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Publication numberUS3655821 A
Publication typeGrant
Publication dateApr 11, 1972
Filing dateSep 3, 1969
Priority dateSep 3, 1969
Publication numberUS 3655821 A, US 3655821A, US-A-3655821, US3655821 A, US3655821A
InventorsRobert A Lofquist, Brendan T Hayes
Original AssigneeAllied Chem, Barbara E Hayes
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polyamide filaments containing antistatic polyether prepared from a polyalkylene and an aliphatic dicarboxylic acid
US 3655821 A
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Description  (OCR text may contain errors)

United States Patent 3,655,821 POLYAMIDE FILAMENTS CONTAINING ANTI- STATIC POLYETHER PREPARED FROM A POLYALKYLENE AND AN ALIPHATIC DI- CARBOXYLIC ACID Robert A. Lofquist, Richmond, Va., and Brendan T. Hayes, deceased, late of Chester, Va., by Barbara E. Hayes, administratrix, Chester, Va., assignors to Allied Chemical Corporation, New York, N.Y. No Drawing. Filed Sept. 3, 1969, Ser. No. 855,469 Int. Cl. C08g 41/04 US. Cl. 260-857 PEG 4 Claims ABSTRACT OF THE DISCLOSURE A filament, having antistatic properties, comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10 weight percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 100 to 15,000 and a compound which has the general formula:

ll i XC(OH2)nCX wherein X is hydroxyl, -OR wherein. R is lower alkyl, or halogen and n is an integer from 2 to about 20.

BACKGROUND OF THE INVENTION This invention relates to compositions suitable for use in imparting antistatic properties to textile materials, to methods for preparing such compositions, to methods employing such compositions for decreasing the tendency of textiles to collect static charges and to textiles so produced.

Many textile fabrics, and particularly fabrics made of the recently developed synthetic yarns, display a marked tendency to collect static charges. This tendency is very objectionable in that it causes, in many instances, garments made therefrom to cling to the skin of the wearer in an undesirable manner. Garments made of such materials also tend to collect lint and fly and, in some instances, to drape in an undesirable manner.

There have previously been available many antistatic compositions which could be applied to yarns or fabrics which display a tendency to collect static charges but such compositions have been known, in most instances, to be easily removed by either washing or dry cleaning. This has limited the usefulness of these products primarily to manufacturing operations since the application of such products has been too expensive and involved to be undertaken by a dry cleaning establishment or laundry each time that garments made from such fabrics are cleaned. As a result, the wearer of garments woven from materials which tend to collect static electricity has been forced to tolerate this undesirable characteristic throughout substantially the entire life of the garments.

Some antistatic agents have been found resistant to Washing or dry cleaning but they impart a harsh hand to yarns and fabrics or adversely affect the dyeability of the yarns and fabrics.

It has now been discovered that the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof is an effective antistatic agent which can be mixed with a hydrophobic synthetic polymer prior to the extrusion of the synthetic polymer into a filament. The mixture of the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof throughout the hydrophobic synthetic filament produces yarns and fabrics containing the filaments which have excellent antistatic properties. Furthermore, the antistatic agents of the present invention resist Washing and dry cleaning since they are mixed throughout the filaments and do not impart a harsh hand to the yarns and fabrics. Finally, the antistatic agents of the present invention do not significantly affect the dyeability of the yarns and fabrics.

SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a filament, having antistatic properties comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10, preferably about 2 to 5, percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about to 15,000, preferably about 200' to 10,000, and a compound which has the general formula:

wherein X is hydroxyl, OR wherein R is lower al=kyl, or halogen such as chlorine or bromine and n is an integer from 2 to about 20, preferably 2 to about 10.

DESCRIPTION OF THE INVENTION The filament-forming hydrophobic synthetic polymer can be a polyolefin, polysulfone, polyphenyl oxide, polycarbonate, polyacrylonitrile, polyamide, polyester and the like or polymer blends thereof. Examples of suitable polymer blends as disclosed above are dispersions of polyester in polyamide such as disclosed in US. Pat. 3,369,057 to Twilley; US. Pats. 3,378,055, 3,378,056, and 3,378,602; British Pat. 1,097,068; Belgian Pat. 702,813; and Netherlands Pats. 6606838 and 6612628. The filament of the present invention can be prepared from these dispersions by known melt spinning techniques.

In a preferred embodiment of the present invention, the filament-forming synthetic polymer is a polyamide or a polyester. The filament of the present invention can be prepared from these polymers by known melt spinning techniques.

Suitable polyamides for use in the present invention include, for example, those prepared by condensation of hexamethylene diamine and adipic acid, condensation of hexamethylene diamine and sebacic acid known as nylon 6,6 and nylon 6,10, respectively, condensation of his (para-aminocyclohexyl)methane and azelaic acid, condensation of bis(paraaminocyclohexyl)methane and dodecanedioic acid, or by polymerization of 6-caprolactam, 7-aminoheptanoic acid, 8-caprylactam, 9-arninopelargonic acid, ll-aminoundecanoic acid, and 12-dodecalactam, known as nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, and nylon 12, respectively.

The polyesters useful in the practice of this invention can be prepared in general by condensation reactions between dicarboxylic acids or their derivatives and compounds containing two hydroxyl groups, or materials possessing both an alcohol group and a carboxylic acid group or derivative thereof; or by polymerization of lactones. Dicarboxylic acid derivatives which can be employed include esters, salts, anhydrides and acid halides. The monomeric species employed in the preparation of the polyesters are preferably not more highly functional than difunctional in their reactivity so as to produce essentially linear, non-crosslinked polymer structures.

Suitable polyesters for use in the present invention include those polymers in which one of the recurring units in the polyester chain is the diacylaromatic radical from terephthalic acid, isophthalic acid, S-t-butylisophthalic acid, a naphthalene dicarboxylic acid such as naphthalene 2,6 and 2,7 dicarboxylic acids, a diphenyl dicarboxylic acid, a diphenyl ether dicarboxylic acid, a diphenyl alkylene dicarboxylic acid, a diphenyl sulphone dicarboxylic acid, an azo dibenzoic acid, a pyridine dicarboxylic acid, a quinoline dicarboxylic acid, and analogous aromatic species including the sulfonic acid analogues, diacyl radicals containing cyclopentane or cyclohexane rings between the acyl groups; and such radicals substituted in the ring, e.g., by alkyl or halo substituents.

The dioxy radical representing the other principal recurring unit in the polyester chain can be an open chain aliphatic such as ethylene glycol or ether thereof, for example, the diether, or can contain rings such as those which form part of the above noted diacyl radicals. The carboxy and/or the oxy chain members can be directly attached to a ring or removed by one or more carbons therefrom, as in the 1,4 dioxymethyl cyclohexane radical.

The preferred polyester is poly( ethylene terephthalate) Other suitable polyesters include poly(dimethylene cyclohexylene terephthalate) and poly(4-ethoxy benzoate).

The antistatic agent of the present invention is the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof.

Suitable polyglycols include polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide. The polyglycol can have a molecular weight from about 100 to 15,000, preferably about 200 to 10,000.

Suitable compounds having the formula X-iJ-(OHM-i'J-X wherein X and n are defined above include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, pimelic acid and their corresponding acid halides such as chlorides and bromides and their lower alkyl esters. The (CH divalent radical in the above formula can be substituted with nonreactive groups such as p-phenylene, m-phenylene, and p-xylylene.

The antistatic agents of the present invention can be prepared by any of the known methods. A typical method comprises charging into a flask, equipped with a heater, stirrer, reflux condenser and a thermometer, a polyethylene glycol having a molecular weight from about 100 to 15,000, preferably about 200 to 10,000; a compound which has the general formula:

wherein X is hydroxyl, --OR wherein R is lower alkyl, or halogen such as chlorine or bromine and n is an integer from 2 to about 20, preferably 2 to about and an inert solvent, such as dry xylene. The reaction mixture can then be heated to the boiling temperature of the reaction mixture and be reacted while refluxing in the presence of a catalytic amount of a suitable esterification catalyst such as p-toluene sulfonic acid or sulfuric acid. The above reaction is usually carried out for a period of about 2 to 8 hours. At the end of the above reaction period, the reflux condenser can be replaced by a moisture trap and refluxing of the reaction mixture can be continued until no additional water appears in the moisture trap. The reaction mixture can then be cooled below its boiling temperature and the reaction flask can be set up to distill off the inert solvent. The distillation temperature should not be allowed to exceed about 150 to 175 C. and the inert solvent should not be distilled at a rate greater than about 2 to 4 ml. per minute. When most of the inert solvent is removed, the reaction mixture can then be transferred to a thin film evaporator and the reaction mixture heated to a temperature of about 150 to 175 C. under a vacuum of about 1 to 10 mm. of mercury for a 4 period of time of about 2 to 6 hours or until no more volatiles can be removed.

Under certain circumstances, the reaction mixture can be reacted in the thin film evaporator in the presence of little or no inert solvent as shown in Examples 2 and 3.

In general, it has been found desirable to prepare the antistatic agents by heating together one molecular portion of the polyglycol with from about 1.0 to 1.1 molecular portions of the dibasic acid. It is preferred that enough excess dibasic acid be added so that both ends of the antistatic agent have carboxyl end groups.

Generally speaking, about 1 to 10 weight percent of the antistatic agent, based upon the weight of the synthetic polymer, will produce the desired antistatic properties in the filament, however, it is preferred that about 2 to 5 weight percent be used.

The antistatic agent can be mixed with the synthetic polymer during the polymerization, preferably at the end of the polymerization, of the synthetic polymer or can be mixed into the molten synthetic polymer by, for example, injection into the mixing portion of the extruder prior to the melt extrusion of the filament. Alternatively, the antistatic agent can be blended with the synthetic polymer granules prior to the melting of the synthetic polymer by conventional addition and mixing procedures.

PREFERRED EMBODIMENTS The following examples illustrate the practice and principles of this invention and a mode of carrying out the invention.

Example 1 Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a one liter flask containing 500 ml. of dry xylene. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table I below. The one liter flask was equipped with a heater, stirrer, reflux condenser and a thermometer. The reaction mixture was heated to the boiling temperature of the reaction mixture and reacted while refluxing was in the presence of 0.1 gram p-toluene sulfonic acid catalyst at the boiling temperature of the reaction mixture for one hour. At the end of the one hour reaction period, the reflux condenser was replaced by a Dean-Stark trap and refluxing of the reaction mixture was continued until no additional water appeared in the Dean- Stark trap. The reaction mixture was then cooled below its boiling temperature and the reaction flask was set up to distill oil? the xylene. The distillation temperature was not allowed to exceed C. and the xylene was distilled at a rate no greater than 10 ml. per minute. When most of the xylene was removed, the reaction mixture was then transferred to a 500 ml. Rinco thin film evaporator and the reaction mixture was heated to a temperature of about 150 to C. under a vacuum of about 2 mm. Hg until no more volatiles could be removed.

TABLE I Polyethylene glycol Dlbasic acid Molecular Wei ht Wei ht Preparation No. weight gins. Type gins:

400 200 Sebaeic 103.12 1,200 200 do 34.37 6,000 200 do 6. 87

Example 2 Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a 500 ml. Rinco thin film evaporator. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table II below. The reaction mixture was heated in the presence of 0.1 gram p-toluene sulfonic acid catalyst under a vacuum to a temperature of about 150 to 175 C. over a period of time of about 4 hours. Water was evaporated from the reaction mixture during the reaction period.

The knitted sleeves were cut into fabric samples having a width of 2.5 inches and a length of 10 inches and the fabric samples were tested for their antistatic property TABLE H in accordance with the procedure described below. Polyethylene g y Dibasic acid A fabric sample was mounted on a grounded vertical l m w weight type 304 stainless steel frame and was stroked downward Prepammm weight E TYPB ten times with a stainless steel rod. The electrostatic volts oo 28 age on the fabric was measured by means of a Rothschild 1.200 3M4 Static Volt Meter, Model No. R-1019', positioned one lnch from the fabric which recorded the voltage on the fabric. The Field Half Time of the fabric was measured P 3 to determine the effectiveness of the various antistatic Antistatic agents of the present invention were preagents mlxed P Fleld Half pared in the following manner. Polyethylene glycol and T fi 9 the fabnc 1S defined as that P requlred for the an aliphatic dibasic acid were added with 10 ml. of dry 15 1n1t1al voltage measured on the fabr c to decrease to one Xylene to a 500 1 Rinco thin film evaporaton The quam half of its origlnal value. The antistatic measurements 6 tities of polyethylene glycol and aliphatic dibasic acid e made immature of and a N for each preparation are contained in Table III below. relatlve humldlty of results P h annstatlc The d mixture was hgated infthe presence f Q1 measurements of the fabrics are contained in Table IV gram-p-toluene sulfonic acid catalyst under a vacuum to belowa temperature of about 180 to 200 C. over a period of TABLE IV time of about hours. Water and xylene were evaporated Antistatic agent reactants from the reaction mixture during the reaction period. 1 th I 0 6 TABLE III ene glyebl, molecular Polyethylene glycol Dibasie acid Fabric sample weight Molecular Weight, Weight, Preparation No. weight gins. Type gms. 1 :38 i o 400 200 Succinic- 59.1 1000 5 H 1, 200 204 .-...do 20.84 6,000 14 1,200 5 238 s 3 110011110- Example 4 1,200 6 A series of glass reactors each equipped with a heater and stirrer were charged with a mixture of 1520 grams of e-caprolactam and 80 grams of aminocaproic acid. The mixture were then flushed with nitrogen and were stirred and heated to 255 C. over a one hour period at atmosperic pressure to produce polymerization reactions. The heating and stirring were continued at atmospheric pressure under a nitrogen sweep for an additional fourteen hours in order to complete the polymerizations. During the last thirty minutes of each polymerization, 48 grams of antistatic agent A, B, C, D, E, F, G, or H as prepared in Examples 1, 2 and 3 was respectively added to one of the polycaproamide polymerization batches and stirring was continued to thoroughly mix each antistatic agent throughout the polymers. Nitrogen was then admitted to the glass reactors and a small pressure was maintained while the polymers were extruded from the glass reactors in the form of polymer ribbons. The polymer ribbons were subsequently cooled, pelleti'zed using a Wiley Mill, washed and then dried. The polymers were white solids having relative viscosities of about 50, as determined at a concentration of 11 grams of polymer in 100 ml. of 90 percent formic acid at 25 C. (ASTM D-789- 62T).

Each of the batches of polyamide pellets containing an antistatic agent were melted at about 285 C. and then melt extruded under a pressure of 2,000 p.s.i.g. through a 14-orifice spinnerette, each of the orifices, haw'ng a diameter of 0.040 inch, to produce 820 denier fibers. The fibers were collected at about 1,500 feet per minute and were drawn about 4 times their extruded length to produce 210 denier yarns. A control yarn containing no antistatic agent was produced in the same manner as described above.

' Example 5 The 210 denier polycaproamide yarns containing an antistatic agent and the control yarn which were produced in Example 4 were knitted into sleeves. The yarns contained /zZ twist. The sleeves were then scoured in a conventional manner and dyed blue in an aqueous dye bath containing a Disperse Blue 3 dye using a conventional dyeing procedure.

No'rE.Fabric samples A through E contained 3 weight percent of antistatic agent based upon the weight of the polyamide.

As can be seen from the data contained in Table IV above, the antistatic agents of the present invention are extremely effective in reducing the electrostatic charge on a fabric.

The degree of polymerization of the antistatic agents of the present invention is generally between about 2 and 20, preferably between about 4 and 10.

[[t is claimed:

1. A filament, having antistatic properties, comprised of a fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain mixed with about 2 to 5 weight percent, based on the weight of the polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.

2. A filament, having antistatic properties, comprised of a polycaproamide mixed with about 2 to 5 weight percent, based on the weight of the polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000 and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.

3. A process for producing a filament, having antistatic properties, comprised of fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain which comprises mixing said polyamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.

4. A process for producing a filament, having antistatic properties, comprised of polycaproamide which comprises mixing said polycaproamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.

References Cited UNITED STATES PATENTS 4/1968 Senoo et a1. 260860 11/ 1968 Crovatt 260-860 5/ 1969 Bonin 260-860 12/ 197 0 East '260857 12/ 1970 Okazaki 260--857 12/1970 Ogata 260-857 I/ 1971 Bonnard 260-860 4/1971 Kimura et al. 260-857 PEO FOREIGN PATENTS 5/ 1967 France. 1/1968 Netherlands.

1964 Japan. 1965 Japan.

PAUL LIEBERMAN, Primary Examiner US. Cl. X.R.

260-823, 857 PE, 860, 897 R, 898

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3839245 *Mar 30, 1972Oct 1, 1974Emery Industries IncPoly(ether-ester-amide) antistatic compositions derived from dimr acids
US3860671 *Mar 22, 1974Jan 14, 1975Akzona IncPolyamide fibers with improved antistatic effect and their preparation
US3944629 *Jun 24, 1974Mar 16, 1976Monsanto CompanyPolyester initiated anionic catalyzed polymerization of lactam
US3993709 *Nov 7, 1975Nov 23, 1976Monsanto CompanyLactam-polyol-polyacyl lactam or acyl polylactam terpolymers
US4032595 *Aug 5, 1975Jun 28, 1977Imperial Chemical Industries LimitedAntistatic agents
US4035341 *Mar 5, 1975Jul 12, 1977Rhone-Poulenc-TextileMelt-spinnable, quaternary ammonium compounds
US4051196 *Aug 4, 1976Sep 27, 1977Allied Chemical CorporationAntistatic fiber containing chain-extended tetrols based on diamines
US4128525 *Feb 20, 1976Dec 5, 1978Texaco Development Corp.Plasticizer, polyamide
US4165303 *Aug 26, 1977Aug 21, 1979Emery Industries, Inc.Polymer compositions containing poly (alkylene ether) esters of polybasic acids
US4182845 *Jun 29, 1978Jan 8, 1980Texaco Development CorporationPreparation of polyamide thermoplastic adhesive from polyoxypropylene polyamine and piperazine
US4207410 *Mar 21, 1978Jun 10, 1980Chemische Werke Huls AktiengesellschaftMolding materials having high impact strength at low temperatures
US4234184 *Feb 15, 1979Nov 18, 1980Ato ChimieThermoplastic polymer cover for golf balls and golf balls comprising such a cover
US4252920 *Aug 31, 1978Feb 24, 1981Ato ChimieMethod for preparing ether-ester-amide block polymers for among other moulding, extruding or spinning uses
US4328331 *Apr 20, 1981May 4, 1982The Upjohn CompanyNovel polyester-amides
US4346024 *Dec 5, 1980Aug 24, 1982Rhone-Poulenc IndustriesHeat-stable polyphase polyamide/polyesteramide compositions
US4346200 *Dec 29, 1980Aug 24, 1982Monsanto CompanyThermoplastic polyamide compositions
US4379913 *May 4, 1982Apr 12, 1983Diamond Shamrock CorporationCompositions useful as internal antistatic additives for polymeric structures
US4468433 *Jul 26, 1982Aug 28, 1984E. I. Du Pont De Nemours And CompanyAntistatic composition and polyester fiber containing same
US4506070 *Mar 21, 1984Mar 19, 1985E. I. Du Pont De Nemours And CompanyPolyether-ester copolymers
US5194319 *Nov 13, 1991Mar 16, 1993Kanebo, Ltd.Shaped polyamide articles and process for manufacturing the same
US5321068 *Nov 24, 1992Jun 14, 1994E. I. Du Pont De Nemours And CompanyFiber of polyadipamide polymer containing added succinic acid
Classifications
U.S. Classification524/321, 525/927, 525/430, 260/DIG.170, 524/910, 524/606, 525/444, 525/425
International ClassificationC08L77/00, C08G65/332
Cooperative ClassificationC08L77/00, Y10S525/927, Y10S260/17, C08G65/3322, Y10S524/91
European ClassificationC08L77/00, C08G65/332D