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Optically anisotropic aromatic polyamide dopes |
| RE30352 |
Optically anisotropic aromatic polyamide dopes
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| Patent Drawings: | |
| Inventor: |
Kwolek |
| Date Issued: |
July 29, 1980 |
| Application: |
05/951,051 |
| Filed: |
October 12, 1978 |
| Inventors: |
Kwolek; Stephanie L. (Wilmington, DE)
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| Assignee: |
E. I. Du Pont de Nemours and Company (Wilmington, DE) |
| Primary Examiner: |
Lieberman; Allan |
| Assistant Examiner: |
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| Attorney Or Agent: |
Fitzpatrick, Cella, Harper & Scinto |
| U.S. Class: |
524/104; 524/210; 524/211; 524/220; 524/225; 524/233; 524/419; 524/422; 524/438; 524/606; 524/98; 524/99 |
| Field Of Search: |
260/30.2; 260/31.2N; 260/3.8R; 260/3.6R; 260/32.6NA; 260/29.2N; 260/29.1R |
| International Class: |
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| U.S Patent Documents: |
3006899; 3063966; 3079219; 3094511; 3109836; 3121766; 3150435; 3154610; 3154613; 3203933; 3225011; 3227793; 3232910; 3240758; 3240760; 3269970; 3322824; 3349062; 3354125; 3414645; 3472819; 3673143; 3817941 |
| Foreign Patent Documents: |
871580; 871581; 901159; 1036471 |
| Other References: |
Cologne et al., Essais sur la polyamidification de quelques p-aminophenylalcanoiques, Memoires Presentes A La Societe Chimique de France,Bulletin T22, Jan.-Jun. 1955, pp. 412-419..
Hasegawa, Studies on the Condensation Polymers of Aromatic Acetoxy Carboxylic Acids, 27 Bull. Chem. Soc'y. of Japan, 327-330..
Preston et al., Thermally Stable Fiber and Film from Polyterephthalamide of 4,4'-Diaminobenzanilide, International Symposium on Macromolecular Chemistry (IUPAC), Brussels, Louvain, Jun. 12-16, 1967, Reported in J. Poly. Sci., C, 22, pp. 885-865,(1969)..
Memorandum by Dr. E. E. Magat to Dr. J. M. Griffing, Jul. 21, 1967..
Preston et al., J. Pol. Sci., B, 4, pp. 1033-1038, (1966)..
Preston et al., J. Pol. Sci., A1, 4, pp. 529-539, (1966)..
Textile World, Oct. 1968, p. 239..
Holsten et al., Fibers of Ordered Aromatic Copolymers Containing the Diphenyl Ether Group, Poly. Preprints, vol. 9, No. 2, pp. 1082-1089..
Orii et al., Crystal Structure of m-Methylbenzamide, Bull. Chem. Soc'y Japan vol. 36, No. 7, pp. 788, 792..
Beintema, The Crystal Structure of 1,5-Dimethyl-naphthalene, 18 Acta Cryst. pp. 647, 653, (1965)..
Mark, J. Poly. Sci., C, No. 9, pp. 1-33, (1965)..
Brown, Liquid Crystals, Indus. Research 21, pp. 53-57, (May 1966)..
Rowland Hill, "Fasern aus synthetischen Polymeren", (Berliner Union Stuttgart), 1956, p. 391..
Flory, Proc. Royal Soc., A234, p. 73-88, (1956)..
Vysokomol. Soyed 8, No. 9, 1529-1534, (1966), (English publication, pp. 1684-1690)..
Hermans, J. Colloid Sci., 17 pp. 638-648, (1962)..
Liebegs Ann. Chem. 708, (1967), pp. 57-68..
The Condensed Chemical Dictionary, 8th Ed., Van Nostrand Reinhold Company, (1971), p. 837..
Rompps Chemie-Lexikon, 7th Ed., vol. 5, p. 3136 (left col.)..
R. W. Moncrieff, Man-Made-Fibers, 1963, p. 47.. |
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| Abstract: |
Compositions or dopes comprising carbocyclic aromatic polyamides in suitable liquid media are prepared which are optically anisotropic (exhibit different light transmission properties in different directions in the dope). These dopes, and related isotropic dopes, are used in preparing fibers of unique internal structure (evidenced by low orientation angle and/or high sonic velocity) and exceptionally high tensile properties (e.g., initial modulus). |
| Claim: |
What is claimed is:
1. Optically anisotropic dope consisting essentially of:
I. at least about 5 percent by weight of a polymer having an inherent viscosity of at least 0.7 and consisting essentially of at least one type of carbocyclic aromatic homo- or copolyamide having chain extending bonds from each aromatic nucleuswhich are coaxial or parallel and oppositely directed, and
II. at least one liquid medium selected from the group consisting of:
A. amides and ureas selected from the group consisting of: N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N,N-dimethylisobutyramide, N,N-dimethylmethoxyacetamide, N,N-diethylacetamide, N-methylpyrrolidone-2,N-methylpiperidone-2, N-methylcaprolactam, N-ethylpyrrolidone-2, .[.N-acetylpyrrolidone.]..Iadd.N-acetylpyrrolidine.Iaddend., N-acetylpiperidine, N,N'-dimethylethyleneurea, N,N'-dimethylpropyleneurea hexamethylphosphoramide, and N,N,N',N'-tetramethylureaand containing a salt from the group consisting of lithium chloride and calcium chloride
B. concentrated sulfuric acid,
C. hydrofluoric acid, and
D. chloro-, fluoro- or methane-sulfonic acids, said polymer being present in the dope in a concentration above the level at which there is a decrease in viscosity with increasing concentration represented by a sharp discontinuity in the slope ofthe plot of the dope viscosity vs. polymer concentration curve without the formation of a solid phase.
2. Dope of claim 1 wherein said liquid medium is concentrated (greater than about 98 percent by weight) sulfuric acid which may contain free SO.sub.3. |
| Description: |
This invention relates to novel,optically anisotropic dopes consisting essentially of carbocyclic aromatic polyamides in suitable liquid media. These dopes, and related isotropic dopes, are used to prepare useful fibers, films, fibrids, and coatings. In particular, fibers of uniqueinternal structure and exceptionally high tensile properties are provided.
SUMMARY OF THE INVENTION
The dopes of this invention which are optically anisotropic (as measured by procedures described hereinafter) comprise ingredients selected from the group of carbocyclic aromatic polyamides whose chain extending bonds from each aromatic nucleusare essentially coaxial or parallel and oppositely directed in suitable liquid media, exemplified hereinafter, which may contain additives. The amount of polymer in the dope exceeds the critical concentration point and preferably comprises at leastabout 5 percent by weight of the dope. These anisotropic dopes are structurally and functionally distinct from known polyamide "solutions" and are uniquely suited for the preparation of high strength shaped articles (e.g., fibers) often withoutpost-shaping treatment (e.g., drawing).
The fibers of this invention are prepared from the above optically anisotropic dopes, or related isotropic dopes, containing specified aromatic polyamides. These fibers are characterized by a unique internal structure and exceptionally hightensile properties, either as-extruded (as described hereinafter) or after being heat treated (as described hereinafter).
This unique internal structure of the fiber is evidenced by the fiber exhibiting a low orientation angle and/or high sonic velocity. Fibers of this invention exhibit orientation angles of less than about 45.degree. and preferably less thanabout 35.degree., most preferably less than about 25.degree., measured as described hereinafter, and/or sonic velocity values of at least about 4 km./sec., preferably at least about 6 km./sec., most preferably at least about 7 km./sec., measured asdescribed hereinafter.
The fiber possesses outstanding tensile properties, in particular, an initial modulus at least about 200 gpd. and preferably at least about 300 gpd., most preferably greater than about 400 gpd. and/or a tenacity at least about 5 gpd. Preferredas-extruded fiber of this invention exhibits an elongation of at least about 5 percent, in addition to high initial modulus and tenacity.
FIGURES
The invention will be more fully explained with reference to the Figures wherein:
FIG. I illustrates a phase diagram of a poly(p-benzamide)/N,N-dimethylacetamide (containing water and lithium chloride) dope of this invention;
FIG. II illustrates a typical relationship of viscosity and polymer concentration for the dopes of this invention, showing the critical concentration point;
FIG. III illustrates a typical trace of an X-ray diffraction pattern of poly(p-benzamide) homopolymer;
FIGS. IV and V further illustrate phase diagrams of dopes of this invention;
FIGS. VI And VII illustrate critical concentration points of particular dopes of this invention as a function of inherent viscosity; and
FIGS. VIII and IX illustrate the relationship of the fiber structural parameters, orientation angle, and sonic velocity, respectively, to an important physical property (initial modulus) of the fiber.
DETAILED DESCRIPTION OF THE INVENTION
Polyamides
Among the suitable aromatic polyamides (of which the preferred anisotropic dopes of this invention are comprised and/or from which the fibers of this invention can be prepared) are those in which the chain extending bonds from each aromaticnucleus are essentially coaxial or parallel and oppositely directed. The term "aromatic nucleus" is used herein to include individual enchained aromatic rings and fused-ring aromatic divalent radicals. The preferred polymers include carbocyclicaromatic polyamides containing up to 2 aromatic rings, including enchained non-fused rings (e.g., 4,4'-biphenylene) or fused rings (e.g., 1,5-naphthalene) per amide linkage. The chain-extending bonds from these aromatic rings are paraoriented and/oressentially coaxial or parallel and oppositely directed.
Highly preferred polyamides are characterized by recurring units of the formula: ##STR1## wherein R and R' (when the chain extending bonds are essentially coaxial) are selected from the group of: ##STR2## and R and R' (when the chain extendingbonds are essentially parallel) are selected from the group of: ##STR3## R and R' may be the same or different and may contain substituents on the aromatic nuclei.
Additional highly preferred polyamides of this invention are characterized by recurring units of the formula: ##STR4## wherein R" is selected from the group of: ##STR5## Similarly R" may contain substituents on the aromatic nuclei.
As previously stated, the aromatic nuclei of the polymers of this invention may bear substituents. These substituents should be non-reactive during the polymerization and preferably also should be non-reactive (e.g., thermally) during subsequentprocessing of the polymer, e.g., heat treating of a shaped article thereof. Such reactivity is undesirable in that it may cause cross-linking of the polymer and may adversely affect the dope and/or fiber properties. Among the preferred non-reactivesubstituents may be named halogens (e.g., chloro, bromo and fluoro), lower alkyl (e.g., methyl, ethyl, isopropyl and n-propyl), lower alkoxy (e.g., methoxy and ethoxy), cyano, acetyl, and nitro. Other suitable substituents non-reactive during thepolymerization will be evident to those skilled in the art and are contemplated herein provided such do not adversely affect the desired properties of the dopes and/or fibers of this invention, e.g., due to factors such as steric hindrance. Generally,it is preferred that no more than two (and more preferably no more than one) suitable substituents be present per aromatic nucleus. However, more than two such substituents may suitably be present if the substituent is a relatively small group, e.g.,methyl.
Both homo- and co-polyamides having substituted or unsubstituted aromatic nuclei, as described above, are well suited for the dopes and fibers of this invention. Random copolymers are preferred copolymers. By the term "random" is meant that thecopolymer consists of molecules containing large numbers of units comprised of two or more different types in irregular sequence. The units may be of AB (e.g., from p-aminobenzoyl chloride hydrochloride), AA (e.g., from p-phenylenediamine or2,6-dichloro-p-phenylene diamine), or BB (e.g., from terephthaloyl or 4,4'-bibenzoyl chloride) type or mixtures of these, provided always that the requirements of stoichiometry for high polymer formation are met. It is not necessary that the relativenumbers of the different types of the unit be the same in different molecules or even in different portions of a single molecule.
One or more of these polymers may suitably be used in the dopes and/or fibers of this invention, i.e., a single homopolymer; a single copolymer; or homopolymer and/or copolymer blends are suitable herein.
While the polymer chains described above consist essentially of amide links (--COHN--) and aromatic ring nuclei as described above, the polymers useful for preparing the products of this invention may also comprise up to about 10 percent (molebasis) of units not conforming to the above-cited description, e.g., aromatic polyamide-forming units whose chain extending bonds are other than coaxial or parallel and oppositely directed, e.g., they may be meta-oriented, or of linkages other thanamide, e.g., urea or ester groups.
Among the suitable aromatic polyamides may be named poly(p-benzamide); poly(p-phenylene terephthalamide); poly(2-chloro-p-phenylene terephthalamide), poly(2,6-dichloro-p-phenylene 2,6-naphthalamide); poly(p-phenylene p,p'-biphenyldicarboxamide);poly(p,p'-phenylene benzamide); poly(1,5-naphthylene terephthalamide); ordered aromatic copolyamides such as e.g., copoly(p,p'-diaminobenzanilide terephthalamide), and random copolyamides such as, e.g., copoly(p-benzamide/m-benzamide) (95/5); and manyothers.
It is to be understood that the designation of position locations of substituent groups on the aromatic nuclei of the polymers useful in this invention refers to the location(s) of the substituent(s) on the diamine, diacid, or other reactantsfrom which the polymer is prepared. Thus e.g., random end-to-end distribution of polymer-forming units in the chain, if possible, is comprehended by the name by which any given polymer is identified herein.
Polyamides, as described above, having an inherent viscosity (as described hereinafter) of at least about 0.7, and preferably greater than about 1.0, are fiber forming and particularly useful herein. Lower inherent viscosities may be utilizedfor films, fibrids and/or coatings.
POLYMER PREPARATIONS
A preferred polyamide of this invention, substantially homopolymeric poly(p-benzamide), which consists essentially of recurring units of the formula: ##STR6## can be readily obtained by certain polymerization techniques from suitable monomersdissolved in particular solvents, which may contain lithium chloride and chain terminating agents if desired.
Suitable monomers include p-aminobenzoyl halide salts of the formula: ##STR7## wherein X.sub.1.sup.- represents a member selected from the group consisting of arylsulfonate, alkylsulfonate, acid sulfonate, and halogen radicals, preferably bromideor chloride radicals, and X.sub.2 represents a halogen radical, preferably bromide or chloride. p-Aminobenzoyl chloride hydrochloride is the preferred monomer. Other monomers suitable are p-aminobenzoyl bromide hydrobromide, p-aminobenzoyl chloridehydrobromide, p-aminobenzoyl chloride methanesulfonate, p-aminobenzoyl chloride benzenesulfonate, p-aminobenzoyl chloride toluenesulfonte, p-aminobenzoyl bromide ethanesulfonate, and p-aminobenzoyl chloride acid sulfate. Other monomers, not withinFormula (IV), e.g., p-aminobenzoyl chloride sulfate, are also suitable. The preferred p-aminobenzoyl chloride hydrochloride may be prepared in high yield from an ethereal solution of p-thionylaminobenzoyl chloride by the general procedure of Graf andLanger, J. prakt. Chem. 148, 161 (1937) under anhydrous conditions. The drying and anhydrous storage of this monomer are preferably performed under room temperature conditions because of the tendency of the compound to polymerize at highertemperatures.
Solvents which are suitable for the polymerization reaction include those selected from the group consisting of:
N,N,N',N'-tetramethylurea,
hexamethylphosphoramide,
N,N-dimethylacetamide,
N-methylpyrrolidone-2,
N-methylpiperidione-2,
1,3-dimethylimidazolidinone-2, (i.e., N,N'-dimethylethyleneurea)
N,N,N',N'-tetramethylmalonamide,
N-methylcaprolactam,
N-acetylpyrrolidine,
N,N-diethylacetamide,
N-ethylpyrrolidone-2,
N,N-dimethylpropionamide,
N,N-dimethylisobutyramide,
N,N-dimethylbutyramide, and
tetrahydro--b 1,3-dimethyl-2(1H)-pyrimidinone (i.e., N,N'-dimethylpropyleneurea).
Salts such as lithium chloride, are preferably added to the polymerization reaction mixture; such addition may assist in the maintenance of a fluid mixture.
Chain terminators, as indicated above, may be used in these polymerizations. By assisting in the control of the molecular weight of the polyamide, the use of chain terminators contributes to the ease by which subsequent processing of the polymeroccurs and enhances the stability of the polymer dope for application in the hereinafter described "coupled" polymerization spinning process. Among the suitable chain terminators are monofunctional compounds which can react with the acid chloride endsof these polyamides such as ammonia, monoamines (e.g., methylamine, dimethylamine, ethylamine, butylamine, dibutylamine, cyclohexylamine, aniline, etc.), compounds containing a single amide-forming group, such as N,N-diethylethylenediamine, hydroxyliccompounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, phenol, water, etc., and monofunctional compounds which can react with the amine ends of the polyamides such as other acid chlorides (e.g., acetyl chloride), acid anhydrides (e.g.,acetic anhydride, phthalic anhydride, etc.), and isocyanates (e.g., phenyl isocyanate, m-tolyl isocyanate, ethyl isocyanate, etc.). Useful difunctional terminators include terephthaloyl chloride, isophthaloyl chloride, sebacyl chloride,4,4'-biphenyldisulfonyl chloride, pyromellitic dianhydride, p-phenylenediisocyanate, benzidine diisocyanate, bis(4-isocyanatophenyl)methane, p-phenylenediamine, m-phenylenediamine, benzidine, bis(4-aminophenyl) ether, N,N'-diaminopiperazine, adipicdihydrazide, terephthalic dihydrazide and isophthalic dihydrazide.
The polymerization reaction may be carried out by dissolving the desired monomer or monomers (as well as the chain terminating agent and lithium chloride, if any is used) in the desired amide or urea solvent and vigorously stirring the resultingsolution, externally cooled, until it develops into a viscous solution or a thick gel-like mass. Alternatively, the desired monomer may first be slurried in a small quantity of an anhydrous, inert organic liquid, such as tetrahydrofuran, dioxane,benzene or acetonitrile, prior to the addition of the amide solvent. Preferably, the resulting monomer/organic liquid mixture is stirred at an increased rate and a relatively large volume of the amide solvent is rapidly added. In a further variation,the amide solvent may be frozen and mixed, while frozen, with the desired monomer. The solvent is permitted to thaw and the resulting mixture stirred until a viscous solution or gel-like mass forms.
In each of the above techniques, the polymerization reaction is maintained at low temperature, i.e., under 60.degree. C. and preferably from -15.degree. to +30.degree. C., by external cooling, if necessary. The reaction mixture is stirredcontinuously until it gradually develops into a viscous solution or thick gel-like mass. The reaction is generally allowed to proceed a period of from about 1 to 48 hours, preferably from about 2 to 24 hours.
For the attainment of the highest molecular weights, these polymerizations are performed under strictly anhydrous conditions. The reaction vessel and auxiliary equipment, solvents, and reactants are carefully dried prior to use and the reactionvessel is continuously swept with a stream of dry, inert gas, e.g., nitrogen, during the polymerization.
The polymerization reaction produces an acidic by-product (e.g., HCl or HBr) which is preferably neutralized. Neutralization is especially preferred in embodiments hereinafter described wherein the reaction mixture is prepared for direct use informing shaped articles of the polymer. In such a situation, it is preferred to add a base selected from the group consisting of:
lithium carbonate,
lithium oxide,
lithium hydroxide,
lithium hydroxide monohydrate,
lithium hydride,
calcium oxide,
calcium hydroxide
calcium hydride, and
calcium carbonate,
or mixtures thereof, to neutralize the reaction mixture. The use of a neutralization agent is highly desired, in that the acid may cause significant corrosion problems in processing equipment (e.g., the spinneret). Neutralization may also benecessary to achieve more fluid compositions which facilitate the formation of shaped articles. If more than the stoichiometric amount of neutralizing agent is used, an insoluble excess may remain. Its removal may be required prior to forming a shapedarticle (e.g., by spinning). The neutralizing agent may be added before, shortly after, or long after monomer is added to the reaction medium depending upon the inherent viscosity desired. Addition of neutralizing agent may result in a sharp increasein polymer molecular weight as determined by measuring the inherent viscosity of polymer isolated from an aliquot of the reaction mixture before and after neutralization.
In addition to excess neutralization agents, the dopes may contain other insoluble material which preferably should be removed, by conventional means, prior to forming a shaped article. For example, when the acidic polymerization system producesbromide ion and lithium hydroxide is used as a neutralizing agent, the lithium bromide produced may be insoluble in particular dopes and should be removed before the dope is spun or cast.
The composition or dope may be concentrated under vacuum to produce a fluid of the desired solids content and/or viscosity for spinning or casting, under the conditions discussed hereinafter.
To isolate the poly(p-benzamide), the polymerization mixture is combined with a polymer nonsolvent, e.g., water in a suitable blender, and thereby is converted to a powder. The powdered polymer, after being washed with both water and alcohol, isdried overnight in a vacuum oven at about 60.degree.-90.degree. C. before being stored or treated for subsequent processing.
The essentially homopolymeric poly(p-benzamide), prepared as previously described, possesses a peak height ratio (PHR) of below 0.86 and, moreover, no sediment is seen in the tube when the polymer is subjected to a sedimentation test, all asdescribed hereinafter. It will be understood, however, that the peak height ratio as measured on a sample of this polymer that has been spun or heated at elevated temperatures may exceed 0.86; the sedimentation properies of such a sample may also bedifferent. Poly(p-benzamide) having a PHR greater than 0.86 is also useful in this invention, e.g., anisotropic dopes of this polymer in HF or oleum.
Other polyamides useful in this invention may be prepared from appropriate coreactants by low temperature solution polymerization procedures (i.e., under 60.degree. C. and preferably from -10.degree. to 30.degree. C.) similar to those shown inKwolek et al. U.S. Pat. No. 3,063,966 for preparing poly(p-phenylene terephthalamide). For example, such polyamides may be prepared by causing p-phenylenediamine or 2-chloro-p-phenylenediamine to react with polyamide-forming derivatives ofterephthalic acid. This dicarboxcyclic acid is conveniently employed in the form of its dihalides which are readily prepared by well-known methods; the diacid chloride is usually preferred. Preferably, these low temperature solution polymerizations areaccomplished by first preparing a cooled solution of the diamine in a solvent or a mixture of solvents selected from the group of hexamethylphosphoramide, N-methylpyrrolidone-2, and N,N-dimethylacetamide. To this solution is added the diacid chloride,usually with stirring and cooling. Polymer precipitation frequently occurs within a few minutes and on other occasions the reaction mixture may gel. It may be desirable in some cases to stir or permit the reaction mixture to stand for 30 minutes toseveral hours or more. The polymer may be isolated by agitating the reaction mixture with a polymer non-solvent, e.g., water, in a suitable blender. The polymer is collected, washed, and dried before being stored or subsequently processed into a dope.
Illustrations of preparations of other useful polymers and copolymers are shown in the examples which follow. These preparations may also include in situ synthesis of directly extrudable anisotropic dopes (e.g., see Example 4 herein).
DOPE PREPARATION
Polymers and copolymers which have been prepared by the previously described methods and which have been isolated after formation, may be combined with a suitable liquid medium (including additives, if any, e.g., LiCl) to form compositions ordopes (such embodiments will hereinafter be referred to as isolated polymer dopes). In certain other embodiments, the polymerization medium is utilized to form such compositions or dopes (such embodiments will hereinafter be referred to as in situpolymer dopes) in a "coupled" polymerization spinning process.
Liquid media useful for forming the anisotropic dopes of this invention, as well as related isotropic dopes, include:
1. Seleced amides and ureas, including N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N,N-dimethylisobutyramide, N,N-dimethylmethoxyacetamide, N,N-diethylacetamide, N-methylpyrrolidone-2, N-methylpiperidone-2,N-methylcaprolactam, N-ethylpyrrolidone-2, N-acetylpyrrolidine, N-acetylpiperidine, N,N'-dimethylethyleneurea, N,N'-dimethylpropyleneurea, hexamethylphosphoramide and N,N,N',N'-tetramethylurea, which may contain lithium chloride and/or calcium chloride.
2. Concentrated sulfuric acid whose concentration is greater than about 90 percent by weight, usually >98-100 percent by weight H.sub.2 SO.sub.4 or oleum (i.e., concentrated sulfuric acid containing up to 20 percent or higher of freeSO.sub.3) which may contain additives (e.g., NaHPO.sub.4, Na.sub.2 SO.sub.4, potassium acetate which may be present in the amount of 2-3 percent by weight of the total dope). The selection of the sulfuric acid concentration most suited for a particulardope preparation is based upon, in part, the inherent viscosity of the polymer employed.
3. Hydrofluoric acid, used alone or in combination with additives such as water (1-2 percent by weight, of the total dope), NaF or KF (1-2 percent by weight of the total dope), an inert chlorinated hydrocarbon (e.g., CH.sub.2 Cl.sub.2) ormixtures thereof (in an amount up to 5 percent by weight of the total dope).
4. Chloro-, fluoro- or methane-sulfonic acids used alone or in combination with additives such as lithium chloride (up to about 2.5 percent by weight).
Mixtures of two or more of the above liquid media may be used in suitable combinations e.g., any of the amides and ureas; hydrofluoric acid and fluoro-sulfonic acid; methane sulfonic acid and sulfuric acid; oleum and chloro-, fluoro- ormethane-sulfonic acid; and the like.
The use of additives, as described above, is preferred in many of the dopes of this invention. It is believed that particular additives aid the solvation of the polyamide in the liquid medium. For the amide and urea media, it is highlydesirable that at least about 2.0 weight percent of lithium chloride and/or calcium chloride be added to provide a reasonably concentrated dope from particular isolated polymers, e.g., poly(1,4-benzamide). In the preparation of amide or urea in situdopes, the salt may be added before, during or after the polymerization, preferably by forming it as a byproduct of a neutralization (e.g., when the monomer is p-aminobenzoyl chloride hydrochloride and the neutralization agent is lithium carbonate, aby-product of the neutralization reaction is lithium chloride). In the preparation of an amide or urea dope from isolated polymer, the salt may be conveniently added to the polymer and/or liquid medium. In either type of dope (isolated or in situ) saltin excess of about 20 weight percent is generally neither necessary nor desired, less than about 15 weight percent is preferred, about 4 to 8 weight percent being most preferred. For liquid media, other than amides and ureas, the use of other solvationadditives (e.g., as indicated above) may also be desirable; generally small amounts (e.g., less than about 5 weight percent) of these additives are used.
Although the dopes consist essentially of the polymer and the liquid medium (including additive, if any), additional substances may be present in the dope, such as small amounts of inert organic liquids (e.g., tetrahydrofuran, dioxane, benzene,or acetonitrile) used to disperse the monomer in the amide or urea dopes, water (either purposefully added or adventitiously present) and the acidic by-product of the polymerization reaction (e.g., if less than the stoichiometric amount of aneutralization agent is used).
The usual additives such as dyes, fillers, delusterants, UV stabilizers, antioxidants, etc., can be incorporated with the polymer or copolymer or dispersed in the dopes of this invention for the purposes intended, prior to the preparation ofshaped articles thereof.
Dopes of this invention may be conveniently prepared e.g., by combining polymer and the liquid medium (and additives, if any) in a conventional manner (e.g., with stirring). Some dopes are formed at room temperature conditions and are useful(e.g., spinnable) under these conditions. Other dopes require specific heating techniques, i.e., flowable compositions may be obtained at room temperature in many instances, while heating, preferably with stirring, and sometimes heating and coolingcycles are required in a few instances. The amount of heating and/or cooling required to form a useful dope or composition varies with the liquid medium, the polymer (the composition, the inherent viscosity, the crystallinity, and the particle size ofthe polymer sample employed) and the quality of the stirring action. In the preparation of these dopes, care must be taken to avoid local overheating and formation of a "dry" or gelled spot at the meniscus of this composition or on the walls of thevessel being employed. Such portions of polymer frequently do not readily redissolve. Numerous suitable techniques useful in preparing specific dopes of this invention are illustrated in the Examples.
The anisotropic dopes of the invention may comprise a single anisotropic phase, or an emulsion of anisotropic and isotropic phases in any proportion or degree of dispersion. The isotropic dopes also useful in preparing fibers of this inventioncomprise a single isotropic phase. Minute quantities of undissolved polymer may be present in these phases or in the emulsion, particularly when the dope is prepared by dissolving isolated polymer. A "dope" is a shaped-structure-forming (e.g.,fiber-forming, film-forming, or fibrid-forming) polymer-solvent system which comprises at least one of the above phases.
Anisotropic Dopes
When the dope-forming ingredients of this invention are combined in particular concentration ranges, the resultant dopes are optically anisotropic, i.e., microscopic regions of a given dope are birefringent; a bulk dope sample depolarizesplane-polarized light (described hereinafter), sometimes referred to herein as light or polarized light, because the light transmission properties of the microscopic areas of the dope vary with direction. This characteristic is associated with theexistence of at least part of the dope in the liquid crystalline or mesomorphic state. As described in Industrial Research, G. H. Brown, May, 1966, pp. 53-57, liquid crystals are intermediate between the liquid and solid states in many of theirproperties. Thus, they have unique structural arrangements partially imparting the order of crystals and the fluidity of liquids.
The dopes of this invention exhibit anisotropy while in the relaxed state. Although conventional polyamide dopes may depolarize plane-polarized light when subjected to appreciable shear (e.g., flow birefringence wherein molecules in a solutionare hydrodynamically oriented), static (i.e., stationary) samples of the dopes of this invention uniquely exhibit this phenomenon.
The extended stiff-chain aromatic polymers which are present in the anisotropic dopes of this invention are believed to be in essentially rod-like entities (aggregates or bundles) in the liquid medium. This extended, stiff-chain configuration ofthe polymer is indicated by values of the exponent, .alpha., in the Mark-Houwink relationship, [.eta.].dbd.KM.sup..alpha., for dilute solutions of lower molecular weight polymer. In this well-known relationship, [.eta.] is the intrinsic viscosity, M isthe molecular weight, and K and .alpha. are constants for a given polymer/solvent system. The great majority of polymers for which this relationship has been evaluated in the literature have had values below 0.9. Among the polymers used in the dopesof this invention, poly(p-benzamide) is determined to have an .alpha. value of 1.6, measured on unfractionated polymer with an inherent viscosity in the range of 0.4 to 2 and weight average molecular weight determinations made in sulfuric acid (95-98percent by weight). When a given system exceeds a certain critical concentration point, an anisotropic phase is formed which gives rise to the characteristics of the anisotropic dopes of this invention.
For a given polyamide/liquid medium dope of this invention, below a particular polyamide concentration, the dope is isotropic. As the concentration of the polyamide increases, the viscosity of the dope increases. However, at a point referred toherein as the "critical concentration point" there is a sharp discontinuity in the slope of the viscosity vs. concentration curve when the dope changes from isotropic to partially anisotropic without the formation of a solid phase. Further addition ofpolyamide results in a decrease in the viscosity of the dope, as the dopes become more anisotropic. An exemplary viscosity vs. concentration curve is described in Example 73 and illustrated in FIG. II.
As previously stated, a given dope of this invention is anisotropic when the ingredients of the dope are present in particular concentration ranges. There is a complex relationship existing among the concentration of the polymer or copolymer,the inherent viscosity thereof, and the temperature which generally determines the ranges in which a given polymer or copolymer/liquid medium dope is anisotropic. Exemplary phase relationships are shown in Example 64 and FIG. I, and Example 74 and FIGS.IV and V. Such relationships for other dopes of this invention can be easily determined by routine experimentation.
The "critical concentration point" varies with the particular polyamide, as well as the weight percent and the inherent viscosity thereof, the particular liquid medium and the temperature. The effect of the weight percent of polymer andtemperature on dopes of two different polyamides is shown in Example 75. The effect of the inherent viscosity on two different polyamides is shown in Example 74 and FIGS. VI and VII.
Anisotropic dopes comprising polymers and copolymers, as previously described, incorporating up to about 10 percent (mole basis) of aromatic units whose chain extending bonds are not essentially coaxial or parallel and oppositely directed may beprepared according to this invention. For example, random high molecular weight copoly(p-benzamide/m-benzamide) (95/5) may be prepared from p-aminobenzoyl chloride hydrochloride and m-aminobenzoyl chloride hydrochloride by the previously described lowtemperature solution polymerization techniques. A dope prepared from such a copolyamide in, e.g., N,N-dimethylacetamide and lithium chloride, exhibits optical anisotropy.
Anisotropic dopes of aromatic copolyamides wherein all chain-extending bonds from each aromatic nucleus are essentially coaxial or parallel and oppositely directed are also comprehended by the present invention. For example, an orderedcopolyamide prepared from 4,4'-diaminobenzanilide and terephthaloyl chloride or 2,6-naphthaloyl chloride may be incorporated into an anisotropic dope comprising the (1) copolymer, an amide mixture, and lithium chloride, or (2) the copolymer, a suitablesulfuric acid or oleum.
One spinnable group of anisotropic dopes comprises about 6-15 percent by weight poly(p-phenylene terephthalamide) whose inherent viscosity is in the range of about 0.7-3.5, from 0.5 percent to up to 5 percent by weight lithium chloride, and thebalance an amide mixture of hexamethylphosphoramide and N-methylpyrrolidone-2 containing greater than 45 percent by volume of hexamethylphosphoramide. The relative amounts of these ingredients, particularly those of the hexamethylphosphoramide andN-methylpyrrolidone-2, contribute to the ease with which these spin dopes are obtained. For instance, as illustrated in the examples which follow, a spin dope fluid at room temperature is obtained from these ingredients when a particular amide mixtureis employed. However, when a different amide mixture containing more hexamethylphosphoramide is employed with the same amounts of the polymer and salt, the combined ingredients must be heated to at least about 35.degree. C. to achieve a liquidanisotropic dope whose birefringence may be observed. Preparation of the dopes is preferably undertaken by vigorous mixing of the ingredients at low temperatures, e.g., as low as 0.degree. to -10.degree. C.
Another spinnable group of anisotropic dope comprises about 5-25 percent by weight poly(2-chloro-p-phenylene terephthalamide) whose inherent viscosity is in the range of about 0.7-3, from 0.5 percent to up to 8 percent by weight of lithiumchloride and the balance being N,N-dimethylacetamide. In addition, anisotropic dopes comprising (1) poly(2-chloro-p-phenylene terephthalamide), lithium chloride, and N,N,N',N'-tetramethylurea (TMU) and (2) the same polymer with N,N-dimethylacetamide andcalcium chloride can be prepared. For example, an anisotropic dope is prepared by combining 2.5 g. of poly(2-chloro-p-phenylene terephthalamide) (.eta.inh=1.27) with 25 ml. of a mixture prepared from 3.56 g. of lithium chloride and 100 ml. of TMU. This dope produces a bright field in a polarizing microscope and displays transmittance value (T) of 81 as measured herein.
There is a complex relationship existing among the amount of poly(2-chloro-p-phenylene terephthalamide) and the inherent viscosity thereof, the amount of salt, and the amount(s) of amide(s) that determine whether or not a given dope preparationis optically anisotropic under otherwise constant conditions. By way of illustration, an isotropic dope may be converted to an anisotropic dope by changing the polymer concentration. For example, a clear dope comprising 10 g. ofpoly(2-chloro-p-phenylene terephthalamide), .eta.inh=1.13, in 100 ml. of a mixture of 100 ml. of N,N-dimethylacetamide and 4.3 g. of lithium chloride is isotropic. However, when an additional 10 g. of the polymer is added thereto, the resulting dopebecomes turbid and anisotropic as shown by light depolarization studies. That the amount of salt present in the dope contributes to the nature of the dope is demonstrated by observing that a dope comprising 20 g. of poly(2-chloro-p-phenyleneterephthalamide), .eta.inh=1.13, and 100 ml. of a mixture of 100 ml. of N,N-dimethylacetamide and 7 g. of lithium chloride is isotropic.
Dopes comprising poly(2-chloro-p-phenylene terephthalamide) can be separated into 2 layers, an isotropic upper layer and a more dense anisotropic lower layer. This separation can be achived by, e.g., permitting a spin dope to stand for a periodof time sufficient to achieve the separation (e.g., one week) or by, e.g., centrifugation. Just as an isotropic poly(2-chloro-p-phenylene terephthalamide) dope can be converted to an anisotropic dope by changing polymer concentration at constant polymerinherent viscosity, a change in the volume of a given anisotropic phase in a two-layer dope system can be attained by incorporating in the dope a polymer of higher inherent viscosity. For example, a dope comprising 10 g. of poly(2-chloro-p-phenyleneterephthalamide), .eta.inh=1.13, in 100 ml. of a mixture obtained by combining 100 ml. of N,N-dimethylacetamide and 3.12 g. of lithium chloride separates into 2 layers on long standing. The bottom layer is 20 percent of the total volume. When thedope is prepared with 10 g. of this polymer with an inherent viscosity of 1.85, the anisotropic bottom layer constitutes 33 percent of the total volume. It has been observed that the maximum amount of salt which may be present in an anisotropic dope ofthis polymer increases as the inherent viscosity of the polymer employed to prepare the dope increases.
It is to be understood that the combinations of the aforesaid ingredients are chosen to provide an anisotropic dope; certain combinations of ingredients may not so provide. For example, poly(p-phenylene p,p'-biphenyldicarboxamide) andpoly(p,p'-phenylene benzamide) which form anisotropic dopes in oleum, do not form anisotropic dopes in HF or in some of the amides and ureas useful with other polymers of this invention. Whether a given dope is anisotropic is readily determined by themethods described hereinafter.
DETERMINATION OF OPTICAL ANISOTROPY
In the examples which follow, the anistropic character of the dopes of this invention is described in terms of e.g., (1) by plotting the relationship of dope viscosity vs. polymer concentration to determine the "critical concentration point,"(2) by numerical values of transmittance of light through crossed polarizers, identified as "T" or "DDA," (3) an observation of the bright field observed in a polarizing microscope, and (4) a visual determination of "stir opalescence."
Critical Concentration Point
A "critical concentration point" characterizes the anisotropic dopes of this invention, i.e., there is a sharp discontinuity in the slope of the dope viscosity v. polymer concentration curve. When the concentration exceeds this point, the dopeis anisotropic and further addition of polymer results in a decrease in the viscosity as the dope becomes more anisotropic. This "point" (as well as the complete viscosity v. concentration curve) is routinely determined using conventional concentrationand viscosity measuring techniques. For example, a polymer dope of this invention may be placed in a polyallomer test tube equipped with a Teflon TFE-fluorocarbon cap through which a viscometer spindle extends into the dope, constant temperature beingmaintained. The viscosity of the stirred dope may be conventionally measured with a viscometer (e.g., a Brookfield Syncho-Lectric Viscometer, Model RV, product of the Brookfield Engineering Laboratories, Inc., Staughton, Mass., or equivalent). Viscosity measurements are made at the initial polymer concentration and at higher concentrations (i.e., after an additional known amount of polymer is added). By this technique (or equivalent) a viscosity vs. concentration curve may be plotted forthis system (the given polymer and liquid medium at that temperature) and the critical concentration point (i.e., the discontinuity in the slope of the curve) is determined.
"T" Test
The determination of the "T" value may be made by placing an anisotropic dope of this invention, prepared as described herein and containing no suspended solid matter, between a crossed polarizer and an analyzer. The dope sample is convenientlyemployed as a layer 80.mu. thick. Thus, a drop taken from the interior of a dope sample of this invention is put on a dry, clean strain-free glass slide; a square cover of glass, supported on one edge by a glass tube or wire of known thickness (1.3 mm. diameter is convenient), is pressed down on the drop so as to form the roof of a liquid wedge. The edges are sealed with a fast-drying binder (e.g., Duco cement, DuPont's registered trademark for a transparent, flexible, waterproof adhesive), avoidingactual contact with the dope. The sharp edge of the wedge is sealed by excess dope which is squeezed out. In the operation, common care should be taken to avoid evaporation, moisture uptake, excessive shearing actions, dirt, and any suspended solidparticles.
The samples are allowed to stand for a sufficient time to permit relaxation of the shear stresses resulting from the slide preparation to assure that the sample is static. For example, the amide or urea dopes are relaxed about 10 minutes, up toabout 11/2 hours is generally needed to relax sulfuric acid dopes (especially the more viscous samples); up to about 1 hour is generally sufficient to relax the other dopes of this invention, e.g., fluoro- and chloro-sulfonic acid dopes.
The wedge is positioned in a light beam, on a microscope stage between crossed polarizer and analyzer. The light beam has the intensity such as is ordinarily used in microscopic examinations. The wedge is positioned so that the thickness of thecenter of the layer of dope through which the light beam passes is 80.mu. in thickness. The intensity is measured with polarizer and analyzer crossed (I.sub..div..sup.s)(superscript s to denote sample present in wedge) and with analyzer removed(I.sub.-.sup.s) and the difference I.sub.-.sup.s -I.sub.+.sup.s is obtained. The transmitted light may be measured by conventional light sensitive detectors (e.g., by photo multipliers, selenium or cadmium light meters, bolometers, etc.). The samemeasurements are then made on a similarly constructed wedge containing air, and the difference I.sub.-.sup.c -I.sub.+.sup.c (superscript c for control) is recorded. When the dopes of this invention are placed in the wedge the expression (I.sub.-.sup.c-I.sub.+.sup.c)-(I.sub.-.sup.s -I.sub.+.sup.s) will be greater than zero and greater than can be accounted for by experimental error, using reasonable care and accurate instrumentation. It represents the increase in light transmittance through theanalyzer due to the presence of the sample. The magnitude of (I.sub.-.sup.c -I.sub.+.sup.c)-(I.sub.-.sup.s -I.sub.+.sup.s) will vary with the solvent being used, polymer concentration, concentration of dissolved salt, and the units in which lightintensity is measured.
In the examples, an apparatus by which the anisotropic character, or "T" value, of the dopes is determined consists essentially of an A. O. Spencer Orthoscope Illuminator which contains a tungsten overvoltage microscope lamp (color temperature3,800.degree. K.), an optical wedge containing the sample, an optical wedge containing air, a Bausch and Lomb Polarizing Microscope having a Leitz 10X objective and a Leitz 10X ocular Periplan, a Gossen "Sinarsix" exposure meter and a Polaroid MP3Industrial Land Camera body. The wedge containing the sample is prepared as previously described and is positioned on the microscope stage (i.e., between the polarizer and the analyzer) to provide a sample layer 80.mu. thick in the path of any lightwhich reaches the analyzer and the light meter. The polarizer and the analyzer are adjusted to provide 90.degree. crossed polarization planes. Light from the lamp which passes the analyzer by the route previously described is projected into the camerabody and is measured in the image plane (at the ground glass level) by the exposure meter (I.sub.+.sup.s). The same measurement is made with the analyzer removed (I.sub.-.sup.s). This is repeated with the control wedge of air 80.mu. thick to giveI.sub.+ .sup.c and I.sub.-.sup.c. The light values from the "Sinarsix" exposure meter, which are expressed in logarithmic units to the base 2, may be converted to logarithmic units to the base 10 by multiplying them by 0.301 (i.e., by log 2); theantilogs.sub.10 of these products are then determined. These antilog values are designated I.sub.+.sup.s', I.sub.-.sup.s', I.sub.+.sup.c', and I.sub.-.sup.c'. Comparative intensity measurements, free from the particular intensity units, areconveniently stated in terms of relative intensities (i.e., intensity ratios or fractions of transmitted light intensities). The expression I.sub.+.sup.s' /I.sub.-.sup.s' is the fraction of light intensities transmitted by the dope being examined. Thefraction I.sub.+.sup.c' /I.sub.-.sup.c' is the fraction of light transmitted by the control wedge. The difference (I.sub.+.sup.s' /I.sub.-.sup.s')-(I.sub.+.sup.c' /I.sub.-.sup.c') represents the increase in intensity of light transmitted due to thepresence in the wedge of the dope being examined.
Since, for a depolarizing sample, the theoretical maximum value of I.sub.+.sup.s' /I.sub.-.sup.s' -I.sub.+.sup.c' /I.sub.-.sup.c' =0.5, an index of the increase of light transmittance (T) may be conveniently taken as 2(I.sub.+.sup.s'/I.sub.-.sup.s' -I.sub.+.sup.c' /I.sub.-.sup.c').times.100 since in this way the maximum value is 100. When measured according to the foregoing procedures, dopes having values greater than 4 are considered herein to be anisotropic in nature.
"DDA" Test
Another measurement from which a numerical quantity differentiates anisotropic dopes from isotropic dopes is shown in the examples; this measurement is identified as "degree of depolarization anisotropy" (DDA) and is used herein. This quantityis a measure of the depolarization of plane polarized light passing through a sample, and is defined by the following equation: ##EQU1## in which the primes denote measurements on a blank (completely isotropic), .epsilon. is an opacity factor in thesense that two thicknesses of a given absorber have an .epsilon. value twice as great as a single thickness, and .pi. and .sigma. denote measurements made with polarizer and analyzer parallel and perpendicular, respectively. This is essentially apercent-difference equation. In practice, the incident light intensity is always adjusted so that a measurement of .epsilon..sub..pi. (and .epsilon.'.sub..pi.) corresponding to unity (i.e., a 100 percent transmission reading) is obtained with parallelpolars for both (1) blank and (2) sample, indicating for (1) a total lack of depolarization and for (2) a complete depolarization for the field observed. In this case the DDA equation is simplified to ##EQU2## The scale is from zero to 100, with theformer indicating perfect isotropy and the latter perfect anisotropy for the field observed.
The apparatus used for making DDA measurements consists of a Bausch and Lomb polarizing microscope (polarizer rotatable, analyzer fixed). The light source is a Silge and Kuhne OrthoIlluminator B with a 100 w G. E. BMY bulb operated at a constant115 v. The light intensity to regulate .epsilon..sub..pi. (and .epsilon.'.sub..pi.) is changed by the neutral filters and iris diaphragm in the illuminator. A light sensitive resistor, G.E. B-1036, operated at 221/2 v. is used to detect transmittedlight, and a 50.mu.a meter is used to register the relative intensity. The light path is through the following components in order: source, polarizer, condenser, sample, microscope objective (20X, N.A.=0.33 Leitz long F.L.), analyzer, ocular (10X,compensating), to photoresistor.
All measurements are made in red light produced by a red band pass filter (with a transmission region from about 600 m .mu. to a maximum of about 650 m.mu. in the visible range) in the illuminator. The photoresistor is calibrated with a seriesof Kodak Color Compensating filter films, CC50R; an opacity of 1 (100 percent transmission on meter) being assigned to a single film, 2 to two films, etc. During calibration the films are placed on the microscope stage and the microscope focusedapproximately at the center of the stack of filter films (vertically). The operating conditions imposed on the photoresistor are designed to produce a linear calibration curve with log meter reading plotted against opacity. Sample opacities are thentaken directly from the calibration curve. This gives a relative "red-opacity" value for the sample.
Samples are prepared for measurement by extracting a drop of dope from the interior of the bulk sample. This is placed on a "Pyrex" glass disk. An annular Teflon fluorocarbon spacer, 0.002 in. (51.mu.) thick is placed on the disk and a secondglass disk closes the cell. This assembly is placed into a special screw-assembly which seats the glass against the spacer--assuring a constant 0.002 in. sample thickness (with the sample substantially filling the cell). These samples are allowed torelax for 1-1.5 hours before measurements are made. Blanks are prepared in the same way with pure solvent.
In making visual observations (crossed polarizers in microscope) on the dopes for which DDA is measured, any positive value for DDA indicates the presence of some anisotropic phase. The higher the DDA, the greater the amount of anisotropic phasepresent in the dope except in the extreme limits with less than about 5 percent of one phase present . This is due partly to the sensitivity of the apparatus. Also when the proportion of anisotropic phase is low and not uniformly distributed ordispersed, small fields of view can be selected which have less than average or even no anisotropic phase. A 100 percent anisotropic dope does not always give a DDA=100, probably because of irregularities in the texture.
Observation Between Light Polarizing Elements
The "T" and "DDA" tests described above, quantitively describe the light transmittance of anisotropic dopes. However, a qualitative determination can also be conveniently made using a light source, analyzer and crossed polarizer (or equivalentsthereof) as described in these tests. When such polarizing elements are crossed, a static (relaxed) dope sample placed between the polarizer and analyzer will transmit essentially no light if the dope is isotropic. However, when the sample isanisotropic, light will be transmitted and a relatively bright field will be observed (the intensity of the light being related to the degree of anisotropy of the sample). A more detailed description of the type of field observed in dopes containinganisotropic and/or isotropic phases is set forth in Example 64.
Stir Opalescence
"Stir opalescense" is a term used herein to describe a property characteristic of anisotropic dopes which is visually observed with the naked eye. Many of the dopes of this invention, when observed in bulk in a transparent vessel, appear turbidor hazy and yet they contain no, or practically no, undissolved solid. When the dope, seen under reflected ordinary light, is disturbed by tilting or rolling of the vessel or by only slow stirring, there is produced a characteristic, readily-observed,satin-like sheen or glow which is observed even after the disturbance ceases and which decreases in intensity thereafter. With some compositions there is produced no sense of color while others may have a bluish tone or even a degree of varigated color,which is described by observers as having a pearly or opalescent quality. Extraneous color in the dope, such as yellows from minor impurities or inherent in some polymers, modifies the observation of color developed under shear. Dopes, which aredisturbed as described above, often give the appearance of having striations and/or graininess in the surface. These visual effects are observed in anisotropic dopes of this invention. While such effects do not conclusively establish that the dope isanisotropic, such dopes generally are anisotropic or will become anisotropic upon the addition of more polymer (providing solubility limits permit). For the sake of brevity, the visual observation of all variations of the phenomenon outlined above isreferred to in the examples as the exhibition of "stir opalescense."
Dopes described as anisotropic hereinafter may have shown this "stir opalescense" effect or may have been shown to be anisotropic by the aforementioned qualitative or quantitative techniques, i.e., the critical concentration point is determinedor the sample is observed between light polarizing elements, as in a microscope, to depolarize plane-polarized light, either qualitatively or quantitatively, as described hereinbefore. Any of the above-described qualitative or quantitative techniquessuitably indicate anisotropy, although one or more of such techniques may be more convenient and/or accurate for a given dope. The determination of "critical concentration point" is the preferred test for determining anisotropy because it isconveniently and accurately used for all anisotropic dopes of this invention. The qualitative test (visual observation between light polarizing elements) is preferred for the convenience in testing a large number of samples. The "stir opalescence"observation is also convenient and generally indicates anisotropy. Among the quantitative tests (other than the critical concentration point determination), the "DDA" test is preferred for sulfuric acid dopes because it is more sensitive in "borderline"anisotropic measurements in such dopes; the "T" test is generally preferred for amide or urea dopes. Although the "T" and "DDA" tests are generally suitable for all dopes of this invention, since hydrofluoric acid (in HF dopes or generated by thefluoro-sulfonic acid in other dopes) attacks glass, care and/or altered testing procedures may be necessary, (e.g., substituting a strain-free, HF-resistant slide for the glass slide and shielding the microscope lens from HF gas).
UTILITY OF THE DOPES--FIBER PREPARATION
The previously described compositions or dopes of this invention can readily be utilized for the production of fibers, films, fibrids, and coatings.
Dopes of this invention containing at least 5 percent by weight of polymer are preferred in that they are particularly useful in preparing fibers. Although these anisotropic dopes are useful in preparing other shaped articles, the preferred useof these dopes (as well as related isotropic dopes) is in the preparation of fibers by conventional techniques and/or techniques described herein. The term "fibers" is used generically herein to include the numerous conventional fiber structures. Forexample, the fiber may be of staple or continuous lengths, similarly, the fiber may consist of a single component or multicomponents (e.g., a bicomponent fiber with the two components consisting of different polyamide compositions of this invention). Furthermore, one or more polyamide compositions of this invention may be in a given fiber (or fiber component) i.e., the fiber may contain a single polyamide composition or blends of two or more of such compositions. The fibers may be employed in singlestrands or multi-fiber bundles (e.g., yarns). All such conventional fiber structures which consist essentially of the polaymide compositions specified herein, having the internal structure and properties specified herein, are contemplated herein.
The compositions or dopes of this invention are extruded into fibers by conventional wet- and dry-spinning techniques and equipment. In wet spinning, an appropriately prepared composition containing the polymer and, e.g., an amide or ureamedium, whose temperature may vary from 0.degree. to about 100.degree. C., is extruded into a suitable coagulating bath, e.g., a water bath maintained at 0.degree.-90.degree. C., depending on the solvent used in the preparation of the dope. Otheruseful coagulants include ethylene glycol, glycerol, mixtures of water, methanol and an amide or urea solvent, mixtures of water and alcohols and aqueous salt baths, e.g., maintained at a temperature of about -20.degree. to +90.degree. C. Dry spinningmay be accomplished by extruding the compositions or dopes of this invention, into a heated current of gas whererby evaporation occurs and filaments of the polyamide are formed.
After being formed, the fibers may be passed over a finish-application roll and wound up on bobbins. Development of maximum levels of fiber and yarn properties may be assisted by soaking the bobbins in water or in mixtures of water andwater-miscible inert organic liquids, (e.g., acetone, ethyl alcohol, glycerol, N,N,N',N'-tetramethylurea, N,N-dimethylacetamide) to remove residual amide liquid and salt or acidic solvents followed by drying. Removal of the residual solvents and/orsalts may also be accomplished by passing the fiber or yarn through aqueous baths on the run, by flushing the bobbins with water as yarn is formed, and by washing or soaking skeins, rather than bobbins, of yarn. Dry-spun yarn may be strengthened bywashing with even a minor amount of water.
The fibers prepared from the anisotropic compositions or dopes of this invention and related isotropic dopes, are characterized by a unique internal structure and exceptionally high tensile properties, either as extruded or after being heattreated.
This unique internal structure of the fiber is evidenced by its low orientation angle and/or high sonic velocity. The physical meaning or orientation angle is that it establishes an angle (i.e., one half of the orientation angle) about the fiberaxis in which a given percentage of crystallites are aligned. In the fiber of the present invention, a high percentage (i.e., greater than about 50 percent, generally about 77 percent) of the crystallites are aligned within this angle (one half of theorientation angle) about the fiber axis; this percentage is determined from an intensity trace of the fiber's diffraction pattern (as described hereinafter). For example, the intensity trace is an essentially Gaussian curve for most of the fibers ofthis invention (i.e., essentially all of the heat-treated fibers and most of the as-extruded fibers). For such a curve, about 77 percent of the diffraction intensity falls within this angle and this is interpreted as showing that a like percentage ofcrystallites is aligned within this angle. For the few fibers (e.g., some of the as-extruded fibers) for which the curve may not be Gaussian-like (e.g., the curve may be a composite of several curves exhibiting partially resolved peaks), greater thanabout 50 percent of the crystallites are aligned within this angle, (see Example 83).
In addition to the orientation angle characterization, fibers of this invention are characterized by some velocity. Sonic velocity is a structural parameter relating to the fiber's molecular orientation along the fiber axis. A higher value ofsonic velocity is the result of a higher degree of molecular orientation along the fiber axis. Sonic velocity and related parameters are described by Charch and Moseley in the "Textile Research Journal," Vol. XXIX, No. 7, 525-535 (1959) and by Moseleyin the "Journal of Applied Polymer Science," Vol. III, No. 9, 266-276(1960).
Orientation angle and/or sonic velocity demonstrate the unique internal structure of the fiber. These structural parameters each relate to orientation and each evidence the uniqueness thereof. Sonic velocity is a measure of the total molecularorientation as contrasted with crystalline orientation. This total molecular orientation differs from the orientation described by orientation angle, i.e., orientation angle is a measure of crystallite orientation determined by X-ray measurements. Theunique internal structure of the fibers of this invention is evidenced by either or both of these orientation parameters, each parameter suitably describes the uniqueness and the parameters are correlated for the fibers of this invention.
The unique internal structure of the fibers of this invention is believed to be responsible for the exceptionally high tensile properties thereof. The relationship between the fiber structural parameters (orientation angle and sonic velocity)and the fiber's tensile properties is illustrated in FIGS. VIII and IX. These figures, prepared from data given in the following examples, show that for fibers of this invention as the orientation angle decreases (FIG. VIII) and/or the sonic velocityincreases (FIG. IX), the initial modulus increases.
In general, as shown in the examples which follow, fibers of this invention possess these high tensile properties "as-spun" or "as-extruded." "As-spun" or "as-extruded" fibers of this invention are defined as those formed in the normal processesof spinning (i.e., forming, shaping, or finishing steps), but which are not submitted to a drawing (elongation) or heat-treating operation which changes the molecular order or arrangement of polymer molecules. However, the fibers may be subjected towashing and drying operations needed to remove solvents or impurities. Other operations which may be carried out without changing the fundamental character of the fibers include (1) application of finishes, dyes, coatings, or adhesives; (2) physicallytreating the fiber by twisting, crimping, cutting into staple; (3) using the fiber in forming snaped objects, fabrics, papers, resin or rubber composites; etc.
As-extruded fibers of this invention are preferred for particular end uses e.g., tire cord. For such uses, it is generally desirable that, in addition to high modulus and tenacity value, the fiber exhibits elongation of at about 5 percent. However, post-shaping treatments (e.g., heat treatment) which improve the modulus and tenacity, often do reduce the elongation (e.g., to below 5 percent). Since particular preferred fibers of this invention possess desirably high moduli and tenacitiesas-extruded, and exhibit elongation values of at least about 5 percent, these as-extruded fibers are well suited for such end uses.
The as-extruded tensile properties of both the wet- and dry-spun as-extruded fibers can be enhanced by subjecting the undrawn fibers to a heat treatment. Hot air ovens, hot pins, hot slots, hot plates, liquid heating baths are useful for suchtreatments. The tensile properties of the as-extruded fibers are preferably enhanced by heating the fiber, maintained in a taut state, or drawn in a nitrogen atmosphere maintained at a temperature in the range of about 300.degree.-1,000.degree. C.,preferably 500.degree.-600.degree. C., for from 0.1 second to 5 minutes, preferably 0.1-10 seconds as subsequently shown.
The fibers of this invention possess excellent chemical and thermal properties. They retain their tensile properties after being heated and boiled for 0.5 hr. in aqueous hydrochloric acid (1 percent) and caustic (1 percent) solutions. Thefibers are essentially unaffected after being soaked for 1 hr. at 60.degree. C. in commercially used dry cleaning solvents such as perchloroethylene and trichloroethylene. The fibers are self-extinguishing when they are removed from an open flame.
The excellent tensile properties of the fibers of this invention make them especially useful as reinforcing agent for plastics, tire cord, V-belts, etc.
The compositions or dopes of this invention may be formed into films by a conventional wet-extrusion method, such films are usually kept under restraint when they are subsequently dried and washed. Compositions prepared in the above-describedmanner also may be formed into fibrids by shear-precipitation techniques (e.g., as described in Morgan U.S. Pat. No. 2,999,788), or applied as a liquid coating to a variety of substrates which may be in the form of sheets, papers, wires, screens,fibers, fabrics, foams, solid or microporous objects, etc. The substrates may be glass, ceramics, brick, concrete, metal (e.g., copper, steel, aluminum, brass), wood and other cellulosic materials, wool, polyamides, polyesters, polyacrylonitrile,polyolefins, polyvinylhalides, cured epoxy resins, cured aldehydeurea resins, etc.
Generally, an anisotropic dope can be used to produce an as-extruded fiber of properties superior to those of fibers produced from an otherwise similar dope which is isotropic or less antisotropic (i.e., an emulsion of isotropic and anisotropicphases in which the isotropic phase is predominant). Contrasts of the properties of a fiber from a highly anisotropic dope to those of a fiber prepared from a dope which is slightly anisotropic or isotropic are shown in the examples.
MEASUREMENTS AND TESTS
Inherent Viscosity: Inherent viscosity (.eta.inh) is defined by the following equation: ##EQU3## wherein (.eta.rel) represents the relative viscosity and (C) represents a concentration of 0.5 gram of the polymer in 100 ml. of solvent. Therelative viscosity (.eta.rel) is determined by dividing the flow time in a capillary viscometer of a dilute solution of the polymer by the flow time for the pure solvent. The dilute solutions used herein for determining (.eta.rel) are of theconcentration expressed by (C), above; flow times are determined at 30.degree. C., using concentrated (95-98 percent) sulfuric acid as a solvent, unless otherwise specified.
Fiber Tensile Properties: Fiber properties of tenacity, elongation, and initial modulus are coded as T/E/Mi and are reported in their conventional units, i.e., grams per denier, percent, and grams per denier. Denier is coded as Den. Suchproperties are conveniently measured in accordance with ASTM operational specifications, D76-53, (Oct. 1962), utilizing a testing machine, e.g., an Instron tester (product of the Instron Engineering Corp., Canton, Mass.), providing a constant rate ofextension. Unless otherwise specified, samples having a break elongation of up to about 8 percent are tested at a rate of extension of 10%/minute; samples of higher break elongation are tested at 60%/minute. Samples are filaments which measure 1 inch(2.54 cm.) in length or yarns having 3 turns/inch which measure 10 inches (25.4 cm.) in length; and testing is done at 21.degree. C. and 65% R.H.
Samples are not boiled off (scoured) but generally are conditioned at 21.degree. C. and 65% R.H. for at least 16 hours (sometimes expressed herein as "as is"), unless otherwise specified. If boil-off is specified, it consists of boiling thefilaments or yarns for 30 minutes in 0.1 percent aqueous sodium lauryl sulfate, rinsing, drying at 40.degree. C. for 1 hr. and conditioning at 21.degree. C. and 65% R.H. for at least 16 hours, unless otherwise specified.
Fiber Heat Treatment: Unless otherwise stated in the examples, the post-extrusion heat treatment process applied to the fibers and yarns obtained from fluid compositions and dopes of this invention comprises washing or soaking the as-extrudedfiber or yarn in water until essentially free of the spinning media and/or salt, drying them, then heating them in one of the devices described below.
Device A
The device consists of an inner stainless steel tube 32 in. (81.3 cm.).times.0.3125 in. (7.94 mm.) (I.D.) mounted concentrically in a second tube [1.06 in. (2.69 cm.) O.D.], the whole assembly being centered in a 12 in. (30.48 cm.) electricfurnace. Nitrogen gas enters through 2 nipples in the outer tube located 10 in. (25.4 cm.) out from either side of the center of the tube, such that the incoming nitrogen passes through the annular space between the two tubes. The nitrogen passes fromthe annular space into the inner tube through a small hole located in the wall of the inner tube to its center and thence out the ends of the inner tube at such a rate as to change the atmosphere in the 12 in. (30.48 cm.) heated zone of the inner tube atleast once a minute. The outer ends of the device which protrude from the furnace are wrapped with asbestos fiber and glass tape to within about 2 in. (5.08 cm.) of each end. The temperature of the furnace is controlled by a thermocouple brazed to thecener of the outside wall of the outer tube and connected to Minneapolis-Honeywell "Pyrovane" controller. The heated tube has a temperature profile with the maximum temperature in the center region. The nominal heat-treating temperature is determinedby a thermocouple brazed to the outer central surface of the inner tube. In passing fibers through the tube, guides are used to keep the fiber centered and out of contact with the tube walls.
Device B
This is identical with Device A, above, in terms of tube dimensions, furnace type, etc., and is operated in the same general manner. This device differs from A, above, in the amount of insulation wound on the ends and in the fact that thenitrogen inlets are on opposite sides of the outer tube in Device A but are on the same side in Device B. Differences in nitrogen flow rates may exist between the two devices.
Device C
The device consists of an inner stainless steel tube 35 in. (89 cm.).times.0.5 in. (1.27 cm.) (I.D.) mounted concentrically in a second tube [i.e., a 1 in. (2.54 cm.) diameter stainless steel pipe, 18 in. (45.7 cm.) long], the whole assemblybeing centered in a 12-in. (30.48 cm.) electric furnace. Nitrogen gas enters through two nipples attached to the ends of the outer tube (one at each end of the outer tube) such that the incoming nitrogen passes through the annular space between the twotubes. The nitrogen passes from the annular space into the inner tube through two small holes located in the wall of the inner tube at its center and thence out the ends of the inner tube at such a rate as to change the atmosphere in the 12 in. (30.48cm.) heated zone of the inner tube at least once a minute. The outer ends of the device which protrude from the furnace are wrapped with glass wool to within about 2 in. (5.08 cm.) of each end. The temperature of the furnace is controlled by aMinneapolis-Honeywell "Pyrovane" controller, by means of a thermocouple in contact with the center of the outside surface of the inside tube. The heated tube has a temperature profile with the maximum temperature in the center region. The nominalheat-treating temperature is determined by a second thermocouple in contact with the outer central surface of the inner tube. In passing fibers through the tube, guides are used to keep the fiber centered and out of contact with the tube walls.
Device D
The device consists of a stainless steel tube, 0.286 inch (7.26 mm.) inside diameter and 32 inches (81.3 cm.) in length. The tube has a hot nitrogen stream piped into its center and out through its ends at a rate which changes the atmosphereinside the tube once per minute. The tube is mounted in a concentric steel pipe through which the nitrogen passes prior to entering the yarn-treating zone. The entire assembly is mounted inside a small 12-inch (0.3 m.) long, combustion furnace. Athermocouple is brazed to the external surface of the steel pipe and is positioned close to the furnace elements. The output of the thermocouple is connected to a Minneapolis-Honeywell "Pyrovane" controller, which controls the temperature of the furnaceand pipe at such a level that a thermocouple brazed to the outside surface of the inner heat treating tube at its center indicates the temperature at that region. Additional heaters are wrapped around the portion of the heat-treating tube whichprotrudes from the combustion furnace. A typical profile of the temperature in the tube (for a center or "nominal" temperature of 536.degree. C.), obtained by varying the position of a test thermocouple, is given below:
______________________________________ TEMPERATURE PROFILE OF HEAT-TREATING TUBE Distance from Entrance, in Temp. (Multiply .times. 2.54 for distance in cm.) .degree.C. ______________________________________ 0 135 6 179 10 336 12 452 14515 15 532 16 537 17 536 18 527 20 474 22 368 24 270 28 213 32 184 ______________________________________
When appropriate in the examples which follow, the use of Device A, B, C and D in treating fibers is indicated, together with the nominal heat-treating temperature observed for the central section (approxiately 1-2 inches) of the inner tube forthat device.
Peak Height Ratio: A measure of the relative intensity of the two major equatorial diffraction peaks for poly(p-benzamide) is given by the peak height ratio (PHR). A suitable method for determining the PHR involves the use of a reflectiontechnique to record the intensity trace of the X-ray diffraction pattern with an X-ray diffractometer.
The measurement is made using poly(p-benzamide) isolated as follows. The polymerization mixture is combined slowly with a large excess of polymer non-solvent, e.g., water, vigorously stirred in a suitable blender, and thereby converted to apowder or finely granular form. The powdered polymer is thoroughly washed with water, and optionally with ethanol, by repeated stirring in the blender followed by filtration, and is dried in a vacuum oven at 60.degree.-90.degree. C. before being storedor treated for subsequent processing.
Approximately 0.5 gram of water- and amide- or urea-free polymer is pressed into a sample holder under an applied pressure of 3,125 lb/in..sup.2 (219.8.times.10.sup.3 g./cm..sup.2). Using CuK.alpha. radiation, a trace of the intensity isrecorded from 6.degree. to 40.degree., 2.theta., and with 0.5.degree. slits, at a scanning speed of 1.degree., 2.theta., per minute, a chart speed of 1 inch (2.54 cm.) per minute, and a time constant of 2; 2.theta. is the angle between theundiffracted beam and the diffracted beam. The full scale deflection of the recorder is set so that the peak with maximum intensity is at least 50 percent of the scale, which is a linear scale. To calculate the PHR, a base line is first established onthe diffractometer scan by drawing a straight line between the points on the curve at 8.degree. and 38.degree., 2.theta.. Vertical lines (at constant 2.theta. values) are drawn from the peaks in the vicinity of 20.3.degree. and 23.4.degree.,2.theta., to the base line, and the height of the peaks, in chart divisions, above the base line is ascertained. The PHR is then calculated from the equation
where A=height of the peak, approximately located at 20.3.degree., 2.theta., above the base line in chart divisions, B=height of the peak, approximately located at 23.4.degree., 2.theta., above the base line in chart divisions.
A typical trace of an X-ray diffraction pattern of powdered poly(1,4-benzamide) homopolymer isolated from preparations in amide or urea media appears in FIG. III. A smooth line was drawn as indicated to compensate for instrument noise and themeasurements are made therefrom.
Sedimentation Test: To a solution of 1.0 g. of dry lithium chloride in 30 ml. of dry N,N-dimethylacetamide is added 0.5 g. of dry polymer powder and comminuted to a particle size of about 20.mu. or less. The tube is stoppered and its contents,heated at 60.degree.-80.degree. C., are subjected to stirring by a mechanical agitator for a period of from 10 min. to 4-5 hrs. If polymer particles remain visible, the contents of the tube are cooled to -70.degree. C. (e.g., by immersion in a bath ofsolid carbon dioxide and acetone), then are allowed to warm up until stirring can be resumed, and are heated as above. The tube is then allowed to stand upright for a further 24 hours without stirring. After this time, if no polymer residue liessettled on the bottom of the tube, the sample is said to satisfy the Sedimentation Test.
Crystallinity: The degree of crystallinity indicated by the X-ray diffraction patterns is assessed in a qualitative manner by visual examination and use of the following terms:
amorphous: having only diffuse rings or arcs,
trace: much diffuse scatter with some sharpening of the principal spots,
low: moderate degree of sharpness in the spots with appreciable surrounding diffuse scatter,
medium: quite sharp spots but with the retention of some diffuse character.
high: very sharp diffraction spots and essential absence of diffuse scattering. With increasing crystallinity, the number of diffraction spots usually increases.
It is to be understood that these ratings are only intended as a differentiation of the range of crystallinities observed for species of fibers within this invention and not as a limitation thereof.
Orientation Angle: The orientation angle of the fiber (filament) is determined by the general method described in Krimm and Tobolsky, Textile Research Journal, Vol. 21, pp. 805-22 (1951). A wide angle X-ray diffraction pattern (transmissionpattern) of the fiber is made using a Warhus pin-hole camera. The camera consists of a collimator tube 3 in. (7.6 cm.) long with two lead (Pb) pin-holes 25 mils (0.0635 cm.) in diameter at each end, with a sample-to-film distance of 5 cm.; a vacuum iscreated in the camera during the exposure. The radiation is generated by Philips X-ray unit (Catalog No. 12045) with a copper fine-focus diffraction tube (Catalog No. 32172) and a nickel beta-filter; the unit is operated at 40 kv. and 16 ma. Afiber-sample holder 20 mils (0.051 cm) thick is filled with the sample; all the filaments that are in the X-ray beam are kept parallel. The diffraction pattern is recorded on Kodak No-Screen medical X-ray film (NS-54T) or equivalent. The film isexposed for a sufficient time to obtain a pattern which is considered acceptable by conventional standards (e.g., a pattern in which the diffraction spot to be measured has a sufficient photographic density, e.g., between 0.2 and 1.0, to be accuratelyreadable). Generally, an exposure time of about 45 minutes is suitable; however, a lesser exposure time may be suitable, and even desirable, for highly crystalline and oriented samples to obtain a more accurately readable pattern. The exposed film isprocessed at a temperature of 68.degree..+-.2.degree. F. in Du Pont Cronex X-ray developer for 3 min., in a stop bath (30 ml. of glacial acetic acid in 1 gal. [3.785 l.] of distilled water) for 15 sec., and in General Electric Supermix X-ray fixer andhardener solution for 10 min. The film is washed in running water for 0.5 hr. and is dried.
The arc length in degrees at the half-maximum intensity (angle subtending points of 50 percent of maximum intensity) of the principal equatorial spot is measured and taken as the orientation angle of the sample. The specific arcs used fororientation angle determinations on fibers described in the following examples (in the order presented in the following section) occurred at the following positions, 2.theta. (degrees):
______________________________________ Fiber of Example 2.theta. (Degrees) ______________________________________ 1(A-1) 22.56 1(H-1) 22.41 1(A-2) 22.56 1(H-2) 22.51 2(A) 22.49 4(A) 24.35 4(H) 15.59 6(A) 22.73 7(A) 22.44 7(H) 21.45 8(A) 22.10 8(H) 22.19 9(A) 21.20 9(H) 22.00 10(A) 22.32 10(H) 21.82 11(A) 21.55 11(H) 21.78 13(A) 22.39 13(H) 22.22 14(A) 22.34 14(H) 22.12 15(A) 22.44 15(H) 22.46 16(A) 22.44 16(H) 22.32 17(A) 22.93 17(H) 22.59 18(A) 22.51 18(H) 22.15 19(A) 22.68 19(H) 22.29 20(A) 22.17 20(H) 22.15 21(A) 21.60 21(H-1) 21.93 21(H-2) 22.00 22(A) 20.83 22(H) 22.12 23A(A) 20.68 23A(H) 22.00 23B(A) 21.05 23B(H) 20.05 24(A) 21.31 24(H) 20.28 25(A) 20.83 25(H) 21.95 26(A) 20.38 26(H-1)21.95 26(H-2) 22.15 27(A) 22.10 27(H) 21.93 28(H) 21.95 29(H) 22.17 30(H) 22.93 31(A) 22.27 31(H) 22.34 32(A) 21.88 32(H) 22.20 33(A) 21.48 33(H) 22.17 34(A) 20.98 34(H) 22.10 35(A) 21.50 35(H) 22.17 36(A) 22.16 36(H) 22.19 37(A) 22.54 37(H) 22.39 38(A) 22.71 38(H) 22.24 39(A) 22.27 39(H) 22.34 40(H) 23.41 41(A) 23.39 41(H) 23.36 42(H) 21.93 43(H) 21.93 44(A) 22.98 44(H) 22.44 45(A) 23.51 45(H) 22.59 46(A) 23.46 46(H) 22.51 47(A) 22.39 47(H) 22.05 48(H) 22.78 51(A)22.29 51(H) 20.20 52(A) 22.69 52(H) 22.07 53(A) 23.22 53(H) 22.34 54(A) 25.69 54(H) 19.97 55(A-1) 26.08 55(H) 18.47 55(A-2) 26.06 56(A-1) 22.98 56(A-2) 22.93 57(A) 23.07 57(H) 22.44 67A(A) 22.64 67D(A) 22.56 68(H) 22.12 76(A) 18.92 76(H) 18.48 77(A) 18.84 77(H) 18.18 79(H) 25.37 80(A) 19.00 80(H) 18.48 81(H) 16.35 ______________________________________ A = As extruded fiber H = Heattreated fiber A1 = First asextruded fiber in example A2 = Second asextruded fiber inexample H1 = First heattreated fiber in example H2 = Second heattreated fiber in example
The orientation angles of fibers of this invention are variously determined by three related densitometer methods (or equivalents thereof) from the X-ray film whose development has been described above.
In one method (Method One) the azimuthal intensity distribution of the diffraction arc is obtained by use of a Joyce-Loebl Automatic Recording Microdensitometer (Model MK III C, having a rotating stage, product of Joyce, Loebl and Co., Gateshead,England). Typical instrument settings used are: lever ratio: 1:1; objective lens: 5/0.10; recorder speed; integrate; slit setting: 187; wedge: 0.087 density units/cm. Variations of these settings, which may be required by the nature of a givendiffraction pattern, are made in accordance with the manufacturer's manual for this equipment (dated August, 1963). In operation, the film is placed on the stage, the instrument is focused on the film, and the center of the diffraction pattern is madecoincident with the stage center; both these centers are made coincident with the light beam of the instrument. The stage and mounted film are moved to permit the light beam to pass through the most intense area of the diffraction spot, the oppositespot is checked to insure true centering, and after any necessary fine adjustments are made, the recording of the azimuthal intensity trace through a 360.degree. rotation of the film is made on suitable linear scale coordinate paper. There is obtaineda curve which has two major peaks. A base line is drawn beneath each peak such that the background density of the film is extended beneath the peak. A perpendicular line is dropped from each peak maximum to the base line. Through the mid-point of eachperpendicular line (i.e., the "half-height" point is drawn a line parallel to the base line which intersects each leg of the respective curves. The leg-to-leg length of each "half-height" horizontal line is converted to the degrees of arc as follows. The horizontal distance (i.e., parallel to the base line) between the two peak maxima is measured and represents 180.degree. of arc. By direct proportion to this peak-to-peak distance, the "half-height" leg-to-leg distance is converted to a degreevalue. The values for the two arcs are averaged and this is the orientation angle referred to herein.
The percentage of crystallites aligned with respect to the fiber axis within one-half of the angle calculated by the above-described method is determined as follows. For each peak of the above-described trace, perpendicular lines are dropped tothe base line from the points of contact on the peak of the leg-to-leg "half-height" horizontal line. This establishes a rectangle bounded by the base line, the two perpendicular lines, and the "half-height" horizontal line. By use of a planimeter, therelative area of the rectangle plus the area of the peak under the curve and above the "half-height" horizontal line is determined (total=Area 1). The total area under the peak above the base line is then determined by the planimeter (Area 2). Thepercent of crystallites aligned within the orientation angle equals: ##EQU4##
A second method (Method Two) used to determined orientation angles in the filaments of the instant invention employs an improved version of the "flying-spot" densitometer described by Owens and Statton in "Acta Cryst." (1957) 10, 560-562. Theequipment used is similar to that described by Owens and Statton in their FIG. 1, with the following differences:
1. The Sola Constant Voltage Transformer No. 80808 is replaced by catalog No. 23-22-112, and this unit is connected only in series between the master switch of the 500 Volt Regulated Supply.
2. The Dumont No. 304 A Display Oscilloscope and the adjacent Calibrating Signal Generator are replaced by a Tektronix 532 Display Oscilloscope combined with a Tektronix Type 53/54 K Preamplifier. The combined units are connected in series onlybetween the Main Switch and the Photomultiplier.
3. The Flying Spot Oscilloscope (Dumont No. 304 A) and its Cathode-Ray Tube are replaced by a Tektronix 536 Oscilloscope having a 536 P 5 Cathode-Ray Tube.
4. The 500 Volt Regulated Supply is connected to the Photomultiplier and also to the Circle Generator (a type of device designated by Owens and Statton as a Scanning Frequency Generator).
5. The Circle Generator is connected at one point through a Tektronix Type 53/54 K Horizontal Pre-amplifier and at a second point through a line-circle switch and a Tektronix Type 53/54 K Vertical Preamplifier to the Tektronix 536 Oscilloscope.
Operation of this device follows the instructions given by Owens and Statton, except that the calibration with a square wave from a signal generator is not necessary. As described in the article, a metal block conveniently establishes theinfinite density level of the display program. A clear portion of the film provides a reference for zero density.
As noted by the authors, the "flying spot" densitometer provides a rapid measure of the orientation angle and the photographic density (optical density).
A third method (Method Three) by which orientation angles of the fibers of this invention are determined comprises a Leeds & Northrup Microphotometer (Catalogue No. 6700-P1) whose electronic components have been replaced by a Keithley 410Microammeter (Keithley Instruments Inc., Cleveland, Ohio). The output of this apparatus is fed to a Leeds & Northrup Speedomax Recorder, Type G. From the curve traced by this apparatus on, e.g., semi-log chart paper, the orientation angle and thecrystallite alignment may be obtained by procedures comparable to those employed with the Joyce-Loebl equipment described above.
Of the above three methods or instrument systems, Method One and Method Three described above, provide the most accurate determinations of the orientation angle. The precision of the "flying-spot" method is about .+-.1.5.degree. of angle valuereported. The orientation angles reported in the following examples are determined using Method Two (the "flying-spot" apparatus), unless otherwise indicated, since it provided speed and convenience of measurement for the large number of fibersanalyzed.
Sonic Velocity: In the following examples, the velocity of sound in fibers of this invention, identified as the sonic velocity (SV) of the fiber, is determined by using (in a conventional manner, according to the manufacturer's directions) a KLHdynamic modulus tester PPM-5 (product of the KLH Research and Development Corp., Cambridge, Mass.), hereinafter identified as "PPM-5," in conjunction with a Speedomax Type G potentiometric recorder (product of the Leeds & Northrup Co., Philadelphia,Pa.), hereinafter identified as "recorder." The latter instrument is operated as a 10-millivolt recorder. These instruments permit measurements to be made as plots of sound propagation time as a function of distance.
The procedure by which the sonic velocity measurements herein are determined may be summarized as follows, with all measurements being taken in an air atmosphere maintained at 70.degree. F. and 65 percent relative humidity, (R.H.). The yarnsare exposed to the latter conditions for a minimum of 16 hours prior to the SV determination.
The range switch of the modular unit of the PPM-5 is set at 100, thus causing the recorder to read 100 microseconds on a full scale deflection basis, or 10 microseconds for each inch across the paper perpendicular to the paper direction. Therecorder is adjusted to advance the chart paper (No. 690489, Leeds & Northrup Co.) at the rate of 0.688 inch/min.
The yarn sample is mounted in the scanner unit of the PPM-5 and is properly weighted to effect a tension on the yarn of 0.1 g./den. The power switch, zero control, and threshold adjustment are activated (in a conventional manner, according tothe manufacturer's directions). Then, while the movable transducer (or yarn probe) of the PPM-5 scanner cyclicly moves away from and toward the stationary transducer (yarn probe) at the rate of 3 in./min., a sonic pulse signal of 10,000 cycles/sec. isapplied to the yarn. As the probe moves along the yarn, on the chart paper is recorded a diagonal line which traverses the paper from side-to-side. The stylus of the recorder reverses direction when the probes are at the points of maximum and minimumseparation from each other.
Since the chart paper is advanced at the rate of 0.688 in./min., the probe speed along the yarn is faster than the chart advancement speed by a ratio of 3/0.688 or 4.36/1 [i.e., for each one inch of chart movement, the moving probe has covered4.36 inches (11.05 cm.) along the yarn].
The velocity of sound between two points in the yarn (sonic velocity, SV) is then determined by multiplying the slope of the recorded chart line by 11.05 km./sec. as follows: ##EQU5## The factor, 11.05 km./sec., results from the combination ofchart and probe speeds and the unit conversion requirements as shown in the calculation below. ##EQU6##
Sonic velocity values reported herein are based on a measurement of the slope of the chart line established as the two probes separate (i.e., as the moving probe travels away from the yarn tension weight). Usually, the slope value which ismultiplied by 11.05 km./sec. is the average of three separate slope determinations made for three separate diagonal chart lines.
EXAMPLES
The following nonlimiting examples are illustrative of the practice of this invention.
EXAMPLE 1
This example illustrates (1) the preparation of poly(p-phenylene terephthalamide), (2) the preparation of anisotropic and isotropic oleum dopes thereof, and (3) fibers thereof.
Polymer Preparation: Powdered terephthaloyl chloride (71.1 g., 0.35 mole) is added at once to a solution of p-phenylenediamine (37.8 g., 0.35 mole) in a mixture of hexamethylphosphoramide (420 ml.) and N-methyl-2-pyrrolidone (210 ml.) containedin a 1-liter resin-making kettle equipped with an air-driven stirrer and a calcium chloride drying tube. The temperature of the reaction mixture is moderated with a water bath at room temperature. A solid mass is obtained within minutes and allowed tostand at room temperature for 4 hrs. The mass is then combined with water and stirred at high speeds in a gallon-size (3.785 liter) blender. The polymer is washed three times with water by being stirred in a blender and isolated by being filtered on asintered-glass coarse-pore Buchner funnel. The polymer is dried overnight in a vacuum oven at about 70.degree. C. The inherent viscosity, measured as a solution of 125 mg. polymer in 25.0 ml. of 95-98 percent (by weight) sulfuric acid, is 2.64.
Anisotropic Dope Preparation: A mixture of 36.0 g. of the above polymer and 264 g. of fuming (3 percent free SO.sub.3) sulfuric acid is mixed anhydrously with an air-driven disc-type stirrer in a 500 ml. resin-making kettle while cooling with anice/water bath. The mixture is stirred overnight and is allowed to stand for 15 days at room temperature. The resulting dope exhibits stir-opalescence and depolarizes plane polarized light.
Fiber Preparation by Wet Spinning Anisotropic Dope: A portion of the spin dope prepared above is centrifuged to remove entrapped air. It is then extruded by means of a mechanically drive syringe through a 0.010 in. (0.254 cm.) thick preciousmetal spinneret having 20 holes of 0.003 in. (0.076 mm.) diameter into an aqueous coagulating bath at 41.degree. C. The bath is about 2 in. (5.1 cm.) wide and about 1 in. (2.54 cm.) deep. After passing through the bath for about 2 ft. (0.61 m.) theyarn is snubbed out of the water at about a 45.degree. angle to an electrically driven wind-up device. The yarn is collected on a perforated bobbin at 65 ft./min. (19.8 m./min.). It is then washed in cool running water for several (i.e., 3 hr.) hoursand dried in air at room temperature. The filaments exhibit low crystallinity and an orientation angle of 34.degree. and a sonic velocity of 4.56 km./sec. Filaments (boiled off) exhibit the following T/E/Mi/Den. values: 5.3/10.4/171/5.0.
Heat Treatment of Fibers from Anisotropic Dope: The above yarn is passed at 25 ft./min. (7.63 m./min.) through a tube [Device A] heated to 600.degree. C. and collected at 27.5 ft./min. (8.34 m./min.). The resulting fibers exhibit highcrystallinity, an orientation angle of 15.degree., and a sonic velocity of 8.37 km./sec. Filaments (boiled off) exhibit the following T/E/Mi/Den. values: 12.8/1.9/817/4.84.
Isotropic Dope Preparation: A mixture of 9.0 g. of the above polymer and 111.0 g. of fuming (2 percent free SO.sub.3) sulfuric acid is mixed anhydrously with an air-driven disc-type stirrer in a 500-ml. resin-making kettle while cooling with anice/water bath. The mixture is stirred overnight or until a clear viscous dope is obtained during which time the cooling bath is allowed to warm to room temperature.
Fiber Preparation by Wet Spinning the Isotropic Dope: A portion of the clear spin dope prepared above is centrifuged to remove entrapped air. It is then extruded by means of a mechanically driven syringe through a 0.010 in. (0.0254 cm.) thickprecious metal spinneret having 20 holes of 0.003 in. (0.076 mm.) diameter into an aqueous coagulating bath at room temperature. The bath is about 2 in. (5.1 cm.) wide and about 1 in. (2.54 cm.) deep. After passing through the bath for about 2 ft. (0.61 m.) the yarn is snubbed out of the water at about a 45.degree. angle to an electrically driven wind-up device. The yarn is collected on a perforated bobbin at 37 ft./min. (11.3 m./min.). It is then washed in cool running water for several hours(i.e., 3 hr.) and dried in air at room temperature. The filaments exhibit low crystallinity and an orientation angle of about 50.degree. as measured from a wide angle X-ray pattern. Filaments (boiled off) exhibit the following T/E/Mi/Den. values:3.1/20.8/106/7.0.
Heat Treatment of Fibers from the Isotropic Dope: The above yarn is passed at 25 ft./min. (7.63 m./min.) through a tube [Device A] heated to 550.degree. C. and collected at 27.5 ft./min.). The resulting fibers exhibit high crystallinity and anorientation angle of 19.degree.. Filaments (boiled off) exhibit the following T/E/Mi/Den. values: 5.3/1.4/401/5.7.
EXAMPLE 2
This examples illustrates (1) the preparation of poly(p-phenylene terephthalamide), (2) an anistropic oleum dope thereof, and (3) high modulus fibers thereof.
Polymer Preparation: Powdered terephthaloyl chloride (101.55 g., 0.5 mole) is added to a solution of p-phenylenediamine (54.0 g., 0.5 mole) in a mixture of hexamethylphosphoramide (600 ml.) and N-methyl-2-pyrrolidone (300 ml.) and stirred at highspeeds in a blender. A solid mass is obtained within minutes. After 20 min., the mass is combined with water and stirred at high speeds in a gallon-size (3.785 liter) blender. The polymer is washed four times with water, once with alcohol, and finallywith acetone by being stirred in a blender and isolated by being filtered on a Buchner funnel. The polymer is dried overnight in a vacuum oven at about 100.degree. C. The yield of polymer is 116 g. (97.5 percent of theoretical). The inherentviscosity, measured as a solution of 125 mg. polymer in 25.0 ml. of 95-98 percent (by weight) sulfuric acid, is 3.8.
Anisotropic Dope Preparation: A mixture of 50.0 g. of the above polymer and 450.0 g. of fuming (0.8 percent free SO.sub.3) sulfuric acid is mixed anhydrously with an air-driven disc-type stirrer in a 500-ml. resin-making kettle while coolingwith an ice/water bath. The mixture is stirred overnight during which time the cooling bath is allowed to warn to room temperature. The resulting dope exhibits stir-opalescence and depolarizes plane polarized light. It exhibits a solution visocity atroom temperature of 5000 poise, measured by a Brookfield (model RVF) viscometer employing a No. 7 spindle, at a spindle rate of 2 r.p.m.; at a rate of 20 r.p.m. the dope exhibits a solution viscosity of only 1,660 poise.
Fiber Preparation by Wet Spinning: The spin dope prepared above is centrifuged to remove entrapped air. It is then extruded at the rate of about 0.8 ml./min. under a pressure of 370 lb./in..sup.2 (26 .sup.Kg /cm..sup.2) through a 0.025 in.(0.064 cm.) thick precious metal spinneret having 20 holes of 0.002 in. (0.0051 cm.) diameter into an aqueous coagulating bath maintained at 43.degree. C. The bath is about 16 in. (40 cm.) wide, 5.5 in. (14 cm.) deep and 37 in. (94 cm.) long withstainless steel rollers placed about 2 ft. (0.61 m.) from each other. The yarn is drawn through the bath and around the rollers such that it makes three passes through the water bath. It is then snubbed out of the bath at about a 45.degree. angle toan electrically driven wind-up device. The yarn is collected on a perforated bobbin at 27 ft./min. (8.24 m./min.) while being wetted on the bobbin by passing through a water reservoir located at the lower portion of the collection bobbin. It is thenwashed in cool running water overnight and a portion is removed for heat treatment. The remainder is dried on the bobbin in air at room temperature. The dry filaments exhibit low crystallinity and an orientation angle of 31.degree. and a sonicvelocity of 5.00 km./sec. Filaments exhibit the following T/E/M.sub.i Den. values: 7.0/9.1/173/1.93 (10 percent rate of extension).
Heat Treatment of Web Fibers: The wet (washed) yarn prepared above is passed at 25 ft./min. (7.63 m./min.) through a tube [Device B] heated to 500.degree. C. and collected at 26.5 ft./min. (8.09 m./min.). The resulting filaments exhibit highcrystallinity and an orientation angle of 11.degree. as measured from a wide angle X-ray pattern. Filaments exhibit the following T/E/M.sub.i /Den. values: 13.7/1.6/888/3.23.
EXAMPLE 3
This example illustrates the preparation of poly(2-methyl-p-phenylene 2,6-naphthalamide) and an anisotropic dope thereof.
Polymer Preparation: 2,6-Naphthaloyl chloride (12.65 g., 0.05 mole) is added at once to a slurry of 2-methyl-p-phenylenediamine dihydrochloride (9.75 g., 0.05 mole) in N,N-dimethyl-acetamide (120 ml., distilled from CaH.sub.2 at reduced pressureand stored over 5 A molecular sieves) contained in a 500 ml. resin-making kettle equipped with an air-driven stirrer and a calcium chloride drying tube. The temperature of the reaction mixture is moderated with a water bath at room temperature. Apaste-like mass is obtained within minutes and is allowed to stand overnight at room temperature, whereupon the paste becomes a hard stiff mass. Lithium oxide (3.0 g., 0.1 mole) is then mixed in with a spatula and the resulting mixture combined withwater and stirred at high speeds in a gallon-size (3.785 liter) blender. The polymer is washed three times with water by being stirred in a blender and isolated by being filtered on a sintered-glass coarse-pore Buchner funnel. The polymer is driedovernight in a vacuum oven at about 70.degree. C. The yield of polymer is 13.9 g. (92.2 percent of theoretical). The inherent viscosity, measured as a solution of 125 mg. polymer in 25.0 ml. of 95-98 percent (by weight) sulfuric acid, is 2.08.
Anisotropic Dope Preparation: A mixture of 7.5 g. of the above polymer and 45.0 g. of 99.5 percent (by weight) sulfuric acid is mixed anhydrously with a mechanically driven paddle-type stirrer in a 200 ml. round-bottom flask while cooling withan ice/water bath. The mixture is stirred overnight during which time the cooling bath is allowed to warm to room temperature. The resulting fluid dope exhibits stir-opalescence and depolarizes plane polarized light.
EXAMPLE 4
This example illustrates the preparation of poly(2,6-dichloro-p-phenylene 2,6-naphthalamide) and the direct preparation of fibers from the anisotropic N,N-dimethylacetamide/lithium chloride reaction mixture.
Polymer and Spin Dope Preparation: 2,6-Naphthaloyl chloride (12.65 g., 0.05 mole) is added at once to a solution of 2,6-dichloro-p-phenylenediamine (8.85 g., 0.05 mole; sublimed) in N,N-dimethylacetamide (120 ml., distilled from CaH.sub.2 atreduced pressure and stored over 5 A molecular sieves) contained in a 500 ml. resin-making kettle equipped with an air-driven stirrer and a calcium chloride drying tube. The mixture is stirred vigorously and the temperature is moderated with a cool(i.e., 20.degree. C.) water bath. After being stirred about 35 min., a stiff mass is obtained and is allowed to stand overnight at room temperature. Lithium oxide (1.50 g., 0.053 mole) is added to the stiff mass and is mixed in with a spatula. Afluid dope is obtained within a few minutes. This dope exhibits stir-opalescence and depolarizes plane polarized light. A small portion of the dope is combined with water and stirred at high speeds in a quart-size (0.946 liter) blender. The polymer iswashed three times with water by being stirred in a blender and isolated by being filtered on a sintered-glass coarse-pore Buchner funnel. The polymer is dried overnight in a vacuum oven at about 70.degree. C. The inherent viscosity, measured as asolution of 125 mg. of polymer in 25.0 ml. of 95-98 percent (by weight) sulfuric acid, is 1.99.
Fiber Preparation by Wet Spinning: The dope described above is centrifuged to remove entrapped gases. It is then extruded at the rate of about 3.5 ml./min. under a pressure of 50 lb./in..sup.2 (3.52 Kg/cm..sup.2) through a 0.010 in. (0.0254 cm.)thick precious metal spinneret having 100 holes of 0.003 in. (0.076 mm.) diameter into an aqueous coagulating bath maintained at about 51.degree. C. The bath is about 16 in. (40 cm.) wide, 5.5 in. (14 cm.) deep and 37 in. (94 cm.) long with stainlesssteel rollers placed about 2 ft. (0.61 m.) from each other. The yarn is drawn through the bath and around the rollers such that it makes three passes through the water bath. It is then snubbed out of the bath at about a 45.degree. angle to anelectrically driven wind-up device. The yarn is collected on a perforated bobbin at 39 ft./min. (11.9 m./min.). It is then washed in cool running water for 3 hr. and dried in air at room temperature. The filaments exhibit low crystallinity and anorientation angle of about 50.degree. as measured from a wide angle X-ray pattern. Filaments exhibit the following T/E/M.sub.i /Den. values: 8.7/8.6/222/3.75.
Heat Treatment of Fibers: The yarn prepared as above is passed at 25 ft./min. (7.63 m./min.) through a tube [Device B] heated to 500.degree. C. and collected at 27.5 ft./min. (8.49 m./min.). The resulting filaments exhibit medium crystallinityand an orientation angle of 10.degree. as measured from a wide angle X-ray pattern. Filaments exhibit the following T/E/M.sub.i /Den. values: 10.5/2.2/518/3.43.
EXAMPLE 5
This example illustrates (1) the preparation of poly(p-phenylene 2,6-naphthalamide), (2) an anisotropic sulfuric acid dope thereof, and (3) fibers thereof.
Polymer Preparation: 2,6-Naphthaloyl chloride (25.3 g., 0.10 mole) is added to a solution of p-phenylenediamine (10.80 g., 0.10 mole; sublimed through silica gel) in a mixture of hexamethylphosphoramide (120 ml., distilled from CaH.sub.2 andstored over 5 A molecular sieves) and N-methyl-2-pyrrolidone (80 ml., distilled from CaH.sub.2 and stored over 5 A molecular sieves) contained in a 500 ml. resin-making kettle equipped with an air-driven stirrer and a calcium chloride drying tube. Themixture is stirred vigorously and the temperature is moderated with a cool (i.e., 20.degree. C.) water bath. After several minutes (i.e., 3 min.) a small amount (i.e., less than -b 0.10 g.) of 2,6-naphthaloyl chloride is added to the hazy solution. Astiff mass is obtained within seconds and is allowed to stand overnight at room temperature. (In another similar but different run, a stiff mass is obtained within 1 min. without requiring the addition of extra 2,6-naphthaloyl chloride). The solid massis then combined with water and stirred at high speeds in a gallon-size (3.785 liter) blender. The polymer is washed three times with water by being stirred in a blender and isolated by being filtered on a sintered-glass coarse-pore Buchner funnel. Thepolymer is dried overnight in a vacuum oven at about 70.degree. C. The yield of poly(p-phenylene 2,6-naphthalamide) is 27.6 g. (95.7 percent of theoretical). The inherent viscosity, measured as a solution of 125 mg. of polymer in 25.0 ml. of 95-98percent (by weight) sulfuric acid, is 2.48.
Dope Preparation: A mixture of 7.5 g. of the above polymer and 67.5 g. of 98.7 percent by weight sulfuric acid is mixed anhydrously with a mechanically driven paddle-type stirrer in a 200-ml. round-bottom flask while cooling with an ice/waterbath. The mixture is stirred overnight during which time the cooling bath is allowed to warm to room temperature. The resulting fluid dope exhibits stir-opalescence and depolarizes plane polarized light.
Fiber Preparation by Wet Spinning: The spin dope prepared above is centrifuged to remove entrapped gases. It is then extruded by means of a mechanically driven syringe through a 0.025 inch (0.064 cm.) thick precious metal spinneret having 20holes of 0.003 inch (0.076 mm.) diameter into an aqueous coagulating bath at 25.degree. C. The water bath is about 2 in. (5.1 cm.) wide and about 1 in. (2.54 cm.) deep. After passing through the bath for about 2 ft. (0.61 m.), the yarn is snubbed outof the water at about a 45.degree. angle to an electrically driven wind-up device. The yarn is collected on a perforated bobbin at 22 ft./min. (6.7 m./min.) while being wetted on the bobbin by passing through a water reservoir located at the lowerportion of the collection bobbin. It is then washed in cool running water overnight and is dried in air at room temperature. Filaments exhibit the following T/E/M.sub.i /Den. values: 3.9/6.3/195/3.20.
Heat Treatment of Fibers: The above yarn is passed at 25 ft./min. (7.63 m./min.) through a tube [Device B] heated to 533.degree. C. and collected at 28 ft./min. (8.59 m./min.). The resulting filaments exhibit the following T/E/M.sub.i /Den. values: 7.6/1.7/540/6.50.
EXAMPLE 6
This example illustrates (1) the preparation of a random copolymer comprised of 54.7% by weight poly(p-phenylene 2,6-naphthalamide) and 44.3% by weight poly(p-phenylene terephthalamide), and (2) an anisotropic dope thereof, and (3) fibersthereof.
Polymer Preparation: Powdered terephthaloyl chloride (5.08 g., 0.025 mole; sublimed) is added at once to a solution of p-phenylene diamine (5.40 g., 0.050 mole; sublimed through silica gel) in a mixture of hexamethylphosphoramide (60 ml.,distilled from CaH.sub.2 at reduced pressure and stored over 5 A molecular sieves) and N-methyl-2-pyrrolidone (40 ml., distilled from CaH.sub.2 at reduced pressure and stored over 5 A molecular sieves) contained in a 500 ml. resin-making kettle equippedwith an air-driven stirrer and a calcium chloride drying tube. After mixing for about 5 min., 2,6-naphthaloyl chloride (6.33 g., 0.025 mole) is added at once. The mixture is stirred vigorously while the temperature is moderated with a cool (i.e.,20.degree. C.) water bath. After about 4 min. a crumb-like mass is obtained and is allowed to stand overnight at room temperature. It is then combined with water and stirred at high speeds in a gallon-size (3.785 liter) blender. The polymer is washedthree times with water by being stirred in a blender and isolated by being filtered on a sintered-glass coarse-pore Buchner funnel.
The inherent viscosity, measured as a solution of 125 mg. of polymer in 25.0 ml. of 95-98 percent (by weight) sulfuric acid is 5.51.
Dope Preparation- A mixture of 7.5 g. of the above polymer and 67.5 g. of 99.2 percent (by weight) sulfuric acid is mixed anhydrously with a mechanically driven paddle-type stirrer in a 200-ml. round-bottom flask, while cooling with an ice/waterbath. The mixture is stirred overnight during which time the cooling bath is allowed to warm to room temprature. The resulting dope is extremely viscous, exhibits stir-opalescence and depolarizes plane polarized light.
Fiber Preparation by Wet Spinning: The spin dope prepared above is centrifuged to remove entrapped gases. It is then extruded by means of a mechanically driven syringe through a 0.025 in. (0.064 cm.) thick precious metal spinneret having 20holes of 0.003 in. (0.076 mm.) diameter into an aqueous coagulating bath at 25.degree. C. The water bath is about 2 in. (5.1 cm.) wide and about 1 in. (2.54 depolarizes cm.) deep. After passing through the bath for about 2 ft. (0.61 m.) the yarn issnubbed out of the water at about a 45.degree. angle onto an electrically driven wind-up device. The yarn is collected on a perforated bobbin at 20 ft./min. (6.1 m./min.) while being wetted on the bobbin by passing through a water reservoir located atthe bottom of the collection bobbin. It is then washed in cool running water overnight and a portion removed for heat treatment. The remainder is dried on the bobbin in air at room temperature. The dry filaments exhibit trace crystallinity and anorientation angle of 37.degree. and a sonic velocity of 5.92 km./sec. Filaments exhibit the following T/E/M.sub.i /Den. values: 8.7/8.4/327/4.79 (10 percent rate of extension).
Heat Treatment of Wet and Dry Fibers: The above wet as-spun (washed) yarn is passed at 25 ft./min. (7.63 m./min.) through a tube [Device B] heated to 547.degree. C. and collected at 29.0 ft./min. (8.84 m./min.). The resulting fibers exhibithigh crystallinity and an orientation angle of 11.degree. as measured from a wide angle X-ray pattern. The yarn exhibits the following T/E/M.sub.i /Den. values: 12.7/1.8/895/87.3. In addition, the dry as-extruded yarn from above is passed at 25ft./min. (7.62 m./min.) through the nitrogen filled tube assembly heated to 535.degree. C. and collected at 28.0 ft./min. (8.54 m./min.). Filaments exhibit the following T/E/M.sub.i /Den. values: 9.5/1.8/633/4.67.
EXAMPLE 7
This example illustrates (1) the preparation of a copolyamide comprised of repeating units selected from the group of ##STR8## (relative molar ratio of 1:1:1, respectively), (2) an anisotropic dope of the copolyamide, and (3) fibers of thecopolyamide.
Polymer Preparation: p-Aminobenzoyl chloride hydrochloride (14.4 g., 0.075 mole) is weighed into a polyethylene bag in a dry-box, i.e., a chamber maintained under anhydrous conditions. The open end of the bag is secured to a glass tube of about3 in. (7.6 cm.) long on one end of which is a 29/26 inner joint. The bag assembly is removed from the dry-box and attached via the joint to a 1,000 ml. resin-making kettle equipped with a stirrer and calcium chloride drying tube. The contents of thebag are emptied as rapidly as possible into a solution of p-phenylenediamine (8.10 g., 0.075 mole) in a mixture of hexamethylphosphoramide (405 ml., distilled from CaH.sub.2 at reduced pressure and stored over 5 A molecular sieves) andN-methyl-2-pyrrolidone (135 ml., distilled from CaH.sub.2 at reduced pressure and stored over 5 A molecular sieves). After mixing 5 min. 2,6-naphthaloyl chloride (19.18 g., 0.075 mole) is added at once with vigorous stirring. The temperature of thereaction mixture is moderated with a cool (i.e., 20.degree. C.) water bath. Less than 0.1 g. of 2,6-naphthaloyl chloride is added after a further 8 min. The mixture sets up to an unstirrable mass in 1 hr. and is allowed to stand overnight at roomtemperature. The mixture is then combined with water and stirred at high speeds in a gallon-size (3.785 liter) blender. The solid is washed three times with water by being stirred in a blender and isolated by being filtered on a sintered-glasscoarse-pore Buchner funnel. The solid is dried overnight in a vacuum oven at about 70.degree. C. The yield of polymer is 30.5 g. (99.6 percent of theoretical). The inherent viscosity, measured as a solution of 125 mg. of polymer in 25.0 ml. of 95-98percent (by weight) sulfuric acid, is 3.22.
Dope Preparation: A mixture of 7.5 g. of the above polymer and 67.5 g. of 99.2 percent (by weight) sulfuric acid is mixed anhydrously with a mechanically driven paddle-type stirrer in a 200 ml. round-bottom flask while cooling with an ice/waterbath. The mixture is stirred overnight during which time the cooling bath is allowed to warm to room temperature. The resulting fluid dope exhibits stir-opalescence and depolarizes plane polarized light.
Fiber Preparation by Wet Spinning: The spin dope prepared above is centrifuged to remove entrapped air. It is then extruded by means of a mechanically-driven syringe through a 0.025 in. (0.064 cm.) thick precious metal spinneret having 20 holesof 0.003 in. (0.076 mm.) diameter into an aqueous coagulating bath at 25.degree. C. The bath is about 2 in. (5.1 cm.) wide and about 1 in. (2.54 cm.) deep. After passing through the bath for about 2 ft. (0.61 m.), the yarn is snubbed out of the waterat about a 45.degree. angle to an elect | | | |
