US3386967A - Polycaproamide having excess number of carboxyl end groups over amino end groups - Google Patents

Polycaproamide having excess number of carboxyl end groups over amino end groups Download PDF

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US3386967A
US3386967A US426632A US42663265A US3386967A US 3386967 A US3386967 A US 3386967A US 426632 A US426632 A US 426632A US 42663265 A US42663265 A US 42663265A US 3386967 A US3386967 A US 3386967A
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polymer
polycaproamide
yarn
end groups
acid
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Ian C Twilley
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Honeywell International Inc
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Allied Chemical Corp
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Priority to CH62266A priority patent/CH478862A/de
Priority to FR46327A priority patent/FR1463736A/fr
Priority to DE19661595253 priority patent/DE1595253A1/de
Priority to BE675293D priority patent/BE675293A/xx
Priority to NL6600662A priority patent/NL6600662A/xx
Priority to ES0321938A priority patent/ES321938A1/es
Priority to GB2521/66A priority patent/GB1117947A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • This invention relates to improved fiber-forming polycaproamide and to continuous multifilament polycaproamide yarn of improved strength andtoughness, obtainable from said polycaproamide.
  • Typical applications include high strength webbing such as safety belts, protective coverings such as tarpaulins, netting, and reinforced structures such as tires, conveyor belts and power transmission belts.
  • improvements in strength and toughness are continually sought since such improvements increase the effectiveness of the yarn in a particular utilization, or permit the use of less yarn to obtain satisfactory performance.
  • the specific properties of the yarn which are of primary interest in the aforesaid textile structures are the ultimate tensile strength, which is the force required to break the yarn, and the toughness index or the total mount of work required to break the yarn.
  • the tenacity of polycaproamide yarn can be increased by drawing the yarn to a higher state of molecular orientation. This expedient, however, results in a decrease in the ultimate elongation of the yarn, tending to diminish the toughness index. Moreover, highly oriented cords exhibit increased shrinkage at elevated temperatures which, in turn, may create difliculties during subsequent fabrication of reinforced rubber structures.
  • Another general approach toward improving the tenacity of polycaproamide yarn is to employ higher molecular Weight polymer in the production of said yarn.
  • the polycaproamide As the molecular weight of the polycaproamide is increased, there is generally an attendant increase in the viscosity of the molten form of the polymer, and this makes more diflicult the production of yarn by standard melt extrusion methods.
  • the polymer can be brought to higher spinning temperatures than the usual range of 250 to 290 C., but degradation of the polymer then sets in causing production of weak, discolored, non-uniform yarn.
  • this invention comprises a linear, fiber-forming e-polycaprolactam wherein the end groups are susbtantially all primary amino groups and carboxyl groups, the primary amino groups being not over about 20 milliequivalents per kilogram of polymer (hereinafter expressed as meq./kg.).
  • the total content of end groups Patented June 4, 1%68 "ice of my polycaproamide analyzes not over about 135 .meq /kg.
  • This polycaproamide is characterized by a relatively low rate of increase of melt viscosity as the number average molecular weight of the polymer increases, i.e. as the total content of end groups goes down.
  • the melt viscosity of the polymer can be determined in apparatus wherein shear is applied to the melt, one particular such apparatus being the Brabender plastograph. Measured as'described below with this plastograph, the logarithm of melt viscosity of my polycaproamide, plotted against number average molecular weight of the polymer, increases at a rate not above 6X l0 units per molecular weight unit.
  • My preferred polymers have number average molecular weights Well above those ordinarily suitable for spinning of polycaproamide, whereby particular advantage is realized from the relatively low melt viscosity of my polymers at high number average molecular weights.
  • These preferred poly-caproamides have been about 50 and about 80 meq./kg. of total end groups, corresponding to number average molecular weights from about 25,000 to about 40,000; have primary amino group analysis not above about 10 meq./kg.; and show Brabender melt viscosity at 265 C. not above about 500 units.
  • My polymers can be produced by polymerizing e-caprolactam and reacting the polymer with a dibasic carboxylic acid containing at least 6 carbon atoms per molecule.
  • the primary amino end groups of the polycaproamide react with the carboxyl groups of the acid.
  • One carboxyl group of the acid may react, thereby eliminating one primary amino group from the polymer and providing a second carboxyl end group in the polymer, this being the second carboxyl group of the dibasic acid.
  • both carboxyl groups of the dibasic acid can react with primary amino groups of the polymer thereby eliminating two primary amino groups.
  • dicarboxylic acid whichever of these reactions occurs, in the final polymer the content of combined dicarboxylic acid will be about equivalent to one half the excess of carboxyl groups analyzed in the polymer over primary amino groups analyzed therein.
  • Suitable quantities of dicarboxylic acid or similarly reactive derivative thereof for use in producing our polymers are about 0.l0.7 mol per 100 mols of lactam, the acid having between 6 and suitably about carbon atoms.
  • T o produce the preferred high molecular weight polymers of our invention, the proportion of dicarboxylic acid preferably used is about 0.2-0.4 mol per 100 mols of lactam.
  • my invention includes the above polymers in the form of continuous filaments e.g. a multifilament yarn, drawn to impart permanent elongation and showing, by X-ray analysis, molecular orientation along the filament axis.
  • the preferred polymers can be formed into such filaments having very high ultimate tensile strength (U.T.S.) of 9.5 grams per denier and higher, combined with very high toughness index of at least 40 as measured by the product of U.T.S. and square root of ultimate elongation at the break.
  • the accompanying drawing is a graph showing relation of Log 10 of Brabender melt viscosity to number average molecular weight for three polycaproamides, viz:
  • (C) Contains the preferred range of less than 10 meg/kg. of primary amino groups.
  • the polycaproamide composition of the present invention is prepared by polymerization of e-caprolactarn in the presence of a dibasic carboxylic acid and water, at elevated temperatures.
  • the polymerization can be carried out batchwise or continuously.
  • Ordinary polycaproamide has roughly equal proportions of amine and carboxyl end groups.
  • the resulting polycaproamide analyzes about 35-40 meq./kg. of primary amino end groups and about 65-60 meq./kg. of carboxyl end groups and has number average molecular weight of about 20,000.
  • the polymers of the present invention contain not more than 20 milliequivalents of amino end groups per kilogram of polymer (abbreviated hereinafter meq./kg.) and have number average molecular weight of at least about 15,000.
  • meq./kg. milliequivalents of amino end groups per kilogram of polymer
  • number average molecular weight of at least about 15,000.
  • the dibasic carboxylic acid employed in the present invention can be aliphatic, alicyclic, aromatic, or alkylaromatic, and must contain at least 6 carbon atoms.
  • suitable species include aliphatic acids such as adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecanedioic and tetradecanedioic; aromatic dicarboxylic acids such as terephthalic acid, alieyclic species such as cyclohexane 1,4-dicarboxylic acid; and heterochain species such as the his carboxymethyl ether of ethylene glycol.
  • the dicarboxylic acid can contain substituent groups which are non-reactive with amine or carboxyl groups in the course of the polymerization reaction.
  • the dibasic acid must be thermally stable and non-volatile under the conditions of polymerization, and will suitably contain 6-20 carbon atoms per molecule.
  • carboxy derivatives thereof, reactive with primary amino groups can be used to form the polycaproamides of this invention, e.g. dibasic acid monoand diesters, dibasic acid anhydrides, etc.
  • a suitable process for producing these polycaproamides involves including in a molten polymerization reaction mixture about 0.1-0.7 mole of dicarboxylic acid per 100 moles of lactam monomer.
  • equilibrium is approached between the carboxyl groups and primary amino groups in the polymerization reaction mixture at number average molecular weight not above about 20,000 under usual atmospheric pressure polymerization conditions; and at least about 30 meq. of primary amino groups per kilogram of polyamide remain present by analysis. Accordingly special measures are required to carry the reaction of the carboxyl groups and amino groups further.
  • a particularly useful method of accomplishing the required further reaction is to remove volatile by-products of the polymerization such as water by flowing at least 2 unit volumes (S.T.P.) of inert gas, capable of removing moisture from the reaction mixture, across the reaction mixture surface per hour per each unit volume of the reaction mixture.
  • volatile by-products of the polymerization such as water by flowing at least 2 unit volumes (S.T.P.) of inert gas, capable of removing moisture from the reaction mixture, across the reaction mixture surface per hour per each unit volume of the reaction mixture.
  • S.T.P. unit volumes
  • Other means which can be used include application of vacuum for prolonged periods during polymerization; and solid state polymerization methods carried out for long periods upon the polymer.
  • Preferred products are obtained under the above conditions and using about 0.2-0.4 mole of dibasic acid per 100 moles of lactam.
  • the number average molecular weight of a given polymer is determined from the relationship:
  • NH milliequivalents of amino end groups per kilogram of polymer
  • COOH milliequivalents of carboxyl end groups per kilogram of polymer.
  • Carboxyl groups are analyzed by dissolving a polymer sample in benzyl alcohol and titrating with sodium hydroxide solution in benzyl alcohol, to the phenolphthalein end point.
  • Primary amino groups are analyzed by dissolving a polymer sample in m-cresol and titrating with p-toluenesul fonic acid solution in methanol, to the thymol blue end point.
  • the acetyl groups are analyzed by dissolving a polymer sample in a 3:1 by volume mixture of phosphoric acid/ o-xylene; distilling off the o-xylene/ acetic acid azeotrope; and titrating it with aqueous sodium hydroxide to the phenolphthalein end point.
  • the minimum number average molecular weight of polymer in accordance with this invention corresponds to total content of end groups of about 135 meq. per kg. of polymer; and the preferred minimum number average molecular weight of 25,000 corresponds to about meq. of end groups per kg. of polymer.
  • number average molecular Weight of 15,000 is about 30-35 F.A.R.V.; 20,000 is about 60-70 F.A.R.V.; and 25,000 is about -100 F.A.R.V. for ordinary polycaproamides; and for polymers of this invention these molecular weights correspond to about 25-30, 40-50 and 55-65 F.A.R.V. and 30,000 number average molecular weight is about 90-95 F.A.R.V.
  • a polymer of this invention may be made to contain various property-modifying additive ingredients such as: flame retardant agents selected from compounds of antimony, phosphorus, and halogen; titanium dioxide delustrant; antistatic agents, adhesion promoting agents including isocyanates, epoxides, and their derivatives; heat and light stabilizers such as inorganic reducing ions; metal ions such as manganese, copper and tin; phosphites; and organic amines such as alkylated aromatic amines and ketone-aromatic amine condensates; thermally stable pigments such as Quindo Magenta (Allied Chemical Corp.) and inorganic pigments; fluorescent agents and brighteners such as Tinopal PCR; latent cross-linking agents; bacteriostats such as phenols and quaternary amines; colloidal reinforcing particles; antisoiling agents; compatible and incompatible fiber-forming polymers such as linear fiber-forming polyesters; and other known additives.
  • flame retardant agents
  • the additives can be incorporated into the polymer generally at any stage of polymerization, as concentrates distributed in monomer or in preformed polyamide, or as pure ingredients. When added as pure ingredients, care must be taken during addition to facilitate the rapid dispersal of the additive throughout the polymer system. This is especially true when the additive is of a corrosive nature and, in pure form would react with metal apparatus. In such cases, corrosion can be minimized by introducing the additives to the caprolactam feed stream via a tube of non-corrosive material which exhausts into the center of said stream and cocurrent therewith. It is also generally important when incorporating these additives, as is known, to obtain a good dispersion thereof in the polymer in order to obtain high quality filaments upon spinning.
  • polycaproamide of this invention can contain minor amounts of units other than caprolactam in the polymer chain, e.g. p-carboxybenzylamino units and the like.
  • the log of the Brabender melt viscosity of linear polycaproamides of given amino end group content approximates a straight line function of the number average molecular weight of these polyamides.
  • the melt viscosity of polymer of the present invention containing about 10-15 milliequivalents of amino end groups per kilogram of polymer approximately obeys the following equation:
  • a polymer of the present invention containing about 12 milliequivalents of primary amino groups per kilogram of polymer will have a Brabender melt viscosity of about 300.
  • a polymer of this invention containing fewer than 8 milliequivalents of amino end groups per kilogram of polymer will have a Brabender melt viscosity of only about 150 or so.
  • a polycaproamide of the prior art of the same number average molecular weight viz. about 26,000 and having equal proportions of amino and carboxyl end groups will have 38 milliequivalents of primary amino groups per kilogram of polymer and will have a Brabender melt viscosity of over 800.
  • the polymer of the present invention will have a melt viscosity 60%80% lower than ordinary polycaproamide of the prior art. Such lowered melt viscosity allows melt spinning polymers of higher molecular weights than can normally be spun to produce the higher strength yarns of this invention.
  • melt spinning of the polyamide of this invention can be carried out using any technique generally suitable for melt spinning polycaproamides.
  • molten polymer at a temperature of 250 C. to 290 C., the higher temperatures being employed with the higher molecular weight compositions, is pumped through filter means such as a bed of sand or screens or both, and thence through the orifices of a spinnerette plate.
  • filter means such as a bed of sand or screens or both
  • the extruded filaments pass downward through a quenching zone wherein the molten polymer extrudate is solidified to form continous filaments.
  • Conventional cooling gas can be employed such as air, nitrogen, carbon dioxide, steam, etc., at controlled temperature and fiow rate. The gas will generally be fiowed'co-current, counter-current, or cross-current to the filaments in one or more distinct regions, and can be quiescent in the zone around the spinnerette.
  • a preferred spinning technique which allows spinning at higher melt viscosities than usual, is to employ quiescent heated inert gas around the spinnerette, with temperatures in the quiescent zone at least 40 C. higher than the temperature of the polymer melt as it reaches the spinnerette, as disclosed and claimed in the copending US.
  • the drawing of the as-spun yarn to produce molecular orientation along the filament axis can be accomplished by conventional operations.
  • the yarn passes via a feed roll to a drawing zone wherein the yarn is subjected to tension and an elevated temperature in the range of -200 C., from which the yarn is withdrawn by a draw roll having a faster peripheral speed than the feed roll.
  • the draw point can be localized by means of a snubbing pin which may be heated or unheated, rotatable or nonrotata'ble.
  • Controlled yarn temperatures may be secured by various means such as: heated contact surfaces which may be flat or curved; radiant heating means; heated baths; heated vapors suitably confined to a region surrounding the travelling yarn; and other suitable means.
  • the ratio of a certain length of yarn after drawing to the length of the same mass of material immediately prior to drawing, or the ratio of the peripheral speeds of the draw roll to feed roll, provided there is no yarn slippage thereon, is the draw ratio of a drawing operation, and is normally expressed for example, as 4 or 5 where the ratio is respectively 4 or 5.
  • the yarn of the present invention is preferably drawn using a non-rotating draw pin, and auxiliary heating means to secure a draw ratio in the range of 4.0 to 6.5.
  • the yarn may be drawn in a single or multiple stages.
  • Tenacity measurements of the yarn of this invention were carried out with a Scott Tensilgraph IP4 using Spruance air-operated cord clamps and a gage length of 10 inches. A total weight of 10 kilograms was used including the carriage weight of 2 kilograms. At least four breaks on each sample are taken so that 4 breaks will fall within one half inch on the load scale; these are then averaged to ascertain the tensile strength. The ultimate elongation is likewise so determined on a Scott Tensilgraph by observation of the extended length of the yarn sample at its breaking point.
  • the toughness index is essentially the area under the stress-strain curve of a yarn sample from the origin or zero stress point out to the breaking point, and thus represents essentially the total amount of work required to rupture the fiber.
  • the area under the stress-strain curve, and thus the toughness index may be approximated by the formula -UTS(UE) wherein UTS is the ultimate tensile strength in grams per denier and UE is the ultimate elongation in percent as determined on an IP4 Scott Tester.
  • EXAMPLE 1 400 pounds of epsilon caprolactam and 0.45 percent by weight, i.e. 1.8 lbs. of sebacic acid (0.25 mole per 100 moles lactarn) were charged to a kettle equipped with a heating jacket and a horseshoe agitator. A trace amount of copper compound soluble in the reaction mixture, and a small amount of ketone/diarylamine condensation product as in Hydr U.S.P. 3,003,995 of October 10, 1961, were incorporated in the reaction mixture as heat stabilizer.
  • the polymer was extruded into a warm water bath and chopped into pellets by ,5 inch in size. The pellets were then hot water washed at 100 C. to reduce the content of hot water soluble constituents to about 12% by weight; and the pellets were dried to less than 0.1% moisture.
  • the polycaproamide thus produced was found to have a number average molecular weight of 30,800. It is designated A in Table I below.
  • polycaproamide polymer C of like number average molecular weight to polymer A was prepared by the process of this example, but omitting the sebacic acid.
  • the polymer melt was so viscous as to require special high strength motors to effect adequate agitation for temperature control in the polymerization kettle.
  • polymer B having about the same melt viscosity shown by the above polymer A was prepared by the procedure of this example, except using acetic acid (instead of sebacic acid) at a concentration of 0.28 mole percent in the polymerization reaction mixture.
  • acetic acid instead of sebacic acid
  • Table I The properties of the several polymers prepared are presented in Table I.
  • the polymers prepared hereinabove were melt spun at polymer melt temperature of 262 C. into a quenching tower employing air as the cooling medium.
  • the air flowed co-current with the filaments for the major course of their travel through the quenching tower.
  • the air was maintained quiescent and was heated to a temperature of about 335 C. by an annular shield around the spinnerette in accordance with copending U.S. application of Swanson, Harlacher and Dulin No. 426,631 filed Ian. 19, 1965.
  • Such use of heated quiescent gas was found to give optimum yarn properties; however, such is not essential and the same procedure except that the tower has no heated annular shield can also be used effectively, as shown in Table I below.
  • the quenching tower had a gas exhauster to remove caprolactam vapor evolved from the filaments as they passed through the quiescent air zone, generally as described and claimed in the copending U.S. application of Dulin Ser. No. 262,546 filed Mar. 4, 1963, now U.S. Patent 3,257,487.
  • the take-up speed of the filaments TABLE '1 Polymer Characteristics Additive Sebucic Acetic None Acid Acid Number average molecular weight 30, 800 20, 400 31,100 Brabeuder melt viscosity 350 335 2, Carboxyl end groups 58 49 31 Amino end groups 7 22 32 Yarn Characteristics With W ithollt With Unspiuheated heated heated nable shield shield shield Draw ratio 4. 9 4. 9 4. 7 Denier 840 840 841 Ultimate tensile strength (g.p.d.), i.e., UTS 10. 1 J. 85 9. 35 Ultimate elongation percent,
  • yarn prepared from the high molecular Weight spinnable polymer of the present invention has considerably higher ultimate tensile strength and considerably higher toughness index than yarn spun by the same procedure from a polymer obtained using a conventional acid terminated polymer, having about the same melt viscosity, but having lower molecular weight.
  • EXAMPLE 2 A series of polycaproamide polymers was prepared using the polymerization procedure of Example 1, cmploying O.20.4 mole percent sebacic acid, and utilizing progressively shorter reaction times and/ or applying water vapor pressure to secure polymers of progressively lower molecular weights having generally increasing contents of primary amino groups in the range about 10-15 meq. per kilogram of polymer. A series of comparison polymers was prepared similarly but omitting the sebacic acid and using approximately 60% lower inert gas sweep rate whereby comparable molecular weights were achieved in about the same reaction times.
  • O1 y Moles of Number Brabcnder p yinei of the present invention contain n .21 mole percent sebacic acid, has a Bar Mole 6r Molecular Viscosity melt viscosity which permits melt spinning up to a molec- 10 Dlabasw Acld Welgilt ular weight of about 28,000. The use of preferred amounts Piinelie Acid 380 26, 600 285 Suberie Acid.
  • the Bra- N b A Brabender Melt Viscosity bender melt viscosity is seen to be dependent upon the um er verage Molecular Weight Polycaprpamide Ordinary Polycaproamide molecular -g and the a ino eI ld group analysis.
  • the polymers of the present invention represented by e pnmary ammo gmups products D, E, F, G and H, made with at least .2 mole 14,500 72 120 percent sebacic acid, have primary amino group analysis 17,000... 80 186 30 170 320 below 20 milliequivalents of amine per kilogram of poly- 21,900-.- 193 405 mer.
  • the preferred products have number average molec- 24 700 245 722 1 340 1,198 ular weights of at least 25,000 and primary amino group 23.38% 32% figg analysis not above about 10 meq./kg., represented by r products D, E and F of Table IV.
  • a dicanboxylic acid of A of slmllar pfl y p was stuflled fewer than 6 Cambon atoms, namely .glutaric acid, was determine the effect of increased molecular weight on found substantially ineffective since, at the number aveir- Y P p Whllfi malmalmng melt VISCOSIW age molecular Weight f the polymer O-btained, the melt r constant at about 350 Brabender units.
  • polycapiroamides were prepared by the primary amino groups in the polymer for given molecular TABLE IV Mole Total Hours Sweep Gas 'lough- End Group Analysis Number Brabender Ultimate Sample Percent of Iolyinerizer Rate, Liters ness Average Mcl t 'lensrle Sebacie on Per Minute Index Amine Carboxyl Molecular Viscosity Strength Acid Temperature Weight 99 9. 0 6 37. 0 50 51 19,800 340 9. 33 .08 9. 5 6 37. 2 35 67 19, 000 342 9. 4 14 s. 5 6 37. 5 27 70 21, 500 945 9. 45 24 13. 5 10 40. 9 10 62 26, 900 350 9. s 24 16. 0 10 41.
  • Example 1 l Milliequivalents per kilogram of polymer. procedure of Example 1, except that the flow of sweep weight of the polymer. These polymers were spun essengas, and the duration of polymerization were varied as tially as in Example 1.
  • the viscosity of the polymer melt shown in Table IV, to obtain products all having about the being spun was adjusted to the exact value of 350 same high but still spinnable melt viscosity (about 340- Brabender units by setting the temperature of the melt 350 Brabender units at 265 C.) when possible; or to 70 to the required level determined by test in the Brabender app-roach maximum obtainable melt viscosity, when the proportion of sebacic acid used was above about 0.3 mole per 100 moles of lactam (e. g. 0.35 mole percent in the table).
  • the data of Table IV show that use of as little apparatus.
  • EXAMPLE 6 This example illustrates production of high strength polyeaproamide yarn from a dispersion of synthetic linear polyester in a polycaproamide of this invention.
  • Granular polyethylene terephthalate polymer was used, melting about 255 C. (DTA) and about 265 C. (optical), having density (when amorphous) of about 1.33 gm. per ml. at 23 C., and about 1.38 gm./ml. in the forms of drawn filament, having reduced viscosity of about 0.85 and having 'IT about 65 C.
  • elongation not above 20% will have tensile modulus (modulus of elasticity) ranging from about 70 to about 140 gm. per denier, depending on spinning conditions employed.
  • This polyester analyzed about 58 milliequivalents of carboxyl groups and about 60 meq. of hydroxyl groups per kilogram.
  • Carboxyl groups in the polyester were determined by dissolving the sample in benzyl alcohol at about reflux temperature of the alcohol and immediately cooling the solution at room temperature for a few seconds, and pouring into chloroform. The resulting solution was titrated with sodium hydroxide in benzyl alcohol to the phenolphthalein end point.
  • the polyester hydroxyl groups were determined by heating a solution of polyester in l-methylnaphthalene with succinic anhydride for 4 hours at 175 C.
  • This polyester (30 parts) was mixed with 70 parts of granular polycaproamide having reduced viscosity (measured at 25 C. and 0.5 gm./ 100 ml. concentration, in purified o-chlorophenol containing 0.1% water) of about 1.04 dl./gm., T about 35 C. and density about 1.14 gm. per ml. at 23 C.
  • the mixture of polyamide and polyester granules was blended in a double cone blender for 1 hour.
  • the granular blend was dried to a moisture content of no more than 0.01%; then melted at 285 C. in a 3 /2" diameter screw extruder operated at a rotational speed of about 39 rpm. to produce a pressure of 3000 p.s.i.g. at the outlet.
  • a dry nitrogen atmosphere was used to protect the blend against absorbing moisture. Residence time in the extruder was 8 minutes.
  • the molten mixture thereby obtained had melt viscosity of about 2000 poises at 285 C.
  • the polyester was uniformly distributed throughout and had average particle diameter of about 2 microns, as observed by cooling and solidifying a sample of the melt, leaching out the polyamide component with formic acid, and examining the residual polyester material.
  • the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 2000 p.s.i.g. and at a temperature of 285 C., and was extruded through a spinneret plate having 136 orifices of circular cross section, each of said orifices having a diameter of .013 inch.
  • the resulting filaments proceeded downwardly through a quenching chamber containing air at 82 C. and relative humidity fiowing cocurrent to the filaments at a rate of about 37 cubic feet per minute.
  • the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1350 feet per minute under a tension of 40 grams.
  • a lubricating finish was applied to the yarn to the extent of about 5% pick-up based upon the weight of the yarn.
  • the yarn thus obtained has an approximate denier of 4600 and a birefringence of .006.
  • the yarn thus produced was then subjected to a drawtwisting operation by running the yarn to an upper draw roll provided with a cot roll to prevent yarn slippage, then in a single Wrap about a stationary ceramic drawpin of 1%" diameter, then to a contact surface heater at C., and then in five wraps about a lower draw roll and associated separator roll.
  • the yarn was drawn 5.4 times its initial length.
  • the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.4 turns per inch of twist to the yarn.
  • the yarn thus obtained is found to have the properties which in Table A below are compared to the properties of a polycaproamide yarn produced similarly but without incorporating polyester therein.
  • polyester microfibers having an average diameter of about 0.20.4 micron and average length of 40-60 microns. These fibers lay generally lengthwise of each filament and numbered at least 2,000 through a 1,000 square micron filament cross section.
  • the fatigue resistance was measured upon a yarn like that of this example but containing 40 ppm. of copper and 0.3% by Weight of BXA (trade name of a Naugatuck Chemical Div. antioxidant further described in US. Patent 3,003,995 to Honey, issued Oct. 10, 1961); and
  • Polycaproamide of claim 1 containing sebacic acid combined therein in an amount about equivalent to onehalf the excess of carboxyl groups in the polymer over the primary amino groups-therein.
  • Polycaproamide of claim 1 in the form of a continuous filament showing, by X-ray analysis, molecular orientation along the filament axis.
  • Filament of claim 3 formed of polycaproamide having total end group content in the range of 50-80 milliequivalents per kilogram of polycaproamide and primary amino end group content not above about 10 milliequivalents per kilogram of polycaproamide, the polycaproamide forming said filament having sebacic acid combined therein in amount about equivalent to one half the excess of carboxyl groups in the polycaproamide over primary amino groups therein; said filament having ultimate tensile strength of at least 9.5 grams per denier and having toughness index of at least 40.
  • Process for the production of a high molecular weight, low melt viscosity polycaproamide comprising forming a molten polymerization reaction mixture at about 240-290 C. from, as essential. ingredients, e-caprolactam and about 0.1-0.7 mol, per 100 mols of lactam, of a dicarboxylic acid having between 6 and 20 carbon atoms per molecule; and smoothly stirring said reaction mixture while flowing over the surface thereof a gas capable of removing moisture from said reaction mixture, at flow rate of at least 2 unit volumes of said gas, measured at standard temperature and pressure, per hour per each unit volume of said reaction mixture, until the totalprimary amine group plus carboxyl groupanalysis of the resulting hot water washed and dried polymer is not above about 135 meq./kg. and the primary amino group analysis thereof is not above about 20 meq./kg. these analyses being in units of milliequivalents per kilogram of polymer. 7

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US426632A 1965-01-19 1965-01-19 Polycaproamide having excess number of carboxyl end groups over amino end groups Expired - Lifetime US3386967A (en)

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Application Number Priority Date Filing Date Title
US426632A US3386967A (en) 1965-01-19 1965-01-19 Polycaproamide having excess number of carboxyl end groups over amino end groups
FR46327A FR1463736A (fr) 1965-01-19 1966-01-18 Poly-2-caproamide à poids moléculaire élevé et fils obtenus, ainsi que son procédé d'obtention
DE19661595253 DE1595253A1 (de) 1965-01-19 1966-01-18 Verfahren zur Herstellung hochfester Garne
BE675293D BE675293A (enrdf_load_html_response) 1965-01-19 1966-01-18
CH62266A CH478862A (de) 1965-01-19 1966-01-18 Verfahren zur Herstellung von Poly-e-caproamid
NL6600662A NL6600662A (enrdf_load_html_response) 1965-01-19 1966-01-18
ES0321938A ES321938A1 (es) 1965-01-19 1966-01-18 Procedimiento para la produccion de un poliepsilon caproamida de baja viscosidad de fundido y alto peso molecular.
GB2521/66A GB1117947A (en) 1965-01-19 1966-01-19 High strength polyamide yarn

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Cited By (20)

* Cited by examiner, † Cited by third party
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US3468975A (en) * 1965-07-02 1969-09-23 Ici Ltd Process for the manufacture of elastomeric block copolymers containing polyamide and polyester segments
US3511815A (en) * 1968-05-08 1970-05-12 Ahmet Nuri Sayin Deep dyeing polycarbonamide filament
US3522328A (en) * 1967-10-11 1970-07-28 Eastman Kodak Co Modified polyester compositions containing polyamides prepared from aromatic diamines
US3527843A (en) * 1968-04-11 1970-09-08 Allied Chem Polylactam with polyester with 0.005 to 0.1 mol of 2,2-bis(hydroxymethyl) propionic acid per mol of lactam
US3544658A (en) * 1965-06-10 1970-12-01 Ici Ltd Polymeric compositions containing polyesters,polyamides and polyethers
US3846532A (en) * 1969-01-29 1974-11-05 Bayer Ag Continuous spinning and stretching process of the production of polyamide-6 filaments
USRE28937E (en) * 1971-11-18 1976-08-24 Allied Chemical Corporation Control of viscosity and polycaproamide degradation during vacuum polycondensation
US4321188A (en) * 1979-01-05 1982-03-23 Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa S.P.A. Process for producing synthetic flame resisting polyamides, flame resisting filaments and fibres and products obtained by using the same
JPS62263319A (ja) * 1986-05-06 1987-11-16 Teijin Ltd ポリアミドの溶融紡糸方法
US5149758A (en) * 1990-06-21 1992-09-22 Basf Aktiengesellschaft Continuous production of polycaprolactam having a regulated amino end group content
US5194319A (en) * 1988-03-07 1993-03-16 Kanebo, Ltd. Shaped polyamide articles and process for manufacturing the same
WO1993025736A1 (de) * 1992-06-06 1993-12-23 Basf Aktiengesellschaft Schnellgesponnene fäden auf der basis von polycaprolactam und verfahren zu ihrer herstellung
US5462802A (en) * 1991-12-02 1995-10-31 Teijin Limited Polyamide hollow and/or non-circular fiber and process for making same
WO1997046746A1 (en) * 1996-06-06 1997-12-11 Dsm N.V. Acid-dyeable fibre
US6194537B1 (en) 1998-01-15 2001-02-27 Karl Fischer Industrieanlagen Gmbh Nylon 6 chip and production of nylon 6 yarn and film and of further industrial articles from nylon 6
US6812323B1 (en) * 1998-03-20 2004-11-02 Basf Aktiengesellschaft Inherently light- and heat-stabilized polyamides with improved wet fastness
US20060292385A1 (en) * 2004-07-27 2006-12-28 Andreas Renekn Method of plating mineral filled polyamide compositions and articles formed thereby
WO2007090602A1 (en) * 2006-02-08 2007-08-16 Dsm Ip Assets B.V. Process for increasing the molecular weight of a polyamide
US10767012B2 (en) 2017-04-10 2020-09-08 Firestone Fibers & Textiles Company, Llc Functionalized polyamides and methods of preparing the same
CN114989422A (zh) * 2022-06-21 2022-09-02 浙江理工大学 一种工业丝用聚酰胺材料及其制备方法、纤维

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DE4421704A1 (de) * 1994-06-21 1996-01-04 Bayer Ag Verfahren zur Herstellung von hochmolekularem Polyamid 6

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US2241322A (en) * 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides from cyclic amides
US2241323A (en) * 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides
US2551702A (en) * 1943-07-28 1951-05-08 Bata Narodni Podnik Process for the production of polyamides by polymerization of lactams
DE766120C (de) * 1941-06-19 1954-06-21 Ig Farbenindustrie Ag Verfahren zur Veredelung von Superpolyamiden aus ªÏ-Aminocarbonsaeuren
DE935696C (de) * 1944-10-27 1955-11-24 Phrix Werke Ag Verfahren zur Herstellung von Superpolyamiden
US2805214A (en) * 1955-05-27 1957-09-03 Du Pont Polymerization of lactam with mixed catalyst
US2989798A (en) * 1955-06-30 1961-06-27 Du Pont Filaments of improved dye-receptivity
US3003222A (en) * 1958-11-17 1961-10-10 Du Pont Controlled relaxation of freshly drawn nylon
GB890437A (en) * 1958-02-20 1962-02-28 Du Pont Polycarbonamides
US3047541A (en) * 1958-08-05 1962-07-31 Inventa Ag Process for the continuous production of polyamide fibers and ribbons
US3090997A (en) * 1958-11-26 1963-05-28 Du Pont Method of continuous treatment of as-spun birefringent polyamide filaments
US3093881A (en) * 1955-06-30 1963-06-18 Du Pont Oriented nylon filaments
US3109835A (en) * 1958-10-08 1963-11-05 Allied Chem Process for producing ultrahigh viscosity polycaprolactam

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Publication number Priority date Publication date Assignee Title
US2241322A (en) * 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides from cyclic amides
US2241323A (en) * 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides
DE766120C (de) * 1941-06-19 1954-06-21 Ig Farbenindustrie Ag Verfahren zur Veredelung von Superpolyamiden aus ªÏ-Aminocarbonsaeuren
US2551702A (en) * 1943-07-28 1951-05-08 Bata Narodni Podnik Process for the production of polyamides by polymerization of lactams
DE935696C (de) * 1944-10-27 1955-11-24 Phrix Werke Ag Verfahren zur Herstellung von Superpolyamiden
US2805214A (en) * 1955-05-27 1957-09-03 Du Pont Polymerization of lactam with mixed catalyst
US2989798A (en) * 1955-06-30 1961-06-27 Du Pont Filaments of improved dye-receptivity
US3093881A (en) * 1955-06-30 1963-06-18 Du Pont Oriented nylon filaments
GB890437A (en) * 1958-02-20 1962-02-28 Du Pont Polycarbonamides
US3047541A (en) * 1958-08-05 1962-07-31 Inventa Ag Process for the continuous production of polyamide fibers and ribbons
US3109835A (en) * 1958-10-08 1963-11-05 Allied Chem Process for producing ultrahigh viscosity polycaprolactam
US3003222A (en) * 1958-11-17 1961-10-10 Du Pont Controlled relaxation of freshly drawn nylon
US3090997A (en) * 1958-11-26 1963-05-28 Du Pont Method of continuous treatment of as-spun birefringent polyamide filaments

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544658A (en) * 1965-06-10 1970-12-01 Ici Ltd Polymeric compositions containing polyesters,polyamides and polyethers
US3468975A (en) * 1965-07-02 1969-09-23 Ici Ltd Process for the manufacture of elastomeric block copolymers containing polyamide and polyester segments
US3522328A (en) * 1967-10-11 1970-07-28 Eastman Kodak Co Modified polyester compositions containing polyamides prepared from aromatic diamines
US3527843A (en) * 1968-04-11 1970-09-08 Allied Chem Polylactam with polyester with 0.005 to 0.1 mol of 2,2-bis(hydroxymethyl) propionic acid per mol of lactam
US3511815A (en) * 1968-05-08 1970-05-12 Ahmet Nuri Sayin Deep dyeing polycarbonamide filament
US3846532A (en) * 1969-01-29 1974-11-05 Bayer Ag Continuous spinning and stretching process of the production of polyamide-6 filaments
USRE28937E (en) * 1971-11-18 1976-08-24 Allied Chemical Corporation Control of viscosity and polycaproamide degradation during vacuum polycondensation
US4321188A (en) * 1979-01-05 1982-03-23 Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa S.P.A. Process for producing synthetic flame resisting polyamides, flame resisting filaments and fibres and products obtained by using the same
JPS62263319A (ja) * 1986-05-06 1987-11-16 Teijin Ltd ポリアミドの溶融紡糸方法
US5194319A (en) * 1988-03-07 1993-03-16 Kanebo, Ltd. Shaped polyamide articles and process for manufacturing the same
US5149758A (en) * 1990-06-21 1992-09-22 Basf Aktiengesellschaft Continuous production of polycaprolactam having a regulated amino end group content
US5462802A (en) * 1991-12-02 1995-10-31 Teijin Limited Polyamide hollow and/or non-circular fiber and process for making same
WO1993025736A1 (de) * 1992-06-06 1993-12-23 Basf Aktiengesellschaft Schnellgesponnene fäden auf der basis von polycaprolactam und verfahren zu ihrer herstellung
WO1997046746A1 (en) * 1996-06-06 1997-12-11 Dsm N.V. Acid-dyeable fibre
BE1010331A3 (nl) * 1996-06-06 1998-06-02 Dsm Nv Zuur aanverfbare vezel.
US6074749A (en) * 1996-06-06 2000-06-13 Dsm N.V. Acid dyeable fibre
US6194537B1 (en) 1998-01-15 2001-02-27 Karl Fischer Industrieanlagen Gmbh Nylon 6 chip and production of nylon 6 yarn and film and of further industrial articles from nylon 6
US6812323B1 (en) * 1998-03-20 2004-11-02 Basf Aktiengesellschaft Inherently light- and heat-stabilized polyamides with improved wet fastness
US20060292385A1 (en) * 2004-07-27 2006-12-28 Andreas Renekn Method of plating mineral filled polyamide compositions and articles formed thereby
WO2007090602A1 (en) * 2006-02-08 2007-08-16 Dsm Ip Assets B.V. Process for increasing the molecular weight of a polyamide
US20090306331A1 (en) * 2006-02-08 2009-12-10 Cornelia Emilie Maria Bronsaer Process for increasing the molecular weight of a polyamide
EA013823B1 (ru) * 2006-02-08 2010-08-30 ДСМ АйПи АССЕТС Б.В. Способ увеличения молекулярной массы полиамида
CN101379116B (zh) * 2006-02-08 2011-05-25 帝斯曼知识产权资产管理有限公司 一种用于提高聚酰胺分子量的方法
US10767012B2 (en) 2017-04-10 2020-09-08 Firestone Fibers & Textiles Company, Llc Functionalized polyamides and methods of preparing the same
CN114989422A (zh) * 2022-06-21 2022-09-02 浙江理工大学 一种工业丝用聚酰胺材料及其制备方法、纤维

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GB1117947A (en) 1968-06-26
NL6600662A (enrdf_load_html_response) 1966-07-20
BE675293A (enrdf_load_html_response) 1966-05-16
FR1463736A (fr) 1966-06-03
DE1595253A1 (de) 1970-03-05
CH478862A (de) 1969-09-30

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