CA1040819A - Antistatic fiber containing chain-extended tetrols based on diamines and phenolic compound - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

It has been suggested that antistatic properties of fibers of polyamide could be improved by uniformly dispersing in the polyamide between about 1 percent and about 12 percent by weight of a predominantly branched, chain-extended propylene oxide-ethylene oxide copolymer base on a diamine. However, with incorporation of this antistatic additive in the polyamide, serious problems have been encountered in melt-spinning due to the frequent occurrence of the "nuba" or enlarged places in the extruded polyamide filament. It has now been found that the occurrence of said nubs in the antistatic polyamide fiber can be greatly reduced by dispersing in the polymer at least 0.5% by weight, based on the weight of the antistatic agent, of a phenol compound represented by the formula:

Description

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BACKGROUND OF THE INVENTION
This invention relates to a process for the melt-spinning of a filamentary structure from a synthetic polyamide polymer. More particularly, it is concerned with an improved process for the formation of an improved antistatic filament, yarn or the like by melt-spinning a synthetic linear fiber-forming polyamide.
It has been suggested that the utility of synthetic fibers could be increased and their properties, in particular their antistatic properties, could be improved if a polyalkylene ether of high molecular weight is included in the polymer. More specifically, -it is disclosed in U.S. Patent 3,475,898 to Magat and Sharkey to use poly(ethylene-propylene)ether glycols for this purpose. More recently, U.S. Patent 3,657,386 discloses that certain propylene oxide-ethylene oxide copolymers based on ethylene diamine are useful in preparation of an antistatic fiber of polyamide. It ~-has also been suggested that the utility of synthetic fiber of polyamide could be increased by dispersing in the polyamide an antistatic compound which is a reaction product of:

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.. ...

-1~4~819 H(ocH2cH2)y(ocHcH2)c \ ~ CH2CHO)a(c~2cH2o)x H(CC~2C~2)Z(cHcH2)d (cH2cHo)b(cH2cH2o~wH

where a, b, c, d, w, x, y and z are each a whole number and A is a difunctional radical from a hydro-carbon containing 1 to 13 carbon atoms, said tetrol compound having a molecular weight between about 4,000 and about 50,000 and at least one compound selected from the group consisting of diepoxides and compounds which yield the following divalent radicals:

O O
~
-C-R'-C-, and O O' " H H "
-C-N-R'-N-C-where R' is a difunctional radical from a hydrocarbon - containing 1 to 30 carbon atoms. However, serious problems were encountered in melt-spinning due to the frequent occurrence of "nubs" in the fiber. The term "nubs" is conventionally ~pplied and is used herein to 25- mean enlarged sections of filament no more than several filament diameters in length. Nubs may be formed by a foreign, non-orientable substance which interferes with normal fiber stretch in a short section, resulting in an enlargement. Foreign substances which are believed to have contributed to nubs in the present instance include charred polymer from the acting surface of the extruder and spinnerette, and gels formed in the polymer. Gels appear to be the chief cause, i.e., the nubs are ,'.~, ' , .
,. ., . ::
', .. ,',, :',. " ,, ' , 1~4~819 probably created by non-orientable gel from cross-linked polymer. Thermal degradation of the polymer may be an important causative factor.
The reactions in thermal degradation of poly~lides containing polyalkylene ether additives are not entirely understood. It is likely that thermal degradation produces a decomposition product which serves to form cross-links between amide groups and adjacent polymer chains. The decomposition reaction proceeds slowly, finally building up a three-dimensional network of molecules which may be called polymer gel and which eventually reaches the stage where it forms -an infusible coating on the walls of the reactor and ~
other equipment. - -A serious difficulty which arises from the -formation of this polymer gel on the interior walls is that from time to time pieces break off and get into ~
the flowing polymer stream where they produce damage -to the spinning equipment.
The greatest difficulty, however, is caused by -polymer gel which has progr-essed to the three-dimensional structural stage, but which has not yet reached the stage of being infusible. This kind of polymer gel is readily carried with the stream of flowing poly~er.
Being still molten or at least softened, it passes 1:hrough the pump and even through the filter medium to show up either as discontinuities or as viscosity differences in the spun filament. When these filaments are later cold drawn, these defects may cause breaks in the filaments which either cause the whole thread to .. . .. . . . . . .
" " ~ , ,,, ,: ,, , . .

-1~463819 break or else form nubs which go through to be counted as quality defects in the final yarns.
SUMMARY OF THE INVENTION
It is an object of this invention to avoid the above difficulties by minimizing gel formations in the molten polyamide. Another object is to avoid accumulation of polymer gel on the walls of the reactor, in the pump, or in the filtering medium when melt-spinning the polyamide. A further object is to improve the uniformity and quality of filaments or fibers formed from the molten polymer, in particular to minimize nub formation in the filaments. Other objects will become apparent from the disclosure and the appended claims.
These objects are accomplished by the present - invention which provides an improvemènt in the process for the formation of an antistatic polyamide fiber from a fiber-forming polyamide polymer containing about 1 percent to 12 percent by weight of an antistatic compound which is a reactlon product of a tetrol . compound represented by the formula:
CH3 C,H3 H(OCH2CH~)y(OCHCH ~ ~CH2CHO)a(CH2CH2O)xH
CH3 N-A-N C,H3 25 H(OCH2CH2)z(OCHCH2)d ~CH2CHO)b(CH2CH2O)WH
: .
- where a, b, c, d, ~ X, y and z are each a whole ~-number and A is a difunctional radical from a hydrocarbon containing 1 to 13 carbon atoms, said tetrol compound . having a molecular weight between about 4,000 and about 50,000,and at least one compound selected from the group .. . ..

' . ~.
, ' ' , . .. .
. , , . ~ : , ; , .

8~9 consisting of diepoxides and compounds which yield the following di~alent radicals:
O O
.. .. .
S '-X'-C-, and O O
~' H H "
--C--N--R '--N--C--where R' iS a difunctional ràdical from a hydrocarbon containing 1 to 30 carbon atoms, by extruding the molten polymer through an orifice into a quenching medium and thereafter stretching the resulting filaments, the improvement comprising dissolving in the extrudate prior 1:
to extrusion at least 0.5 percent by weight, preferably lS 0.5 to 35 percent based on the weight of the antistatic compound, of a phenol compound of the formula: ~

~H3 CH3 .
114~0~1 ~_ _ R ~ ;

~1 Rl .
where R is an alkyl hydrocarbon group containing less than nine chrbon atoms, a~d Xl is a tertiary alkyl group of at least four carbon atoms but not more than twelve carbon atoms. Such compounds may be economically prepared and give excellent results in the present - `
invention.
As stated above, the present invention relates to an :- .

,, ~ , ' :., , , '. ', , ' ~ ' :
.

1~4(~819 improved antistatic fiber containing a novel antistatic compound. The novel antistat~c compound is prepared by reacting a tetrol compound, as described above, with a chain-e~tender compound, for example a diepoxide, a dicarboxylic acid or a diisocyanate, to form predominantly branched, chain-extended polymer having a melt viscosity of about 800 to 50,000 centipoises, preferably 1,500 to 25,000 centipoises, at 100C. Preferably, the ethylene oxide moiety makes up 10 to 90% of the molecular weight of the antistatic compound. The mol ratio of chain-extender compound to tetrol compound is preferably between about 0.7 and 1Ø
The phenol compounds useful in the present invention are known compounds and some are commercialiy available. The phenol compounds of the invention may be prepared in accordance with U.S. Patent 2,818,945.
The tetrol compound which is chain-extended for use as an antistatic additive in this invention is fully described in U.S. 2,979,528 to Lundsted, assignor to Wyandotte. These tetrol compounds are commercially available as Tetronic series block copolymers having molecular weights between 1,650 and over 26,000. This series varies in length of poly(oxyethylene) chain and poly(oxypropylene) chain. A 3 and 4 digit code number indicates the molecular composition. When four digits are employed, the first two explain the average molecular weight of the hydrophobe (poly(oxypropylene) branches on the alkylene-diamine). When three digits are used only the first number serves this purpose.
The last digit of each code number represents the weight :- , . , :

.. ' ; . ' ,,: ' . ... .
,... . . . .
,; , ... ..

1~34(:i8~9 percentage of hydrophilic (poly(oxyethylene)) units to the nearest 10%. The tetrol compounds in the examples are described this way.
As diamines upon which the tetrols are based, in addition to ethylene diamine, diamines of a hydrocarbon containing 1 to 13 carbon atoms, preferably the lower alkyl diamines, where the lower alkyl radical contains 1-6 carbon atoms, can be used.
The polyepoxy compounds can be prepared ~y the method taught in British 793,913, Example I. The other classes of compounds can be similarly prepared, as in Example 10 in U.S. 3,009,884.
Typical of the acids and their esters to provide the chain-extending difunctional radical are the dialkyl phthalic, isophthalic or terephthalic esters, such as dimethyl terephthalate and adipic, phthalic, terephthalic sebacic, glutaric, pimelic, isocinchomeronic acids and their esters.
Typical of the polyepoxy compounds which provide -the difunctional or divalent compounds, used to chain extend the tetrols based on diamines, are those polyepoxy compounds described in British specification 793,915 -to Union Carbide on page 2, line 48 to line 121.
Also useful to form chain-extending divalent radicals are the aromatic or aliphatic diisocyanates, having a structure OCN-R'-NCO, where Rt is defined as above.
The antistatic fiber of this invention may also contain conventional fiber additives such as antioxidants, stabilizers, delusterants, dyeing assists, and colorants.

A
.
.

, DESCRIPTION OF THE PREFERRED EMBODIMENTS
.
The invention will now be further described in the following specific examples which are to be regarded sole~ as illustrative and not as restricting the scope of the invention. Parts are by weight.

This example shows a method of preparing a preferred antistatic additive. The instant chain-extended polymer is pxepared from a tetrol compound covered by U.S. Patent 2,9~9,528 to Lundsted, and sold commercially as Tetronic 1504.
Three hundred grams of Tetronic 1504 (molecular weight 12,500) ~as placed in a three-neck flask fitted with a thermometer, stirrer, and addition funnel.
The Tetronic 1504 was stirred and heated to 100C., and 5.24 grams of 4,4' methylene bis (cyclohexyl) isocyanate, ~ ~ 2 OCN-C \ ~H-NCO

2 2 (molecular weight 262.4) was added dropwise to the material in the flask. Agitation was continued for one hour at 100-105C. after the addition was completed. Then the ;
product was cooled to room temperature. It was a soft solid having a melt viscosity of 8,300 centipoises at 100C. measured with the Brookfield viscometer. The viscosity of the original Tetronic 1504 was 200 centipoises at 100C.

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8~9 ExAI~qPLE ?
~ g]ass reactor e~uipped'with a heater and stirrer '' was charged with a mixture of 1,520 grams of e-caprolactam and 80 grams of aminocaproic acid. The mixture was then flushed with nitrogen and was stirred and heated to 255C. over a 1 hour period at atmospheric pressure to produce a polymerization reaction. The heating and stirring was continued at atmospheric pressure under a nitrogen sweep for an additional 4 hours in order to complete the polymerization. During the last 30 minutes ! of the polymeri~ation, 1.7 grams of 4,4'-butylidene-bis-~6-tert. butyl m-cresol) and 48 grams of the antistatic compound of Example 1, were added to the po~ycaproamide and stirring was continued to thoroughly mix the additives ' throughout the polymer. Nitrogen was then admitted to the glass reactor and a small pressure was maintained ; while the polymer was extruded from the glass reactor in the form of a polymer ribbon. The polymer ribbon was subsequently cooled, pelletized, washed and then dried. The polymer was a white solid having a relative -viscosity of about 55 to 60 as determined by a concentration of 11 grams of polymer in 100 milliliters -'-; of 90 percent formic acid at 25C. tASTMD-789-62T). ~ -~
' l'he polycaproamide pellets containing the antistatic agent and phenol additive were melted at about 285C. and then melt-extruded under a pressure of about 1500 psig through a 16-orifi,ce spinnerette, each of the orifices having a diameter of 0.014 inch, to produce a 250-denier fiber. The ~iber was then collected at about 1,000 feet ~er mi~ute and was drawn , about 3.5 times its extruded length to produce a 70-denier yarn. For conv~nience, this yarn hereinafter will be called Yarn A. A control yarn containing the anti~tatic agent but no additional additive was produced in the same manner as described above.
For convenience, this yarn hereinafter will be called Yarn B. A second control y~rn containing no antistatic compound and no phenol compound was produced in the same manner as described above; for convenience this yarn hereinafter will be called Yarn C.
Yarn A, Yarn B and Yarn C were woven into conventional plain weave fabrics. The fabrics were cut into fabric ~ test samples having a width of 3 inches and a length ; of 9 inches. The fabric samples were tested for their antistatic property in accordance with the -- -general procedure described in the Technical Manual of the American Association of Textile Ch~mists and Colorists, 1969 edition, Volume 45, at pages 206-207.
This test procedure is entitled "~lectrostatic Clinging - -of Fabrics: Fabric-to-Metal Test" and is numbered AATCC 115-1969. In accordance with this test, Yarn C
showed poor antistatic properties, i.e., the average time for fabric samples to decling from metal completely -on their own was over 300 seconds after 5 to 25 wash cycles. In contrast, Yarn A and Yarn B both showed excellent antistatic properties, for example, average - time for fabric samples to decling from metal completely on their own was about 120 seconds after 25 wash cycles.
Yarn A, Yarn B and Yarn C were also tested for the number of nubs per pound as shown in Example 3.

; -12-.. . .
. "
. .

This example outlines the method used for locating, identifying and calculating the nubs per pound in Yarn A, Yarn B and Yarn C as prepared in Example 2. In this method a nub is defined as an enlarged place in a filament which is no more than several filament diameters in length. This method may be used for either monofilament or multifilament yarns;
however, it is not applicable to most types of crimped yarn.
In accordance with the test, the 70-denier yarn is drawn directly from the package by means of an air ;
aspirator and is passed through an opening of known -~ -width, specifically, 0.0030 inch in width. Such an opening is conveniently provided by use of a ceramic cleaner gap, which is well-known in the art. The presence of a nub is detected when it stops the yarn passage through the opening. The filaments are separated and the cause of the yarn stopping identified as a nub or as the twisted end of a broken filament. For representative results, about 75 grams of yarn is passed through the gap and the number of nubs counted. Table I -below shows the results of testing on Yarn A, Yarn B
and Yarn C.
TABLE I
Determination of Nubs Per Pound YarnNub Count Per SamPlePound of Yarn Yarn A 3,500 Yarn B 17,850 Yarn C 2,300 , It will be noted that polyamide yarn made without additives had a relatively low nub count of 2,300 nubs per pound of yarn. Addition of the antistatic compound to the p~lyamide caused the nub count to increase to 17,850 per pound of yarn. However, the addition of the antistatic compound plus the phenol compound of the invention reduced the nub count to-3,500 nubs per pound of yarn.
EXAMP~E 4 The procedure of Example 2 (Yarn A) was followed except that the various additives were charged with the caprolactam initially. The antistatic fiber nub count was only 3,200 per pound of yarn.

The procedure of Example 2 (Yarn A) was followed except that the antistatic additive was charged with the caprolactam but no phenol compound was added.
The antistatic fiber had a high nub count of 16,700 nubs per pound of yarn.

The procedure of Example 2 (Yarn A) was followed except that the antistatic additive was obtained from the reaction product of Tetronic 1504 and dimethyl terephthalate in a 1 to 0.7 mol ratio. The additive has a melt viscosity of 1,600 centipoises at 100C.
Sixty grams of the antistatic compound was added together with 1.13 grams of 4,4'-butylidene bis-(6-tert. amyl m-cresol) and 6.4 grams of 50% aqueous TiO
dispersion. The fiber nub count was 3,160 per pound of yarn.

.. . . . .
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., ~

1~4~8~9 The procedure o~ Example 2 (Yarn A) was followed except tha~ 90 grams o~ the antistat.ic additive of Example 6~ was used together with 1 gram of 4,4'-heptylidene bis-(6-tert. butyl m-cresol). The fiber produced had a low nub count of 3,245 nubs per pound of yarn.

Polymer pellets were prepared in accordance with Example 2 which contained 90 gr~ms antistatic agent of Example 1 together with 2.7 grams of 4,4'-butylidene bis-(6-tert.butyl-m-cresol), were melted at about 285C.
and then melt extruded under pressure of 1,500 psig to a 70-orifice spinnerette, each of the orifices having a diameter of 0.018 inch to produce a fiber having about 4,500 denier. The fiber was collected at about 1,-000 feet per minute and was drawn at about 4 times - the extruded length to produce yarn having a denier of about 1125. This yarn will hereinafter be called Yarn D. A control yarn containing no antistatic agent or phenol additive was prepared in the same manner as described above. This yarn will hereinafter be called Yarn E.
The yarns were textured using a steam ~et and - -. .
then two-plied by twisting two ends together with a 1-1/2 "S" twist. The yarns were tufted into a level loop 20 oz. carpet at about 6.5 stitch rate, about -~
9/32 to 10/32 inch pile height, dyed and latexed.
Static buildup of the carpet was tested by measuring the electrostatic ~oltage buildup on a person walking with a series of steps on a piece of carpet according ' , 10~81g to the st~ndard CRI Walk Test for static propensity in carpets, also labeled AATCC 134-1969. Carpet was conditioned at 70F. at 20 percent relative humidity.
Results are shown in the following Table.
Static Walk CarPet Test Made with Yarn D 4.9 KV
Made with Yarn E 14.1 KV ~-The untextured yarn was also tested for nubs using the nub count procedure of Example 3 except that the ceramic cleaner gap used had an openlng of 0.006 inch.
The nub count of Yarn D was 108 nubs per pound while that of Yarn E was 250 nubs per pound.

Ninety-four parts of polyhexamethylene adipamide and six parts of the antistatic material of structure of Example 1 and 0.18 parts of 4,4'-butylidene-bis-(6-tert.butyl-m-cresolj are melt blended by mixing the additive with the molten polyamide at about 285C.
- 20, The melt is extruded from a spinneret and the fibers are drawn as described in Example 8. Carpet samples prepared from this fiber ar.d tested in accordance --with Example 8 showed a static build-up of 5.2 KV.
Discussion `~-In additional tests it was determined that the ` molecular weight of the tetrol compound used to prepare -- . -the chair.-extended a~tistatic compound is preferably between about 4,000 and about 50,000, the ethylene oxide moieties making up about 10% to about 90% of the 30. molecular weight of said compound. Preferably, the -16- ;-, ' ' .

., ,: , , , , , , i . , , , ~ . :. ........ .

1~4(~819 antistatic fiber contains from about 2~ to about 8% of the chain-extended antistatic compound. Normally, the chain-extended antistatic compound has a melt viscosity of 800 to 50,000 centipoises at 100C.
By "antistatic" fiber is meant fibers that will ` pass the cling test and the shuffle test as described in U.S. Patent 3,657,386. By "fibe.~" is meant multi-filament yarn, monofilament, and all the known physical forms of synthetic fibers. By ''polyamide" is meant the polymers made by condensation of diamines with dibasic acids or by polymerization of lactams or amino acids, resulti~g in a synthetic resin characterized by the recurring group -CONH-. By "ethylene oxide moiety"
is meant the portion of the hemical molecule -(C82C~O~-.

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., ' . . .
.

Claims (10)

WE CLAIM:

1. In a process for the formation of an antistatic polyamide fiber from a fiber-forming polyamide polymer containing about 1% to 12% by weight of an antistatic compound which is a chain-extended reaction product of a tetrol compound represented by the formula:

where a, b, c, w, x, y and z are each a whole number and A is a difunctional radical from a hydrocarbon containing 1 to 13 carbon atoms, said tetrol compound having a molecular weight between about 4,000 and about 50,000, and at least one compound selected from the group consisting of diepoxides and compounds which yield the following divalent radicals:

, and where R' is a difunctional radical from a hydrocarbon containing 1 to 30 carbon atoms, by extruding the molten polymer through an orifice into a quenching medium and thereafter stretching the resulting filaments, the improvement comprising dissolving in the extrudate prior to extrusion at least about 0.5% by weight, based on the weight of the antistatic compound, of a phenol compound of the formula:

where R is an alkyl hydrocarbon group containing less than nine carbon atoms and R1 is a tertiary alkyl group containing at least four but not more than 12 carbon atoms.

2. The process of claim 1 wherein the ethylene oxide moieties make up about 10% to about 90% of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at 100°C.

3. The process of claim 2 wherein the phenol compound is 4,4'-butylidene bis-(6-tert. butyl m-cresol).

4. The process of claim 2 wherein the phenol compound is 4,4'-butylidene bis-(6-tert. amyl m-cresol).

5. The process of claim 2 wherein the phenol compound is 4,4'-heptylidene bis-(6-tert. butyl m-cresol).

6. An antistatic polyamide fiber having less than 4 x 103 nubs per pound of fiber, said fiber containing about 1% to 12% by weight of an antistatic compound which is a chain-extended reaction product of a tetrol compound represented by the formula:

where a, b, c, d, w, x, y and z are each a whole number and A is a difunctional radical from a hydrocarbon containing 1 to 13 carbon atoms, said tetrol compound having a molecular weight between about 4,000 and about 50,000, and at least one compound selected from the group consisting of. diepoxides and compounds which yield the following divalent radicals:

, and where R' is a difunctional radical from a hydrocarbon containing 1 to 30 carbon atoms; and at least 0.5%
by weight, based on the weight of the antistatic compound, of a phenol compound of the formula:

where R is an alkyl hydrocarbon group containing less than nine carbon atoms and R1 is a tertiary alkyl group containing at least four but not more than twelve carbon atoms.

7. The fiber of claim 6 wherein the ethylene oxide moieties make up about 10% to about 90% of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at 100°C.

8. The fiber of claim 7 wherein the phenol compound is 4,4'-butylidene bis-(6-tert. butyl m-cresol).

9. The fiber of claim ? wherein the phenol compound is 4,4'-butylidene bis-(6-tert. amyl m-cresol).

10. The fiber of claim 7 wherein the phenol compound is 4,4'-heptylidene bis-(6-tert. butyl m-cresol).