US3655819A - Polyamide filaments containing polyalkylene ethers and phenolic anti-oxidants - Google Patents

Polyamide filaments containing polyalkylene ethers and phenolic anti-oxidants Download PDF

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Publication number
US3655819A
US3655819A US782432A US3655819DA US3655819A US 3655819 A US3655819 A US 3655819A US 782432 A US782432 A US 782432A US 3655819D A US3655819D A US 3655819DA US 3655819 A US3655819 A US 3655819A
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poly
polyamide
ether
nylon
sterically hindered
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US782432A
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Lamberto Crescentini
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Honeywell International Inc
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Allied Chemical Corp
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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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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

  • This invention relates to a filament of a synthetic polymer. More particularly, this invention relates to a filament, having improved resistance to light, of a polyamide having mixed therethrough a small amount of a poly (alkylene ether) and a sterically hindered phenolic compound.
  • the soiling of synthetic fibers has always been a problem to the textile industry and various different chemical compounds have been used in the prior art to alleviate this problem.
  • the poly(alkylene ethers) have been found to be particularly effective soil resistance additives for polyamide filaments, however, they have the disadvantage of reducing the resistance of the polyamide filaments to light.
  • the incorporation of a poly(alkylene ether) in a polyamide filament in an amount sufiicient to impart soil resistance significantly reduces the percent breaking strength retention of the filament when it is exposed to light.
  • the incorporation of a poly (alkylene ether) in a polyamide filament in an amount sufficient to impart soil resistance significantly reduces the dyelightfastness of a dyed filament when it is exposed to light.
  • a filament having improved resistance to light, of a polyamide having incorporated therethrough about 0.3 to 7, preferably about 2 to 5, weight percent, based on the weight of the polyamide, of a poly(alkylene ether) said poly(alkylene ether) having a molecular weight from about 600 to 3,000,000, preferably about 1,000 to 100,000, and about 0.05 to 2, preferably about 0.1 to 1, weight percent, based on the weight of the polyamide, of a sterically hindered phenolic compound which can be of one having the general formulas:
  • R is a sterically hindering radical selected from the group consisting of cyclohexyl, phenyl, and alkyl containing about 3 to 8 carbon atoms, which is preferably tertiary alkyl and most preferably is tertiary butyl;
  • R is a lower alkyl radical containing up to about 8 carbon atoms;
  • R is hydrogen or a lower alkyl radical containing up to about 8 carbon atoms;
  • R is hydrogen, lower alkyl containing up to about 8 carbon atoms, or
  • R is an alkyl radical containing about 4 to 20, preferably about 6 to 10 and most preferably 8 or 9, carbon atoms which is preferably in the meta or para position;
  • R is a lower alkyl radical containing up to about 8 carbon atoms;
  • x is an integer of 0 to 5, preferably 0 to 3;
  • y is an integer of 1 to 6, preferably 1 to 3; the sum of x and y is no greater than 6 and
  • Suitable polyamides for use in the present invention include, for example, those prepared by condensation of hexarnethylene diamine and adipic acid, condensation of hexamethylene diamine and sebacic acid known as nylon 6,6 and nylon 6,10, respectively, condensate of bis(paraaminocyclohexyl)methane and azelaic acid, condensation of bis(para-aminocyclohexyl)methane and dodecanedioic acid, or by polymerization of 6-caprolactam, 7-aminoheptanoic acid, S-caprylactam, 9-aminopelargonic acid, ll-aminoundecanoic acid, and l2-dodecalactam, known as nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, and nylon 12, respectively.
  • the poly(alkylene ethers) which can be incorporated in the polyamide are either ethylene oxide, propylene oxide or ethylene oxide-propylene oxide condensation products including ethylene oxide propylene oxide copolymers, that is, the products contain from two to three carbon atoms in the alkylene group with two of the carbon atoms being intralinear carbon atoms connecting intralinear ether-oxygen atoms.
  • the poly(a1kylene ether) is an ethylene oxide polymer.
  • the poly(alkylene ether) can be a glycol ether, and thus terminated or capped by hydroxyl groups, or it can be an oxyalkylated ether of a monohydric or polyhydric alcohol.
  • Suitable alcohols are methanol, ethanol, i-octanol, decanol, laurol, tridecanol, glycerol, pentaerythritol, sorbitol, mannitol, their partial esters and the like.
  • Other suitable terminating or capping agents are primary and secondary amines, mercaptans, and amides.
  • the poly(alkylene ether) can be an oxyalkylated condensation product of a phenol.
  • the preferred poly (alkylene ethers) are those which are substantially linear, and are terminated by hydroxyl groups, or by one or two ether end groups of the formula OR, wherein R is an alkyl, aryl, or aralkyl, such as methyl, ethyl, i-octyl, decyl, lauryl, tridecyl, nonylphenyl, dodecylphenyl, phenyl, naphthyl and the like. They are preferably water soluble or readily water dispersible. Residues of coupling compounds or chain-initiating agents, such as bis-phenol, can be present.
  • the poly(alkylene ether) can, as just mentioned, be a propylene oxide polymer or an ethylene oxidepropylene oxide copolymer. Indeed, when the specified number of ethylene oxide units are present, copolymer, constituents in addition to those mentioned can be included in the polymer chain. Other elements or radicals may be introduced into the R groups provided they are not reactive with the hydrophobic polymer. The necessity for the absence of groups which are reactive with the synthetic polymer will be readily apparent since durability, molecular weight and other physical properties of the hydrophobic polymer are adversely affected by copolymerization with poly(alkylene ether).
  • the polyether compound employed should preferably be of high purity. In addition, it should be free from color forming compounds, particularly those of an aldehyde nature. This is especially important where the polyether compound is to be subjected to the high temperatures involved in melt extrusion.
  • the poly(alkylene ethers) can have a molecular weight of about 600 to 3,000,000, preferably about 1,000 to 100,- 000.
  • the preferred poly(alkylene ethers) are the polyethylene glycols having a molecular weight of about 1,000 to 30,000.
  • the sterically hindered phenolic compounds used in this invention are well-known compounds.
  • the phenolic group is sterically hindered by the presence of at least one alkyl substituent on the ring ortho to the phenolic group.
  • Alkyl groups of from about 3 to 8 carbon atoms are effective. Tertiary alkyl groups are preferred.
  • Typical examples of sterically hindered phenolic compounds and methods for their preparation are disclosed in US. Pats. 2,877,209 and 3,112,286.
  • Representative sterically hindered phenolic compounds suitable for use in this invent-ion are 1,1,3 tris(-tertbutyl, 4-hydroxy, 2 methylphenyl)butane; 2,2 bis(3-tert-butyl, 4 hydroxyphenyl)propane; 2,2 bis(3,5-di-tert-butyl, 4 hydroxyphenyl) propane; 2(3-tert-butyl, 4 hydroxyphenyl) 2(4 hydroxyphenyl)propane; mono-4-(1,1,3,3 tetramethylbutyl)phenyl, bis ⁇ 2-tert-butyl, 4-[dimethyl(3-tert-butyl, 4 hydroxyphenyl)methyl]phenyl ⁇ phosphite; bis(4 nonylphenyl), mono ⁇ 2-tert-butyl, 4-[dimethyl(3-tert-butyl, 4 hydroxyphenyl)methyl]phenyl ⁇ phosphite; tris(3,
  • the poly(alkylene ether) and the sterically hindered phenolic compound can be dry blended with the polyamide granules or pellets prior to the melting of the polymer by conventional addition and dry mixing procedures.
  • the sterically hindered phenolic compound and the poly (alkylene ether) are mixed together and added to the 4 molten polyamide by, for example, injection into the mixing portion of the extruder prior to the melt extrusion of the filament. In this manner, the poly(alkylene ether) and the sterically hindered phenolic compound are mixed throughout the polyamide.
  • Example I Synthetic multifilament yarns were produced in the following manner. 0.5 weight percent of a sterically hindered phenolic compound (chosen from those indicated in Table I) and 3.0 weight percent of a poly(ethylene ether) having a molecular weight of about 15,000 and a softening point of about 50 to 55 C. (marketed by Union Carbide Corporation under the tradename of Carbowax 20M or polyethylene glycol compound 20M) were added to nylon 6 (polycaproamide) pellets or granules and the mixtures were blended in a double cone blender for one hour. The granular blends were then melted at 260 C. and melt extruded under a pressure of 3,000 p.s.i.g.
  • the yarns were collected at about 800 feet per minute and were drawn about 4 times their extruded length to produce 210 denier yarns.
  • the yarns had a relative viscosity of 55, as determined at a concentration of 11 grams of polymer in 100 ml. of percent formic acid at 25 C. (ASTMD-789-62T), and a tenacity of 3.8 grams per denier.
  • Swatches of knit sleeves were prepared from the above yarns and the knit sleeves were subjected to ageing in an Atlas carbon arc Weather-Ometer for and 200 hours, respectively.
  • the percent breaking strengths retained by the various knit sleeves after ageing for 100 and 200 hours, respectively, are contained in Table II below.
  • the weight ratio of dye bath to fabric was maintained at 40:1.
  • the knit sleeves were immersed in the above aqueous dye bath for one hour at a temperature of 205 F.
  • the knit sleeves were then rinsed in warm water and dried.
  • the knit sleeves were tested for fading in an Atlas carbon arc Fade-Ometer and the number of hours of exposure required for the dyed samples to break, that is to show evidence of fading, was observed. The results are contained in Table III.
  • Example III The yarns prepared in Example I were texturized and carpet samples were prepared. The carpet samples were then mock-dyed and tested for soiling at ambient temperature and 15-20 percent relative humidity. The apparent soiling, A(K/S), of each carpet sample was calculated according to the Kubelka-Munk equation:
  • R is a sterically hindering radical selected from the group consisting of cyclohexyl, phenyl, and alkyl containing about 3 to 8 carbon atoms;
  • R is a lower alkyl radical containing up to about 8 carbon atoms;
  • R is selected from the group consisting of hydrogen and a lower alkyl radical containing up to about 8 carbon atoms;
  • R is selected from the group consisting of hydrogen, lower alkyl containing up to about 8 carbon atoms, and R R is an alkyl radical containing about 4 to 20 carbon atoms which is positioned on the benzene ring in positions selected from the meta and para positions;
  • R is a lower alkyl radical containing up to about 8 carbon atoms;
  • x is an integer of to 5;
  • y is an integer of 1 to 6; the sum of x and y is no greater than 6 and is at least 1;
  • z is an integer of 1 to 7;
  • a is an integer of 1 to 3
  • R is a tertiary alkyl radical containing about 3 to 8 carbon atoms and R is an alkyl radical containing about 6 to 10 carbon atoms.
  • polyamide filament of claim 1 wherein the polyalkylene ether is present in an amount of about 2 to 5 Weight percent, based upon the weight of the polyamide, and the sterically hindered phenolic compound is present in an amount of about 0.1 to 1 Weight percent, based on the weight of the polyamide.
  • poly- (alkylene ether) has a molecular weight from about 1,000 to 100,000.
  • poly- (alkylene ether) is a poly(ethylene ether) having a molecular weight from about 1,000 to 30,000.
  • the polyamide filament of claim 1 wherein the sterically hindered phenolic compound comprises 1,1,3 tris(5-tert-butyl, 4-hydroxy, 2 methylphenyDbutane.
  • the polyamide filament of claim 1 wherein the sterically hindered phenolic compound comprises mono- 4-(l,1,3,3 tetramethylbutyl)phenyl, bis ⁇ 2-tert-butyl, 4-[dimethyl(3 tert butyl, 4 hydroxyphenyl)methyl]phenyl ⁇ phosphite.
  • the polyamide filament of claim 1 wherein the sterically hindered phenolic compound comprises bis- (4 nonylphenyl), mono ⁇ 2-tert-butyl, 4[dimethyl(3-tertbutyl, 4-hydroxyphenyl)methyl]phenyl ⁇ phosphite.
  • the polyamide filament of claim 1 wherein the sterically hindered phenolic compound comprises tris(3,5- di-tert-butyl, 4-hydroxyphenyl)phosphate.
  • polyamide filament of claim 1 wherein the polyamide is poly(methylenedicyclohexylazelamide).
  • polyamide filament of claim 13 wherein the polyamide is poly(methylenedicyclohexyl dodecanedioicamide).
  • a process for producing a filament, having improved resistance to light, extruded from a polyamide which comprises mixing in the polyamide prior to extrusion thereof about 0.3 to 7 weight percent, based on the weight of the polyamide, of a poly(alkylene ether) said poly(alkylene ether) having a molecular weight from about 600 to 3,000,000 and about 0.05 to 2 weight percent, based on the weight of the polyamide, of a sterically hindered phenolic compound selected from the group having the general formulas:
  • R is a sterically hindering radical selected from the group consisting of cyclohexyl, phenyl, and alkyl containing about 3 to 8 carbon atoms, R is a lower alkyl radical containing up to about 8 carbon atoms; R is selected from the group consisting of hydrogen and a lower alkyl radical containing up to about 8 carbon atoms; R; is selected from the group consisting of hydrogen, a lower alkyl radical containing up to about 8 carbon atoms, and R R is an alkyl radical containing about 4 to 20 carbon atoms which is positioned on the benzene ring in positions selected from the meta and para positions; R is a lower alkyl radical containing up to about 8 carbon atoms; x is an integer of 0 to 5; y is an integer of 1 to 6; the sum of x and y is no greater than 6 and is at least 1; z is an integer of 1 to 7; a is an integer of 1 to 3; b is
  • poly(alkylene ether) is a poly(ethylene ether) having a molecular weight from about 1,000 to 30,000.
  • the sterically hindered phenolic compound is m0n0-4-(1,1,3,3 tetramethylbutyl)phenyl, bis ⁇ 2-tert-butyl, 4-[dimethyl(3-tertbutyl, 4 hydroxyphenyl)methyl]phenyl ⁇ phosphite.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)
US782432A 1968-12-09 1968-12-09 Polyamide filaments containing polyalkylene ethers and phenolic anti-oxidants Expired - Lifetime US3655819A (en)

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BE (1) BE742752A (de)
CH (1) CH525291A (de)
DE (1) DE1961162A1 (de)
FR (1) FR2025655A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5410015A (en) * 1991-06-22 1995-04-25 Basf Aktiengesellschaft Polyamides having a low water absorptivity
US20090105107A1 (en) * 2006-01-13 2009-04-23 Andrew Paul Chapple Care Composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120661A1 (de) * 1991-06-22 1992-12-24 Basf Ag Polyamide mit geringer wasseraufnahmekapazitaet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5410015A (en) * 1991-06-22 1995-04-25 Basf Aktiengesellschaft Polyamides having a low water absorptivity
US20090105107A1 (en) * 2006-01-13 2009-04-23 Andrew Paul Chapple Care Composition

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FR2025655A1 (de) 1970-09-11
DE1961162A1 (de) 1970-10-15
CH525291A (de) 1972-07-15
BE742752A (de) 1970-05-14

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