US2177637A - Polymeric material - Google Patents

Polymeric material Download PDF

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Publication number
US2177637A
US2177637A US229972A US22997238A US2177637A US 2177637 A US2177637 A US 2177637A US 229972 A US229972 A US 229972A US 22997238 A US22997238 A US 22997238A US 2177637 A US2177637 A US 2177637A
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US
United States
Prior art keywords
formaldehyde
polyamide
treated
polyamides
bristles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US229972A
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English (en)
Inventor
Donald D Coffman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US229972A priority Critical patent/US2177637A/en
Priority to FR860239D priority patent/FR860239A/fr
Priority to GB25698/39A priority patent/GB534698A/en
Priority to DEP79744A priority patent/DE711682C/de
Priority to NL53134D priority patent/NL53134C/xx
Application granted granted Critical
Publication of US2177637A publication Critical patent/US2177637A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • 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
    • C08G69/48—Polymers modified by chemical after-treatment
    • C08G69/50—Polymers modified by chemical after-treatment with aldehydes

Definitions

  • This invention relates to synthetic linear polyamides, and more particularly to a process for improving the properties of shaped articles prepared from fiber-forming synthetic linear polyamides.
  • the synthetic linear polyamides used in the practice of this invention are of the type described in Patents 2,071,250 and 2,071,253, and in application Serial Number 136,031 filed April 9, 1937 10 by W. H. Carothers. These polyamides may be spim into filaments which can be cold drawn into fibers exhibiting by X-ray examination molecular orientation. along the fiber axis. This orientation may also be obtained by cold rolling the 16 polyamide in the form of sheets or ribbons.
  • polyamides from which the filaments, fibers, fabrics, bristles, films, and the like are made are of two types, namely, those obtainable frompolymerizable monoaminomonocarboxylic acids or their 2o amide-forming derivatives, and those obtainable from suitable diamines by reaction with suitable dicarboxylic acids or amide-forming derivatives of dibasic carboxylic acids.
  • the. amide groups form an integral part of the main chain of atoms.
  • An object of this invention is to improve the properties of filaments, fibers, bristles, films, fabrics, and the like derived from synthetic linear polyamides. Further objects are to increase the recovery from deformation of such polyamides, and to increase their resistance to deterioration in the presence of ultraviolet light. Other objects 'will appear hereinafter.
  • the treatment of the polyamide articles with formaldehyde results in several beneficial effects.
  • the formaldehyde treatment effects a setting action which imparts to the polyamide articles a more or less permanent form to which they tend to recover after deformation.
  • formaldehyde treatment of crimped polyamide fibers improves the permanency of the crimp.
  • formaldehyde treatmentof polyamide bristles increases their ability to recover from deformation; in other words, it decreases their tendency to curl in use. Under certain conditions treatment with formaldehyde decreases the stiffness of polyamide bristles.
  • Percent residual deformation m Table I Percent improvement in recovery Percent residual Bristle treatment deformation Conditioned 2 hours in boiling water control Conditioned as above and then treated with formaldehyde.
  • ExAMPLE HI A sample of 83-denier, 10-filament yarn, which was' obtained by spinning polyhexamethylene, adipaniide and cold drawing the resultant filaments 425% (i. e.'until their length wasincreased' 5.25 times), was treated with formaldehyde as described for the bristles in Example II. After washing with water and drying, the intrinsic viscosity of the yarn was found to have risen from 0.82 to 0.99. The tensile strength was not impaired by this treatment whereas a sample of the same yarn heated in a similar bath containing potassium acid phthalate and sodium hydroxide but no formaldehyde suffered a dropin tensile strength from 4.35 to 1.64 grams per denier.”
  • EXAMPLE V may be seen in Table III below, the treated ma-. terial has a much greater resistance to degrada--- tion by ultraviolet light as measured by the loss in tenacity and elongation.
  • the reaction mixture (solution of formaldehyde or formaldehyde-generating material) should not contain enough acid 'to cause hydrolysis of the polyamide. For this reason the pH value of the formaldehyde solution should not be permitted to go below 3.0. Buffers, such as potassium hydrogen phthalate, may be added to the reaction mixture when necessary to prevent the formaldehyde from becoming too acidic. With pure formaldehyde, however, the formaldehyde solution can be refluxed for 24 hours without developing suiilcient acidity to aifect materially the strength of the polyamide fibers.
  • the invention is not limited to the particular polyamide cited in the foregoing examples but is applicable generally to synthetic linear polyamides containing amide groups as integral members of the main chain of atoms.
  • polyamides of the diamine-dibasic acid type may be mentioned polytetramethylene sebacamide, polytetramethylene adipamide, polypentamethylene adipamide, polypentamethylene sebacamide, polyhexamethylene sebacamide, polyoctamethylene adipamide, polydecamethylene adipamide, and poly-p-xylylene sebacamide.
  • Polyamides of the amino acid type such as those obtainable by polymerizing 5-aminocaproic acid, caprolactam, 9-aminononanoic acid and ll-aminoundecanoic acid may also be used.
  • -Interpolyamides i. e., polyamides derived from a mixture of polyamide-forming reactants capable of yielding more than one polyamide if reacted in suitable combinations, can also be successfully treated with formaldehyde and certain of its derivatives as described above.
  • the polymer derived from equimolecular quantities of hexaarticlescontaining modifying agents e. g., plasticizers, pigments, dyes, agents for the modification of luster, antioxidants, oils, and resins.
  • polyamide treated may also contain urea or a phenol, in which case the formaldehyde reacts also with the urea or phenol to give novel effects.
  • the invention can also be applied to mixed yarns and fabrics, i. e., yarns and fabrics composed of filaments of more than one polyamide or yarns and fabrics containing types of filaments other than polyamides.
  • Formaldehyde derivatives other than those mentioned above may be used, as for instance polymers of formaldehyde, hexamethylene tetramine, formaldehyde in the gaseous state, meth-.
  • Treatment and reaction may be carried out in the presence of catalysts, parsuperatmospheric or 'subatmospheric pressure, in
  • reaction is completed within 24 hours and usually within minutes to 5 hours.
  • This invention furnishes a convenient and economical method .for improving polyamide articles.
  • the beneflcial effects include increasing the resiliency and decreasing the stiffness of polyamide filaments,
  • yarns, fabrics and bristles increasing the crimp 4 retention of crimped polyamide filaments, stabilizing polyamide articles to ultraviolet light and imparting water repellency to polyamide filaments and fabrics.
  • polyamide bristles treated with formaldehyde are suitable for'the manufacture of brushes where recovery from deformation is important.
  • formaldehyde-treated polyamide bristles are suitable for the production of surgical sutures and fishing leaders where a low degree of stiffness is required.
  • dimethylol urea treatment'of a polyamide fabric results in a desirable product for uses such as flags where stability toward sunlight is desirable.
  • methylol stearamide treatment of polyamide yarns or fabrics results in a product having desirable properties for the manufacture of splash-proof stockings where water repellency is necessary.
  • a process for improving the properties of articles formed from fiber-forming synthetic polyamides which comprises treating such arholes with a compound of the class consisting of formaldehyde and formaldehyde-liberating substances.
  • a process which comprises heating a fiberforming synthetic linear polyamide below its melting point in the presence of-a solution of a compound of the class consisting of formaldehyde and formaldehyde-liberating substances in a non-solvent for the polyamide.
  • a process for improving the properties of articles formed from fiber-forming synthetic linear polyamides which comprises heating such articles with a solution of a compound of the class consisting of formaldehyde and formalde- 'hyde-liberating substances in a non-solvent for 20 polyamide which comprises heating said articles in the presence of a compound of the class consisting of formaldehyde and formaldehyde-libcrating substances.
  • polyamides are those obtainable by condensation polymerization of diamines and dibasic carboxylic acids.
  • a process which comprises heating a fiberfoi'ming synthetic polyamidecontaining phenol with a compound oi the class consisting of formaldehyde and formaldehyde-liberating substances.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
US229972A 1938-09-14 1938-09-14 Polymeric material Expired - Lifetime US2177637A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US229972A US2177637A (en) 1938-09-14 1938-09-14 Polymeric material
FR860239D FR860239A (fr) 1938-09-14 1939-09-13 Procédé pour l'amélioration de polyamides synthétiques linéaires
GB25698/39A GB534698A (en) 1938-09-14 1939-09-13 Treatment of synthetic polyamide filaments, fabrics, films and other articles, to improve their resilience and other properties
DEP79744A DE711682C (de) 1938-09-14 1939-09-14 Verfahren zur Veredlung von gefoermten Gebilden aus fadenbildenden synthetischen linearen Polyamiden
NL53134D NL53134C (enrdf_load_stackoverflow) 1938-09-14 1939-09-14

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US229972A US2177637A (en) 1938-09-14 1938-09-14 Polymeric material

Publications (1)

Publication Number Publication Date
US2177637A true US2177637A (en) 1939-10-31

Family

ID=22863443

Family Applications (1)

Application Number Title Priority Date Filing Date
US229972A Expired - Lifetime US2177637A (en) 1938-09-14 1938-09-14 Polymeric material

Country Status (5)

Country Link
US (1) US2177637A (enrdf_load_stackoverflow)
DE (1) DE711682C (enrdf_load_stackoverflow)
FR (1) FR860239A (enrdf_load_stackoverflow)
GB (1) GB534698A (enrdf_load_stackoverflow)
NL (1) NL53134C (enrdf_load_stackoverflow)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2424883A (en) * 1941-10-14 1947-07-29 Ici Ltd Paraformaldehyde modified reaction products of diisocyanates with linear polyester polyamide
US2425334A (en) * 1943-01-18 1947-08-12 Ici Ltd Modification of filaments, etc., derived from synthetic linear polyamides
US2430953A (en) * 1945-02-20 1947-11-18 Du Pont Process for improving the properties of polyamide fibers
US2432148A (en) * 1943-02-10 1947-12-09 Ici Ltd Curing of diisocyanate-modified polyester
US2434247A (en) * 1944-08-15 1948-01-13 Ici Ltd Production of elastic nylon articles
US2441085A (en) * 1945-02-20 1948-05-04 Du Pont Process of making nylon fabrics elastic by treatment with formaldehyde
US2477156A (en) * 1946-04-12 1949-07-26 Du Pont Treatment of synthetic linear polyamide threads
US2514550A (en) * 1948-02-14 1950-07-11 Celanese Corp Treatment of synthetic fibers with formaldehyde
US2516562A (en) * 1946-12-03 1950-07-25 Du Pont Process of making artificial wool from nylon fibers
US2540726A (en) * 1946-12-03 1951-02-06 Du Pont Treatment of a heat set, oriented nylon fabric with formaldehyde
US2645266A (en) * 1950-12-13 1953-07-14 Specialties Dev Co Reinforced rubber structure and method of treating nylon yarn for use in making same
DE910284C (de) * 1946-04-26 1954-04-29 Dunlop Rubber Co Verfahren zur Verringerung der Dehnbarkeit kaltgezogener Polyamidfaeden
US2836509A (en) * 1954-10-08 1958-05-27 Berry Kenneth Ollerenshaw Stretchable plastic-coated fabric and method of making the same
US3318658A (en) * 1962-12-21 1967-05-09 Minnesota Mining & Mfg Polypyrrolidone fibers and process
US3344098A (en) * 1961-10-31 1967-09-26 Dainichiseika Color Chem Method of making a chromogen bonded polymer and products thereof
US3514248A (en) * 1965-06-12 1970-05-26 Basf Ag Production of bulked yarn from thermoplastic high polymers
US5139725A (en) * 1982-12-17 1992-08-18 Rhone-Poulenc Viscosuisse S.A. Process for manufacture of crimped polyester yarn from cold drawn polyester-poy yarn

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE953916C (de) * 1942-10-22 1956-12-06 Bayer Ag Verfahren zur Verbesserung der Schrumpffestigkeit von geformten Erzeugnissen aus Polyacrylsaeurenitril
DE864436C (de) * 1942-12-18 1953-01-26 Ici Ltd Verfahren zur Herstellung von Faeden oder Fasern mit verbesserten Eigenschaften aus synthetischen linearen Polyamiden
US2606155A (en) * 1946-11-26 1952-08-05 Koppers Co Inc Cleaning and pickling composition for metals
US2685497A (en) * 1948-05-12 1954-08-03 Celanese Corp Treatment of polymeric materials
DE1009152B (de) * 1952-03-08 1957-05-29 Inventa Ag Verfahren zur Erhoehung des Schmelzpunktes von Garnen und Faeden aus synthetischen linearen Polyamiden
US2895287A (en) * 1956-09-21 1959-07-21 American Viscose Corp Production of bulky resin spun rayon yarn
US2895288A (en) * 1956-09-21 1959-07-21 American Viscose Corp Production of bulky colorspun rayon yarn
DE1238613B (de) * 1963-12-07 1967-04-13 Hoechst Ag Verfahren zur Herstellung von Faeden aus Poly-4, 4-dimethylazetidin-2-on

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2424883A (en) * 1941-10-14 1947-07-29 Ici Ltd Paraformaldehyde modified reaction products of diisocyanates with linear polyester polyamide
US2425334A (en) * 1943-01-18 1947-08-12 Ici Ltd Modification of filaments, etc., derived from synthetic linear polyamides
US2432148A (en) * 1943-02-10 1947-12-09 Ici Ltd Curing of diisocyanate-modified polyester
US2434247A (en) * 1944-08-15 1948-01-13 Ici Ltd Production of elastic nylon articles
US2430953A (en) * 1945-02-20 1947-11-18 Du Pont Process for improving the properties of polyamide fibers
US2441085A (en) * 1945-02-20 1948-05-04 Du Pont Process of making nylon fabrics elastic by treatment with formaldehyde
US2477156A (en) * 1946-04-12 1949-07-26 Du Pont Treatment of synthetic linear polyamide threads
DE910284C (de) * 1946-04-26 1954-04-29 Dunlop Rubber Co Verfahren zur Verringerung der Dehnbarkeit kaltgezogener Polyamidfaeden
US2516562A (en) * 1946-12-03 1950-07-25 Du Pont Process of making artificial wool from nylon fibers
US2540726A (en) * 1946-12-03 1951-02-06 Du Pont Treatment of a heat set, oriented nylon fabric with formaldehyde
US2514550A (en) * 1948-02-14 1950-07-11 Celanese Corp Treatment of synthetic fibers with formaldehyde
US2645266A (en) * 1950-12-13 1953-07-14 Specialties Dev Co Reinforced rubber structure and method of treating nylon yarn for use in making same
US2836509A (en) * 1954-10-08 1958-05-27 Berry Kenneth Ollerenshaw Stretchable plastic-coated fabric and method of making the same
US3344098A (en) * 1961-10-31 1967-09-26 Dainichiseika Color Chem Method of making a chromogen bonded polymer and products thereof
US3318658A (en) * 1962-12-21 1967-05-09 Minnesota Mining & Mfg Polypyrrolidone fibers and process
US3514248A (en) * 1965-06-12 1970-05-26 Basf Ag Production of bulked yarn from thermoplastic high polymers
US5139725A (en) * 1982-12-17 1992-08-18 Rhone-Poulenc Viscosuisse S.A. Process for manufacture of crimped polyester yarn from cold drawn polyester-poy yarn

Also Published As

Publication number Publication date
FR860239A (fr) 1941-01-09
GB534698A (en) 1941-03-14
DE711682C (de) 1941-10-14
NL53134C (enrdf_load_stackoverflow) 1942-09-15

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