US3106442A - Method of producing dimensionally stable polypropylene fibers - Google Patents

Method of producing dimensionally stable polypropylene fibers Download PDF

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Publication number
US3106442A
US3106442A US671256A US67125657A US3106442A US 3106442 A US3106442 A US 3106442A US 671256 A US671256 A US 671256A US 67125657 A US67125657 A US 67125657A US 3106442 A US3106442 A US 3106442A
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Prior art keywords
yarn
fibers
roll
stretched
heat
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US671256A
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English (en)
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Compostella Mario
Denti Franco
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Montedison SpA
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Montecatini Societa Generale per lIndustria Mineraria e Chimica SpA
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    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02JFINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/229Relaxing
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene

Definitions

  • This invention relates to textile fibers and more particularly to textile fibers of high polymers of propylene composed of, or containing a predominant proportion of, isotactic macromolecules as defined by Natta et al., and to processes for producing such fibers.
  • Isotactic macromolecules as defined by Natta et al. are macromolecules in which,
  • the tertiary asymmetric carbon atoms have, on the same chain section, the same steric configuration, and the main chain of which, if fully extended in a plane, shows all of the R groups bound to the tertiary carbon atoms of the monomeric units making up said chain section on one side of the plane and all of the H atoms bound to said tertiary carbon atoms on the opposite side of the plane.
  • the isotactic macromolecules which are crystallizable or crystalline, have a stereoregular structure of the kind shown in the model below:
  • the filament proceeding from the stretching stage having a high elasticity and being under tension, can be wound up on a bobbin but shrinks thereon so that the inner windings are compressed by the outer windings and the filament or yarn is, as a consequence, differentially strained and has different residual shrinkage capacities along the length thereof which are expended during further processing, e.g., dyeing, and result in uneven effects, such as uneven or non'le-vel dyeing.
  • An object of this present invention is to provide filaments and yarns of isotactic polypropylene which are less susceptible to heat-shrinkage (more heat-stable), may have modified elastic characteristics, and which have, in general, better mechanical characteristics than is normally the case.
  • the fibers or yarns are heat-treated under special conditions, after stretching thereof, the heat-treatment being performed, at least in part, before the fibers or yarns are twisted and Wound up.
  • the stretched fibers or yarns are stabilized against excessive shrinkage by heating them at a temperature which may be somewhat higher than the stretching temperature and while they are held under a tension
  • the delayed elastic recovery is such that they are not free to shrink or can shrink to only a controlled extent not greater than 15% of the initial length.
  • the heat-treatment In order to insure maximum relaxation of the strains introduced into the fibers and yarns during the earlier processing thereof, the heat-treatment must be carried out at a temperature as close as possible to the first order transition temperature for the isotactic polypropylene, which is about 169170 C.
  • the stabilization can be carried out continuously.
  • the yarn can be stretched at temperatures between 80 C. and 140 C. and then held under conditions of non-shrinkage or of controlled shrinkage at a temperature between 80 C. and 160 C., preferably between 135-145 C., i.e., at a temperature which is the same as or only slightly than the stretching temperature, for a time varying from a fraction of a second to a few seconds, e.g., about 5 seconds.
  • FIGURE 1 is a diagrammatic showing of apparatus suitable for use in stretching and annealing the yarns of isotactic polypropylene.
  • FIGURE 2 is a fragmentary view of one element of the apparatus.
  • FIGURE 1 there is shown a roll 2, a heater 3, a second roll 4, a second heater 5, a roll 6 and a winding system 7 of the ring type.
  • the yarn passes over roll 2 into the heater 3 and thence over roll 4, being stretched between rolls 2 and 4 which are rotated at different peripheral speeds to effect stretching of the yarn to the predetermined extent.
  • roll 2 may be rotated at a peripheral speed of 415 m./minute
  • roll 4 may be rotated at a peripheral speed of 20 to 100 m./minute, to impart the desired stretch to the yarn as it proceeds through heater 3.
  • the stretched yarn then passes from roll 4 into the heater 5 and over roll 6 to the wind-up.
  • the peripheral speed of roll 6 may be lower (15%) than, the same as, or somewhat higher than that of roll 4, so that the yarn passing through heater is held against shrinkage or shrinks to a controlled extent.
  • Rolls 2, and 6 may be driven by means of continuous speed-variators to adjust the stretching ratios. The rate of feed of the yarn to the heaters and the heating times are correlated so that at the selected stretching and stabilizing temperatures, the desired objectives are accomplished.
  • Heaters 3 and 5 may be heated in any suitable manner, for example by hot air, may have a length of, for instance 30 centimeters (for peripheral speeds of the rolls within the ranges already stated), and are provided with inlet and outlet openings as shown in FIGURE 2 for entry and exit of the yarn.
  • the heaters may be opened as shown at 8 in order to facilitate the introduction of the yarn.
  • the stretched yarn may be stabilized against excessive heat-shrinkage in two stages.
  • the fibers or yarns may be heat-treated under conditions of controlled shrinkage between 0 and twisted, wound on bobbins, and then given a further heat-treatment on the bobbin, the second heat-treatment being preferably performed at a temperature somewhat higher than the first heat-treatment.
  • the heating time on the bobbin may be a few seconds or it may be increased to about 60 minutes.
  • the stabilized yarn obtained by completing the heattreatment on the bobbin has substantially the same characteristics as the yarn which is stretched and annealed continuously in what may be regarded as essentially a single-stage process.
  • the stretched and heat-stabilized yarn can be wound up without diificulty, has satisfactory dimensional stability, and has improved mechanical characteristics, as compared to the yarns which are not annealed under heating and conditions of controlled shrinking.
  • the isotactic polypropylene produced by polymerizing propylene with the aid of the catalysts prepared from the transition metal compounds and the metal alkyls may contain some atactic polypropylene.
  • Such products may be used in making fibers and yarns provided the content of atactic polypropylene is not in excess of about 30%.
  • the extent to which the yarn is allowed to shrink between the limits of zero to 15 during the heat-stabilization is determined by the final characteristics desired for the yarn.
  • Thermal treatment of the yarn under controlled shrinkage which favors the return to a certain disorder or irregularity of the molecular structure, results in a slight decrease in the elastic characteristics of the yarn, a phenomenon which is useful for certain applications of the yarn.
  • the thermal treatment of the stretched yarn is carried out under conditions such that the yarn is not free to shrink, or is even held under a slight tension, the heattreatment fixes the orientation of the molecules effected by the stretching and the elastic properties of the yarn are not substantially altered as a result of the heat-stabilization. This is generally advantageous for most purposes for which the yarn is to be used, but the yarn tends to shrink to a somewhat higher extent in water at 100 C. than when the yarn is allowed to shrink to the limited controlled extent during the heat-treatment, other conditions being equal.
  • the high elastic characteristics normally possessed by the isotactic polypropylene fibers and yarns are at most only slightly reduced.
  • the final yarn therefore is not only dimensionally stable, and easy to wind, unwind, process and fabricate, but such stability is achieved without any substantial sacrifice of the desirable elastic properties.
  • the residual shrinkage capacity is uniform along the length of the yarn and is not greater than 34% as a maximum, which is acceptable and permits preparation of the cops and subsequent weaving operations to be carried out smoothly, without breaking of the yarn, and in the most satisfactory manner.
  • the extent to which the yarn shrinks during the heat-stabilization may be between zero and 15%. Increase in the percent shrinkage, within that range and up to the limit of 15 generally results in an increased elongation at break, the tenacity remaining almost constant.
  • Example 1 Using the apparatus shown in FIGURE 1, yarn of polypropylene having an intrinsic viscosity of 0.9 and consisting of isotactic polypropylene mixed with about 15% of atactic polypropylene, and having a titer of 100 den. were processed in diiferent ways with the results shown in the table below, items 1-8.
  • the yarns were- Stretched on a warm plate (yarns of items l3) After-stretched and stabilized under controlled shrinkage (yarns of items 4-6) Stretched and stabilized while prevented from shrinking (yarn of item 7) and Stretched-and stabilized under'tension (yarn of item 8) Mechanical Character Alter Stretching and Mechanical Oharac. after immersion in Setting boiling Water for 30 min. at free shrinking Rel. Tens. No V1 V2 V3 RS. Per- Per- T T Td cent cent I II Shrin. Shrin.
  • V speed of roll 2 (m./min.).
  • Vi speed of roll 4 (m./min.).
  • Va speed of roll 6 (UL/111111.).
  • Tons. Percent tension between rolls 4 and 6.
  • R ultimete strength, gJden.
  • R.E.R. percent perccnt recovery after a 10% strain of 5 minutes.
  • R.E.I. percent percent recovery after a 10% strain of 5 seconds.
  • M.E. elastic modulus, gJden.
  • Example 2 The yarn processed had a tenacityof 0.7 g./den., an elongation of 580%, and a titer of 300 denier, and was obtained by melt-spinning an isotactic polypropylene having an intrinsic viscosity of 0.8 and containing about 12% of atactic polypropylene. Apparatus asshown in FIG- URE 1 was used.
  • the yarn was stretched between roll 2 (peripheral speed 4.5 m./min.) and roll 4 (peripheral speed 27 m./min.) while passing through the warm air heater 8, having a length of 300 mm, and maintained at 130 C.
  • the stretched yarn was passed from roll 4 into warm air heater 5 (300 mm. long) maintained at 140 C., and thence to roll 6 rotating at a peripheral speed of 24.8 m./min.
  • the yarn was thus allowed to shrink 8% during travel thereof between rolls 4 and 6.
  • Example 3 The yarn processed had a tenacity of 0.8 g./den., an elongation of 610%, and a titer of 300 deniers. it was obtained by melt-spinning a crystallizable polypropylene having an intrinsic viscosity of 0.95 and containing about 12% of atactic polypropylene. Using apparatus as shown in FIGURE 1, the yarn was stretched between roll 2 (peripheral speed 4 m;/min.) and roll 4 (peripheral speed 2 6 m./min.) While passing through heater 3 having a length of 300 mm. and maintained at 130 C. by hot air circulating therein.
  • the stretched yarn was passed to roll 6 (peripheral speed 23.4 m./min.) thruogh the heater 5 maintained at 145 C. and 300 mm. in length. The yarn was thus allowed to shrink 10% during the second heattreatment.
  • the shrunk, heat-stabilized yarn was taken up on the dominant proportion of isotactic macromolecules and which is melt-spun to the fibers that can be processed by the present method may have, in general and preferably, an intrinsic viscosity of 0.3 to 2.0.
  • a polypropylene may be obtained by separation from the polymerizate resulting from polymerization of propylene with the catalysts aforesaid, by direct polymerization, or by heat-degradation of an isotactic polypropylene having a higher intrinsic viscosity.
  • Fibers formed by other methods such as wetand dryspinning techniques, may also be stretched and heat-stabi lized against subsequent excessive shrinkage by the present process, and either continuously or in successive stages.
  • the method of orienting the fibers and then setting them in the oriented condition while rendering them dimensionally stable without any substantial reduction in their elastic properties which method consists of the stepsof 1) passing the unor-iented fibers through a heating and stretching-for-orientation zone in which they are oriented by being stretched 5 to 10 times their initial length while being heated, in the absence of applied pressure, at a temperature of about C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
US671256A 1956-07-17 1957-07-11 Method of producing dimensionally stable polypropylene fibers Expired - Lifetime US3106442A (en)

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IT813891X 1956-07-17

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3217074A (en) * 1963-05-02 1965-11-09 Gould Charna Process for producing a filament having a fibrous linearly oriented core
US3241212A (en) * 1961-02-27 1966-03-22 Deering Milliken Res Corp Apparatus for crimping thermoplastic yarn
US3257490A (en) * 1962-10-17 1966-06-21 Du Pont Process for producing flat dimensionally stable, biaxially oriented polypropylene film
US3323190A (en) * 1963-06-12 1967-06-06 Hercules Inc Elastic polypropylene yarn and process for its preparation
US3330721A (en) * 1963-05-02 1967-07-11 Gould Charna Synthetic filaments and method of making the same
US3330897A (en) * 1961-02-07 1967-07-11 Chemcell 1963 Ltd Production of fibers of improved elastic recovery
US3432590A (en) * 1963-07-10 1969-03-11 Nat Plastic Products Co Inc Process for spinning elastic polypropylene fibers
US3491178A (en) * 1964-02-04 1970-01-20 Mitsubishi Rayon Co Method for spinning bicomponent polypropylene filaments
US3630205A (en) * 1969-07-31 1971-12-28 Ethicon Inc Polypropylene monofilament sutures
US3684782A (en) * 1967-09-12 1972-08-15 Paolo Longi Manufactured shaped articles of unsaturated olefinic copolymers
US4446690A (en) * 1982-10-18 1984-05-08 Milliken Research Corporation Bar balloon control
US4449354A (en) * 1982-10-18 1984-05-22 Milliken Research Corporation Disc type yarn tension control
US4449356A (en) * 1982-11-10 1984-05-22 Milliken Research Corporation Continuous A.C. tension control
US4449355A (en) * 1982-10-18 1984-05-22 Milliken Research Corporation A.C.-D.C. Slotted type yarn tension control
US4454710A (en) * 1982-10-18 1984-06-19 Milliken Research Corporation Balloon control for yarn texturing machine
US4457129A (en) * 1982-10-18 1984-07-03 Milliken Research Corporation Slotted disc type yarn tension control
US4462557A (en) * 1982-10-18 1984-07-31 Milliken Research Corporation Spring biased electromagnetically controlled tension control
US4478036A (en) * 1983-02-22 1984-10-23 Milliken Research Corporation Method, apparatus and intermittently textured yarn
US4532760A (en) * 1984-02-21 1985-08-06 Milliken Research Corporation D. C. Yarn tension control
US4560734A (en) * 1982-09-07 1985-12-24 Chisso Corporation Polypropylene fibers having improved heat-shrinkability and tenacity
US4911165A (en) * 1983-01-12 1990-03-27 Ethicon, Inc. Pliabilized polypropylene surgical filaments
EP0526759A1 (en) * 1991-07-12 1993-02-10 United States Surgical Corporation Polypropylene monofilament suture and process for its manufacture
US5277859A (en) * 1990-06-23 1994-01-11 Extrusion Systems Limited Method for the production of polypropylene yarn
US5494620A (en) * 1993-11-24 1996-02-27 United States Surgical Corporation Method of manufacturing a monofilament suture
US5871502A (en) * 1996-04-08 1999-02-16 Ethicon, Inc. Process for manufacturing a polypropylene monofilament suture
US6287499B1 (en) 1998-10-09 2001-09-11 United States Surgical Corporation Process of making bioabsorbable block copolymer filaments
US20060125142A1 (en) * 2002-10-04 2006-06-15 John Kennedy Process of making bioabsorbable filaments
US20100292730A1 (en) * 2002-10-04 2010-11-18 John Kennedy Process of making bioabsorbable filaments

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3073002A (en) * 1960-03-28 1963-01-15 E B & A C Whiting Non-distorting polypropylene fibers
US3161709A (en) * 1960-11-21 1964-12-15 Celanese Corp Three stage drawing process for stereospecific polypropylene to give high tenacity filaments
US3152380A (en) * 1961-05-05 1964-10-13 Du Pont Process for treating polypropylene fibers
GB1109448A (en) * 1965-02-02 1968-04-10 Ici Ltd Process for the production of ropes and cordage
US3214899A (en) * 1965-02-12 1965-11-02 Eastman Kodak Co Cordage product

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2325060A (en) * 1942-02-25 1943-07-27 Du Pont Nonshrinking yarn
US2411474A (en) * 1944-10-18 1946-11-19 Du Pont Method of improving filaments of hydrolyzed olefin/vinyl organic ester interpolymers
US2421334A (en) * 1944-04-26 1947-05-27 Ind Rayon Corp Method of treating twisted filamentary materials
US2439814A (en) * 1943-05-13 1948-04-20 American Viscose Corp Crimped artificial filament
US2455173A (en) * 1946-05-25 1948-11-30 Du Pont Yarn treating apparatus
US2509741A (en) * 1942-11-03 1950-05-30 Du Pont Production of filamentous structures
US2517694A (en) * 1943-09-14 1950-08-08 American Viscose Corp Crimped artificial filament
US2584779A (en) * 1947-11-12 1952-02-05 Courtaulds Ltd Production of threads of thermoplastic cellulose derivatives
US2669001A (en) * 1949-09-29 1954-02-16 Collins & Sikman Corp Method and apparatus for treating yarns
BE538782A (fr) * 1954-06-08 1955-12-06 Procédé de polymérisation d'oléfines, polymères ainsi obtenus et leurs applications
US2778090A (en) * 1952-12-30 1957-01-22 Duplan Corp Method of treating synthetic yarn
US2882263A (en) * 1954-12-16 1959-04-14 Montedison Spa Process for the polymerization of certain unsaturated hydrocarbons using iron-based polymerization agents
US2953428A (en) * 1955-06-22 1960-09-20 Union Carbide Corp Production of polychlorotrifluoroethylene textiles

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2325060A (en) * 1942-02-25 1943-07-27 Du Pont Nonshrinking yarn
US2509741A (en) * 1942-11-03 1950-05-30 Du Pont Production of filamentous structures
US2439814A (en) * 1943-05-13 1948-04-20 American Viscose Corp Crimped artificial filament
US2517694A (en) * 1943-09-14 1950-08-08 American Viscose Corp Crimped artificial filament
US2421334A (en) * 1944-04-26 1947-05-27 Ind Rayon Corp Method of treating twisted filamentary materials
US2411474A (en) * 1944-10-18 1946-11-19 Du Pont Method of improving filaments of hydrolyzed olefin/vinyl organic ester interpolymers
US2455173A (en) * 1946-05-25 1948-11-30 Du Pont Yarn treating apparatus
US2584779A (en) * 1947-11-12 1952-02-05 Courtaulds Ltd Production of threads of thermoplastic cellulose derivatives
US2669001A (en) * 1949-09-29 1954-02-16 Collins & Sikman Corp Method and apparatus for treating yarns
US2778090A (en) * 1952-12-30 1957-01-22 Duplan Corp Method of treating synthetic yarn
BE538782A (fr) * 1954-06-08 1955-12-06 Procédé de polymérisation d'oléfines, polymères ainsi obtenus et leurs applications
US2882263A (en) * 1954-12-16 1959-04-14 Montedison Spa Process for the polymerization of certain unsaturated hydrocarbons using iron-based polymerization agents
US2953428A (en) * 1955-06-22 1960-09-20 Union Carbide Corp Production of polychlorotrifluoroethylene textiles

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330897A (en) * 1961-02-07 1967-07-11 Chemcell 1963 Ltd Production of fibers of improved elastic recovery
US3241212A (en) * 1961-02-27 1966-03-22 Deering Milliken Res Corp Apparatus for crimping thermoplastic yarn
US3257490A (en) * 1962-10-17 1966-06-21 Du Pont Process for producing flat dimensionally stable, biaxially oriented polypropylene film
US3217074A (en) * 1963-05-02 1965-11-09 Gould Charna Process for producing a filament having a fibrous linearly oriented core
US3330721A (en) * 1963-05-02 1967-07-11 Gould Charna Synthetic filaments and method of making the same
US3323190A (en) * 1963-06-12 1967-06-06 Hercules Inc Elastic polypropylene yarn and process for its preparation
US3432590A (en) * 1963-07-10 1969-03-11 Nat Plastic Products Co Inc Process for spinning elastic polypropylene fibers
US3491178A (en) * 1964-02-04 1970-01-20 Mitsubishi Rayon Co Method for spinning bicomponent polypropylene filaments
US3684782A (en) * 1967-09-12 1972-08-15 Paolo Longi Manufactured shaped articles of unsaturated olefinic copolymers
US3630205A (en) * 1969-07-31 1971-12-28 Ethicon Inc Polypropylene monofilament sutures
DK155869B (da) * 1969-07-31 1989-05-29 Ethicon Inc Isotaktisk polypropylenmonofilamentsutur og fremgangsmaade til fremstilling deraf
US4560734A (en) * 1982-09-07 1985-12-24 Chisso Corporation Polypropylene fibers having improved heat-shrinkability and tenacity
US4454710A (en) * 1982-10-18 1984-06-19 Milliken Research Corporation Balloon control for yarn texturing machine
US4446690A (en) * 1982-10-18 1984-05-08 Milliken Research Corporation Bar balloon control
US4457129A (en) * 1982-10-18 1984-07-03 Milliken Research Corporation Slotted disc type yarn tension control
US4462557A (en) * 1982-10-18 1984-07-31 Milliken Research Corporation Spring biased electromagnetically controlled tension control
US4449355A (en) * 1982-10-18 1984-05-22 Milliken Research Corporation A.C.-D.C. Slotted type yarn tension control
US4449354A (en) * 1982-10-18 1984-05-22 Milliken Research Corporation Disc type yarn tension control
US4449356A (en) * 1982-11-10 1984-05-22 Milliken Research Corporation Continuous A.C. tension control
US4911165A (en) * 1983-01-12 1990-03-27 Ethicon, Inc. Pliabilized polypropylene surgical filaments
US4478036A (en) * 1983-02-22 1984-10-23 Milliken Research Corporation Method, apparatus and intermittently textured yarn
US4532760A (en) * 1984-02-21 1985-08-06 Milliken Research Corporation D. C. Yarn tension control
US5277859A (en) * 1990-06-23 1994-01-11 Extrusion Systems Limited Method for the production of polypropylene yarn
EP0526759A1 (en) * 1991-07-12 1993-02-10 United States Surgical Corporation Polypropylene monofilament suture and process for its manufacture
US5217485A (en) * 1991-07-12 1993-06-08 United States Surgical Corporation Polypropylene monofilament suture and process for its manufacture
US5494620A (en) * 1993-11-24 1996-02-27 United States Surgical Corporation Method of manufacturing a monofilament suture
US5871502A (en) * 1996-04-08 1999-02-16 Ethicon, Inc. Process for manufacturing a polypropylene monofilament suture
US6287499B1 (en) 1998-10-09 2001-09-11 United States Surgical Corporation Process of making bioabsorbable block copolymer filaments
US20060125142A1 (en) * 2002-10-04 2006-06-15 John Kennedy Process of making bioabsorbable filaments
US20100292730A1 (en) * 2002-10-04 2010-11-18 John Kennedy Process of making bioabsorbable filaments
US8262963B2 (en) 2002-10-04 2012-09-11 Tyco Healthcare Group Lp Process of making bioabsorbable filaments

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GB813891A (en) 1959-05-27
FR1184613A (fr) 1959-07-23

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