CA1104155A - Process for the production of n, n-bis (hydroxyalkyl) taurine-salts - Google Patents
Process for the production of n, n-bis (hydroxyalkyl) taurine-saltsInfo
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- CA1104155A CA1104155A CA363,271A CA363271A CA1104155A CA 1104155 A CA1104155 A CA 1104155A CA 363271 A CA363271 A CA 363271A CA 1104155 A CA1104155 A CA 1104155A
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Abstract
ABSTRACT OF THE DISCLOSURE
The subject invention relates to a process for the preparation of the N,N-bis(hydroxyalkyl) taurine salts. These compounds are useful in the preparation of novel polyesters entering in the composition of polymeric shaped objects as antistatic additives.
The subject invention relates to a process for the preparation of the N,N-bis(hydroxyalkyl) taurine salts. These compounds are useful in the preparation of novel polyesters entering in the composition of polymeric shaped objects as antistatic additives.
Description
This is a division of the original canadian patent application No. 289.412 filed on October 25, 1977.
The invention of ~he original application relates to man-made ibers and other molded objects prepared from synthetic polymers having durable antistatic properties.
Generally, antistatic synthetic fibers, in ~he form of continuous filament or spun yarns are obtained by first melt-spinning a linear fiber-forming synthetic polymer in combination with an antistatic agent. It has often been suggested that antistatic polymer fibers, such as polyamide fibers, can be produced by melt-spinning a mixture of the fiber-forming polymer with such antista~ic agents as polyal-kylene oxides or their reaction products~ For instance ?
suitable tetrol compounds can be chain extended for use as antistatic additives as described in U.S. Patent No. 2,979,528.
It is known from the teachings of U.S. Patent `3,147,301 that organic polymers can be modified to impart a slightly ionic or hydrophilic character thereto and to improve the dyeability and antistatic properties of the polymer by the use of sulfo-organic esters of fumaric and maleic aCidSL, Such esters contain the salt of a sulfonic acid. In U.S.
Patent 3,894,077 there is disclosed a nitrogen containing - antistatic agent for a plastic comprising a compound of the formula I ~
Rl - ~l ~ (CH2) mS03 1~ , . . .
'i A
wherein R1 is a hydroxyalkyl group of the formula OH
in which R4 is an alkyl group having 6 to 16 carbon atoms, R2 is a lower alkyl group having 1 to 4 carbon atoms or hydroxyalkyl group of the same kind as Rl, R3 iS a lower alkyl group having 1 to 4 carbon atoms and m is an integer of 1 to 4. Partly because such antistatic agents ~or plastics are not polymeric, these compounds are not permanent and tend to be-removed by exposure to washing or drycleaning solvents.
The antlstatic agent compounds utilized as reactants herein are disclosed in U. S. Patent 2,830,082.
These compounds are N-(hydroxyalkyl) taurine compound~
having the following structure:
R' wherein R is a member of the group consisting of hydrogen and alkali metals, R' is a member of the group consisting of hydrogen~ the methyl radical and hydroxyalkyl radicals containing from 2 to 4 carbon atoms. These compounds also lack permanence to washing and drycleaning of the anti-static effect when they are incorporated in a tex~ile fabric. Because they are derived Erom taurines these compounds are more expensive to prepare than many other antistatic agents presently existing in the prior art.
ss .
In German Paten~ 2,~18,308 there is disclosed an antistatic agen~ for polyamide fibers which is a polyoxyalkylated amino acid. These compositions can contain monovalent groups o~ the formula:
H - (X)x N - R - Z ~
H - (Y)y in which X and Y are oxyalkylene uni~s, R is an aliphatlc, aromatic or cycloaliphatic group, Z is -C00- residue, -S020- residue or a metal salt, x is 1 to 1,500 and y is 0 to 1,500. These materials attempt to combine the increased conductivity of polyoxyalkylated compounds with the polarizing effects of amine, carboxyLate, sulfonate or other sal~ groups. While these materials can be of high molecular welght, such materia.ls differ from the antistatic agent polyester composi~ions o the invention which contain repeating amino and sulfonate salt groupings along the polymer chain, thus making lt possible to incorporate a greater proportion of amino and sulfonate groups in the molecular structure and obtain the advantages attendant thereon.
Generally, antistatic agents are incorporated in plastic materials, especially iibers~ by processes which either involve impregnating the synthe~ic polymer fiberJ for lnstance~ a polyamide flber subsequent to its being woven into a ~abric or alternately by incorporating the antistatic agent into the polymer melt prior ~o spinning into filaments. Fibers extruded from such a melt are believed to contain the additive as an insoluble i5 phase in the form of fine fibrils aligned with and dispersed throughout the fiber. Desirable fiber properties are generally not altered by the use of minor amounts of such additives, however, a substan*ial reduction in their tendency to acquire a static charge can result by the incorporation of an antistatic agent therein.
The purpose of the invention of the original appli-cation is to provide (l) novel polyester antistatic a~ents for polymeric shaped objects especially textile fibers, (2) novel polyesters having improved antistatic properties, (3) a process for the production of said agents and (4) a process for the production of antistatic shaped objects such as synthetic fibers. The present divisional application relates to a process for the production of N,N-bis(hydroxyalkyl) taurine salts. The pol~ester antistatic agents can be incorporated into, for instance, a polypropylene fiber prior to melt-spinning into fibers. It has been found that the incorporation of both amino and sulfonate groups along the backbone of an oligomeric polyester antistatic agent provides a desirable balance of properties such that satisfactory antistatic properties are obtained upon incorporation of said agent in a polymeric shaped object.
'rhe amphoteric amino sulfonate salt reactants of the divisional application are known from U.S~ Patent 2,830~082 as previously indicated. However, it has now been discovered that a more economical process for the preparation of such amphoteric amino sulfonate sa]ts can be utilized to prepare such compounds rather tha~ the prior art routc of preparation from ar, alkali metal salt of taurine or N-methyltaurine with a 1,2- or 2-3-alkylene oxide having 2 to 4 carbon atoms.
The novel process of the divisional application for the preparation of amphoteric amino sulfonate salts s~
(N,N-bis~hydroxyalkyl) taurine salts~ comprises the reaction of excess dialkanolam.ine with an alkali metal or alkaline earth metal salt of a hydroxyalkylsulfonic acid corresponding to the general formula :
ll l3
The invention of ~he original application relates to man-made ibers and other molded objects prepared from synthetic polymers having durable antistatic properties.
Generally, antistatic synthetic fibers, in ~he form of continuous filament or spun yarns are obtained by first melt-spinning a linear fiber-forming synthetic polymer in combination with an antistatic agent. It has often been suggested that antistatic polymer fibers, such as polyamide fibers, can be produced by melt-spinning a mixture of the fiber-forming polymer with such antista~ic agents as polyal-kylene oxides or their reaction products~ For instance ?
suitable tetrol compounds can be chain extended for use as antistatic additives as described in U.S. Patent No. 2,979,528.
It is known from the teachings of U.S. Patent `3,147,301 that organic polymers can be modified to impart a slightly ionic or hydrophilic character thereto and to improve the dyeability and antistatic properties of the polymer by the use of sulfo-organic esters of fumaric and maleic aCidSL, Such esters contain the salt of a sulfonic acid. In U.S.
Patent 3,894,077 there is disclosed a nitrogen containing - antistatic agent for a plastic comprising a compound of the formula I ~
Rl - ~l ~ (CH2) mS03 1~ , . . .
'i A
wherein R1 is a hydroxyalkyl group of the formula OH
in which R4 is an alkyl group having 6 to 16 carbon atoms, R2 is a lower alkyl group having 1 to 4 carbon atoms or hydroxyalkyl group of the same kind as Rl, R3 iS a lower alkyl group having 1 to 4 carbon atoms and m is an integer of 1 to 4. Partly because such antistatic agents ~or plastics are not polymeric, these compounds are not permanent and tend to be-removed by exposure to washing or drycleaning solvents.
The antlstatic agent compounds utilized as reactants herein are disclosed in U. S. Patent 2,830,082.
These compounds are N-(hydroxyalkyl) taurine compound~
having the following structure:
R' wherein R is a member of the group consisting of hydrogen and alkali metals, R' is a member of the group consisting of hydrogen~ the methyl radical and hydroxyalkyl radicals containing from 2 to 4 carbon atoms. These compounds also lack permanence to washing and drycleaning of the anti-static effect when they are incorporated in a tex~ile fabric. Because they are derived Erom taurines these compounds are more expensive to prepare than many other antistatic agents presently existing in the prior art.
ss .
In German Paten~ 2,~18,308 there is disclosed an antistatic agen~ for polyamide fibers which is a polyoxyalkylated amino acid. These compositions can contain monovalent groups o~ the formula:
H - (X)x N - R - Z ~
H - (Y)y in which X and Y are oxyalkylene uni~s, R is an aliphatlc, aromatic or cycloaliphatic group, Z is -C00- residue, -S020- residue or a metal salt, x is 1 to 1,500 and y is 0 to 1,500. These materials attempt to combine the increased conductivity of polyoxyalkylated compounds with the polarizing effects of amine, carboxyLate, sulfonate or other sal~ groups. While these materials can be of high molecular welght, such materia.ls differ from the antistatic agent polyester composi~ions o the invention which contain repeating amino and sulfonate salt groupings along the polymer chain, thus making lt possible to incorporate a greater proportion of amino and sulfonate groups in the molecular structure and obtain the advantages attendant thereon.
Generally, antistatic agents are incorporated in plastic materials, especially iibers~ by processes which either involve impregnating the synthe~ic polymer fiberJ for lnstance~ a polyamide flber subsequent to its being woven into a ~abric or alternately by incorporating the antistatic agent into the polymer melt prior ~o spinning into filaments. Fibers extruded from such a melt are believed to contain the additive as an insoluble i5 phase in the form of fine fibrils aligned with and dispersed throughout the fiber. Desirable fiber properties are generally not altered by the use of minor amounts of such additives, however, a substan*ial reduction in their tendency to acquire a static charge can result by the incorporation of an antistatic agent therein.
The purpose of the invention of the original appli-cation is to provide (l) novel polyester antistatic a~ents for polymeric shaped objects especially textile fibers, (2) novel polyesters having improved antistatic properties, (3) a process for the production of said agents and (4) a process for the production of antistatic shaped objects such as synthetic fibers. The present divisional application relates to a process for the production of N,N-bis(hydroxyalkyl) taurine salts. The pol~ester antistatic agents can be incorporated into, for instance, a polypropylene fiber prior to melt-spinning into fibers. It has been found that the incorporation of both amino and sulfonate groups along the backbone of an oligomeric polyester antistatic agent provides a desirable balance of properties such that satisfactory antistatic properties are obtained upon incorporation of said agent in a polymeric shaped object.
'rhe amphoteric amino sulfonate salt reactants of the divisional application are known from U.S~ Patent 2,830~082 as previously indicated. However, it has now been discovered that a more economical process for the preparation of such amphoteric amino sulfonate sa]ts can be utilized to prepare such compounds rather tha~ the prior art routc of preparation from ar, alkali metal salt of taurine or N-methyltaurine with a 1,2- or 2-3-alkylene oxide having 2 to 4 carbon atoms.
The novel process of the divisional application for the preparation of amphoteric amino sulfonate salts s~
(N,N-bis~hydroxyalkyl) taurine salts~ comprises the reaction of excess dialkanolam.ine with an alkali metal or alkaline earth metal salt of a hydroxyalkylsulfonic acid corresponding to the general formula :
ll l3
2 4 wherein Rl, R2, R3 and R4 can be the same or different hydrocarbon radical selected from the group consisting of aliphatic hydrocarbons having about 2 to about 12 carbon atoms and M is an alkali metal or an alkaline earth metal derived cation. Representative hydroxyalkylsulfonic acids from which these salts are prepared by known methods are as follows :
2-hydroxyethanesulfonic acid (isethionic acid~, 2-hydroxy-1-propanesulfonic acid, l-hydroxy-2-propanesulfonic acid, 2-hydroxy-1-butanesulfonic acid, l-hydroxy-2-butanesulfonic acid,
2-hydroxyethanesulfonic acid (isethionic acid~, 2-hydroxy-1-propanesulfonic acid, l-hydroxy-2-propanesulfonic acid, 2-hydroxy-1-butanesulfonic acid, l-hydroxy-2-butanesulfonic acid,
3-hydroxy-2-butanesulfonic acid t 1-hydroxy-2-methyl-2-propanesulfonic acid, 2-hydroxy-2-methyl-1-propanesulfonic acid, l-hydroxy-3-methoxy-2-propanesulfonic acid, 2-hydroxy-3-methoxy-1-propanesulfonic acid, JD~
l-hydroxy-2-oc~anesulonic acid, l-hydroxy~2-dodecanesulfonic acid, l-hydroxy-2-hexanedecanesulfonic acid, 2-hydroxycyclohexanesulfonic acid The hydroxyalkylsulfonic acids listed above are used in the form of their alkali metal or alkaline earth me~al salt~ such as the sodium, potassium, calclum, magnesium, etc. These salts are readily prepared by neutralization of the hydroxysul~onic acid with an equivalent amount of an alkali metal or alkaline earth metal hydroxide or carbonate.
The amphoteric amino sulfonate salt reactants are prepared by reacting at least l mole of a hydroxyalkyl-sulfonic acid metal salt with 2 or more moles of a dialkanolamine in ~he presence of a ca~alytic amount of a strong base at a temperature of about 180 C. to about 200~ C. The water of condensatlon is removed during the process so that there is ohtained upon completlon of the reaction the desired amphoteric amino sulfonate salt.
This is further reacted with an organic polycarboxylic acid to produce the polyester antistatic agents of the invention. Suitable strong base catalysts are the alkali metal hydroxides and carbonates illustrated by sodium hydroxide, potassium hydroxide, lithiurn hydroxide, sodium carbonate, and potassium carbonate The alkaline earth metal hydroxides and carbonates and the alkali metal alkoxides having 1 to about 4 carbon a~oms are also useful. Representative examples are sodium methoxide, potassium methoxide and magnesium and calciurn hydroxides, magnesium and calcium carbonates.
The dialkanolamines have the structural formula :
~N(CH2cHROH)2 wherein R is a hydrogen atom or an alkyl radical having O to 21 carbon atoms. Non-limiting examples o~ the dialkanolamines are :
diethanolamine, dipropanolamine, diisopropanolamine, 2,2'-iminodibutanol-1, 3~3'-iminodibutanol-1,
l-hydroxy-2-oc~anesulonic acid, l-hydroxy~2-dodecanesulfonic acid, l-hydroxy-2-hexanedecanesulfonic acid, 2-hydroxycyclohexanesulfonic acid The hydroxyalkylsulfonic acids listed above are used in the form of their alkali metal or alkaline earth me~al salt~ such as the sodium, potassium, calclum, magnesium, etc. These salts are readily prepared by neutralization of the hydroxysul~onic acid with an equivalent amount of an alkali metal or alkaline earth metal hydroxide or carbonate.
The amphoteric amino sulfonate salt reactants are prepared by reacting at least l mole of a hydroxyalkyl-sulfonic acid metal salt with 2 or more moles of a dialkanolamine in ~he presence of a ca~alytic amount of a strong base at a temperature of about 180 C. to about 200~ C. The water of condensatlon is removed during the process so that there is ohtained upon completlon of the reaction the desired amphoteric amino sulfonate salt.
This is further reacted with an organic polycarboxylic acid to produce the polyester antistatic agents of the invention. Suitable strong base catalysts are the alkali metal hydroxides and carbonates illustrated by sodium hydroxide, potassium hydroxide, lithiurn hydroxide, sodium carbonate, and potassium carbonate The alkaline earth metal hydroxides and carbonates and the alkali metal alkoxides having 1 to about 4 carbon a~oms are also useful. Representative examples are sodium methoxide, potassium methoxide and magnesium and calciurn hydroxides, magnesium and calcium carbonates.
The dialkanolamines have the structural formula :
~N(CH2cHROH)2 wherein R is a hydrogen atom or an alkyl radical having O to 21 carbon atoms. Non-limiting examples o~ the dialkanolamines are :
diethanolamine, dipropanolamine, diisopropanolamine, 2,2'-iminodibutanol-1, 3~3'-iminodibutanol-1,
4,4'-iminodibutanol-1, di-tertiary-butanolamine, and 3,3'-iminodipentanol-1, 6,6'-iminodihexanol-1.
Such dialkanolamines can be prepared by several methods well known to those skilled in the art. One method is by the direct addition reaction between ammonia and an epoxy compound such as ethylene oxide or propylene oxide. Another less direct process invol~les the reaction between ammonia and a halogenated alcohol such as 2-chlorobutanol-1.
The polyester of the original patent application comprises the reaction product of a substantially e~uivalent amount of a polycarboxylic acid or mixtures thereof with an amino amphoterlc sulfonate salt (N,N bis(hydroxyallcyl) taurine salt) having the generalized formula :
HO - R N - R - OH
IRl wherein R and Rl are alkyl and individually selected from alkyl groups having about 2 to about 8 carbon atoms, and M is a metal selected from the group consisting of an allcali metal, an alkaline earth metal and mixtures thereof.
In the preparation of the polyester antistatic agent of the invention, the amphoteric amino sulfonate salt reactant prepared is further reacted with an organic polycarbo-xylic acid reactant. Said reactant is defined as any aliphatic, cycloaliphatic or aromatic polycarboxylic acid anh~dride, a~
-s~
ester and acid halide or mixtures thereof. Examples o~ such acids are phthalic, terephthalic, isophthalic, trimellitic, pyromellitic, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, and fumaric acids.
Also useful are 1,3~cyclopentane dicarboxylic, 1l2-cyclohexane dicarboxylic, 1,3-cyclohexane dicarboxylic, 1,4-cyclohexane dicarboxylic, 2,5-norbornane dicarboxylic, 1,4-naphthalic, diglycolic, thiodipropionic, and 2,5-naphthalene dicarboxylic acids. Suitable mixtures of these polycarboxylic acids can be utilized to obtain optimal physical propert1es in the polyester composition of the invention as is well known by those skilled in the art. The corresponding acid anhydrides, esters and acid halides, i.e., acid chlorides of the above enumerated polycarboxylic acids can also be used.
The novel polyester of the original patent application is uniformly dispersed into shaped polymer such as a fiber-forming polymer and spun into fiber by methods well known in the art to produce an antistatic fiber. Generally, the novel polyester is incorporated into a shaped polymer fiber in the proportions of from about 1 to about 15%, preferably about 3 to about 10% by weight.
Generally, the polyester antistatic agent is added to the polymeri~ation reactor at elevated temperature under an inert atmophere during the last 30 minutes of the polymerization of the polyamide or other polymer which is desired to be rendered antistatic~ The agent is thoroughly mixed into the polymer with stirring. The mixture is then extruded in the desired form, cooled, washed and dried.
The following examples will further illustrate the method for preparing the amphoteric amino sulfonate salts, the nature and method for preparing the polyester anti-static ~L
Such dialkanolamines can be prepared by several methods well known to those skilled in the art. One method is by the direct addition reaction between ammonia and an epoxy compound such as ethylene oxide or propylene oxide. Another less direct process invol~les the reaction between ammonia and a halogenated alcohol such as 2-chlorobutanol-1.
The polyester of the original patent application comprises the reaction product of a substantially e~uivalent amount of a polycarboxylic acid or mixtures thereof with an amino amphoterlc sulfonate salt (N,N bis(hydroxyallcyl) taurine salt) having the generalized formula :
HO - R N - R - OH
IRl wherein R and Rl are alkyl and individually selected from alkyl groups having about 2 to about 8 carbon atoms, and M is a metal selected from the group consisting of an allcali metal, an alkaline earth metal and mixtures thereof.
In the preparation of the polyester antistatic agent of the invention, the amphoteric amino sulfonate salt reactant prepared is further reacted with an organic polycarbo-xylic acid reactant. Said reactant is defined as any aliphatic, cycloaliphatic or aromatic polycarboxylic acid anh~dride, a~
-s~
ester and acid halide or mixtures thereof. Examples o~ such acids are phthalic, terephthalic, isophthalic, trimellitic, pyromellitic, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, and fumaric acids.
Also useful are 1,3~cyclopentane dicarboxylic, 1l2-cyclohexane dicarboxylic, 1,3-cyclohexane dicarboxylic, 1,4-cyclohexane dicarboxylic, 2,5-norbornane dicarboxylic, 1,4-naphthalic, diglycolic, thiodipropionic, and 2,5-naphthalene dicarboxylic acids. Suitable mixtures of these polycarboxylic acids can be utilized to obtain optimal physical propert1es in the polyester composition of the invention as is well known by those skilled in the art. The corresponding acid anhydrides, esters and acid halides, i.e., acid chlorides of the above enumerated polycarboxylic acids can also be used.
The novel polyester of the original patent application is uniformly dispersed into shaped polymer such as a fiber-forming polymer and spun into fiber by methods well known in the art to produce an antistatic fiber. Generally, the novel polyester is incorporated into a shaped polymer fiber in the proportions of from about 1 to about 15%, preferably about 3 to about 10% by weight.
Generally, the polyester antistatic agent is added to the polymeri~ation reactor at elevated temperature under an inert atmophere during the last 30 minutes of the polymerization of the polyamide or other polymer which is desired to be rendered antistatic~ The agent is thoroughly mixed into the polymer with stirring. The mixture is then extruded in the desired form, cooled, washed and dried.
The following examples will further illustrate the method for preparing the amphoteric amino sulfonate salts, the nature and method for preparing the polyester anti-static ~L
5~
agents of the invention and for treati.ng synthetic fiber-forming polymeric materials therewi.th, These examples, however, are not to be considered as limiting the inventions of the original and divisional applications. In the specification, claims and the examples which follow all proportions are by weight and all temperatures are in degrees centrigrade unless otherwise noted.
An amphoteric amino sulfonate salt was prepared as follows :
Into a two liter, three-necked flask equipped with a mechanical stirrer, thermometer, thermometer well and a vacuum distillation take-off there was charged 470 yrams of 97% ethanolamine, 331 grams of isethionic acid, sodium salt (2-hydroxyethanesulfonic acid sodium salt) and 1.5 grams of sodium hydroxide. The resulting slurry was warmed to 60C
and briefly placed under a pressure less than or equal to 5 millimeters of mercury. The vacuum was relieved with nitrogen in order to deoxygenate the mixture and the entire reaction was . .
_ g _ `
conducted under a nitrogen blanket. The flask was heated so as to evolve water, the evolution of water beginning at 180 C. The temperature was slowly increased over a period of 8 hours to a temperature of 195 C. to facili-tate removal of water. The theoretical amount o~ watex of condensation (36 grams) had been collected after a period of 8 hours. The mixture was then cooled to 165 C.
and the above vacuum established. Rapid removal of diethanolamine occurred at a temperature of 139 C. al~d at a pressure of 0.1 millimeter of mercury. At a pot temperature of 165 C., a total of 236 grams of diethanoL-amine was removed/ In order to distill out the remalnder of the diethanolamine, the pot temperature was increased to 180 C. Another 47 grams of distillate was obtained bringing the total of unreacted diethanolamine to ` ` 258 grams. The product had a hydroxyl number of 469 and
agents of the invention and for treati.ng synthetic fiber-forming polymeric materials therewi.th, These examples, however, are not to be considered as limiting the inventions of the original and divisional applications. In the specification, claims and the examples which follow all proportions are by weight and all temperatures are in degrees centrigrade unless otherwise noted.
An amphoteric amino sulfonate salt was prepared as follows :
Into a two liter, three-necked flask equipped with a mechanical stirrer, thermometer, thermometer well and a vacuum distillation take-off there was charged 470 yrams of 97% ethanolamine, 331 grams of isethionic acid, sodium salt (2-hydroxyethanesulfonic acid sodium salt) and 1.5 grams of sodium hydroxide. The resulting slurry was warmed to 60C
and briefly placed under a pressure less than or equal to 5 millimeters of mercury. The vacuum was relieved with nitrogen in order to deoxygenate the mixture and the entire reaction was . .
_ g _ `
conducted under a nitrogen blanket. The flask was heated so as to evolve water, the evolution of water beginning at 180 C. The temperature was slowly increased over a period of 8 hours to a temperature of 195 C. to facili-tate removal of water. The theoretical amount o~ watex of condensation (36 grams) had been collected after a period of 8 hours. The mixture was then cooled to 165 C.
and the above vacuum established. Rapid removal of diethanolamine occurred at a temperature of 139 C. al~d at a pressure of 0.1 millimeter of mercury. At a pot temperature of 165 C., a total of 236 grams of diethanoL-amine was removed/ In order to distill out the remalnder of the diethanolamine, the pot temperature was increased to 180 C. Another 47 grams of distillate was obtained bringing the total of unreacted diethanolamine to ` ` 258 grams. The product had a hydroxyl number of 469 and
6.3~ nitrogen. This compares with a calculated theoreticaL
value of 47g for hydrox~l number and 5.8 for percent nitrogen.
EX~MPLE 2 The antistatic agent polyester of the invention was prepared using the amphoteric amino sulfonate salt prepared in Example 1 by the following procedure:
A 500-milliliter, three-necked flask equip~ed with a mechanical stirrer, thermometer and complete with a vacuum distillation take-off consi.sting o a Clalsen head with ~hermometer, condenser, vacuum adaptor and receiving flask was charged with 334 grams of a 66~
aqueou~ solution of the amphoteric amino suLfonate salt prepared in Example 1. To this flask there was then added 143 grams of azelaic acid. The mixture was di.stilled under reduced pressure to remove water. After one hour all the water had been removed and the temper-a~ure was increased until water of condensation appeared.
At a temperature of 140 C. to 160 C. and a pressure of 0.5 millimeter of mercury, rapid evoLution of water of condensation was noted by vigorous bubbling and conden-sation of water in the condenser and recelving flask.
After a reaction time o ~ hours, the homogeneous, viscous and transparent reaction product was discharged from the 1as~, and on cooling solidified into a hard and brittle resin. The product had an OH number of 44 and an acid number of 57.
. EXAMPLE ~
The procedure of Example 2 was repeated except that sebacic acid lnstead of azelaic acid was utilized to produce an antistatic agent polyester having an OH
number of 6.l~ and an acid number of 79.
The reaction procedure of Example 2 was repeated using adipic acid instead of the azelaic acld used in Example 2 to produce a polyester having a hydroxyl number of 22 and a acid number of 70.
EXAMPLES 7 and 8 Resistivity determinations in accordance with ASTM D-257 test method were made using a Keithly elcctrometcr and s~atic detector. Polyamide films containing the polyester antistatlc agent o~ the invention were prepared by dissolving the polyamide (sold under the trademark "Nylon 6") and the polyester in trifluoroethanol and casting film samples therefrom containing five percent .
~ 5 ~
and ten percent of the polyester antistatic agent of the invention. Resistivity determina~ions were made under controlled temperature and humidity and results obtained a~ 25 C. at ten, twenty and thirty percent relative humidity. Results are shown in Table I.
Table I
RESISTIVITY OF POLY~MIDE FILM
CONTAINING THR
ANTISTATIC AGENT OF THE INVENTION
_ . . .
10 - ~ Resistivity, Log1O
Antistatic Relative Humidity (%) ExampleAgent _ 10 20 SO
value of 47g for hydrox~l number and 5.8 for percent nitrogen.
EX~MPLE 2 The antistatic agent polyester of the invention was prepared using the amphoteric amino sulfonate salt prepared in Example 1 by the following procedure:
A 500-milliliter, three-necked flask equip~ed with a mechanical stirrer, thermometer and complete with a vacuum distillation take-off consi.sting o a Clalsen head with ~hermometer, condenser, vacuum adaptor and receiving flask was charged with 334 grams of a 66~
aqueou~ solution of the amphoteric amino suLfonate salt prepared in Example 1. To this flask there was then added 143 grams of azelaic acid. The mixture was di.stilled under reduced pressure to remove water. After one hour all the water had been removed and the temper-a~ure was increased until water of condensation appeared.
At a temperature of 140 C. to 160 C. and a pressure of 0.5 millimeter of mercury, rapid evoLution of water of condensation was noted by vigorous bubbling and conden-sation of water in the condenser and recelving flask.
After a reaction time o ~ hours, the homogeneous, viscous and transparent reaction product was discharged from the 1as~, and on cooling solidified into a hard and brittle resin. The product had an OH number of 44 and an acid number of 57.
. EXAMPLE ~
The procedure of Example 2 was repeated except that sebacic acid lnstead of azelaic acid was utilized to produce an antistatic agent polyester having an OH
number of 6.l~ and an acid number of 79.
The reaction procedure of Example 2 was repeated using adipic acid instead of the azelaic acld used in Example 2 to produce a polyester having a hydroxyl number of 22 and a acid number of 70.
EXAMPLES 7 and 8 Resistivity determinations in accordance with ASTM D-257 test method were made using a Keithly elcctrometcr and s~atic detector. Polyamide films containing the polyester antistatlc agent o~ the invention were prepared by dissolving the polyamide (sold under the trademark "Nylon 6") and the polyester in trifluoroethanol and casting film samples therefrom containing five percent .
~ 5 ~
and ten percent of the polyester antistatic agent of the invention. Resistivity determina~ions were made under controlled temperature and humidity and results obtained a~ 25 C. at ten, twenty and thirty percent relative humidity. Results are shown in Table I.
Table I
RESISTIVITY OF POLY~MIDE FILM
CONTAINING THR
ANTISTATIC AGENT OF THE INVENTION
_ . . .
10 - ~ Resistivity, Log1O
Antistatic Relative Humidity (%) ExampleAgent _ 10 20 SO
7 5 14.8 14.0 12.9
8 10 13 9 13.0 12.2 Control 0 14.3 1307 ~3.2 The polyester antistatic agent of the invention prepared in Example 2 was used to prepare an antistatic polypropylene fiber by incorporation o~ about one percent by weight thereof in a polypropylene polymer prior to extrusion into filaments. Samples o polypropylene were extruded both with and without the polyester prepared in Example 2 using a CSI Max-Mixing Extruder. Samples of fiber obtained were conditioned at 10, 20 and 3~ percent relative humidity at 25 C. and then surface resi~tlvity was measured as described in Examples 7 and 8. All samples were conditioned for 72 hours at 10 percent relative humidity at 25 C. Those to be tested at this condition are evaluated and the remainder of t~e samples are further conditioned at 20 percent reLative humldity i5 for 24 hours. Samples to be evaluated at 30 percent relative humidity are urther conditioned at this condition ~or 24 hours prior to testing. Results are shown in Table II.
Table II
RESISTIVITY OF PO~YPROPYLENE FIBER
CONTAINING THE
ANTISTATIC AGENT OF THE INVENTION_ ~ Resistivity, LoglO
Antistatic Relative_Humidlty (~) Exam~le Agent _ 10 20 ~
Table II
RESISTIVITY OF PO~YPROPYLENE FIBER
CONTAINING THE
ANTISTATIC AGENT OF THE INVENTION_ ~ Resistivity, LoglO
Antistatic Relative_Humidlty (~) Exam~le Agent _ 10 20 ~
9 1 13.7 1~.6 12.2 Control 0 14.4 14,6 14.6 While this lnvention has been described ~ith reference to certain specific embodiments, it will be recognized by those skilled in the art that many variations are possible without departing ~rom the scope and spirit of the invention.
- 13 - :
- 13 - :
Claims (5)
1. A process for the preparation of an N,N-bis(hy-droxyalkyl) taurine metal salt having the formula :
wherein R and R1 are alkyl and individually selected from alkyl groups having about 2 to about 8 carbon atoms and M
is a metal selected from the group consisting of the alkali metals, alkaline earth metals and mixtures thereof comprising :
A. reacting an excess of a dialkanolamine with a hydroxyalkylsulfonic acid metal salt in the presence of a strong base catalyst, B. removing the water of condensation and excess dialkanolamine and C. recovering a product having said formula;
wherein said hydroxyalkylsulfonic acid metal salt has the formula :
wherein R1, R2, R3 and R4 can be hydrogen or the same or different and are individually selected from the group consisting of aliphatic hydrocarbons having about 2 to about 12 carbon atoms and M is a metal selected from the group consist-ing of the alkali metals, the alkaline earth metals and mixtures thereof.
wherein R and R1 are alkyl and individually selected from alkyl groups having about 2 to about 8 carbon atoms and M
is a metal selected from the group consisting of the alkali metals, alkaline earth metals and mixtures thereof comprising :
A. reacting an excess of a dialkanolamine with a hydroxyalkylsulfonic acid metal salt in the presence of a strong base catalyst, B. removing the water of condensation and excess dialkanolamine and C. recovering a product having said formula;
wherein said hydroxyalkylsulfonic acid metal salt has the formula :
wherein R1, R2, R3 and R4 can be hydrogen or the same or different and are individually selected from the group consisting of aliphatic hydrocarbons having about 2 to about 12 carbon atoms and M is a metal selected from the group consist-ing of the alkali metals, the alkaline earth metals and mixtures thereof.
2. A process according to claim 1, wherein said catalyst is selected from the group consisting of the alkali and alkaline earth metal hydroxides and carbonates and alkali metal alkoxides.
3. A process according to claim 1, wherein said dialkanolamine is diethanolamine.
4. A process according to claim 3, wherein said hydroxyalkylsulfonic acid metal salt is the alkali or alkaline earth metal salt of 2-hydroxyethanesulfonic acid.
5. A process according to claim 4, wherein said hydroxyalkylsulfonic acid metal salt is the sodium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA363,271A CA1104155A (en) | 1976-11-08 | 1980-10-24 | Process for the production of n, n-bis (hydroxyalkyl) taurine-salts |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/739,497 US4080315A (en) | 1976-11-08 | 1976-11-08 | Polyesters of N,N-bis(hydroxyalkyl) taurine salts as antistatic agents for synthetic polymers |
| US739,497 | 1976-11-08 | ||
| CA289,412A CA1111189A (en) | 1976-11-08 | 1977-10-25 | Polyesters of n,n-bis(hydroxyalkyl)taurine salts as antistatic agents for synthetic polymers |
| CA363,271A CA1104155A (en) | 1976-11-08 | 1980-10-24 | Process for the production of n, n-bis (hydroxyalkyl) taurine-salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104155A true CA1104155A (en) | 1981-06-30 |
Family
ID=27165343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA363,271A Expired CA1104155A (en) | 1976-11-08 | 1980-10-24 | Process for the production of n, n-bis (hydroxyalkyl) taurine-salts |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1104155A (en) |
-
1980
- 1980-10-24 CA CA363,271A patent/CA1104155A/en not_active Expired
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