US3557060A - Internal antistatic agent for super polyamides and polyamide compositions having improved antistatic property - Google Patents

Internal antistatic agent for super polyamides and polyamide compositions having improved antistatic property Download PDF

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Publication number
US3557060A
US3557060A US723875A US3557060DA US3557060A US 3557060 A US3557060 A US 3557060A US 723875 A US723875 A US 723875A US 3557060D A US3557060D A US 3557060DA US 3557060 A US3557060 A US 3557060A
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United States
Prior art keywords
antistatic agent
antistatic
polyamide
added
propyleneoxide
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Expired - Lifetime
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US723875A
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English (en)
Inventor
Hiroshi Kitagawa
Ataru Suwada
Satoyoshi Ohno
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Sanyo Chemical Industries Ltd
Toray Industries Inc
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Sanyo Chemical Industries Ltd
Toyo Rayon Co Ltd
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups

Definitions

  • An internal antistatic agent for synthetic polyamide use which comprises a compound which is an addition product of an alkylene oxide and a carbonamide group-containing compound containng a structural unit of the formula wherein A stands for ethyleneoxide B stands for propyleneoxide, ⁇ -A,B stands for a homopolymer of ethyleneoxide or propyleneoxide or a block or random copolymer of ethyleneoxide and propyleneoxide and n is an integer from to 1000.
  • This invention relates to a new internal antistatic agent for synthetic polyamide use and also to the synthetic polyamide composition containing said antistatic agent.
  • the synthetic fibers possess such characteristics as durability, tenacity and chemical inertness but, on the other hand, their insulation resistance being high, they have a tendency to become charged with static electricity. Hence, this becomes a serious matter during the production of textile materials or in wearing clothes made of such statically charged material.
  • the invention provides polyamide compositions whose antistatic property has been improved as a result of having been incorporated with 0.1 to 10 parts by weight of the aforesaid antistatic agent per parts by weight of said super polyamide.
  • lactams whose ring are formed by 312 carbon atoms, oligomers up to hexamers of said lactams, low molecular weight polycondensation products up to hexamers of w-aminocarboxylic acids of 312 carbon atoms or low molecular weight polycondensation products of a molecular weight less than 3000 and up to hexamers of dicarboxylic acids and diamines, or the mixture of these.
  • lactams useable are the lactams of the formula wherein R is hydrogen or alkyl radical and n is a number from 1 to 10, particularly preferred being e-caprolactam, capryllactam and laurolactam.
  • the oligomers of the polymerizable lactams i.e. the oligomers of lactams whose degree of polymerization is from 2 to 6 can also be used in the invention. These oligomers may either be those of cyclic or chain configuration. Those having a degree of polymerization from 24 are particularly to be preferred in the invention.
  • the oligomers of e-caprolactam or the mixtures thereof are especially desirable from the standpoint of the utilization of by-products, since they are available as by-products in the process of producing 6 nylon.
  • R" and R' are each a hydrocarbon residue of 2-25 carbon atoms or an alkylene group having a cyclic or hetero atom, and m is a number from 1 to 6.
  • Suitable diamines are exemplified by such as hexamethylenediamine and m-xylylenediamine, while examples of suitable dicarboxylic acids include such as adipic, sebacic, dodecandioic and isophthalic acids.
  • the low molecular weight polycondensation products of the waminocarboxylic acids such, for example, as w-aminoundecanoic acid, w-aminoheptanoic acid and w-aminocaproic acids can also be used.
  • the alkylene oxides include such, for example, as ethylene oxide, propylene oxide, and the mixture of ethylene oxide and propylene oxide.
  • any method may be used.
  • the alkylene oxide is addition-polymerized to the carbonamide group-containing compound in customary manner in the presence of an acid or alkali catalyst at, say, a temperature of 140 C. and a pressure of 3 atmospheres.
  • an acid or alkali catalyst at, say, a temperature of 140 C. and a pressure of 3 atmospheres.
  • the alkylene oxide can be added in the singular, random or block form.
  • the number of moles of the alkylene oxide added may be chosen optionally in accordance with the objective desired but generally a better antistatic property is demonstrated in the case of the higher moles of addition products.
  • the use of to 1000 mole equivalents, and especially suitably 20 to 500 mol equivalents, of the alkylene oxide, based on the carbonamide group of the aforesaid carbonamide group-containing compound is to be preferred.
  • the invention antistatic agent thus obtained has in its molecules at least one structural unit of the formula Ozi i T wherein the groups A, B in the oxyalkylene block may be the same or different throughout the whole block.
  • the oxyalkylene block may be constituted of either polyoxyethylene, an oxyethylene/oxypropylene random copolymer, or a polyoxyethylene/polyoxypropylene block copolymer.
  • the invention antistatic agent is incorporated in the synthetic linear super polyamide in an amount of 0.1 to 10% by Weight, and preferably 0.5 to 5% by weight, based on the polyamide.
  • the synthetic linear super polyamides to which the invention antistatic agent is applicable included are the usual super polyamides such as 6 nylon (poly-w-caprolactam), 66 nylon (polyhexamethylene adipamide), 7 nylon (poly-w-aminoheptanoic acid), 8 nylon (polycapryllactam), 9 nylon (poly-w-aminononanoic acid) 6, 1O nylon (polyhexamethylene sebacamide), 11 nylon (poly-waminoundeeanoic acid) and 12 nylon (polylaurolactam); polyamides having an aromatic ring such as polyamide obtained from p-xylylenediamine and dodecandioic acid; and other polyamides having in their main chain an ether bond, or an alicyclic or heterocyclic ring.
  • 6 nylon poly-w-caprolactam
  • 66 nylon polyhexamethylene adipamide
  • 7 nylon poly-w-aminoheptanoic acid
  • 8 nylon
  • the aforesaid antistatic agent must be mixed homogeneously in these super polyamides.
  • the antistatic agent is mixed in the polyamides before the latter are molded.
  • the super polyamide chips and the antistatic agent are first blended in an extruder, then the antistatic agent is dispersed uniformly by melting the mixture, and thereafter the mixture is extruded and made into filaments.
  • the master batch technique which is carried out in the following manner.
  • a master chip which contains the antistatic agent in a high concentration.”Next, this is mixed with polyamide chips to which the antistatic agent has not been added to accomplish the dilution of the mixture to the desired concentration thereby obtaining a mixture and hence products in which the antistatic agent is well dispersed.
  • the polyamide chips can be treated with the antistatic agent dissolved in a solvent to effect the uniform blending of the antistatic agent with the polyamide chips, followed by removal of the solvent and spinning of the chips in customary manner.
  • the antistatic agent can be added to the monomer during the polymerization reaction, if necessary.
  • the polyamide compositions containing the invention antistatic agent can be readily formed into fiber, film, sheet, rod tube, casting and other articles by means which are generally known. An especially satisfactory antistatic effect can be manifested when the invention polyamide composition is formed into fibers.
  • This antistatic effect does not decline with the passage of time, and furthermore this effect can not only withstand laundering but also its decline under harsh dry cleaning conditions is also small.
  • the invention antistatic agent possesses an excellent thermal stability. It withstands the elevated temperatures which are encountered during the manufacturing and processing steps of the polyamide shaped articles, and even when mixed with the polyamide it does not have an especially adverse effect on such textile product production steps of spinning of the filaments, drawing, spinning of staples, weaving and knitting, there being noted no substantial change in the physical properties and coloration of the products.
  • the invention antistatic agent can be used in conjunction with antioxidant, delustrants, pigments and similar substances without its antistatic property being substantially affected.
  • the invention antistatic agent comprising an addition product of a carbonamide group-containing low molecular weight compound and an alkylene oxide does not adversely affect the manufacturing operations of shaped articles even when incorporated in the poly amide, as hereinabove described, and furthermore imparts a durable antistatic property to the polyamide while substantially maintaining its excellent physical properties is truly surprising.
  • a polyalkylene oxide is merely mixed and spun with a polyamide, the phase separation of the two components take place to greatly reduce the spinnability and, in addition, the antistatic property of the resulting fiber is as yet unsatisfactory.
  • EXAMPLE 1 Ethylene oxide in the amounts of respectively 660, 1320 and 2640 parts were addition polymizered to 113 parts of e-caprolactam in customary manner at a reaction temperature of ISO-180 C., a reaction pressure of 4-5 kilograms per square centimeter and a reaction time of 4 hours.
  • Ten parts each of three classes of antistatic agents (molecular weights 773, 1433 and 2753) were mixed respectively with 100 parts of polycaprolactam chips (inherent viscosity 2.45) to prepare by the master batch method chips containing the antistatic agents in high concentration.
  • tricot D was made in like manner from unmodified chips to which the antistatic agent had not been added.
  • the so obtained four classes of test specimens A, B, C and D were subjected to four cycles of harsh laundering followed by ironing at the usual temperature after each cycle.
  • the results of the antistatic performance, as evaluated by the frictional electrification voltage, of tricots A, B, C and D after the four cycles of washing and pressing as well as their voltage measurements before laundering are shown in Table I.
  • the measurements were made at a temperature of 20 C. and a relative humidity of 55%, the several specimens being measured 48 hours after they were adjusted to the same temperature and humidity.
  • a rotary static tester (a product of Koa Shokai, Ltd., Japan) was used and the voltage of frictional charge was measured in customay manner by mounting the tricot specimen to the rotating drum and causing it to rub at a speed of 452 meters per minute with a polyethylene terephthalate film suspended with a 20-gram load, and measuring the electric charge generated.
  • EXAMPLE 2 A 1:5 (weight ratio) mixture of propylene oxide and ethylene oxide was added randomly to e-caprolactam in customary manner (reaction temperature 100-130 C., reaction pressure 2-3 kilogram per quare centimeter, reaction time 10 hours) and two classes of soft, light yellow compounds of molecular weights about 3000 and 6000 were prepared.
  • Example 2 2.5 parts of the foregoing antistatic agent were added to 100 parts of polycaprolactam chips, blended uniformly and pelletized, after which the pellets were spun into filaments and drawn. The so obtained filaments were then cut and staples A and B were prepared.
  • 9 g g gg gi D i 0 2,00% 000 parts of ethylene oxide were added to a mixture of 80 parts of the oligonier of Example 3 and 20 parts of 6- EXAMPLE 6 caprolactam followed by the addition of 100 parts of propylene oxide, thereby obtaining a light yellow, soft A11 yl OXlde added p f l deflvatlve reaction product (molecular weight 2422).
  • taffeta C was woven prepared from salt of diamine containing polyethylene oxide of an averan unmodified polymer not containing the antistatic agent. age molecular weight of 1000 was mixed with e-capro- Next, the specimens of the fabrics to be tested were lactam and the polymerization reaction was carried out washed for one hour under boiling conditions in a 0.5% while mixing the mixture uniformly at 280 C. The resultaqueous solution of sodium salt of higher unsaturated ing polymer was melt-spun at 260 C. in customary manalcohol sulfate followed by water-washing and drying. ner and filament C was obtained.
  • EXAMPLE 7 1) One percent by weight of metallic potassium was added at about C. to distilled n-pyri'olidone in a stream of dried N After the polymerization reaction was carried out for 12 hours, the polymeric mass was comminuted (polymer A).
  • a 6,6 salt was prepared in customary manner from hexamethylene diamine and adipic acid, following which this salt was heated for 1.5-2 hours at 215 C. in a polymerization tube. After cooling to room temperature, purging with N was repeated several times and thereafter the salt was heated at 270 C. An hour later, further heating for one hour was carried out at a reduced pres.- sure of 0.2-1.5 mm. Hg. After cooling, a white opaque polymer was separated (polymer C).
  • a fiber forming synthetic linear saturated aliphatic polycarbonamide composition having an improved antistatic property said composition consisting essentially of 0.1 to 10 percent by weight, based on said polycarbonamide, a homogeneously distributed compound which is an addition product of an alkylene oxide of 2 to 3 carbon atoms and a carbonamide group-containing compound selected from the group consisting of lactams whose ring is 3-12 carbon atoms, oligomers up to hexamers of said lactams, low molecular weight polycondensation products up to hexamers of w-aminocarboxylic acids of 3-12 carbon atoms, said addition product containing a structural unit of the formula wherein X stands for ethyleneoxide, Y stands for propyleneoxide, (X, Y). stands for a homopolymer of ethyleneoxide or propyleneoxide or a block or random copolymer of ethylene oxide and propyleneoxide and n is an integer from 10 to 1000.
  • composition according to claim 1 wherein said synthetic polyamide is selected from the group consisting of polycaprolactam and polyhexamethylene adipamide.

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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)
  • Polyamides (AREA)
US723875A 1968-04-24 1968-04-24 Internal antistatic agent for super polyamides and polyamide compositions having improved antistatic property Expired - Lifetime US3557060A (en)

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US72387568A 1968-04-24 1968-04-24
FR149884 1968-04-29

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DE2217527C3 (de) * 1972-04-12 1980-02-14 Basf Ag, 6700 Ludwigshafen Aus der Schmelze geformte, ein Antistatikum enthaltende Fäden oder Fasern aus Polyamiden sowie ein Verfahren zu deren Herstellung

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