene tetracarboxylic acid; 3,3',4,4'-diphenyl tetracarboxylic acid; 1,4,5,8-naphthalene tetracarboxylic acid; 2,2',3,3'-diphenyl tetracarboxylic acid; 2,2-big(3,4-dicarboxyphenyl) propane acid; 65 bis(3,4-dicarboxyphenyl) sulfone acid; 3,4,9,10-peryiene tetracarboxylic acid; bis(3,4-dicarboxyphenyl) ether acid; ethylene tetracarboxylic acid; naphthalene-1,2,4,5-tetracarboxylic acid; 70 decahydronaphthalene-1,4,5,8-tetracarboxylic acid; 4,8-dimethyl-1,2,3,5,6-hexahydronaphthalene-1,215,,6z tetracarboxylic acid; 2,6-dichloronaphthalene-1,4,518-tetracarboxylic acid,,, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid; 75 2,3,6,7-tetrachloronaphthalene- 1,4,5,8-tetracarboxylic acid; phenanthrene-1,8,9,10-tetracarboxylic acid; cyclopentane-1,2,3,4-tetracarboxylic acid; pyrrolidine-2,3,4,5-tetracarboxylic acid; pyrazine-2,3,5,6-tetracarboxylic acid; 2,2-bis(2,3-dicarboxypbenyl) propane acid; 1,1-bis(2,3-dicarboxyphenyl) ethane acid; 1,1-bis(3,4-dicarboxyphenyl) ethane acid; bis(2,3-dicarboxyphenyl) methane acid; bis(3,4-dicarboxyphenyl). methane acid; bi,s(3,4-dicarboxypheiayl) sulfone acid; benzeno--1,2,3,4-tetracaiboxylic acid. @l,@,3,4-b@tane, tetiacarboxylic acid;, thiophene-2,3,4,5-tetracarboxylic acid; and similar acids, as well as the dianhydrides of such acids. In a preferred embodiment, the pre@ent inv@ention is directed to fibers formed from poly(bisbenzimidazobenzophenanthroline), i.e., BBB polymers.@ Such polymers are formed from 1,4,5,8 - naphthalene tetracarboxylic acid and 3,3'-diamino benzidine according to Equation A: HOOC-<@::>-COOH ]El NH2 A N-I^ + 6nll2O L A preferable method of preparing BBB polymers includes effecting the polymerization in polyphosphoric acid (PPA) where the reaction according to Equation A occurs producing fully cyclized polymer. Use of polyphosphoric acid as the solvent permits reactions to be carried out over a wide range of temperatures, e.g., 80' to 300' C. The polyphosphoric acid preferably employed has a P205 equivalent of about 82% to 84% which is a solution of approximately 5% to 20% ortho- and pyrophosphoric acids mixed with various polyphosphoric acid, mostly trimers, titramers, pentamers and hexamers. Both the reaction temperature and the reaction period used significantly affects the degree of polymerization. GeneT411y, reaction periods can range from about 0.5 to 100 hours at the abovementioned reaction temperdtures. Higher reaction temperatures tend to result in. polymer products having higher inherent viscosity than polymers produced at lower temperatures and at comparable reaction periods ' If the polymerization reaction is carried only to an intermediate stage, a solution containing the intermediate amine substituted polyamide acids in the form of a tr-actable polymer can be cast into a film or dry spun through a spinneret or otherwise converted into the desired polymer shapes. On the other hand, if the polymerization is carried more nearly to completion by extensive heating, a dark red insoluble solid is formed which precipitates from the solution and can be separated by filtration. Such a polyiner can be characterized as being tough, that is, extremely difficult to grind. A typical pulverized sample is completely amorphous by X-ray defraction,aiad has no softening point up to 450' C., the limiting;temperature of the apparatus used. Solutions,of these polymers in concentrated sulphuric acid, polyphosphoric acid, benzene sulphonic acid, or methane sulphonic acid are intensively red. Aqueous KOH. solutions are. brown. BBB polymers cyclized by heat- appeat to-,be essentially insoluble in @dimethylformamide, dimethylacetamide, dimethylsulphoxide, cresol, tetramethylene4 sulphone, hexamethyl phosphoramide and other common organic Solvents. Low viscosity polymers exhibit some tendencies to dissolve in perfluoroacetic acid ana fbrmic acid. -COOH H2 H2 -> + HO O c@<
[3]5 PREPARATION OF FIBER As has been previously described in the art, the polymers of the type just described can be formed into filaments by wet-spinnin.- methods, i.e., extruding a solution of the polymer in an appropriate solvent, such as sulphuric acid, through an opening of predetermined shape into a coagulation bath, e.,-., sulphuric acid/water coagulation bath, which results in a filamentary material of the desired cross-section. Polymer solution@ may be prepared, for example, by dissolving sufficient polymer in the solvent t<) yield a final solution suitable for extrusion which contains about 2% to 15% by wei.-ht, preferably about 3% to 10% by weight, of polymer based on the total weight of the solution it is found that the polymer dissolves most readily on warming to a temperature of 'between about 50' to 70' C. to produce a viscous, deep purple solution. If sulphuric acid is employed, from 85 to 107 equivalent weight percent sulphuric acid, preferably 92 to 102 equivalent weight percent sulphuric acid, is employed as the solvent. The polymeric spinning solution is then extruded into a coagulation bath, i.e., wet spun, to form filaments. These are then washed to remove free acid and dried, and hot drawn and passed through a hot flame or an equivalent high temperature zone in accordance with the present invention. Hot drawing or some other form of adequate orientation of the polymer molecules in the fiber, film or other article to be improved in accordance with the present invention generally should precede the novel heat treating step, and the degree of orientation obtained should b-. sufficient to overcome the inherent weakness of this kind of polymer and enable it to resist the mechanical stress to which it is subsequently exposed. Such preliminary orientation and strengthening of the fiber or film is particularly important when the heat treatment is effected in a hi.-h speed, dynamic process as described in subsequent parts of this specification. ParticulaTly desirable process@-s and conditions for hot drawing this kind of fiber or film are illustrated and described in my companion application Ser. No. 681,137, filed concurrently herewith, the disclosure of which is incorporated herein in toto by reference. As su.-gested above, a suitable heat treating zone maY be established simply by combustion of a liquid or gaseous hydrocarbon in an oxygen-containing gas, e.g.' by combustion of propane in air. However, in commercial practice other types of heat treating zones, e.g., an externally heated muffle furnace maintained at the desired temperature, may be preferred. A muffle furnace containing an inert atmosphere such as argon may be particularly preferred for effecting the desired kind of heat treatment with a minimum of deleterious side effects. As has been described in copendin.- application S,-r. No. 657,868, filed jointly by the present applicant and Arnold J. Rosenthal, while filaments of satisfactory properties can be made from BBB type polymers under a variety of spinning conditions, filaments possessing superior properties which make them particularly suitable for use in the present invention can be obtained by maintaining the coagulation bath within certain parameters. For instance, when spinning a BBB polymer solution having an inherent vi@scosity between about 1.0 and 4.0, preferably between 2 and 3, and using an aqueous sulphuric acid coagulation bath, it is desirable to maintain such a bath at a temperature between about 45' and 80' C., preferably between about 55' and 70' C., and to maintain the sulphuric acid concentration in the bath between about 50% and 80% by weight, optimally between 70% and 75%. When operatin.- within these parameters, a precursor (as-spun) fiber is obtained which is suitable for producing after-drawn fibers of superior tensile properties and strength retention at the extreme elevated temperatures for which the present invention is intended. 3)5231151 6 After such wet spinning, the resulting precursor (asspun) fibers are washed thoroughly in order to remove excess acid and to minimize contamination. Then, they are dried pior to being drawn in order to improve their physical characteristics, e.g., tenacity, elongation, thermal resistance, etc. After drawing of the spun filaments is desirably performed at temperatures between about 500' and 700' C. at a draw ratio of from about 1.1: 1 to about 3: 1. BBB fibers drawn in this manner have strength in 10 excess of 3 grams per denier and thermal resistance at temperatures as high as 700' or 800' C. To illustrate the practice of the pregent invention more concretely, a typical embodiment thereof will next be described with reference to the attached drawing. It should 15 be understood that while the following description is made in connection with the treatment of a fiber, the invention can be- similatly applied to film by making orily minor and obvious modifiactions in the equipment used. Referring to the attached drawing, afterdrawn BBB 20 polymer fiber 1 is unwound at a rate between about 20 and 100 m./min., at about 30 m./min., from a perforated feed bobbin 2 by means of a conventional Alsimag guide, passed through a hot air (muffle) furnace 4 at between a:bout 500' and 700' C., e.g. 600' C., the length of the 25 flirnace and the rate of fiber travel being coordinated such that the fiber has a residence time of between about 0.1 and 2 seconds at the desired preheated temperature. From the furnace the fiber is then immediately passed througl@l an ultra-high tem@perature zone maintained at a 30 temperature between about 750' and 1500' C., preferably between about 1000' and 1300' C., e.g., through a propane flame of appropriate, width having a temperature of about 1200' C. The residence time of the fiber in such a flame is desirably maintained at not more than 35 0.03 second to minimize fiber dissipation, preferably at between about 0.005 and 0.02 second. The optimum residence time of course depends somewhat on the fiber diameter, the specific polymer from which it was made, as well as the specific temperature and other characteris40 tics of the high temperature zone and is best determined empirically by a few preliminary runs. By proper treatment in this manner, the high temperature stability of the fiber can be increased by 10% or more, comparing the high temperature tenacity of the 45 fiber treated in accordance with this invention with the high temperature tenacity of the same fiber after the customary hot drawing but before treatment in accordance with the present invention, the tenacities being determined at a test temperature of 600' C. on fiber samples pre50 conditioned at this temperature for 1 minute. After passage through the high temperature zone such as propane flame 5 the fiber is then guided with the aid of another guide 6 onto a draw bobbin 7 at a rate which preferably is substantially the same as the rate of the fiber on the 55 feed bobbin, that is at a draw ratio of between about 1: I and 1.5: 1, preferably not greater than 1.2: 1. The invention will now be further described in terms of some s ecific, illustrative examples. Absent other indicap tions, it should be understood that all quantities and pro60 portions of materials are expressed on a weight basis throughout this entire specification. EXAMPLE I In this example an afterdrawn BBB fiber was preheated 65 in a hot air furnace at an intermediate temperature and then passed immediately through a propane flame at about 1200' C. This fiber was composed of BBB polymer, i.e., the reaction product of 1,4,5,8-naphthalene tetracarboxylic acid and 3,3'-diaminobenzidine made in an otherwise 70 known manner as described earlier herein. The polymer had an inherent viscosity of 3.2 dl./g. in 97% H2SO4. The fiber was made from this polymer by dissolving it in 4To concentration in 97% sulphuric acid and extruding this solution from a bomb under pressure of 70 p.s.i. nitrogen 75 through a 5-fil, 100-micron spinneret into an aqueous
[4]3,523,151 7 sulphuric acid coagulation bath. The dope or srinning solution had a viscosity of 4000 poises at 30' C. Coagulation bath was aqueous sulphuric acid clontaining 68% H2SO1. It was maintained at 60' C. and had an effective length of 100 cm. The spun fiber was taken up from the bath at a rate of 4.0 m. /min. The resulting spun fiber was washed 30 minutes in 0.1% ammonia solution in deionized water at 50' C., dried in air at about 25' C., and then drawn irk a hot-air muffle furnace having an effective length of 15 cm. The fumace was maintained at a temperature of about 600' C. and the fiber was drawn therethrough at a draw ratio of 1.52. This afterdrawn fiber was then unwound at a rate of 20 m./min. from a perforated bobbin and, by means of a conventional Alsimag guide, passed through a I./ft., hotair muffle furnace maintaiiaed at 600' C. (effective length, 15 cm.) and from the muffle furnace immediately throu-h the full width of a propane flame which was I cm. wide aiad had a temperature of about 1200' C. The flame treated fiber was then guided onto a bobbin also at 20 m./min., i.e., without any additional draw. Accordingly, the fiber had a residence time of about 0.5 second in the muffle furnace and a residence time of about 0.03 second in the flame. At these conditions, the fiber glowed in and was blackened by the propane flame, but retained its fiber character and did not dissipate. By contrast when the same fiber was passed from the feed bobbin directly into the propane flame without any preheating at an intermediatetemperature, the fiber dissipated in the flame. The BBB fiber flame treated in accordance with this invention had outstanding high temperature resistance as indicated by the fact that when held in the flame of'a propane torch it glowed but retained its fibrous form. By contrast, polybenzimidazole fiber, i.e.,..fiber made from a polymer such as that described in U.S. Pat. 3,174,947 to Marvel and which heretofore has been considered a particularly good fiber forming polymer for high temperature use, shrivelled and formed a friable bead when held in the propane flame. When the successful flame treatment described above was repeated under the same conditions as described except that the fiber was passed through the furnace and the flame at lower rates, i.e., at 6 m./min. and 10 ' 5 m./min., the fiber dissipated in each instance in the flame as at these reduced rates the residence time of the fiber in the high temperature flame was excessive. The drawn and flamed fiber was insoluble in sulfuric acid. The drawn and flamed fiber retained at least 60% of its strength at 600' C. and is not destroyed at temperatures up to about 900' C. or higher. Flame residence times of less than 0.02 second, preferably between 0.05 and 0.015 second are preferred to keep loss in fiber yield low. EXAMPLE 2 A series of evaluations was made with fibers made from BBB polymers each having a different inherent viscosity or molecular weight. Each of the fibers was treated essentially as described in Example 1, except for the specific treating conditions noted in the footnotes under Table 1, which table contains a summary of the significant data. The physical properties of the fibers were determined both on the afterdrawn fibers before flame treatment and on flame treated fibers, i.e., on the fibers treated in accordance with the present invention and the change inproperties noted. The data in Table I show that overall flame treatment is advantageous in enhancing fiber properties and that the degree of enhancement increases with the inherent viscosity of the polymer. EXAMPLE3 While Example 2 shows the advantage of the flamed fibers in terins of thcir performance characteristics at 8 room temperature, the data summarized in Table IT show the advantage of the flame treated fibers in terms of their properties at elevated temperatures. As indicated in the table, the fiber in Run No. II-1 was drawn at 600' C. but not further treated whereas the fiber in Run No. II-2. TABLE I.-FLAME-TREATING OF DRAWN BBB FIBERS Average Average Polymer Drawn After-Flame Percent I.V., dl.)g. Pammeter Properties 1 PropertieS 2 Change 10 1.4 ---------- D.p.f ------------- 55 5.0 -9 Ten. (g./d.) ------- 3' 0 3.1 +3 EIong. (percent) - - 10.0 11.0 +10 TEI/2 - ----------- 9.5 10.3 +9 Mi (g./d.) --------- 93 96 +3 2.6 ---------- D.p.L ------------- 5.0 4.5 -10 15 Ten. (g./d.) ------- 4.3 4@ 6 +7 Elong. (percent) - - 6.3 7.0 +11 TE 1/2 ------------- 10.8 12.0 +11 Mi (g./d-) --------- 124 143 +15 3.2-- D.p.f ------------- 4.8 4.2 -12 ------- Ten. (g./d.) ------- 3.8 C 2 +10 20 Elong. (percent) - - 6.0 9.5 +58 TE'/' ------------- 9.3 15 +40 Mi (g./d.) --------- 130 151 +16 I Drawn at 600' C., 2.0 diaw ratio, 4 see. in fuimance. 2 Dra,@Nn as above, then preheated 0.2 see. in furnance at 60T C. and flamed 0.015 see. in 1,2001 C. flarne. 25 TABLE II. BBB FIBER PROPERTIES AT ELEVATED TEMPERATURES Run Number II-2 30 P<)Iymer I.V -------Draw ratio --------Flame treated ------ 3.2 dl./g. 2.Ox ,it 600P C. 2.57 dl./g. 2.Ox at 6001 C. D.p.f --------------- No. 4.3 0.002 see. at 1,2001 C@ 3 4.5 - El., T@,n., m i, El,, Ten., Ali, Test Temp., I C. I percent g.,d. 9./d. percent g./d. g./d. 35 25 ------------------ 5 4.6 l,4 6 4.4 135 100 ----------------- 4 4.1 133 6 4.2 146 200 ----------------- 4 4.0 146 4 3.7 138 300@ ---------------- 5 3.5 137 4 3.7 132 400 ----------------- 5 3.2 127 5 3.4 129 .500 2.8 115 5 3.4 125 600 2 ---------------- 6 2.3 106 C) 2.6 99 40 samples conditioned one minute at test temperature. @, Limit of testing oven. 3 After preheating 0.2 see. at 600' C. was flame treated in accordance with the present invention after having been hotdrawn. Though the flber H-1 was 45 made from a polymer having a higher inherent viscosity and had a higher tenacity at room temperature than fiber 11-2 it is evident from the data that the flame treated fiber retains its tensile properties at elevated temperatures to a substantially higher degree than the fiber which was 50 only hot-drawn. For instance, while the &awn fiber II-1 had a significantly higher tenacity and initial modulus at room temperature, the two fibers had very nearly the same properties in the temperature range between about 200' and 400' C., and at the still higher temperatures 55 the flame treat(@d fiber was markedly superior to the dra@wnonly fiber not oray in terms of percent retention of tenacity and initial modulus but also in terms of aebsolute tenacity. in another series of tests a measure of thermal stability 60 was obtained by observing the loss of strength which the ifibers undergo af ter storage at elevated temperature. In this test, samples were suspended in a circulating hot air oven at 360, C. and removed after a specified time for testing. Hot-drawn BBB fiber, hot-drawn and flame treated 65 BBB fiber aiad PBI (polybenzimidazole) fiber were tested in this man-ner. The data obtained (not reproduced here) have shown that the two BBB fibers retained a@bout the same percent of their initial strength after 30 hours as the PBI futer after I hour. After 2 hours the BBB fibers 70 surpassed PBI in both tenacity and elongation whereas little effect on modulus with time is noted for either fiber. After 18 hours exposure the PBI same disappeared from the oven as a result of either breaking away from 7.5 its mounting or degrading whereas the BBB fibers still
[5]325232151 9 retained a high degree of utility after 30 hours as indicated above. In each instance the flame treated BBB fiber showed a noticeable advantage over the drawn-only BBB fiber. An additional indication of the high temperature behavior of BBB drawn and flame treated fiber is obtained by determiiaing its temDerature/weight retention properties. In such a test samples of the fiber are heated in an oven, in air or nitro-en, and the weight of the fiber samples is determined after they have been heated to specified temperatures. The fibers are heated in the oven at a rate of 15' C./min. The data are siimmarized in Table HI below. As this table shows the BBB fibers have a temperature/ wei.-ht retention advanta.ae over a prior art fiber such as Nomex fiber, described in "New Linear Polymers" (Lee, Stoffey and Neville), p. I 1, and U.S. Pat. No. 3,414,645 to Mor.@an, of about 150' C. in air and about 350' C. in nitro,-en. Furthermore, particularly in the temperature range above 700' C. there is a si,-nificant temperature/ wei.-ht retention advantage for the BBB fiber which was TA'BLE III. WEIGHT RETENTION (PERCENT OF R00ill TEMPERATURE WEIGHT) B B B i; r t BBB Dr5Nvn at 600' C. and NO',@IEX 600P C. Flained at 1,2001 C. Temp.,' C. In air In N2 In Air In N2 In Air In N2 25 ---------- 100 100 100 100 100 100 ,)Oo ---------- 98 95 99 ---------------------------- ioo --------- 95 90 98 ---------- 98 6 500 --------- 74 75 97 ------------------------------ 600 --------- 10 65 97 98 96 97 700 --------- 2 55 40 93 60 95 800 ------------------- 45 15 78 30 85 900 ------------------- 33 ---------- 70 2S 73 11 000 ----------------- 30 ---------- 60 ---------- 65 1,100 -------------------------------------- 50 ---------- 60 - drawn and flame treated over merely drawn BBB fiber. In air, the flame treated BBB fiber retains a given percenta,,e of its room temperature weight at a temperattire about 20' C. hi-her than the BBB fiber which was merely &awn; and in nitrogen the flame treated BBB fiber retains about the same percentage of its original weight at a temperature which is about 40' to 100' C. Mgher than the merely drawn BBB fiber and the advantage in favor of the flame treated fiber appears to increase with teniperature. Having described the invention, it is particularly pointed out in the appended claims. 1. A process for improvin.@ the thermal stability of oriented bisbenzimidazobenzophenanthroline polymer fiber Nvhich comprises passing said fiber throti,@h a preheating zone maintained at a preheat temperature @between about 500' and 700' C. at a rate such that the fiber has a residence time of between about 0.05 and about 0'5 second at said preheat temperature, and then immediately passing said fiber from said preheating zone to and through a flame treatin@ zone maintained at a temperature between about 1000' and 1300' C., said fiber being passed through t@e said flame treating zone at a rate such that the fiber 10 residence time therein is less than 0.03 second but sufficient to improve the thermal sta:bility of the fiber. 2. A process according to claim I wherein the fiber being fed to the process is a wet spun and after-drawn fiber. 3. A process wlierein poly(bisbenzimidazobenzophenanthroline) having an inherent viscosity of between about 0.5 and 5.0 in 97% sulphuric acid is formed into fiber by extruding thin streams of a solution of said nolymer in concentrated stilphuric acid into a coagulation bath, 10 the resu'@ting fiber is washed and dried and then drawn at a draw ratio of between about 1.1:1 and 3:1 and at a draw temperattire between about 500' and 700' C. to increase its tenacity to at least 3 grams per denier and the 15 drawn fiber is recovered for further use, the improvement which comprises continuously preheatin- said drawn fiber to a temperature between about 500. and 700' C. and continuously passing said preheated fiber immediately through a hi,-h temperature zone maintained at between 20 about 1000' and 1500' C. at a rate such that the residence time of the preheated fiber in said high temperature zone is not more than about 30 milliseconds but sufficient to increase its temperature tenacity by at least 10% as compared with its high temperattire tenacity prior to the 25 aforesaid preheating and high temperature heating steps, said tenacity being measured at a test temperature of 600' C. on fiber samples preconditioned at said test temperature for I miniite. 4. A process according to claim 3 wherein said high 30 temperature zone is formed by the combustion of a hyclrocarbon gas. S. A process according to claim 3 wherein said high temperature zone comprises a propane flame. 6. A process according to claim 3 wherein said high 35 temperature zone is an externally heated zone containing an inert gaseous atmosphere. 7. A process according to claim 3 wherein said higta temperature zone is an externauy heated zone contain40 ing an argon atmosphere. References Cited UNITED STATES PATENTS 3,414,543 12/1968 Pauffer. 45 3 414,645 12/1968 Morgan. 3:415,782 12/1968 Irwin et al. 3,441,640 4/1969 Santangelo --------- 264-203 OTHER REFERENCES 50 Lee, Stoffey and Neville: "New Linear Polymers," 1967, McGraw Hill, N.Y., p. II. DONALD, J. ARNOLD, Primary Examiner 55 H. MINTZ, Assistant Examiner U.S. Cl. X.R. 260-47, 78, 78.4; 264-290, 345, 334, 80
