CA1048690A - Conductive aliphatic polyesters, aliphatic n-alkyl polycarbonamides or polyetheresters having units containing phosphonium sulfonate groups - Google Patents
Conductive aliphatic polyesters, aliphatic n-alkyl polycarbonamides or polyetheresters having units containing phosphonium sulfonate groupsInfo
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- CA1048690A CA1048690A CA75219126A CA219126A CA1048690A CA 1048690 A CA1048690 A CA 1048690A CA 75219126 A CA75219126 A CA 75219126A CA 219126 A CA219126 A CA 219126A CA 1048690 A CA1048690 A CA 1048690A
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Abstract
ABSTRACT OF THE DISCLOSURE
A synthetic polymer having a glass transition temperature Tg (NMR) of less than 25°C. and a log Rs of less than 8 wherein the polymer is selected from the group consisting of aliphatic N-alkyl polycarbonamides, aliphatic polyesters, and polyetheresters containing up to 50 mol percent of phosphonium sulfonate groups based on the total moles of carboxylate components in the polymer.
A synthetic polymer having a glass transition temperature Tg (NMR) of less than 25°C. and a log Rs of less than 8 wherein the polymer is selected from the group consisting of aliphatic N-alkyl polycarbonamides, aliphatic polyesters, and polyetheresters containing up to 50 mol percent of phosphonium sulfonate groups based on the total moles of carboxylate components in the polymer.
Description
i6~48~90 mis invention concerns polymers containing organic phosphonium salt groups which provide improved conductivity for use as antistatic agehts in filaments and fibers of syn-thetic, fiber-forming polymers, particularly when employed as a continuous core within those filaments or fibers.
Improved polymeric antistatic compounds are con-stantly being sought. British Patent 1,237,589 describes certain N-alkyl polyamides which are employed as antistatic agents dispersed as a separate phase in synthetic fibers and filaments. me use of metal sulfonate salts to improve the antistatic performance of polyether-polyamide block copolymers is shown in U.S. Patent 3,514,498. U.S. Patent 3,732,183 discloses that high-melting, fiber-forming poly-.j .
~; esters having links containing pnosphonium sulfonate ~ . .
; groups have improved dyeing propertie~ and states as an ~ object that they have improved antistatic properties.
r~ Antistatic biQomponent filaments having polyether-polyamide ~;
~: block copolymers as the sheath or core are disclosed in '~ U.S. 3,558,419.
., m e effectiveness of a defined class of poly-meric antistatic agents has been found to be greatly ~,, ;~l improved by copolymerization or reaction with certain organic phosphonium salts, thus increasing their adaptability to specific fiber requirements and final ~ product usage.
5~-~ m is invention ls a synthetic polymer having a glass transition temperature, Tg(NMR), of less than 25C. and a log Rs of less than 8 and containing up to .~ about 50 mol percent of phosphonium sulfonate groups -~i, 30 (based on the moles of the phosphonium groups divided i~ :
~ 2 i~. ~, ..
'!. ', ',i~.`
7: .
:" ~ . ~' ~' ' ' ' , ~' ;~ ' ' '. ' ~ 8~;90 by the total moles of carboxyl components in the polymer X
-100~. Preferred molecular units linking the phosphonium sulfonate group to the polymer are o~ the formula:
f R
~ P+ ~ (803 ~ ~ Y-(Z~)~
where Rl, ~, R3 and R~ represent monovalent hydrocarbon groups, preferably from 1 to 18 carbon atoms each and with the proviso that Rl and ~ may jointly represent an alkylene group, -Y- is a hydrocarbon group of up to 24 carbon atoms in which any unsaturation i9 aromatic and which can be interrupted by oxygen, sulfonamide or sulfonyl groups, -Z-.,, "
is selected from -~-, -0- and -C- groups and n and m are 1 or 2. Rl, ~, R3, and R4 may be the same or different, but are alkyl when in an N-alkyl polycarbonamide, and preferably ~ 20 Rl, ~, and R3, ~re the same. R is hydrogen or an alkyl group :of 1-18 and preferably 1-4 carbon atoms. The (S03)n-Y-(Z-)m unit is preferably an aromatic monosulfonate where m is 2 , and Z is carbonyl :Linking it to the polymer chain.
m e term "Carboxyl component" used herein refers to .
any polymer reactant monomer containing one or more carboxyl (or equivalent) groups which groups are involved in the polymer chain formation. m e carboxyl component may also contain a phosphonium sulfonate group.
:For a significant improvement in conductivity the -phosphonium sul~onate groups should be present in the anti-static polymer at a concentration of at least 0.01 mol percent.
The sub~ect modified polymers are selected from ~the group consisting of N-alkyl polycarbonamides, aliphatic ,:
_ 3 _ -"; :
48t;~0 polyesters, and polyetheresters. The polymers can have sufficient phosphonium sulfonate groups to give a log Rs of less than 7. For higher thermal stability, the N-alkyl polycarbonamides and aliphatic polyesters are preferred over -polyether-containing polymers.
The conductive polymers of the invention provide -~
antistatic fibers when contained either as a separate, dispersed phase or as a continuous core within the fibers. -When dispersed throughout the fiber, they are particularly effective when present in the amount of ~rom 2 to 15~ by wei~ht of the fiber. When contained within the fiber as a core consisting essentially of the conductive polymer throughout the length of the fiber, the core may constitute from 0.1 to 50% of the fiber volume. Core percentages above 15~ are particularly useful in fibers for blending with non-antistatic ~ibers.
The conductive polymers of the lnvention are prepared by the process wherein up to 50 mol % (moles of phosphonium groups divided by total moles of carboxyl components X 100) of a phosphonium sulfonate having at least one polymer-reactive group (carbonamide- or carboxylecter-forming group) is mixed with polymer-forming reactants of polymers selected from the group consisting of N-alk~l polycarbonamides, aliphatic poly-esters and polyetheresters, the mixture is sub~ected to polymerization conditions and the resulting modified polymer is isolated. Said polymer-forming reactants include preformed or partially formed polymers.
.jj. :
~; Polymerization processes include the condensation ~- 30 melt polymerization of diammonium dicarboxylate salts of - dlamines and dicarboxylic acids, of lactams and of aminocar-boxylic acids for the polyamides and also of diols with di-carboxlic acids and esters thereof by direct esterification or transesterification for the polyesters.
' ~ ' "'~ , ' ' , . ' ' .
, . , - . . . . .
~)48f~90 The conductive polymers of the invention have a ` fluidlike molecular mobility at normal ambient temperatures as re~lected by having a glass transition temperature of less than 25C. ~s described herein, the glass transition temperature is determined using nuclear magnetic resonance technique. Such glass transition temperatures can be approxi-mated by using less complicated techniques such as differential thermal analysis for convenience. Such materials are readily and permanently deformable when stressed and vary in their physical nature from rubbery compositions to low melting solids and liquids. They are not suitable for forming useful textile filaments by themselves. For processibility reasons, it is desirable that the polymers of this invention have a vi~cosity of at least 10 centipoises at the filament spinning temperature to be employed which is commonly above 250C., and more desirably a viscosity of at least 100 centipoises.
Their melt viscosity can be controlled by molecular weight and by the use of branching or cross-linking `
agents.
The Tg of these polymers may be adversely affected for the purposes of thls inventlon by increasing aromatic character in the polymer. Surprisingly, aromaticity in the phosphonium -sulfonate containing units is more than offset in its effect on conductivity by the increase in conductivity provided by the phosphonium sulfonate group. Furthermore, in the pre-sence of this fluidlike molecular mobility, the phosphonium ion is particularly helpful in improving conductivity as -compared to metallic sulfonate salts.
; 30 me preparation of conductive N-alkyl .. :
' ` ' :` ' ~ `
.
" , : ` ' ` ~4~690 polycarbonamides is disclosed in Br. 1 237 589. They are prepared from aliphatic N-alkylated diamines and ~liphatic dicarboxylic acids and/or N-alkyl aminocarboxylic acids or their amide-forming derivative6. Suitable diamines include the N,N'-diethyl-, -diisobutyl-, -di-n-butyl-, -dihexyl-~-diheptyl-, -didecyl- and -distearyl- derivitives of ethylene propylene, tetramethylene, hexamethylene, nonamethylene and decamethylene diamines and the mono-N-alkyl derivatives of these diamines. Suitable dicarboxylic acids include æuccinic, glutaric, adlpic, pimelic, su~eric, azelaicJ sebacic, ; dodecanedioic and higher dicarboxylic acids and also such aclds as N-N'-biS (vi-carboxyalkyl) piperazine. Suitable amino-carboxylic acids include N-methyl-, -ethyl-, -isobutyl-, -n-butyl-, -hexyl-, -decyl-, ll-aminostearic and ~-amino-stearic acids.
The molecular weight may be regulated to the desired degree by polymerization conditions and by the use of viscoslty stabilizers. -Branching agents, i.e., polymer reactants having more than two functional groups can be added when it is desired to increase the viscosity of the antistatic polymers.
~; Suitable branching agents include pyromellitic dianhydride, trimethylol propane, pentaerythritol and bis(hexamethylene)-triamine as appropriate for polyamides or polyesters.
Various suitable reactants for forming conductive polyetheresters are disclosed in Br. 1 176 648 and others are disclosed herein. Reactants and conditions for prepara-tion of polyetheresters are also shown in U.S. 3 655 821, and herein however, for the purposes of this invention it is preferred ' ,,:.
....
"
8~0 that the polyether glycol reactant be poly (ethyleneether) glycol (polymerized ethylene oxide) of from 200 to 2000 molecular weight and that the diacid be either aliphatic or aromatic, (e.g., succinic, sebacic, dodecanedioic acid or ; terephthalic acid). m us the polyetheresters are preferably esters of polyethers or copolyethers and diacids.
Reactants for preparlng the aliphatic polyesters are aliphatic glycols having 2 to 12 carbon atoms and aliphatic dibasic acids, or their ester-forming derivativesg having 4 10 to 36 carbon atoms. Minor amounts of aromatic dibasic acids~
or their ester-forming deri~atives, can be used in con~unction with the aliphatic dibasic acids. Excessive aromatic character in thepoly~er is reflected by a high log Rs value. Suitable ; reactants for preparing these polyesters are ethylene glycol, ; 1,3-propanediol, 1,4-butanediol; 1,6-hexanediol; 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; 2-methyl-2-propyl-1,3-propanediol; 2,2,4,-trimethylhexanediol, 2,4,4-tremethylhexanediol; glutaric acid, succinic acid, adipic acid, azelaic acid, dodecanedioic acid, ; 20 terephthalic acid and dimer ~cid (defined below) and their ester-forming derivatives.
< The organic phosphonium sulfonate to be reacted with the other polymer-forming ingredients contains 1 or 2 sulfonate groups. m e sulfonate group is attached to a hydrocarbon group which is aromatic or aliphatic (including cycloaliphatic) ~ree of unsaturation. The hydrocarbon group may be interrupted by ether, sulfonamide or sulfonyl groups;
-~ that is, the sulfonate group may be attached to one of two or more hydrocarbon groups which are connected by ether, 30 sulfonamide or sulfonly groups. For example, there are -:;
.-.- :
.
, , . . . .,.,. .. ,. :: . ~ ~ . . .
~` lQ48690 ~ contemplated phosphonium salts of alkyl- and arylsulfonates ; as well as of aryloxyalkylsulfonates, alkyloxyarylsulfonates, - and arylsulfonamidoalkylsulfonates. The hydrocarbon group bears one or two reactive groups which can form carbonàmide ,i or carboxylester linkages with the polymer-forming reactants.
The reactive groups include carboxyl, carboalkoxy, primary or .; secondary amine, or hydroxyl.
~j The organlc phosphonium sulfonates are conveniently prepared using known techniques from known compounds, generally 10 by metathesis reactions involving ion exchange to obtain the deslred anion. For example, one may react in aqueous medium, a phosphonium halide with an alkali metal sulfonate and ,. . .
separate the phosphonium sulfonate from the aqueous medium.
Suitable alkali metal sulfonates are commercially available or readily prepared. -Suitable phosphonium salt reactants include methyl-triphenylphosphonium 3J5-dicarbomethoxybenzenesulfonate;
~ tetra-(n-butyl)-phosphonium 3,5-dicarboethoxybenzenesulfonate;
r,.' methyltrioctylphosphonium 3J5-dicarbomethoxybenzenesulfonate ;; 20 and others set ~orth in the examples below. The preferred salts are phosphonium 3J5-dicarbo-methoxy-benzenesulfonates.
; m e presence of the phosphonium salt units in the polymer ls highly effective in improving the electrical conductivity of these amorphous, fluidlike polymers. In addltion, their thermal stability permits normal processing of the antistatic polymers when used to prepare antistatlc -1 filaments, partlculary melt-spun polyamide and polyester ;, :
antistatic filaments.
Antistatic filaments of the invention can have the .j .
;~ 30 conductive polymer containing the phosphonium salt un~ts ....
~, '.':
,.
~.
:.............. . .
; dispersed as known in the art as minute particles distributed : throughout. Alternatively the conductive polymer containing the phosphonium salt units can be present as a single con-; tinuous core throughout the length of a filament or fiber.
The latter method makes maximum use of the improved conduc_ ; tivity since the conductive system is continuous and anti-static performance is essentially independendent of the surrounding fiber-forming sheath.
', Synthetic, fiber-forming polymers which can be made antistatic by the polymer of this invention include polymers and copolymers from the classes of poly-amides, polyesters, polyolefins~ including polyethylene and polypropylene. The resulting antistatic fibers may be blended with conventlonal fibers to ~ive a blended product having antistatic properties.
The specific resistance, RSJ is determined at room temperature on the dry (water-free) polymer con-taining the phosphonium salt. The polymer is dried at 100C. in an oven at a pressure less than 50 torr for at least 12 hours. More stringent drying condltions are usually not required but may be used when convenient. The -~; cell used for the measurements consists of a "Pyrex" hard glass tube of 2 + 0~25 millimeter inside diameter and 8 millimeters outside diameter. Copper electrodes are inserted through rubber end-caps at each end of the tube with 33 centimeter electrode separation. The current transmitted through the sample at a potential difference of 220 volts DC is recorded uslng a Beckman Vibrating Reed .....
~ Model 1051 microammeter. Specific resistance is calculated .
from the equation:
_ g _ :
, .
. . .
'',,~' - . : .
~ 8~
R (ohms) = _ Kc The cell constant, Kc, is determined with a liquid of known specific resistance in ohm-cm. The values reported herein used 7.63 x 10 2 as the cell constant. Fsr convenience the Rs value is reported as its log10 value. The lower the Rs value, the h~gher is the conductivity o~ the sample.
The static propensity of antistatic filaments reported herein is determined on fabric made with them.
The filaments are converted to fabric~ and the static propensity determined by measuring the amount of direct current that passes through the fabric at a tempera-ture of 22C. and 26~ relative humidity. In order to assure electrical contact between the electrode and the core-containing filament of khe fabric for better measurements, it may be desirable to paint the fabric with an electrically sonductlve paint in the area of electrode contact. In the e~amples below, no conductive paint is used unless it is .
speciflcally mentioned. m e ohms per square unit of area of fabric surface is determined according to the AATCC Method, 76-59 ("Technical Manual of the AATCC", Volume 41, 1965, pages B-188). This value, given as log R, is the logarithm to the base 10 of the fabric resistance in ohms. Higher values indicate a greater tendency to acquire and retain an electrostatic charge. This method provides an approximate measure of static propensity. However, to compare ~ilaments and yarns of dif~erent deniers one should determine the log rho of the ~ilaments, which takes into account dif~erences in total yarn cross-section, and is obtained ~rom the expression:
: -- 10 --".~
~1:
.. . .
~Q48ti9(1 log rho (fllament) = log R (fabric) - log (9 x 105 D) ~:, log (Pd) where D is the density of the polymer, P is the number of . picks (yarn ends) per centimeter in the fabric and d is the total denier of each pick. In the examples, the following values of D are used: 1.15 for 66 polyamide;
1.0 for 612 polyamide; 1.0 for the polyamide from bis (4- -aminocyclohexyl) methane and dodecanedioic acid, 1.4 for poly (ethylene terephthalate); and 0.9 for polypropylene.
The (Pd) value, which gives the amount of yarn in ~ ~ -the fabric, is corrected in a mixed filament yarn bundle -by the fraction of the filaments which are conductive to obtain the log rho for the conductive filaments therein.
Fibers which produce a log rho value of 11 or ` less are considered to have acceptable antistatic properties with the lower values again representing the more desirable antistatic properties.
Some fabrics are given a number of "home" wash- -dry cycles in a tumble washing machine with a synthetic detergent in water at 38C., spun-dried, and tumble-dried at 77C. These cycles are referred to as "C" washes.
Static propensity of the filaments also can be determined by a measurement of decling time in a procedure referred to as the Sail Test. The Sail Test used herein measurss the severity and duration of garment cling due to static under simulated use condit~ons. In this test, static is induced in a garment, which may be a slip, a skirt or a dress, worn over cotton briefs by a technician, by rubbing . - 11-. .
. .
,' 1~48~;90 against a fabric held between two vertical poles. A
poly (ethylene terephatalate) fabric is used with a poly-amide garment and a poly (hexamethylene adipamide) ~abric is used with a polyester garment. The time taken for the garments to uncling (or decling) while being worn - durlng walking around the room is determined. The room is maintained at 21C. and 20~ relative humidity. The decling time is the time in mlnutes required for the garment to be ~udged comfortable with no detectable cling from static charges.
The results commonly are reported after a ~umber of 'tC't washes with the garments containing acceptable anti-static filaments having decling times less than 10 minutes and preferably less than 2 minutes.
,.:
For carpets, the static propensity o* the anti-static filaments can be determined by using the filamentsi,,;
: to make a carpet and measuring the electrostatic voltage built up on a person walking upon a section of the carpet at 21C. and 20~ relative humidity. Filaments used in this 20 measurement, referred to as the shuffle test, preferably should provide voltages less than 2KV. The procedure ~or the shuffle test is described in AATCC Test Method 134-1964 .; wlth changes adopted by the Carpet & Rug Institute, ~- September, 1971.
The Tg (NMR) is the temperature above which there is a rapid rise in the NMR narrow peak height and the peak ratio with an increase in temperature. The NMR peak ratio is determined from the NMR broadline spectrum measured at a given temperature on the dry polymer (e.g., drled at 125C. for 15 minutes in r ` 30 dry nitrogen) in an atmosphere of dry nitrogen using a ''' - ~V4~690 radio frequency of 56.4 megacycles at an attenuation setting o~ 17 decibels with a sweep modulation amplitud~ of one ~
gauss. The NMR spectrum is measured using the nuclear -magnetic resonsance equipment of Varian Associates, Model V - 4302 Dual Purpose Spectrometer and their high tempera-ture probe insert, Model No. V - 4331 TWL. The NMR spectro-gram at a given temperature shows a broad absorption "hump"
upon which is superimposed a very narrow peak. m e deriva-tive curve of the spectrogram is recorded by the spectro-meter; 'Ipeak ratio" measurments are made on this curve.
The height o~ the narrow peak divided by the height of the "hump" gives the "peak ratio", as described in J. Polymer Science Part C, Polymer Symposia, No. 3, pp. 3-8 (1963).
The precision of this peak ratio determination is about + O.2 and of the Tg (NMR) is about + 5C.
The % core by volume in the filament conveniently is determined from the ~ of the cross-sectional area of the filament occupied by the core material. The cross-sectional area is determined by photographing a cross- ~ ~
section of the filament under a microscope at a known mag- -nification of 50 to 1500X and determining the % core from measurement on the photograph. In the case of irregularities, the average of 5 to 10 determinations is used. For round filaments with round cores, the % core can also be determined . , .
by photographing the filaments in a longitudinal view immersed in a medium having a refractive index closely matching the refractive index of the filament, and meaSuriQg the filament and the core diameters and calculating the ~ core. -~ormulas for some of the phosphonium salts used in -- 30 the examples appear below.
- 13 _ . . .
, '';', - .
lV4~f~9Q
: Salt A
~`
., .
CH O C
~ S03 P(-CH2-C~2-cH2 C~3)4 CH -O-C
~' . ~' ', .'' :
Salt E
CH3-0-C- ~ -O-CH2-CH2-cH2-s03 P(-cH2-cH2 CH2 C 3)4 . .
.
~, . Salt F
' ~3\
C S03 P(-CH2-C~2-cH2-cH3)4 C3H2 ~H2 CH2 c~2 .; IC=O C=O
~ O-CH3 0-CH3 "
.~
. - 14 -' ., Salt G 9 ---- .
-CH2-CH2- O-CH2-~H2-OH
+P-O-SO. SO3 p(-cH2-cH2-cH2-cH3)4 ~2 4 ~- :
,i Salt H
;. -- :.
.;
O . ' CH O-C
3 ~ O H
~o2-N-cH2-cH2-so3 P(-cH2-cH2-cH2-cH3)4 : ~
:. O .
C=O ~-O
... CH3 Salt J
.:
O
. . .~ .
SO3 +P(-CH2-cH2~cH2-cH3)4 ~ .
. , .
.
- 15 ~ :
:
, , , ~ ' ~' .` .
1~48~90 e expression "relative viscosity" as used herein signifies the ratio of the flow time in a viscometer of a polymer solution relative to the flow time of the solvent by itself measured in the same units at 25C, Unless other-wise specified the relative viscosity for polyamides is deter-mined using an 8.4~, by weight, based on total weight, solution in 90%, by weight, based on total weight, formic acid.
Inherent viscosity,~inh~ is determined from the expression:
~ inh = loge ~/C
where~ is the viscosity of a dilute solution of the polymer in m-cresol divided by the viscoæity of m-cresol in the same units and at the same temperature and C is the concentration of the dilute solution in grams of polymer per 100 ml. of - solution. In the examples, the temperature used is 25C. and ~-!' the value of C is 0.5.
In the procedure and examples that follow, all C percentages are by weight, based on total weight~ unless indicated otherwise and all conductive polymer characteriza-20 tions are made at a temperature above 25C.
; PREPARATION OF PHOSPHONIUM SULFONATE MONOMERS
Tetra-n-Butylphosphonium 3,5-Dicarbomethoxybenzenesulfonate (Salt A) A solution of 295 grams of tetra-n-butylphosphonium chloride and 296 grams of sodium 3,5-dicarbomethoxybenzene-; sulfonate in 1.5 liters of water is stirred for 1 hour at 60C. The phosphonium salt separates as clear liquid at the bottom. It is separated and dried overnight at : 100C. at a pressure less than 50 torr. On cooling to 30 room temperature it solidifies to a white solid which melts at 73C.
., :
1~4~
Tetraphenylphosphonium 3,5-Dicarbomethoxybenzenesulfonate (Salt B) A solution of 21 grams of tetraphenylphosphonium bromide in 25 ml. of water at 80C. is added ko 15 grams of sodium 3,5-dicarbomethoxybenzenesulfonate in 50 ml. of water also at 80C. The solution is cooled and crystals o~ tetra-phenylphosphonium 3,5-dicarbomethoxybenzenesulfonate are filtered from the solution. After 18 hours drying under nitrogen at about 60C. at a pressure less than 250 torr 10 nitrogen, the crystals are found to melt at 203C. ~ --Tri-n-Octyl-n-Butylphosphonium 3,5-Dicarbomethoxybenzene-sulfonate -(Salt C~
- , . . . _ .
Tri-n-octyl-n-butylphosphonium bromide is prepared -by slowly adding tri-(n-octyl) phosphine (740 grams) into refluxing l-bromobutane (500 grams) in a nltrogen atmosphere.
Reflux is continued one hour after ~inal addition then the :, - solution is cooled with stirring for about 18 hours, ~ollowed by vacuum removal of excess l-bromobutane at 60C. This product, 1210 grams from two successive preparations, is added to 880 grams of sodium 3,5-dicarbomethoxybenzenesulfonate in 2500 ml. of water and stirred for at least one hour at 85C. then the heat is removed and the oil in water mixture is allowed to stirr and cool ~or about 18 hours. The oil layer is separted from the water, rinsed with 1000 ml. of water and dried at about 80C. at a pressure less than 2 torr for 18 hours. m is product, an oil, is tri-_-octyl-n-butyl-phosphonium 3,5-dicarbomethoxybenzenesulfonate with 4.2% phosphorous and 4.7% sulfur by analysis.
Triphenyl-n-Octadecylphosphonium 3,5-Dicarbomethoxybenzene-sulfonate (Salt D~
, . .
Triphenyl-n-octadecylphosphonium bromide is prepared by refluxing n-octadecyl bromide (1000 grams) and '.
," ., :;, 1. ' ' ~4~ 0 triphenyl phosphlne (787 grams) in about 1400 ml. of toluene for 16 hours at about 110C. The product is precepitated from the cooled solution by the addition of about 500 ml.
of ethyl acetate and the crystals filtered from solution.
These crystals, 1550 grams, are added to 890 grams of sodium 3,5-dicarbomethoxybenæenesulfonate in 3000 ml. of water which is heated to 80-85C. and stirred for one hour.
~A The oil layer is washed twice with about 2000 ml. of 25C.
room temperature water, then dried at 50C. under nitrogen ~ 10 for 16 hours at a pressure less than 100 torr. The product, ; triphenyl-n-octadecylphosphonium 3,5-dicarbomethoxybenzene-sulfonate, solldifies on cooling.
Tetra-n-Butylphosphonium 3-(4-Carbomethoxyphenoxy) propane-sul~onate (Salt E) Sodium 3-(4-carbomethoxyphenoxy) propanesulfonate - is prepared by adding sodium methoxide (54 grams) to 4-carbomethoxyphenol (152 grams) dissolved in 600 ml. of methanol followed by addition of propane sulfone (122 grams).
; After 2 hours o~ reflux, the crystals formed are filtered (186 grams) and added to tetra-_-butylphosphonium chloride (185 grams) in 400 ml. of water at 40C. to prepare tetra-n-butylphosphonium 3-(4-carbomethoxyphenoxy) propanesulfonate. To ` remove this phosphonium salt from water, 70-ml. portions of chloroform are shaken with 70-ml. portions of the water solution and then separated from the water and combined with a repeat of this procedure with 100 ml. o~ chloroform ~; and 100 ml. of the water solution. Evaporation of the two combined chloro~orm extracts yields 98 grams of the above phos-phonium salt E.
~, , .:
~,, : , - . . . .
`; 1~4~90 ^ Tetra-n-butylphosphonium 9,9-di(2-Carbomethoxyethyl) fluorene-3-sulfonate tSalt F) Forty three grams of tetra-n-butylphosphonium chloride and 53 grams of sodium 9,9-di(2-carbomethoxyethyl)-3-~luorenesulfonate are heated to 80C. in 250 ml. of water --with stirring. The desired product is obtained as an oil.
me oil layer is separated from the water and dried for 16 hours at 60C. under nitrogen at a pressure less than 10 torr. After 5 d~ys, the oil crystallizes. These crystals melt at 96C. and are found to contain 4.5% phosphorous and 4.3% sulfur.
1,8-Di(2-Hydroxyethoxy)napthalene 3,6-di(tetra-n-butylphos-~honium)sulfonate (Salt G~ , -.
1,8-Di(2-hydroxyethoxy-naphthalene 3,6(disodium sulfonate is prepared by reacting two moles of ethylene oxide with one mole of 1,8-hydroxynaphthalene 3,6-disodium sulfonate (about 40% monosulfonate) in a concentrated water solution. This solution, 125 ml., containing about 35 grams of -the ethoxylated product, is washed with 125 ml. of benzene then heated to boil to remove impurities. Sodium chloride, 37,5 grams, in 125 ml. of water i6 added to the solution followed by 46 grams of tetra-n-butylphosphonium chloride. After g hours ; of vigorous stirring, the oil layer i8 removed and dried 18 hours at 60C. under a pressure of less than 5 torr. Thls product is mixed with 23 grams o~ tetra-n-butylphosphonium chloride in 100 ml. of water, heated to 80C. and then cooled. The oil layer is removed, dried at 60C. for 18 hours under nitrogen at a pressure less than 2 torr to give 1,8-di(2-hydroxyethoxy)naphthalene-3,6-di(tetra-n-butylphos- -; 30 phonium)sulfonate, analyses indicate that about 40~ of this product is present as the monosulfonate.
,,~
,................................ - 19 -,:
.,, 6i90 Tetra-n-Butylphosphonium 2-(3,5-Dicarbomethoxybenzene Sul~~namldO)ethanesulfonate (Salt H~
~ To 43.8 grams oi 3,5-dlcarbomethoxybenzenesulfonyl ; chlorlde ln 150 ml. benzene 1~ added with vlgorous ~tlrring,~:, 50 grams of 2-aminoethanesulfonic acld ln 190.5 ml. Or 2 N
sodlum hydroxide. The mixture i8 stirred for an hour and then for an additional hour at 60C. The product is ieo-lat~d as a crystalllne precipitate by adding æodium chloride ;~ (60 grams) and 100 ml. of water to the aqueous layer. To separate the product from some undissolved sodium chloride, the product is dissolved in 500 ml. methanol filtered, then reproclpitated by adding 600 ~1. of ether. This product ~s dried 16 hours at 60C. under nitrogen at a - pressure of le68 than 10 torr. The dried product (20 gram~) iB mixed with tetra-_-butylphosphonium chloride . (15 grams) in 35 ml. of water to obtain tetra-n-butylphos-phonium 2-(3,5-dicarbomethoxybenzenesulfonamido)ethane-~ulfonate. Thi~ pho~phonium sulfon~te is extracted from i the wat~r solution by vigorously shaking 30 ml. of chloro-form ~ith the solution. The chloro~orm l~yer yields the phosphoniu~ sulfon3te upon evaporation and lt contains 5.3%
phosphorous~ 9.1% sulrur and 2.1~ nitrogen.
, .. .
Tetra-n-Butylphosphonium 3-Carboxybe~zenesulfonate (Salt J) Tetra-n-butylphosphonium 3-carboxybenzenesulfonate ls prepared by mixing tetra-n-butylphosphonium chloride (58.8 grams) wlth sodium 3-carboxybenzenesulfonate (48.8 grams) ln 250 ml. of water at 60C. The oil layer which , ; for~s i8 removed a~ter cooling the solution and ls dried at 60C. at a pressure les~ than 5 torr. The phosphonium 39 sulfonate crystallizes upon standing at 25C. and has a melting point of 62C.
.
.
.
..... . . . . ~ .
lV48690 `~ EXAMPLE 1 Thls example illustrates the use of Salt A to improve the conductivity of the polymer of N,N'-diethyl-hexamethylene diamine and dodecanedioic acid.
In three separate runs, the salt of the diamine -: and the acid, Salt AJ and bis (hexamethylene) triamine (hereinafter BHMT) are polymerized in a sealed, heavy- -w~lled polymer tube at 215C. for 2 hours and then at 283C.
at a pressure less than 5 torr for 4 hours. me log Rs values of the resulting polymers all Tg (NMR) ~25C. are given - in Table I.
. TABLE I
` Phosphonium Salt, BHMT, RunMol %* M~l % lo~ R~ -I 4.8 2.6 7.0 ~ II 8.3 3.7 6-7 ; III14.1 8.2 6.5 :; .
,',r' In 4 additional runs, an autoclave is charged -- with 3218 gramæ of N,N'-diethylhexamethylene diamine and u dodeca~edioic acid saltJ 129 grams of N,N'-diethylhexa-~!, 20 methylene dlamine, 17.2 grams of BHMT, Salt A, 7.0 grams of boric acid, 20 grams of formic acid, and 4.5 grams of ,:
- potassium phenylphosphinate. The autoclave is purged with nitrogen and heated at 215C. for 2 hours with an agitator speed of 6 to 8 rpm. me pressure generated in the auto-,. .
clave during the preceding step ls about 10 kilograms per ~,~ square centimeter gage. The pressure inside the autoclave is reduced to atmospheric over a period of 60 minutes, .,.
and the temperature is raised to 300C. me batch is held at this temperature for 2 hours under a presæure of less than 2 torr. me agitator is turned off and the pressure :; ~Based on moles of phosphonium group and total moles of Salt A and dodecanedioic acid ~ . .
, ,"
, :`
, ' ;9o is brought to atmospheric with nitrogen. The polymer is ,~
extruded at 275C. under a blanket of nitrogen. Thie amount : of phosphonium salt used, the relative viscoaity and the log - Rs f the polymers all having Tg (NMR) c 25C. are shown in Table II.
;~ TABLE II
Phosphonium Salt Relative ` Runi Mol % ~ y log R~
;~ IV 3.61 17.4 7.1 - 10 V 2.25 27.1 7.2 ~I 1.54 36.2 7.3 VII 1.50 68.9 7-5 - None _ 9.o The composltion of Run VII, whlch has a log Rs f 7.5, is spun as 2.3% core in poly (hexamethylcne adipamide) filaments. A 7X395 mil (0.178 ~ 10.0 mm.) capillary is used to . ..
mcter the core polymer to each orifice. A 10-filament yarn made therefrom is drawn to a denier of 30. The yarn is 2-plied and ` woven as the filling in a fabric. After boiling the fabric in -:
; ~:
water for 3 hours, drying and applying a conductive silver paint, the filament log rho is 9.9.
i'.:i ;~ EXAMPLE 2 "
; Thiis example illustrates the use of Salt A to .; .
improve the conductivity of a polyetherester.
In Run I, an autoclave equipped with an agitator ~-; is charged with 5550 grams of dodecanedioic acid, 4640 grams of polyethylene glycol of 200 average molecular weight, ~, 1160 grams of Salt A, 375 grams of 2-ethyl-2-hydroxymethyl-, 1,3-propanediol (branchin~ agent), 11 grams of p-toluene-,~i 30 sulfonic acid~ and 11 grams of manganese acetate. The i~i autoclave is purged with nitrogen. The reactants are then ~- heated at 200C, and the agitator is started at 15 rpm.
''i:
.
_ 22 -,; .
_ . ~ . . . ` !
~? ~
)48f~90 The batch is held at 200C. for 3 hours under a gentle bleed o~ nitrogen. The pressure is then reduced to less than 5 torr and the temperature is raised to 240C. over a period of about 60 mlnutes. It is held at 240C. for 6 hours at a pressure less than 5 torr. The batch is then brought to atmospheric pressure with nitrogen and extruded at 120C. under a blanket of nitrogen. The yield is about 26 lbs. (11.8 kilograms). The inherent viscosity o~ this material is about 1.O. m e gummy polymer has a log Rs f 5.7 and Tg (NMR) of -35C.
In two additional runs, II and III, additional .:. :
phosphonium salt A is mixed with the pre-formed polymer pre- -~, pared as above for 10 minutes under polymerization conditions ~;
~ust before extruding. The effect of the amount of phosphonium ;~
~- salt on the conductivity of this polyetherester i8 shown in i . .i .
~ Table III. Increaslng the concentratlon above 10 mol % has a .....
~ reduced effect on log Rs.
s~ TABLE III
'r~ Phosphonium Salt, JJ;'~. ~ 20 Run Mol % log Rs I 8.7 5.7 '~:
;~ II 12.5 5.5 III 16.0 5.4 - None ~-8.5 j,~ ,;
A copolymer prepared similarly to Run I which has 8.7 mol % of the phosphonium salt (log Rs of 5.7) is spun as about 50% core in poly(hexamethylene adipamide) filaments.
Sections of capillary tubing are used to meter the core polymer to the spinneret orifices having plateaus as described in Kilian ' 30 U.S. 2,936,482. The 10-filament yarn iæ drawn 3.2X and the ~ denier of the drawn filaments is 20. Twelve o~ the 200-denier ,~; drawn yarns are plied and then bulked using a hot-air jetO
, ~ - 23 -~ .
~` .
~ ~ . . . . . . .
A carpet is tufted from the bulked yarn and mock-dyed. It is hand latexed and dried at 121C. The static propensity of the carpet is only 1.6 kilovolts. Without antistatic agents, the static propensity of nylon 6/6 carpets exceeds 10 k~lovolts.
This example illustrates the use of Salt A to improve the conductivity of another polyetherester.
A still is charged with 3500 grams of polyethylene glycol having an average molecular weight of 400, 4500 grams o~ polyethylene glycol having an average molecular weight of 600, 250 grams of Salt A, 3880 grams of dimethyl tere-phthalate, 2480 grams of ethylene glycol, and 14.0 grams of tetrabutyl titanate. The temperature of the still is raised to 210C. and about 1310 grams of methanol is removed by distillation. m e batch is then transferred to an autoclave at 220C. which has been purged with nitrogen. The autoclave is provided with an agitator which is operated at 15-30 rpm. m e pressure is reduced to less than 2 torr in 45 minutes as the temperature is raised to 260C. dur~ng this period. m e batch is held at a pressure of less than 2 torr ~or 4 to 6 hours. The pressure is then brought to atmospheric with nitrogen and the batch is cooled to 220C. and extruded under a blanket of nitrogen. The rubbery polymer contains 2.3 mol percent of the phosphonium salt, based on the starting ingredient~, has . .~
1~ an inherent viscosity of 1.2, a log Rs f 6.8 and Tg(NMR) of less than 25C. as shown by its rubbery state at room temperature.
;~ A polyetherester without the phosphonium salt is ., prepared by the above procedure using the following ingre-dients: 2950 grams of polyethylene glycol having an average molecular we~ght of 400, 4450 grams of polyethylene glycol . .
, ~
86;90 having an average molecular weight of 600, 4000 grams of dimethyl terephthalate, 2480 grams of ethylene glycol, 300 grams of 1,3,5-trimethyl-2,4,6-tri (3,5-ditertiarybutyl(-4-hydroxy-benzyl)benzene and 14.0 grams of tetrabutyl titanate. m e log R8 of the resulting polymer i8 9.6 and the Tg (NMR) ls less than 25C.
- The polyethereæter, with the phosphonium sulfonate .. ; , modification, is spun as 2% core metered by 3 X 90 mils (o.76x ,i 2.28 mm.) capillaries in poly(ethylene terephtalate) contin-10 uous filament yarns of 34 filaments. The polyethylene tereph- ~-thalate polymer has a relatlve viscosity of 30 and contains 0.3~ of TiO2. The relatlve viscosity is determined using a 10%, by weight, based on total weight, solution of polymer in a mixture of 10 part~, by weight, of phenol and 7 parts of
Improved polymeric antistatic compounds are con-stantly being sought. British Patent 1,237,589 describes certain N-alkyl polyamides which are employed as antistatic agents dispersed as a separate phase in synthetic fibers and filaments. me use of metal sulfonate salts to improve the antistatic performance of polyether-polyamide block copolymers is shown in U.S. Patent 3,514,498. U.S. Patent 3,732,183 discloses that high-melting, fiber-forming poly-.j .
~; esters having links containing pnosphonium sulfonate ~ . .
; groups have improved dyeing propertie~ and states as an ~ object that they have improved antistatic properties.
r~ Antistatic biQomponent filaments having polyether-polyamide ~;
~: block copolymers as the sheath or core are disclosed in '~ U.S. 3,558,419.
., m e effectiveness of a defined class of poly-meric antistatic agents has been found to be greatly ~,, ;~l improved by copolymerization or reaction with certain organic phosphonium salts, thus increasing their adaptability to specific fiber requirements and final ~ product usage.
5~-~ m is invention ls a synthetic polymer having a glass transition temperature, Tg(NMR), of less than 25C. and a log Rs of less than 8 and containing up to .~ about 50 mol percent of phosphonium sulfonate groups -~i, 30 (based on the moles of the phosphonium groups divided i~ :
~ 2 i~. ~, ..
'!. ', ',i~.`
7: .
:" ~ . ~' ~' ' ' ' , ~' ;~ ' ' '. ' ~ 8~;90 by the total moles of carboxyl components in the polymer X
-100~. Preferred molecular units linking the phosphonium sulfonate group to the polymer are o~ the formula:
f R
~ P+ ~ (803 ~ ~ Y-(Z~)~
where Rl, ~, R3 and R~ represent monovalent hydrocarbon groups, preferably from 1 to 18 carbon atoms each and with the proviso that Rl and ~ may jointly represent an alkylene group, -Y- is a hydrocarbon group of up to 24 carbon atoms in which any unsaturation i9 aromatic and which can be interrupted by oxygen, sulfonamide or sulfonyl groups, -Z-.,, "
is selected from -~-, -0- and -C- groups and n and m are 1 or 2. Rl, ~, R3, and R4 may be the same or different, but are alkyl when in an N-alkyl polycarbonamide, and preferably ~ 20 Rl, ~, and R3, ~re the same. R is hydrogen or an alkyl group :of 1-18 and preferably 1-4 carbon atoms. The (S03)n-Y-(Z-)m unit is preferably an aromatic monosulfonate where m is 2 , and Z is carbonyl :Linking it to the polymer chain.
m e term "Carboxyl component" used herein refers to .
any polymer reactant monomer containing one or more carboxyl (or equivalent) groups which groups are involved in the polymer chain formation. m e carboxyl component may also contain a phosphonium sulfonate group.
:For a significant improvement in conductivity the -phosphonium sul~onate groups should be present in the anti-static polymer at a concentration of at least 0.01 mol percent.
The sub~ect modified polymers are selected from ~the group consisting of N-alkyl polycarbonamides, aliphatic ,:
_ 3 _ -"; :
48t;~0 polyesters, and polyetheresters. The polymers can have sufficient phosphonium sulfonate groups to give a log Rs of less than 7. For higher thermal stability, the N-alkyl polycarbonamides and aliphatic polyesters are preferred over -polyether-containing polymers.
The conductive polymers of the invention provide -~
antistatic fibers when contained either as a separate, dispersed phase or as a continuous core within the fibers. -When dispersed throughout the fiber, they are particularly effective when present in the amount of ~rom 2 to 15~ by wei~ht of the fiber. When contained within the fiber as a core consisting essentially of the conductive polymer throughout the length of the fiber, the core may constitute from 0.1 to 50% of the fiber volume. Core percentages above 15~ are particularly useful in fibers for blending with non-antistatic ~ibers.
The conductive polymers of the lnvention are prepared by the process wherein up to 50 mol % (moles of phosphonium groups divided by total moles of carboxyl components X 100) of a phosphonium sulfonate having at least one polymer-reactive group (carbonamide- or carboxylecter-forming group) is mixed with polymer-forming reactants of polymers selected from the group consisting of N-alk~l polycarbonamides, aliphatic poly-esters and polyetheresters, the mixture is sub~ected to polymerization conditions and the resulting modified polymer is isolated. Said polymer-forming reactants include preformed or partially formed polymers.
.jj. :
~; Polymerization processes include the condensation ~- 30 melt polymerization of diammonium dicarboxylate salts of - dlamines and dicarboxylic acids, of lactams and of aminocar-boxylic acids for the polyamides and also of diols with di-carboxlic acids and esters thereof by direct esterification or transesterification for the polyesters.
' ~ ' "'~ , ' ' , . ' ' .
, . , - . . . . .
~)48f~90 The conductive polymers of the invention have a ` fluidlike molecular mobility at normal ambient temperatures as re~lected by having a glass transition temperature of less than 25C. ~s described herein, the glass transition temperature is determined using nuclear magnetic resonance technique. Such glass transition temperatures can be approxi-mated by using less complicated techniques such as differential thermal analysis for convenience. Such materials are readily and permanently deformable when stressed and vary in their physical nature from rubbery compositions to low melting solids and liquids. They are not suitable for forming useful textile filaments by themselves. For processibility reasons, it is desirable that the polymers of this invention have a vi~cosity of at least 10 centipoises at the filament spinning temperature to be employed which is commonly above 250C., and more desirably a viscosity of at least 100 centipoises.
Their melt viscosity can be controlled by molecular weight and by the use of branching or cross-linking `
agents.
The Tg of these polymers may be adversely affected for the purposes of thls inventlon by increasing aromatic character in the polymer. Surprisingly, aromaticity in the phosphonium -sulfonate containing units is more than offset in its effect on conductivity by the increase in conductivity provided by the phosphonium sulfonate group. Furthermore, in the pre-sence of this fluidlike molecular mobility, the phosphonium ion is particularly helpful in improving conductivity as -compared to metallic sulfonate salts.
; 30 me preparation of conductive N-alkyl .. :
' ` ' :` ' ~ `
.
" , : ` ' ` ~4~690 polycarbonamides is disclosed in Br. 1 237 589. They are prepared from aliphatic N-alkylated diamines and ~liphatic dicarboxylic acids and/or N-alkyl aminocarboxylic acids or their amide-forming derivative6. Suitable diamines include the N,N'-diethyl-, -diisobutyl-, -di-n-butyl-, -dihexyl-~-diheptyl-, -didecyl- and -distearyl- derivitives of ethylene propylene, tetramethylene, hexamethylene, nonamethylene and decamethylene diamines and the mono-N-alkyl derivatives of these diamines. Suitable dicarboxylic acids include æuccinic, glutaric, adlpic, pimelic, su~eric, azelaicJ sebacic, ; dodecanedioic and higher dicarboxylic acids and also such aclds as N-N'-biS (vi-carboxyalkyl) piperazine. Suitable amino-carboxylic acids include N-methyl-, -ethyl-, -isobutyl-, -n-butyl-, -hexyl-, -decyl-, ll-aminostearic and ~-amino-stearic acids.
The molecular weight may be regulated to the desired degree by polymerization conditions and by the use of viscoslty stabilizers. -Branching agents, i.e., polymer reactants having more than two functional groups can be added when it is desired to increase the viscosity of the antistatic polymers.
~; Suitable branching agents include pyromellitic dianhydride, trimethylol propane, pentaerythritol and bis(hexamethylene)-triamine as appropriate for polyamides or polyesters.
Various suitable reactants for forming conductive polyetheresters are disclosed in Br. 1 176 648 and others are disclosed herein. Reactants and conditions for prepara-tion of polyetheresters are also shown in U.S. 3 655 821, and herein however, for the purposes of this invention it is preferred ' ,,:.
....
"
8~0 that the polyether glycol reactant be poly (ethyleneether) glycol (polymerized ethylene oxide) of from 200 to 2000 molecular weight and that the diacid be either aliphatic or aromatic, (e.g., succinic, sebacic, dodecanedioic acid or ; terephthalic acid). m us the polyetheresters are preferably esters of polyethers or copolyethers and diacids.
Reactants for preparlng the aliphatic polyesters are aliphatic glycols having 2 to 12 carbon atoms and aliphatic dibasic acids, or their ester-forming derivativesg having 4 10 to 36 carbon atoms. Minor amounts of aromatic dibasic acids~
or their ester-forming deri~atives, can be used in con~unction with the aliphatic dibasic acids. Excessive aromatic character in thepoly~er is reflected by a high log Rs value. Suitable ; reactants for preparing these polyesters are ethylene glycol, ; 1,3-propanediol, 1,4-butanediol; 1,6-hexanediol; 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; 2-methyl-2-propyl-1,3-propanediol; 2,2,4,-trimethylhexanediol, 2,4,4-tremethylhexanediol; glutaric acid, succinic acid, adipic acid, azelaic acid, dodecanedioic acid, ; 20 terephthalic acid and dimer ~cid (defined below) and their ester-forming derivatives.
< The organic phosphonium sulfonate to be reacted with the other polymer-forming ingredients contains 1 or 2 sulfonate groups. m e sulfonate group is attached to a hydrocarbon group which is aromatic or aliphatic (including cycloaliphatic) ~ree of unsaturation. The hydrocarbon group may be interrupted by ether, sulfonamide or sulfonyl groups;
-~ that is, the sulfonate group may be attached to one of two or more hydrocarbon groups which are connected by ether, 30 sulfonamide or sulfonly groups. For example, there are -:;
.-.- :
.
, , . . . .,.,. .. ,. :: . ~ ~ . . .
~` lQ48690 ~ contemplated phosphonium salts of alkyl- and arylsulfonates ; as well as of aryloxyalkylsulfonates, alkyloxyarylsulfonates, - and arylsulfonamidoalkylsulfonates. The hydrocarbon group bears one or two reactive groups which can form carbonàmide ,i or carboxylester linkages with the polymer-forming reactants.
The reactive groups include carboxyl, carboalkoxy, primary or .; secondary amine, or hydroxyl.
~j The organlc phosphonium sulfonates are conveniently prepared using known techniques from known compounds, generally 10 by metathesis reactions involving ion exchange to obtain the deslred anion. For example, one may react in aqueous medium, a phosphonium halide with an alkali metal sulfonate and ,. . .
separate the phosphonium sulfonate from the aqueous medium.
Suitable alkali metal sulfonates are commercially available or readily prepared. -Suitable phosphonium salt reactants include methyl-triphenylphosphonium 3J5-dicarbomethoxybenzenesulfonate;
~ tetra-(n-butyl)-phosphonium 3,5-dicarboethoxybenzenesulfonate;
r,.' methyltrioctylphosphonium 3J5-dicarbomethoxybenzenesulfonate ;; 20 and others set ~orth in the examples below. The preferred salts are phosphonium 3J5-dicarbo-methoxy-benzenesulfonates.
; m e presence of the phosphonium salt units in the polymer ls highly effective in improving the electrical conductivity of these amorphous, fluidlike polymers. In addltion, their thermal stability permits normal processing of the antistatic polymers when used to prepare antistatlc -1 filaments, partlculary melt-spun polyamide and polyester ;, :
antistatic filaments.
Antistatic filaments of the invention can have the .j .
;~ 30 conductive polymer containing the phosphonium salt un~ts ....
~, '.':
,.
~.
:.............. . .
; dispersed as known in the art as minute particles distributed : throughout. Alternatively the conductive polymer containing the phosphonium salt units can be present as a single con-; tinuous core throughout the length of a filament or fiber.
The latter method makes maximum use of the improved conduc_ ; tivity since the conductive system is continuous and anti-static performance is essentially independendent of the surrounding fiber-forming sheath.
', Synthetic, fiber-forming polymers which can be made antistatic by the polymer of this invention include polymers and copolymers from the classes of poly-amides, polyesters, polyolefins~ including polyethylene and polypropylene. The resulting antistatic fibers may be blended with conventlonal fibers to ~ive a blended product having antistatic properties.
The specific resistance, RSJ is determined at room temperature on the dry (water-free) polymer con-taining the phosphonium salt. The polymer is dried at 100C. in an oven at a pressure less than 50 torr for at least 12 hours. More stringent drying condltions are usually not required but may be used when convenient. The -~; cell used for the measurements consists of a "Pyrex" hard glass tube of 2 + 0~25 millimeter inside diameter and 8 millimeters outside diameter. Copper electrodes are inserted through rubber end-caps at each end of the tube with 33 centimeter electrode separation. The current transmitted through the sample at a potential difference of 220 volts DC is recorded uslng a Beckman Vibrating Reed .....
~ Model 1051 microammeter. Specific resistance is calculated .
from the equation:
_ g _ :
, .
. . .
'',,~' - . : .
~ 8~
R (ohms) = _ Kc The cell constant, Kc, is determined with a liquid of known specific resistance in ohm-cm. The values reported herein used 7.63 x 10 2 as the cell constant. Fsr convenience the Rs value is reported as its log10 value. The lower the Rs value, the h~gher is the conductivity o~ the sample.
The static propensity of antistatic filaments reported herein is determined on fabric made with them.
The filaments are converted to fabric~ and the static propensity determined by measuring the amount of direct current that passes through the fabric at a tempera-ture of 22C. and 26~ relative humidity. In order to assure electrical contact between the electrode and the core-containing filament of khe fabric for better measurements, it may be desirable to paint the fabric with an electrically sonductlve paint in the area of electrode contact. In the e~amples below, no conductive paint is used unless it is .
speciflcally mentioned. m e ohms per square unit of area of fabric surface is determined according to the AATCC Method, 76-59 ("Technical Manual of the AATCC", Volume 41, 1965, pages B-188). This value, given as log R, is the logarithm to the base 10 of the fabric resistance in ohms. Higher values indicate a greater tendency to acquire and retain an electrostatic charge. This method provides an approximate measure of static propensity. However, to compare ~ilaments and yarns of dif~erent deniers one should determine the log rho of the ~ilaments, which takes into account dif~erences in total yarn cross-section, and is obtained ~rom the expression:
: -- 10 --".~
~1:
.. . .
~Q48ti9(1 log rho (fllament) = log R (fabric) - log (9 x 105 D) ~:, log (Pd) where D is the density of the polymer, P is the number of . picks (yarn ends) per centimeter in the fabric and d is the total denier of each pick. In the examples, the following values of D are used: 1.15 for 66 polyamide;
1.0 for 612 polyamide; 1.0 for the polyamide from bis (4- -aminocyclohexyl) methane and dodecanedioic acid, 1.4 for poly (ethylene terephthalate); and 0.9 for polypropylene.
The (Pd) value, which gives the amount of yarn in ~ ~ -the fabric, is corrected in a mixed filament yarn bundle -by the fraction of the filaments which are conductive to obtain the log rho for the conductive filaments therein.
Fibers which produce a log rho value of 11 or ` less are considered to have acceptable antistatic properties with the lower values again representing the more desirable antistatic properties.
Some fabrics are given a number of "home" wash- -dry cycles in a tumble washing machine with a synthetic detergent in water at 38C., spun-dried, and tumble-dried at 77C. These cycles are referred to as "C" washes.
Static propensity of the filaments also can be determined by a measurement of decling time in a procedure referred to as the Sail Test. The Sail Test used herein measurss the severity and duration of garment cling due to static under simulated use condit~ons. In this test, static is induced in a garment, which may be a slip, a skirt or a dress, worn over cotton briefs by a technician, by rubbing . - 11-. .
. .
,' 1~48~;90 against a fabric held between two vertical poles. A
poly (ethylene terephatalate) fabric is used with a poly-amide garment and a poly (hexamethylene adipamide) ~abric is used with a polyester garment. The time taken for the garments to uncling (or decling) while being worn - durlng walking around the room is determined. The room is maintained at 21C. and 20~ relative humidity. The decling time is the time in mlnutes required for the garment to be ~udged comfortable with no detectable cling from static charges.
The results commonly are reported after a ~umber of 'tC't washes with the garments containing acceptable anti-static filaments having decling times less than 10 minutes and preferably less than 2 minutes.
,.:
For carpets, the static propensity o* the anti-static filaments can be determined by using the filamentsi,,;
: to make a carpet and measuring the electrostatic voltage built up on a person walking upon a section of the carpet at 21C. and 20~ relative humidity. Filaments used in this 20 measurement, referred to as the shuffle test, preferably should provide voltages less than 2KV. The procedure ~or the shuffle test is described in AATCC Test Method 134-1964 .; wlth changes adopted by the Carpet & Rug Institute, ~- September, 1971.
The Tg (NMR) is the temperature above which there is a rapid rise in the NMR narrow peak height and the peak ratio with an increase in temperature. The NMR peak ratio is determined from the NMR broadline spectrum measured at a given temperature on the dry polymer (e.g., drled at 125C. for 15 minutes in r ` 30 dry nitrogen) in an atmosphere of dry nitrogen using a ''' - ~V4~690 radio frequency of 56.4 megacycles at an attenuation setting o~ 17 decibels with a sweep modulation amplitud~ of one ~
gauss. The NMR spectrum is measured using the nuclear -magnetic resonsance equipment of Varian Associates, Model V - 4302 Dual Purpose Spectrometer and their high tempera-ture probe insert, Model No. V - 4331 TWL. The NMR spectro-gram at a given temperature shows a broad absorption "hump"
upon which is superimposed a very narrow peak. m e deriva-tive curve of the spectrogram is recorded by the spectro-meter; 'Ipeak ratio" measurments are made on this curve.
The height o~ the narrow peak divided by the height of the "hump" gives the "peak ratio", as described in J. Polymer Science Part C, Polymer Symposia, No. 3, pp. 3-8 (1963).
The precision of this peak ratio determination is about + O.2 and of the Tg (NMR) is about + 5C.
The % core by volume in the filament conveniently is determined from the ~ of the cross-sectional area of the filament occupied by the core material. The cross-sectional area is determined by photographing a cross- ~ ~
section of the filament under a microscope at a known mag- -nification of 50 to 1500X and determining the % core from measurement on the photograph. In the case of irregularities, the average of 5 to 10 determinations is used. For round filaments with round cores, the % core can also be determined . , .
by photographing the filaments in a longitudinal view immersed in a medium having a refractive index closely matching the refractive index of the filament, and meaSuriQg the filament and the core diameters and calculating the ~ core. -~ormulas for some of the phosphonium salts used in -- 30 the examples appear below.
- 13 _ . . .
, '';', - .
lV4~f~9Q
: Salt A
~`
., .
CH O C
~ S03 P(-CH2-C~2-cH2 C~3)4 CH -O-C
~' . ~' ', .'' :
Salt E
CH3-0-C- ~ -O-CH2-CH2-cH2-s03 P(-cH2-cH2 CH2 C 3)4 . .
.
~, . Salt F
' ~3\
C S03 P(-CH2-C~2-cH2-cH3)4 C3H2 ~H2 CH2 c~2 .; IC=O C=O
~ O-CH3 0-CH3 "
.~
. - 14 -' ., Salt G 9 ---- .
-CH2-CH2- O-CH2-~H2-OH
+P-O-SO. SO3 p(-cH2-cH2-cH2-cH3)4 ~2 4 ~- :
,i Salt H
;. -- :.
.;
O . ' CH O-C
3 ~ O H
~o2-N-cH2-cH2-so3 P(-cH2-cH2-cH2-cH3)4 : ~
:. O .
C=O ~-O
... CH3 Salt J
.:
O
. . .~ .
SO3 +P(-CH2-cH2~cH2-cH3)4 ~ .
. , .
.
- 15 ~ :
:
, , , ~ ' ~' .` .
1~48~90 e expression "relative viscosity" as used herein signifies the ratio of the flow time in a viscometer of a polymer solution relative to the flow time of the solvent by itself measured in the same units at 25C, Unless other-wise specified the relative viscosity for polyamides is deter-mined using an 8.4~, by weight, based on total weight, solution in 90%, by weight, based on total weight, formic acid.
Inherent viscosity,~inh~ is determined from the expression:
~ inh = loge ~/C
where~ is the viscosity of a dilute solution of the polymer in m-cresol divided by the viscoæity of m-cresol in the same units and at the same temperature and C is the concentration of the dilute solution in grams of polymer per 100 ml. of - solution. In the examples, the temperature used is 25C. and ~-!' the value of C is 0.5.
In the procedure and examples that follow, all C percentages are by weight, based on total weight~ unless indicated otherwise and all conductive polymer characteriza-20 tions are made at a temperature above 25C.
; PREPARATION OF PHOSPHONIUM SULFONATE MONOMERS
Tetra-n-Butylphosphonium 3,5-Dicarbomethoxybenzenesulfonate (Salt A) A solution of 295 grams of tetra-n-butylphosphonium chloride and 296 grams of sodium 3,5-dicarbomethoxybenzene-; sulfonate in 1.5 liters of water is stirred for 1 hour at 60C. The phosphonium salt separates as clear liquid at the bottom. It is separated and dried overnight at : 100C. at a pressure less than 50 torr. On cooling to 30 room temperature it solidifies to a white solid which melts at 73C.
., :
1~4~
Tetraphenylphosphonium 3,5-Dicarbomethoxybenzenesulfonate (Salt B) A solution of 21 grams of tetraphenylphosphonium bromide in 25 ml. of water at 80C. is added ko 15 grams of sodium 3,5-dicarbomethoxybenzenesulfonate in 50 ml. of water also at 80C. The solution is cooled and crystals o~ tetra-phenylphosphonium 3,5-dicarbomethoxybenzenesulfonate are filtered from the solution. After 18 hours drying under nitrogen at about 60C. at a pressure less than 250 torr 10 nitrogen, the crystals are found to melt at 203C. ~ --Tri-n-Octyl-n-Butylphosphonium 3,5-Dicarbomethoxybenzene-sulfonate -(Salt C~
- , . . . _ .
Tri-n-octyl-n-butylphosphonium bromide is prepared -by slowly adding tri-(n-octyl) phosphine (740 grams) into refluxing l-bromobutane (500 grams) in a nltrogen atmosphere.
Reflux is continued one hour after ~inal addition then the :, - solution is cooled with stirring for about 18 hours, ~ollowed by vacuum removal of excess l-bromobutane at 60C. This product, 1210 grams from two successive preparations, is added to 880 grams of sodium 3,5-dicarbomethoxybenzenesulfonate in 2500 ml. of water and stirred for at least one hour at 85C. then the heat is removed and the oil in water mixture is allowed to stirr and cool ~or about 18 hours. The oil layer is separted from the water, rinsed with 1000 ml. of water and dried at about 80C. at a pressure less than 2 torr for 18 hours. m is product, an oil, is tri-_-octyl-n-butyl-phosphonium 3,5-dicarbomethoxybenzenesulfonate with 4.2% phosphorous and 4.7% sulfur by analysis.
Triphenyl-n-Octadecylphosphonium 3,5-Dicarbomethoxybenzene-sulfonate (Salt D~
, . .
Triphenyl-n-octadecylphosphonium bromide is prepared by refluxing n-octadecyl bromide (1000 grams) and '.
," ., :;, 1. ' ' ~4~ 0 triphenyl phosphlne (787 grams) in about 1400 ml. of toluene for 16 hours at about 110C. The product is precepitated from the cooled solution by the addition of about 500 ml.
of ethyl acetate and the crystals filtered from solution.
These crystals, 1550 grams, are added to 890 grams of sodium 3,5-dicarbomethoxybenæenesulfonate in 3000 ml. of water which is heated to 80-85C. and stirred for one hour.
~A The oil layer is washed twice with about 2000 ml. of 25C.
room temperature water, then dried at 50C. under nitrogen ~ 10 for 16 hours at a pressure less than 100 torr. The product, ; triphenyl-n-octadecylphosphonium 3,5-dicarbomethoxybenzene-sulfonate, solldifies on cooling.
Tetra-n-Butylphosphonium 3-(4-Carbomethoxyphenoxy) propane-sul~onate (Salt E) Sodium 3-(4-carbomethoxyphenoxy) propanesulfonate - is prepared by adding sodium methoxide (54 grams) to 4-carbomethoxyphenol (152 grams) dissolved in 600 ml. of methanol followed by addition of propane sulfone (122 grams).
; After 2 hours o~ reflux, the crystals formed are filtered (186 grams) and added to tetra-_-butylphosphonium chloride (185 grams) in 400 ml. of water at 40C. to prepare tetra-n-butylphosphonium 3-(4-carbomethoxyphenoxy) propanesulfonate. To ` remove this phosphonium salt from water, 70-ml. portions of chloroform are shaken with 70-ml. portions of the water solution and then separated from the water and combined with a repeat of this procedure with 100 ml. o~ chloroform ~; and 100 ml. of the water solution. Evaporation of the two combined chloro~orm extracts yields 98 grams of the above phos-phonium salt E.
~, , .:
~,, : , - . . . .
`; 1~4~90 ^ Tetra-n-butylphosphonium 9,9-di(2-Carbomethoxyethyl) fluorene-3-sulfonate tSalt F) Forty three grams of tetra-n-butylphosphonium chloride and 53 grams of sodium 9,9-di(2-carbomethoxyethyl)-3-~luorenesulfonate are heated to 80C. in 250 ml. of water --with stirring. The desired product is obtained as an oil.
me oil layer is separated from the water and dried for 16 hours at 60C. under nitrogen at a pressure less than 10 torr. After 5 d~ys, the oil crystallizes. These crystals melt at 96C. and are found to contain 4.5% phosphorous and 4.3% sulfur.
1,8-Di(2-Hydroxyethoxy)napthalene 3,6-di(tetra-n-butylphos-~honium)sulfonate (Salt G~ , -.
1,8-Di(2-hydroxyethoxy-naphthalene 3,6(disodium sulfonate is prepared by reacting two moles of ethylene oxide with one mole of 1,8-hydroxynaphthalene 3,6-disodium sulfonate (about 40% monosulfonate) in a concentrated water solution. This solution, 125 ml., containing about 35 grams of -the ethoxylated product, is washed with 125 ml. of benzene then heated to boil to remove impurities. Sodium chloride, 37,5 grams, in 125 ml. of water i6 added to the solution followed by 46 grams of tetra-n-butylphosphonium chloride. After g hours ; of vigorous stirring, the oil layer i8 removed and dried 18 hours at 60C. under a pressure of less than 5 torr. Thls product is mixed with 23 grams o~ tetra-n-butylphosphonium chloride in 100 ml. of water, heated to 80C. and then cooled. The oil layer is removed, dried at 60C. for 18 hours under nitrogen at a pressure less than 2 torr to give 1,8-di(2-hydroxyethoxy)naphthalene-3,6-di(tetra-n-butylphos- -; 30 phonium)sulfonate, analyses indicate that about 40~ of this product is present as the monosulfonate.
,,~
,................................ - 19 -,:
.,, 6i90 Tetra-n-Butylphosphonium 2-(3,5-Dicarbomethoxybenzene Sul~~namldO)ethanesulfonate (Salt H~
~ To 43.8 grams oi 3,5-dlcarbomethoxybenzenesulfonyl ; chlorlde ln 150 ml. benzene 1~ added with vlgorous ~tlrring,~:, 50 grams of 2-aminoethanesulfonic acld ln 190.5 ml. Or 2 N
sodlum hydroxide. The mixture i8 stirred for an hour and then for an additional hour at 60C. The product is ieo-lat~d as a crystalllne precipitate by adding æodium chloride ;~ (60 grams) and 100 ml. of water to the aqueous layer. To separate the product from some undissolved sodium chloride, the product is dissolved in 500 ml. methanol filtered, then reproclpitated by adding 600 ~1. of ether. This product ~s dried 16 hours at 60C. under nitrogen at a - pressure of le68 than 10 torr. The dried product (20 gram~) iB mixed with tetra-_-butylphosphonium chloride . (15 grams) in 35 ml. of water to obtain tetra-n-butylphos-phonium 2-(3,5-dicarbomethoxybenzenesulfonamido)ethane-~ulfonate. Thi~ pho~phonium sulfon~te is extracted from i the wat~r solution by vigorously shaking 30 ml. of chloro-form ~ith the solution. The chloro~orm l~yer yields the phosphoniu~ sulfon3te upon evaporation and lt contains 5.3%
phosphorous~ 9.1% sulrur and 2.1~ nitrogen.
, .. .
Tetra-n-Butylphosphonium 3-Carboxybe~zenesulfonate (Salt J) Tetra-n-butylphosphonium 3-carboxybenzenesulfonate ls prepared by mixing tetra-n-butylphosphonium chloride (58.8 grams) wlth sodium 3-carboxybenzenesulfonate (48.8 grams) ln 250 ml. of water at 60C. The oil layer which , ; for~s i8 removed a~ter cooling the solution and ls dried at 60C. at a pressure les~ than 5 torr. The phosphonium 39 sulfonate crystallizes upon standing at 25C. and has a melting point of 62C.
.
.
.
..... . . . . ~ .
lV48690 `~ EXAMPLE 1 Thls example illustrates the use of Salt A to improve the conductivity of the polymer of N,N'-diethyl-hexamethylene diamine and dodecanedioic acid.
In three separate runs, the salt of the diamine -: and the acid, Salt AJ and bis (hexamethylene) triamine (hereinafter BHMT) are polymerized in a sealed, heavy- -w~lled polymer tube at 215C. for 2 hours and then at 283C.
at a pressure less than 5 torr for 4 hours. me log Rs values of the resulting polymers all Tg (NMR) ~25C. are given - in Table I.
. TABLE I
` Phosphonium Salt, BHMT, RunMol %* M~l % lo~ R~ -I 4.8 2.6 7.0 ~ II 8.3 3.7 6-7 ; III14.1 8.2 6.5 :; .
,',r' In 4 additional runs, an autoclave is charged -- with 3218 gramæ of N,N'-diethylhexamethylene diamine and u dodeca~edioic acid saltJ 129 grams of N,N'-diethylhexa-~!, 20 methylene dlamine, 17.2 grams of BHMT, Salt A, 7.0 grams of boric acid, 20 grams of formic acid, and 4.5 grams of ,:
- potassium phenylphosphinate. The autoclave is purged with nitrogen and heated at 215C. for 2 hours with an agitator speed of 6 to 8 rpm. me pressure generated in the auto-,. .
clave during the preceding step ls about 10 kilograms per ~,~ square centimeter gage. The pressure inside the autoclave is reduced to atmospheric over a period of 60 minutes, .,.
and the temperature is raised to 300C. me batch is held at this temperature for 2 hours under a presæure of less than 2 torr. me agitator is turned off and the pressure :; ~Based on moles of phosphonium group and total moles of Salt A and dodecanedioic acid ~ . .
, ,"
, :`
, ' ;9o is brought to atmospheric with nitrogen. The polymer is ,~
extruded at 275C. under a blanket of nitrogen. Thie amount : of phosphonium salt used, the relative viscoaity and the log - Rs f the polymers all having Tg (NMR) c 25C. are shown in Table II.
;~ TABLE II
Phosphonium Salt Relative ` Runi Mol % ~ y log R~
;~ IV 3.61 17.4 7.1 - 10 V 2.25 27.1 7.2 ~I 1.54 36.2 7.3 VII 1.50 68.9 7-5 - None _ 9.o The composltion of Run VII, whlch has a log Rs f 7.5, is spun as 2.3% core in poly (hexamethylcne adipamide) filaments. A 7X395 mil (0.178 ~ 10.0 mm.) capillary is used to . ..
mcter the core polymer to each orifice. A 10-filament yarn made therefrom is drawn to a denier of 30. The yarn is 2-plied and ` woven as the filling in a fabric. After boiling the fabric in -:
; ~:
water for 3 hours, drying and applying a conductive silver paint, the filament log rho is 9.9.
i'.:i ;~ EXAMPLE 2 "
; Thiis example illustrates the use of Salt A to .; .
improve the conductivity of a polyetherester.
In Run I, an autoclave equipped with an agitator ~-; is charged with 5550 grams of dodecanedioic acid, 4640 grams of polyethylene glycol of 200 average molecular weight, ~, 1160 grams of Salt A, 375 grams of 2-ethyl-2-hydroxymethyl-, 1,3-propanediol (branchin~ agent), 11 grams of p-toluene-,~i 30 sulfonic acid~ and 11 grams of manganese acetate. The i~i autoclave is purged with nitrogen. The reactants are then ~- heated at 200C, and the agitator is started at 15 rpm.
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.
_ 22 -,; .
_ . ~ . . . ` !
~? ~
)48f~90 The batch is held at 200C. for 3 hours under a gentle bleed o~ nitrogen. The pressure is then reduced to less than 5 torr and the temperature is raised to 240C. over a period of about 60 mlnutes. It is held at 240C. for 6 hours at a pressure less than 5 torr. The batch is then brought to atmospheric pressure with nitrogen and extruded at 120C. under a blanket of nitrogen. The yield is about 26 lbs. (11.8 kilograms). The inherent viscosity o~ this material is about 1.O. m e gummy polymer has a log Rs f 5.7 and Tg (NMR) of -35C.
In two additional runs, II and III, additional .:. :
phosphonium salt A is mixed with the pre-formed polymer pre- -~, pared as above for 10 minutes under polymerization conditions ~;
~ust before extruding. The effect of the amount of phosphonium ;~
~- salt on the conductivity of this polyetherester i8 shown in i . .i .
~ Table III. Increaslng the concentratlon above 10 mol % has a .....
~ reduced effect on log Rs.
s~ TABLE III
'r~ Phosphonium Salt, JJ;'~. ~ 20 Run Mol % log Rs I 8.7 5.7 '~:
;~ II 12.5 5.5 III 16.0 5.4 - None ~-8.5 j,~ ,;
A copolymer prepared similarly to Run I which has 8.7 mol % of the phosphonium salt (log Rs of 5.7) is spun as about 50% core in poly(hexamethylene adipamide) filaments.
Sections of capillary tubing are used to meter the core polymer to the spinneret orifices having plateaus as described in Kilian ' 30 U.S. 2,936,482. The 10-filament yarn iæ drawn 3.2X and the ~ denier of the drawn filaments is 20. Twelve o~ the 200-denier ,~; drawn yarns are plied and then bulked using a hot-air jetO
, ~ - 23 -~ .
~` .
~ ~ . . . . . . .
A carpet is tufted from the bulked yarn and mock-dyed. It is hand latexed and dried at 121C. The static propensity of the carpet is only 1.6 kilovolts. Without antistatic agents, the static propensity of nylon 6/6 carpets exceeds 10 k~lovolts.
This example illustrates the use of Salt A to improve the conductivity of another polyetherester.
A still is charged with 3500 grams of polyethylene glycol having an average molecular weight of 400, 4500 grams o~ polyethylene glycol having an average molecular weight of 600, 250 grams of Salt A, 3880 grams of dimethyl tere-phthalate, 2480 grams of ethylene glycol, and 14.0 grams of tetrabutyl titanate. The temperature of the still is raised to 210C. and about 1310 grams of methanol is removed by distillation. m e batch is then transferred to an autoclave at 220C. which has been purged with nitrogen. The autoclave is provided with an agitator which is operated at 15-30 rpm. m e pressure is reduced to less than 2 torr in 45 minutes as the temperature is raised to 260C. dur~ng this period. m e batch is held at a pressure of less than 2 torr ~or 4 to 6 hours. The pressure is then brought to atmospheric with nitrogen and the batch is cooled to 220C. and extruded under a blanket of nitrogen. The rubbery polymer contains 2.3 mol percent of the phosphonium salt, based on the starting ingredient~, has . .~
1~ an inherent viscosity of 1.2, a log Rs f 6.8 and Tg(NMR) of less than 25C. as shown by its rubbery state at room temperature.
;~ A polyetherester without the phosphonium salt is ., prepared by the above procedure using the following ingre-dients: 2950 grams of polyethylene glycol having an average molecular we~ght of 400, 4450 grams of polyethylene glycol . .
, ~
86;90 having an average molecular weight of 600, 4000 grams of dimethyl terephthalate, 2480 grams of ethylene glycol, 300 grams of 1,3,5-trimethyl-2,4,6-tri (3,5-ditertiarybutyl(-4-hydroxy-benzyl)benzene and 14.0 grams of tetrabutyl titanate. m e log R8 of the resulting polymer i8 9.6 and the Tg (NMR) ls less than 25C.
- The polyethereæter, with the phosphonium sulfonate .. ; , modification, is spun as 2% core metered by 3 X 90 mils (o.76x ,i 2.28 mm.) capillaries in poly(ethylene terephtalate) contin-10 uous filament yarns of 34 filaments. The polyethylene tereph- ~-thalate polymer has a relatlve viscosity of 30 and contains 0.3~ of TiO2. The relatlve viscosity is determined using a 10%, by weight, based on total weight, solution of polymer in a mixture of 10 part~, by weight, of phenol and 7 parts of
2,4,6-trichlorophenol. The yarn is drawn to a denier of 150, woven as the filling in a fabric, a conductive silver paint applied, and the log rho determined. Skirts were made from textured yarn double-knit, dyed ~abrics (0.07 gmæ./cm.2) and tested in a sail test against a nylon sail fabric. me values for log rho and decling time are given in Table IV.
TABLE IV
~..
Log Rho After Decling Time, Min.
Core lO"C"Washes After 30 "C" Washes "', Polyetherester i Having Phosphonium 9.7 0.5 Sulfonate Units - None ~13.1 ~10 This example illustrates the use of Salt A to ~.i improve the conductivity of a polyester.
~ An autoclave equipped with an agitator is charged '~ with 2480 grams of di(2-hydroxyethyl)azelate, 680 grams of ~ 25 -,, ~ ~ .
; ~ .
, : . . . .
.
~48~i90 the di(2-hydroxyethyl)ester of dimer acid, 270 grams o~
Salt A, 700 grams of ethylene glycol, 5 grams of 2-ethyl-Z
hydroxymethyl-1,3-propanediol and 1 milliliter of tetrabutyl titanate. Dimer acid is a 36-carbon, long-chain, aliphatic diba3ic acid containing alkyl groups near the center of the molecule. m e autoclave is purged with nitrogen and heated.
m e agitator is turned on at 8 rpm ~hen the autoclave tem-perature is 150C. Nitrogen is passed through the bottom of the clave to increase agitation of the contents. When the temperature reaches 180C. the agitator speed is in-creased to about 24 rpm. The pressure is reduced to less than 50 torr. The batch is held at 240C. for 2 hours and then at 260C. for 4 hours at a pressure of less than 50 torr. At the end of this period the nitrogen and the :.
agitator are turned off. me polymer is extruded at 260C.
` under nitrogen. The rubbery polymer, Tg(NMR) less than 25C., contains 4.9% of the phosphonium salt based on starting ingredients a~d has a log Rs f 6.7; without the phoæphonium salt, the polymer has a log R9 greater than 9Ø
m e polyester with the phosphonium sulfonate (log -Rs of 6.7) is spun as 8% core metered by 3x90 mil (o.76x 2.28 mm.) capillaries in five filaments of a 10-filament yarn. me ~ilament polymers are the same as in Example 5. m e polymer of the sheath ls prepared from the salt of bis-(4-, , .
aminocyclohexyl)methane (containing about 70% of the trans- -; trans stereoisomer) and dodecanedioic acid. The yarn is drawn to a denier of 30. m e yarn is 2-plied and woven as - :
the filling in a fabric, a conductive silver paint applied, and the log rho determined. The yarn is also used to knit a ~, .
tricot fabric for preparing half-slips for sail testing.
.
., .:, .
`: :
~48690 ..;..
Control yarns without the core but otherwise the same also are ev~luated. Log rho and sail results are given in Table V.
TABLE V
,: -Antistatic Log Rho After Fabric Declin~ Ti~e, Yarn30 "C" Washes Min., After 30 ~C" Washes Sheath-Core 9.7 1.4 Filaments Control ~ 13.1 > 10 ; EXAMPLE 5 , ;;;; 10 This example illustrates the use of Salt A to .~
improve the conductivity of another aliphatic polyester.
` A still is charged with 11,700 grams of di~ethyl azelate, 2250 grams of 2,2-dimethyl-1,3-propanediol~ 1360 grams (4.5 mol %) of Salt A, 100 grams oi 2-ethyl-2-hydroxymethyl-1,3-propanediol, 4 grams of sodium acetate trihydrate, 11.2 grams of manganese acetate tetrahydrate, 7.7 grams of antimony oxide and 6200 grams of ethylene glycol. m e temperat~re o~ the still is raised to 230C.
and about 2700 grams of methanol and about 1600 grams of ethylene glycol are removed by distillation. The batch is - then transferred to an autoclave at 230C. which has been purged with nitrogen and 8.3 milliliters of 85%, by weight, ' phosphoric acid is added. m e autoclave is provided with an agitator which is operated at 30 rpm. The pressure is reduced to less than 2 torr and the temperature is raised to 270C. me batch is held at 270C and at less than 2 torr for 4-5 hours. me pres~ure is then brought to 3.85 kg./
; cm.2 gauge with helium and extruded under a blanket of nitrogen.
m e resulting rubbery polymer has an inherent viscosity of 1.4 by analysis contains 4.5 mol percent of the phosphonium salt units~
'~ ~
'' :`
. .
' ,. . .
;~.
and hae a log Rs f 6.4; without the phosphonium salt added, - a polymer has a log Rs f 10Ø
m e phosphonium sulfonate copolyester Tg (NMR) of -22C. is spun as 4% core in 5 filaments of a 10-filament ., polyamide yarn. The filaments have a trilobal cross-section.
e polymer of the sheath of the 5 sheath/core filaments is prepared from the salt of bis(4-aminocyclohexyl)methane having 70% trans-trans-isomer and dodecanedloic acid. m e .;
other 5 filaments are spun from a copolymer of the polymer - 10 of the sheath and contains 8 mol percent isophthalamide units and 92 mol percent dodecanedlo~mide units. Half-.. ~ slip8 made from finished tricot ~abric of this yarn after .. ,j .
~; 30 "C" washes give an average decling time of 3.9 minutes ~
'~ while the control has greater than 10 minutes decling time. ~ -., ~ .
~ ml~ e~ample illustrates the use of Salt D to . ;~ .
improve the conductivity of a polyester.
A polyester is prepared as in Example 5 except 1360 grams of Salt D ls used in place of the 1360 grams o~
Salt A. The resulting gummy polymer Tg (NMR) less than 25C., has an inherent visc06it~ of 0.9, a log Rs ~ 6.2 and contains
TABLE IV
~..
Log Rho After Decling Time, Min.
Core lO"C"Washes After 30 "C" Washes "', Polyetherester i Having Phosphonium 9.7 0.5 Sulfonate Units - None ~13.1 ~10 This example illustrates the use of Salt A to ~.i improve the conductivity of a polyester.
~ An autoclave equipped with an agitator is charged '~ with 2480 grams of di(2-hydroxyethyl)azelate, 680 grams of ~ 25 -,, ~ ~ .
; ~ .
, : . . . .
.
~48~i90 the di(2-hydroxyethyl)ester of dimer acid, 270 grams o~
Salt A, 700 grams of ethylene glycol, 5 grams of 2-ethyl-Z
hydroxymethyl-1,3-propanediol and 1 milliliter of tetrabutyl titanate. Dimer acid is a 36-carbon, long-chain, aliphatic diba3ic acid containing alkyl groups near the center of the molecule. m e autoclave is purged with nitrogen and heated.
m e agitator is turned on at 8 rpm ~hen the autoclave tem-perature is 150C. Nitrogen is passed through the bottom of the clave to increase agitation of the contents. When the temperature reaches 180C. the agitator speed is in-creased to about 24 rpm. The pressure is reduced to less than 50 torr. The batch is held at 240C. for 2 hours and then at 260C. for 4 hours at a pressure of less than 50 torr. At the end of this period the nitrogen and the :.
agitator are turned off. me polymer is extruded at 260C.
` under nitrogen. The rubbery polymer, Tg(NMR) less than 25C., contains 4.9% of the phosphonium salt based on starting ingredients a~d has a log Rs f 6.7; without the phoæphonium salt, the polymer has a log R9 greater than 9Ø
m e polyester with the phosphonium sulfonate (log -Rs of 6.7) is spun as 8% core metered by 3x90 mil (o.76x 2.28 mm.) capillaries in five filaments of a 10-filament yarn. me ~ilament polymers are the same as in Example 5. m e polymer of the sheath ls prepared from the salt of bis-(4-, , .
aminocyclohexyl)methane (containing about 70% of the trans- -; trans stereoisomer) and dodecanedioic acid. The yarn is drawn to a denier of 30. m e yarn is 2-plied and woven as - :
the filling in a fabric, a conductive silver paint applied, and the log rho determined. The yarn is also used to knit a ~, .
tricot fabric for preparing half-slips for sail testing.
.
., .:, .
`: :
~48690 ..;..
Control yarns without the core but otherwise the same also are ev~luated. Log rho and sail results are given in Table V.
TABLE V
,: -Antistatic Log Rho After Fabric Declin~ Ti~e, Yarn30 "C" Washes Min., After 30 ~C" Washes Sheath-Core 9.7 1.4 Filaments Control ~ 13.1 > 10 ; EXAMPLE 5 , ;;;; 10 This example illustrates the use of Salt A to .~
improve the conductivity of another aliphatic polyester.
` A still is charged with 11,700 grams of di~ethyl azelate, 2250 grams of 2,2-dimethyl-1,3-propanediol~ 1360 grams (4.5 mol %) of Salt A, 100 grams oi 2-ethyl-2-hydroxymethyl-1,3-propanediol, 4 grams of sodium acetate trihydrate, 11.2 grams of manganese acetate tetrahydrate, 7.7 grams of antimony oxide and 6200 grams of ethylene glycol. m e temperat~re o~ the still is raised to 230C.
and about 2700 grams of methanol and about 1600 grams of ethylene glycol are removed by distillation. The batch is - then transferred to an autoclave at 230C. which has been purged with nitrogen and 8.3 milliliters of 85%, by weight, ' phosphoric acid is added. m e autoclave is provided with an agitator which is operated at 30 rpm. The pressure is reduced to less than 2 torr and the temperature is raised to 270C. me batch is held at 270C and at less than 2 torr for 4-5 hours. me pres~ure is then brought to 3.85 kg./
; cm.2 gauge with helium and extruded under a blanket of nitrogen.
m e resulting rubbery polymer has an inherent viscosity of 1.4 by analysis contains 4.5 mol percent of the phosphonium salt units~
'~ ~
'' :`
. .
' ,. . .
;~.
and hae a log Rs f 6.4; without the phosphonium salt added, - a polymer has a log Rs f 10Ø
m e phosphonium sulfonate copolyester Tg (NMR) of -22C. is spun as 4% core in 5 filaments of a 10-filament ., polyamide yarn. The filaments have a trilobal cross-section.
e polymer of the sheath of the 5 sheath/core filaments is prepared from the salt of bis(4-aminocyclohexyl)methane having 70% trans-trans-isomer and dodecanedloic acid. m e .;
other 5 filaments are spun from a copolymer of the polymer - 10 of the sheath and contains 8 mol percent isophthalamide units and 92 mol percent dodecanedlo~mide units. Half-.. ~ slip8 made from finished tricot ~abric of this yarn after .. ,j .
~; 30 "C" washes give an average decling time of 3.9 minutes ~
'~ while the control has greater than 10 minutes decling time. ~ -., ~ .
~ ml~ e~ample illustrates the use of Salt D to . ;~ .
improve the conductivity of a polyester.
A polyester is prepared as in Example 5 except 1360 grams of Salt D ls used in place of the 1360 grams o~
Salt A. The resulting gummy polymer Tg (NMR) less than 25C., has an inherent visc06it~ of 0.9, a log Rs ~ 6.2 and contains
3.3 mol % of the phosphonium sulfonate.
~; The copolyester is spun as a 5.8% core in a 34-filament yarn. The fllaments have a round cross-section.
e polymer of the sheath ls the same as in Example 5. m e yarn is drawn to a denier of 150 and is woven into ~abric, heat-set for 20 seconds at temperatures Qf 121.1C., 171.1C. and 190.6C.
i' .
The fabric ls scoured for 20 minutes at 71.1C. in a bath containing 0.01% trisodium phosphate and 0.05~ of an ionic surfactant, The fabric is rinsed, dried and a conductive .. ..
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. .
, .
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.
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; silver paint applied. The log rho of the filament6 is found to be 9.7. Filaments without the antistat treated in the same manner have a log rho o~ about 11.6.
:.
Thls example illustrates the use of Salts B~ EJ
F, G and H to improve the conductivity o~ a polyester.
. .
i~ A round-bottom flask with a side-arm condenser to permit the removal o~ volatile products is charged with 62 grams of ethylene glycol, 117 grams of demethyl azelate, s 10 22.5 grams of 2,2-dimethyl-1,3-propanediol, 1.0 gram i"
(except 10 grams for run using Salt E) of 2-ethyl-2-hydroxymethyl-1,3-propanediol, 0.04 gram sodium acetate trihydrate, 0.112 gram manganese acetate tetrahydrate, 0-077 gram of antimony oxide and 13.6 grams of the selected phosphonium salt 15.4 grams with Salt B. Five separate runs are made using Salts B and E-H. After heating at 180-220C. for 3-4 hours under a nitrogen blanket to remove methanol by-product by distillation, o.o8 milliliter of 85% phosphoric acid is added to the solution and a thin glass capillary tube for feeding nitrogen at atmospheric pressure is inserted below the liquid level. The temperature is raised to 260-270C.
and vacuum is applied to the system at a pressure less than 10 torr. This vacuum pulls nitrogen through the capillary ,, .
~or agitation. The reaction is allowed to proceed for 6-7 ; hours except ~or the run involving Salt B when it is stopped a~ter 4 hours. With the runs involving ~alts E, F, G and -~ H, a magnetic stirrer is also used. Properties for the resulting polymers Tg (NMR) ~25C. are shown in Table Vl.
~ -.
.,~ . .
~ :
;.
~ .
.',:, .~ .
,;, .
` ~48ti~0 . .
TABLE VI
.
; Phosphonlum Phosphonium Sulfonate Sulfonate log Rs Mol ~ Added Salt B 7.4 4.8 Salt E 7.5 4.1 Salt F 6.8 3.2 Salt G 7-5 5.0 ~; Salt H 6.5 2.2 . .
~'.' 10 The copolyester whereln Salt F was employed is dispersed ln polypropylene at a concentration o~ 3~ and spun into a 5-filament yarn. The filaments have a round `~ cross-section. The yarn ls drawn 2X and is plied to give a yarn havlng a denler of 100 and woven into fabric. The fabric is scoured at 100C. in a 0.2% trisodium phosphate solution, dried and a conductive silver paint applied. m e ~
filaments are found to have a log rho of 10.8. Filaments ~ -~' without the antistat treated ln the same manner have a log 20 rho of 12.7.
~XAMPLE 8 This example illustrates the use of Salt J to :,:
improve the conductivity of an N-alkyl polycarbonamide.
The dry salt of N,N'-di(n-butyl)/N-(n-butylhexa-methylene diammonium) (50/50 weight ratio~ dodecanedioate (50 grams) and Salt J (1.5 grams) are sealed in an evacuated, ~-heavy-walled polymer tube and heated for two hours at 220C. --Upon cooling the tube is opened and re-heated to 295C. for ; two hours in a nltrogen atmosphere, then four hours at 295C. at a pressure less than 2 torr. The rubbery ., .
''~,.:
''~"' .. .. . . . . . . . . .
.4"
-: . . , ' ' .: .
1~48~;90 polymer, Tg(NMR) or -35C., has a log Rs f 7.2 and contains 2.7 mol ~ phosphonium sulfonate based on starting lngredients.
!. . .
'~ The N-alkyl polycarbonamide log Rsis 8.5 when the phos-phonium sulfonate is not added.
This example illustrates the use of Salt C to improve the conductivity o~ a polyester.
A polyester is prepared as in Example 5 except 1360 grams of Salt C is used in place of the 1360 grams of Salt A. The resulting gummy polymer Tg (NMR) less than 25C. has a log Rs ~ 6.3-6.5 and contains 3.6 mol percent .~
phosphonium sulfonate. me lnherent viscosity is 1.2.
The polyester is spun as 4~ core in 9 filaments of an 18-filament polyamide yarn. The fil~ments have a trilobal cross-section. The polymer of the sheath is the ~ same as that of Example 5 and the other 9 filaments are of -.; the copolymer Or Example 5. The yarn is drawn to a denier o~ 30. Half-slips made from finished tricot fabric of this .~ yarn after 30 "Ct' washings give an average decling time of
~; The copolyester is spun as a 5.8% core in a 34-filament yarn. The fllaments have a round cross-section.
e polymer of the sheath ls the same as in Example 5. m e yarn is drawn to a denier of 150 and is woven into ~abric, heat-set for 20 seconds at temperatures Qf 121.1C., 171.1C. and 190.6C.
i' .
The fabric ls scoured for 20 minutes at 71.1C. in a bath containing 0.01% trisodium phosphate and 0.05~ of an ionic surfactant, The fabric is rinsed, dried and a conductive .. ..
."'. .
. .
, .
!:;. ' . i ' .' ' ', ' ' ' . ''' ,', ' ' ~ , :' .
.
~)4t~69(~
; silver paint applied. The log rho of the filament6 is found to be 9.7. Filaments without the antistat treated in the same manner have a log rho o~ about 11.6.
:.
Thls example illustrates the use of Salts B~ EJ
F, G and H to improve the conductivity o~ a polyester.
. .
i~ A round-bottom flask with a side-arm condenser to permit the removal o~ volatile products is charged with 62 grams of ethylene glycol, 117 grams of demethyl azelate, s 10 22.5 grams of 2,2-dimethyl-1,3-propanediol, 1.0 gram i"
(except 10 grams for run using Salt E) of 2-ethyl-2-hydroxymethyl-1,3-propanediol, 0.04 gram sodium acetate trihydrate, 0.112 gram manganese acetate tetrahydrate, 0-077 gram of antimony oxide and 13.6 grams of the selected phosphonium salt 15.4 grams with Salt B. Five separate runs are made using Salts B and E-H. After heating at 180-220C. for 3-4 hours under a nitrogen blanket to remove methanol by-product by distillation, o.o8 milliliter of 85% phosphoric acid is added to the solution and a thin glass capillary tube for feeding nitrogen at atmospheric pressure is inserted below the liquid level. The temperature is raised to 260-270C.
and vacuum is applied to the system at a pressure less than 10 torr. This vacuum pulls nitrogen through the capillary ,, .
~or agitation. The reaction is allowed to proceed for 6-7 ; hours except ~or the run involving Salt B when it is stopped a~ter 4 hours. With the runs involving ~alts E, F, G and -~ H, a magnetic stirrer is also used. Properties for the resulting polymers Tg (NMR) ~25C. are shown in Table Vl.
~ -.
.,~ . .
~ :
;.
~ .
.',:, .~ .
,;, .
` ~48ti~0 . .
TABLE VI
.
; Phosphonlum Phosphonium Sulfonate Sulfonate log Rs Mol ~ Added Salt B 7.4 4.8 Salt E 7.5 4.1 Salt F 6.8 3.2 Salt G 7-5 5.0 ~; Salt H 6.5 2.2 . .
~'.' 10 The copolyester whereln Salt F was employed is dispersed ln polypropylene at a concentration o~ 3~ and spun into a 5-filament yarn. The filaments have a round `~ cross-section. The yarn ls drawn 2X and is plied to give a yarn havlng a denler of 100 and woven into fabric. The fabric is scoured at 100C. in a 0.2% trisodium phosphate solution, dried and a conductive silver paint applied. m e ~
filaments are found to have a log rho of 10.8. Filaments ~ -~' without the antistat treated ln the same manner have a log 20 rho of 12.7.
~XAMPLE 8 This example illustrates the use of Salt J to :,:
improve the conductivity of an N-alkyl polycarbonamide.
The dry salt of N,N'-di(n-butyl)/N-(n-butylhexa-methylene diammonium) (50/50 weight ratio~ dodecanedioate (50 grams) and Salt J (1.5 grams) are sealed in an evacuated, ~-heavy-walled polymer tube and heated for two hours at 220C. --Upon cooling the tube is opened and re-heated to 295C. for ; two hours in a nltrogen atmosphere, then four hours at 295C. at a pressure less than 2 torr. The rubbery ., .
''~,.:
''~"' .. .. . . . . . . . . .
.4"
-: . . , ' ' .: .
1~48~;90 polymer, Tg(NMR) or -35C., has a log Rs f 7.2 and contains 2.7 mol ~ phosphonium sulfonate based on starting lngredients.
!. . .
'~ The N-alkyl polycarbonamide log Rsis 8.5 when the phos-phonium sulfonate is not added.
This example illustrates the use of Salt C to improve the conductivity o~ a polyester.
A polyester is prepared as in Example 5 except 1360 grams of Salt C is used in place of the 1360 grams of Salt A. The resulting gummy polymer Tg (NMR) less than 25C. has a log Rs ~ 6.3-6.5 and contains 3.6 mol percent .~
phosphonium sulfonate. me lnherent viscosity is 1.2.
The polyester is spun as 4~ core in 9 filaments of an 18-filament polyamide yarn. The fil~ments have a trilobal cross-section. The polymer of the sheath is the ~ same as that of Example 5 and the other 9 filaments are of -.; the copolymer Or Example 5. The yarn is drawn to a denier o~ 30. Half-slips made from finished tricot fabric of this .~ yarn after 30 "Ct' washings give an average decling time of
4.1 minutes ~n the sail test. Control ~abrics that do not contain the conductive polymer have a decling time greater than lO minutes.
' -~'`'~ ~, .", ~
";.':
,';' "!, , .
, ~, , ., i ' ',' ; .'~
~ ' .
,~
:.
~' :;~
,: -, `;'3 "'' ,',~
:' .
' -~'`'~ ~, .", ~
";.':
,';' "!, , .
, ~, , ., i ' ',' ; .'~
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,~
:.
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:' .
Claims (18)
1. A synthetic polymer having a glass transition temperature Tg (NMR) of less than 25°C. and a log Rs of less than 8 wherein the polymer is selected from the group consisting of aliphatic N-alkyl polycarbonamides, aliphatic polyesters, and polyetheresters, said polymer containing phosphonium sulfonate groups in an amount of from 0.01 mol percent to about 50 mol percent.
2. The polymer of Claim 1 wherein the phosphonium sulfonate-containing units are of the formula:
where R1, R2, R3 and R4 represent monovalent hydrocarbon groups with the proviso that they are alkyl when part of an N-alkyl polycarbonamide and that R1 and R2 may jointly represent an alkylene group, Y is a linking hydrocarbon group of up to 24 carbon atoms in which any unsaturation is aromatic and which may be interrupted by oxygen, sulfonamide or sulfonyl groups, Z is selected from , -O- and groups wherein R is hydrogen or an alkyl group of 1-18 carbon atoms and n and m are 1 or 2.
where R1, R2, R3 and R4 represent monovalent hydrocarbon groups with the proviso that they are alkyl when part of an N-alkyl polycarbonamide and that R1 and R2 may jointly represent an alkylene group, Y is a linking hydrocarbon group of up to 24 carbon atoms in which any unsaturation is aromatic and which may be interrupted by oxygen, sulfonamide or sulfonyl groups, Z is selected from , -O- and groups wherein R is hydrogen or an alkyl group of 1-18 carbon atoms and n and m are 1 or 2.
3. The polymer of Claim 2 wherein the polymer comprises an N-alkyl polycarbonamide.
4. The polymer of Claim 2 wherein the polymer comprises an aliphatic polyester.
5. The polymer of Claim 2 wherein the polymer comprises a polyetherester.
6. The polymer of Claim 2 wherein the phosphonium sulfonate-containing units are phosphonium 3,5-dicarbonyl-benzene sulfonate radicals.
7. The polymer of Claim 6 wherein the sulfonate is a tetraalkyl phosphonium salt.
8. The polymer of Claim 7 wherein the sulfonate is a tetra-n-butyl phosphonium salt.
9. The polymer of Claim 7 wherein the sulfonate is a trioctyl-n-butyl phosphonium salt.
10. An antistatic filament of a synthetic fiber-forming polymer containing a conductive polymer of Claim 1.
11. A filament of Claim 10 wherein the conductive polymer constitutes a single core occupying up to 50 percent of the filament volume.
12. The filament of Claim 11 wherein the filament is comprised of a synthetic, linear fiber-forming polycarbon-amide.
13. The filament of Claim 12 wherein the polycar-bonamide is a polymer of bis(4-aminocyclohexyl) methane and dodecanedioic acid.
14. The filament of Claim 11 wherein the filament is comprised of a fiber-forming polyolefin.
15. The filament of Claim 14 wherein the filament is comprised of a fiber-forming polyester.
16. A process for the preparation of a polymer of Claim 1 by condensation polymerization of the polymer-forming reactants wherein prior to completion of the polymerization a phosphonium sulfonate-containing compound having at least one polymer reactive group is mixed with the polymer-forming reactants; the mixture is subjected to polymerization conditions and the resulting polymer is collected.
17. The process of Claim 16 wherein the phosphonium sulfonate-containing compound contains an amide-forming group and the polymer-forming reactants are polyamide-forming.
18. The process of Claim 16 wherein the phos-phonium sulfonate-containing compound contains a carboxyl ester-forming group and the polymer-forming reactants are polyester-forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA75219126A CA1048690A (en) | 1975-01-31 | 1975-01-31 | Conductive aliphatic polyesters, aliphatic n-alkyl polycarbonamides or polyetheresters having units containing phosphonium sulfonate groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA75219126A CA1048690A (en) | 1975-01-31 | 1975-01-31 | Conductive aliphatic polyesters, aliphatic n-alkyl polycarbonamides or polyetheresters having units containing phosphonium sulfonate groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048690A true CA1048690A (en) | 1979-02-13 |
Family
ID=4102180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75219126A Expired CA1048690A (en) | 1975-01-31 | 1975-01-31 | Conductive aliphatic polyesters, aliphatic n-alkyl polycarbonamides or polyetheresters having units containing phosphonium sulfonate groups |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1048690A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646145A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Low-dielectric-constant TPEE elastomer and preparation method and application thereof |
-
1975
- 1975-01-31 CA CA75219126A patent/CA1048690A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646145A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Low-dielectric-constant TPEE elastomer and preparation method and application thereof |
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