US3651010A - Synthetic polyamide compositions - Google Patents

Synthetic polyamide compositions Download PDF

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Publication number
US3651010A
US3651010A US740195A US3651010DA US3651010A US 3651010 A US3651010 A US 3651010A US 740195 A US740195 A US 740195A US 3651010D A US3651010D A US 3651010DA US 3651010 A US3651010 A US 3651010A
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Prior art keywords
polyamide
phenol
polyamides
yarns
deformation
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US740195A
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English (en)
Inventor
Clifton Douglas Cowell
Karl Anthonie Martin
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to synthetic polyamide and co-polyamide compositions for making shaped articles such as filaments, bristles, yarns, films and the like having improved resistance to deformation and also to articles made therefrom.
  • Synthetic polyamides for instance nylon 6 or nylon 66
  • nylon 6 or nylon 66 have long been used for the manufacture of yarns and fabrics on account of their desirable properties such as good wear resistance and high strength.
  • Such yarns or fabrics normally exhibit a floppy, pliable feel or easy drape and in some cases, such as curtains, this easy deformation or pliability is an advantage.
  • yarns and fabrics are desirable which have more resistance to deformation, than is obtainable with normal nylon yarns and which, at the same time, exhibit the advantages of the good wear resistance and high strength associated with nylon.
  • tanning One known way to increase the resistance to deformation of the constituent filaments of a nylon fabric, is by tanning.
  • Either the made-up fabric or the yarn used to make it may be treated for this purpose in a bath containing a tanning agent such as tannic acid.
  • a tanning agent such as tannic acid.
  • the effect so obtained can be relatively easily removed almost completely by hot water or steam unless a further fixing treatment, such as treatment with metallic salts, is performed.
  • the molten polymer is extruded through holes to form filaments, which filaments are usually then stretched or drawn in order to orientate their constituent molecules and develop their superior properties.
  • Treatment of undrawn or drawn filaments, or of yarns comprising them in a tanning bath is not only an undesirable extra operation but when such filaments or yarns are in the form of a wound package it is also almost impossible to carry out in a practical manner owing to diificult and uneven penetration of the tanning agent into the package.
  • Resistance to deformation of a filament may refer to resistance to stretching or to bending. Such resistance may be measured for instance in terms of a modulus.
  • the stretch modulus can be defined by the force per unit area to stretch the filament by a given percentage of its original length.
  • the bending modulus or fiexural rigidity can be defined with reference to the couple required to bend a filament of given dimensions through a given angle. With synthetic polyamide or co-polyamide filaments the bending modulus is generally positively related to the stretch modulus and so this latter property alone is usually used to define the general resistance of such a filament to deformation.
  • the stretch modulus can be measured in terms of any suitable stretch percentage. In this specification We shall cite the 1% nominal modulus, usually called the Initial Modulus.
  • the Initial Modulus is measured for a filament or yarn as follows:
  • a 50 cm. length of the filament or yarn is stretched at a rate of 10% of its original length per minute on an Instron tester in a room atmosphere at approximately 67% RH. and 72 F.
  • the tension in the yarn changes with the degree of stretching and the two variables, length and tension, are automatically plotted by the machine.
  • the maximum tension-extension gradient at the point where the stretch is approximately 1% is multiplied by and divided by the initial yarn denier and the figure so obtained is called the Initial Modulus.
  • An object of the present invention is to provide a composition comprising one or more synthetic polyamides or co-polyamides, which compositions can be melt-spun or shaped and if necessary drawn to produce filaments, bn'stles, yarns, films and the like having improved resistance to deformation.
  • compositions of the present invention may comprise one or more synthetic polyamides or polyamide copolymers of a random or block nature.
  • phenolic compounds Since many tanning agents, used in aqueous solutions are phenolic compounds, such compounds were considered by applicants for addition to molten polyamides. Furthermore, phenolic compounds are frequently added in very small amounts to molten polyamides in order to reduce oxidative degradation.
  • the phenolic compounds concerned in the present invention also have the surprising advantage that mixtures of them with polyamides or co-polyamides in the molten state are sufiiciently thermally stable for normal meltspinning or shaping to be performed, even when such mixtures contain a relatively high proportion of the phenol and articles so produced can be drawn in the conventional manner to produce useful drawn articles having improved resistance to deformation.
  • the phenolic compounds for use in the present invention are substantially pure, well defined chemical compounds with a characteristic molecular weight, substantially ascertainable from their chemical formula, and are not impure oligomers or mixtures of oligomers or polymers or resins.
  • the phenolic compounds are selected from the group consisting of poly(alkyl) phenols, poly(hydroxyalkaryl) alkanes and poly(hydroxyalkaryl) arylenes. They are further defined as follows:
  • each benzene ring has not more than one hydroxyl group attached thereto,
  • the compounds should be soluble to an extent of l40 wt. percent in admixture with one or more polyamides or co-polyamides.
  • the limiting desiderata determining the size and nature of any substituent groups, or the number of benzene rings, in the molecule are the solubility of the compound in the polyamide or co-polyamide and the production of a composition which is sufiiciently thermally stable to be meltspun or shaped, and, if necessary, drawn to produce articles having increased resistance to deformation.
  • Benzene rings in the phenol molecule may be linked together by any suitable groups or chains, for instance methylene groups or chains, or sulphone or amide links and the like, consistent with the fulfilment of aforesaid desiderata.
  • One or more such phenolic compounds should be present in the polyamide mixture for the accomplishing of the objects of the present invention, in a total amount between 2 and 20 Hydroxyl Equivalents per hundred Amide Equivalents and preferably between 3 and 10 such equivalents.
  • Hydroxyl Equivalent we mean the molecular weight in grams of the phenolic compound divided by the number of hydroxyl groups in the molecule.
  • tAmide Equivalents we mean the molecular weight in grams of a notional polyamide or copolyamide containing one hundred carbonamide links.
  • phenolic compounds having one or two benzene rings in their molecule do exert an effect in increasing resistance to deformation, the preferred phenols contain three or more benzene rings in their molecule.
  • the present invention therefore provides a composition comprising one or more synthetic polyamides or co-polyamides, which composition can be melt-spun or shaped and if necessary drawn to produce filaments, bristles, yarns, films and the like having improved resistance to deformation and which composition contains a phenol, which is a substantially pure, well defined chemical compound with a characteristic molecular weight, substantially ascertainable from its chemical formula, and is not an impure oligomer or a mixture of oligomers or a polymer or resin, is selected from the group consisting of poly (alkyl) phenols, poly(hydroxyalkaiyl) alkanes and poly (hydroxyalkaryl) arylenes and is further defined as follows:
  • each benzene ring has not more than one hydroxyl group attached thereto,
  • Hydroxyl Equivalents being defined as the molecular weight in grams of the phenolic compound divided by the number of hydroxyl groups in the molecule
  • Amide Equivalents being defined as the molecular weight in grams of a notional polyamide or co-polyamide containing one hundred carbonamide links.
  • the phenolic compounds may be added to the polyamide at any stage before melt-spinning or shaping. For instance, they may be added during the manufacture of the polyamide, preferably just before it is cast to make granules for use in melt-spinning. Alternatively, they may be mixed with said granules or added to the molten polyamide in a melt-spinning or shaping apparatus.
  • Another convenient method of addiiton is to make granules comprising a suitable blend of one or more polyamides or co-polyamides and comprising a high percentage of one or more of said compounds. Such concentrated, pre-blend granules can then be mixed, in suitable proportion, with the polyamides or co-polyamides used for melt spinning or shaping.
  • EXAMPLE -1 Each of the compounds shown in Table l was dissolved in molten nylon 66 by stirring for 15 mius. at 280 C., in a nitrogen atmosphere. The mixtures, containing 4% by weight of the compound, were cooled and the products melt-spun to produce spun yarns comprising ten continuous filaments each of about nine denier. These yarns were then cold drawn and hot drawn under the conditions shown in Table 2. Both the spinning and drawing behaviour were good. The drawn yarns were then immersed in boiling water for 15 mius., dried in air at approximately 67% RH. and 72 F. for 24 hours and their Initial Modulus, Extensibility and Tenacity then measured.
  • the Tenacity is the breaking load of the yarn, expressed in grams per denier.
  • the Extensibility is the length by which the yarn can be extended before breaking, expressed as a percentage of its original length.
  • the Initial Modulus is as hereinbefore defined. The results obtained are shown in Table 2 as a function of the number of phenolic hydroxyl groups in the molecule of the phenolic additive. It can be seen that none of the compounds added produced any unacceptable change in Extensibility or Tenacity and that in general the Initial Modulus increased with the number of hydroxyl groups in the molecule.
  • a thermally, stable fiber-formable composition comprising a synthetic linear, fiber-formable polyamide having improved resistance to deformation containing an amount sufficient to improve said resistance to deformation of a phenol, said phenol being a substantially pure well-defined chemical compound with a characteristic molecular weight substantially ascertainable from its chemical formula, said phenol being selected from the group consisting of poly(alkyl)phenols, poly(hydroxyalkaryl) alkanes, poly(hydroxyalkaryl) arylenes, said phenol being further defined as follows:
  • said phenol being present in said composition in an amount between 2 and hydroxyl equivalents per hundred amide equivalents, said hydroxyl equivalents being defined as the molecular weight in grams of the phenolic compound divided by the number of hydroxyl groups in the molecule, and said amide hundred equivalents being defined as the molecular weight in grams of a notional polyamide or copolyamide containing one hundred carbonamide links.
  • composition as claimed in claim 1 wherein said amount is between 3 and 10 hydroxyl equivalents per one hundred amide equivalents.
  • composition as claimed in claim 1 ' wherein said polyamide is polyhexamethylene adipamide.
  • composition as claimed in claim 1 wherein said phenol contains 3 or more benzene rings.
  • composition of claim 1 wherein said phenol contains 1 to 4 benzene rings which are each substituted by a single hydroxyl group.
  • composition as claimed in claim 4 wherein said phenol contains 3 or more benzene rings.
  • composition of claim 5 wherein said phenol contains only one phenol selected from the group consisting of 2,4,6-trialkyl phenol; 2,2-bis alkylene(4,6-dialkyl phenol); 1,1,3-tri[ (2,5-dialkyl-4 hydroxy)phenol]butane; 1,1,5,5- tetra[ (2,5 dialkyl 4-hydr0xy)phenol]pentane; o-dialkyl bis-phenol A; 2,2-di(4-hydroxy-3-alkyl phenyl) propane; 2,2,5 ,5 -tetra (4-hydroxy-3,5-dialkyl phenyl)hexane and 1,4- bis di 5-alkyl-4-hydr0xy-2-alkylphenyl] alkyl) benzene.
  • 2,4,6-trialkyl phenol 2,2-bis alkylene(4,6-dialkyl phenol)
  • 1,1,3-tri[ (2,5-dialkyl-4 hydroxy)phenol]butane 1,1,5,5- t
  • composition as claimed in claim 1 wherein said phenol contains 2 to 6 benzene rings.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US740195A 1967-06-26 1968-06-26 Synthetic polyamide compositions Expired - Lifetime US3651010A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB29430/67A GB1203283A (en) 1967-06-26 1967-06-26 Synthetic polyamide compositions

Publications (1)

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US3651010A true US3651010A (en) 1972-03-21

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US (1) US3651010A (en:Method)
BE (1) BE717197A (en:Method)
DE (1) DE1769662A1 (en:Method)
FR (1) FR1569548A (en:Method)
GB (1) GB1203283A (en:Method)
NL (1) NL6809033A (en:Method)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4745146A (en) * 1985-12-06 1988-05-17 Bayer Aktiengesellschaft Reinforced polyamides having improved flow behavior
US5410015A (en) * 1991-06-22 1995-04-25 Basf Aktiengesellschaft Polyamides having a low water absorptivity
US20100173070A1 (en) * 2004-02-02 2010-07-08 Nanosys, Inc. Porous Substrates, Articles, Systems and Compositions Comprising Nanofibers and Methods of Their Use and Production

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3248329A1 (de) * 1982-12-28 1984-06-28 Bayer Ag, 5090 Leverkusen Polyamide mit verminderter wasseraufnahme
US4849474A (en) * 1986-01-06 1989-07-18 General Electric Company Moisture reduction in polyamide compositions
US5212224A (en) * 1986-04-11 1993-05-18 Bayer Aktiengesellschaft Free flowing moulding materials based on polyamides containing bisphenols
DE3612159A1 (de) * 1986-04-11 1987-10-22 Bayer Ag Fliessfaehige formmassen auf polyamidbasis
EP0301005A1 (en) * 1987-02-12 1989-02-01 General Electric Company Moisture reduction in polyamide compositions
DE4120661A1 (de) * 1991-06-22 1992-12-24 Basf Ag Polyamide mit geringer wasseraufnahmekapazitaet

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4745146A (en) * 1985-12-06 1988-05-17 Bayer Aktiengesellschaft Reinforced polyamides having improved flow behavior
US5410015A (en) * 1991-06-22 1995-04-25 Basf Aktiengesellschaft Polyamides having a low water absorptivity
US20100173070A1 (en) * 2004-02-02 2010-07-08 Nanosys, Inc. Porous Substrates, Articles, Systems and Compositions Comprising Nanofibers and Methods of Their Use and Production

Also Published As

Publication number Publication date
GB1203283A (en) 1970-08-26
FR1569548A (en:Method) 1969-05-30
DE1769662A1 (de) 1970-12-03
NL6809033A (en:Method) 1968-12-27
BE717197A (en:Method) 1968-12-27

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