US3404941A - Vat dyeing with an aminoethyl-piperazine-dicarboxylic acid polyamide leveller - Google Patents
Vat dyeing with an aminoethyl-piperazine-dicarboxylic acid polyamide leveller Download PDFInfo
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- US3404941A US3404941A US200955A US20095562A US3404941A US 3404941 A US3404941 A US 3404941A US 200955 A US200955 A US 200955A US 20095562 A US20095562 A US 20095562A US 3404941 A US3404941 A US 3404941A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/655—Compounds containing ammonium groups
- D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
Definitions
- the invention is vat dyeing with a polyamide made from a water soluble condensate of N-aminoethyl piperazine and adipic acid. Other diamines and dibasic acids are also shown-The amide can be quaternized with dimethyl sulfate, ethylene chlorohydrin, 'glycolchlorohydrin or chloroacetic acid.
- the present invention relates to a process for the production of level vat dyeings, wherein polyamides are allowed to act on the fibrous material either during or after dyeing with vat dyestuffs, the said polyamides consisting mainly of:
- the polyamides can be prepared in the usual manner by polycondensation of the polyamines defined under (a) with dicarboxylic acids.
- the said polyamines contain at least three nitrogen atoms, of which at least one must be a tertiary or quaternary atom.
- polyamines of the formula group may form a heterocyclic ring.
- derivatives of dipropylenetriamine that is to say, polyamines of the Formula 1 whose N-alkylene-N-alkylene-N radical has the formula
- derivatives of triethylene tetraamine may also be used.
- cyano-alkyl radicals such as cyano-ethyl
- advantageously alkyl radicals such as methyl, ethyl, isopropyl and n-butyl.
- R and R can be identical or dilferent from one another. Two such substituents can also be joined together so that, together with an N-alkylene-N group, they form a heterocyclic ring
- the polyamines are advantageously condensed with aliphatic dicarboxylic acids; There are used for this purpose more especially the simple aliphatic acids that: contain at least 5 carbon atoms and that have the formula (4) HOOCC H COOH and more especially those of the formula (5) HOOC (CH COOH in which k represents a whole number of a value of at least 3, but preferably not more than 8. Examples are glutaric acid, suben'c acid, azelaic acid, sebacic acid and especially adipic acid.
- polyamides of the constitution defined above there can also be used poly: amines such as the dialkylenetriamine of the formula that do not contain a tertiary nitrogen atom, the secondary basic nitrogen atoms present being converted into tertiary atoms after polycondensation, for example, withthe aid of alkylatin'g or hydroxyalkylating agents, such as dimethyl sulfate or ethylenechlorohydrin.
- amines such as the dialkylenetriamine of the formula that do not contain a tertiary nitrogen atom, the secondary basic nitrogen atoms present being converted into tertiary atoms after polycondensation, for example, withthe aid of alkylatin'g or hydroxyalkylating agents, such as dimethyl sulfate or ethylenechlorohydrin.
- alkylatin'g or hydroxyalkylating agents such as dimethyl sulfate or ethylenechlorohydrin.
- the polyamides can be manufactured by a method in itself known, advantageously by heating the two reaction components in a molecular ratio of 1:1, if necessary in the presence of inert solvents and/or agents that split off water, such as toluene sulfonic acid. It is of advantage to WOIk in such a manner that only a low degree of condensation is achieved.
- the amount of reaction water should be at least 20 cc., advantageously about 25 cc. Thiscorresponds to an average degree ofcondensation of 2, that is to say, the linkage of 2 dicarboxylic acid molecules with 2 polyamine molecules. If con densation is taken further until approximately 29 cc. of water are split off, which corresponds to an average linkage of 3 dicarboxylic acid molecules with 3 polyamine molecules, the levelling action is generally not improved, but remains approximately the same.
- n represents a whole number of a value not greater than 2
- R R and R represent aliphatic radicals, whereby two such radicals, together with an group, can also form a heterocyclic ring.
- the alkylene groups are for example, n-propylene groups or advantageously ethylene groups.
- the polyamides of the aforesaid constitution are used as levelling agents for vat dyeings. They are specially suitable for cellulosic fibers and can be used in all cases where the dyestuii used and/ or the material dyed are expected to give rise to unlevel dyeings or have already given rise to unlevel dyeing.
- the polyamides can be added to the dyebaths so that they exert a levelling action during the dyeing process.
- unlevel vat dyeings can subsequently be levelled up with the assistance of the polyamides in an alkaline bath that contains hydrosulfite.
- the quantity of polyamide that can be added to the treatment baths can vary between fairly wide limits; the quantity used is advanageously 0.25 to 5 parts of polyamide per 1000 parts by volume of water.
- Example 1 A dyebath is prepared from 1000 parts of water, 16 parts of sodium hydroxide solution of 30% strength, 2 parts of sodium hydrosulfite, 0.1 part of the dyestuif of the formula Qggb (--01),
- the polyamide is manufactured as follows: A reaction mixture consisting of 146 parts of adipic acid (1 mol), 126 parts of N-amino-ethylpiperazine of Formula 3 (1 mol), 1.5 parts of para-toluene-sulfonic acid and 500 parts of xylene is allowed to boil for hours while a current of nitrogen is passed through it, and the water that is formed is continually removed with the assistance of a suitable separator. After this period, there are about parts of water in the separator. The xylene is then distilled off in vacuo. A highly viscous mass remains which is dissolved in the same amount by weight of water, thus giving a solution of the polyamide. g
- a polyamide in place of this polyamide, when dyeing according to the instructions given in the first paragraph of this example, a polyamide can be used that is obtained by maintaining the aforesaid reaction components at 160 to 165 C. for about 7 hours, without a solvent andwith a descending condenser until 29 parts of water have collected .inmthe receiver which is. cooled with ice, and. then dissolving the reaction product so obtained in water in the same manner.
- Example 2 1 mol of tetrabromo-pyranthrone 2 mols 0f l-amino-anthraquinone black 2 mols of amino-dibenzanthrone
- Example 2 The same procedure is adopted as described in Example 1, but one of the polyamides described below under A, B and C is used. A levelling action is likewise obtained.
- Example 3 An unlevel dyeing on cotton tricot produced with 0.5% of the green dyestutf of the formula is treated for 1 hour at 60 C. in a goods-to-liquor ratio (1 mol), 1.5 parts of para-toluenesulfonic acid and 500 parts of xylene is maintained at the boil for 20 hours while a current of nitrogen is passed through, and the water that is formed is continually removed with the aid of a suitable separator. After this period, there are about 20 parts of water in the separator. Xylene is distilled away from the polyamide so formed, which is insoluble in xylene, and the residue is maintained at about 160 C. for 5 hours under a reduced pressure of about 50 mm. Hg. The viscous product so obtained is then dissolved in the same amount by weight (about 250 parts) of water.
- An unlevel dyeing produced with the blue dyestuff of the Formula 9 can also be levelled up in the same manner.
- Example 4 10 parts of cotton satin are dyed for 1 hour at 60 C. in a dyebath prepared from 800 parts of water, 13 parts by volume of a sodium hydroxide solution of 30% strength, 1.6 parts of sodium hydrosulfite, 0.3 part of a concentrated aqueous paste of a dyestuff that is obtained from methyl benzanthrone by sulfur fusion, and 0.8 part of one of the preparations described below under D, E or F. The dyeing is then oxidized and finished in the usual manner. A level blue dyeing is obtained.
- Example 5 Dyeing is carried out by the method described in Example 4, but there is used 0.05 part of a dyestuff (obtained by the alkaline fusion of benzanthrone with subsequent bromination) in the form of a finely dispersed powder, or 0.05 part of the dyestuff of the formula likewise in the form of a finely dispersed powder, and, as levelling agent, there is used 0.8 part of one of the preparations G or H described below. The dyeings obtained are level.
- the preparations G and H are prepared in the following manner:
- a process for the production of level vat dyeings which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CH -CH,
- a process for the production of level vat dyeings which comprises applying to the fibrous material in com: bination with the vat dyestuff as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CH -CH: HN ⁇ N-GHr-CHz-NI-Iz GHQ-H2 and of (b) about 1 mol of adipic acid.
- a process for the production of level vat dyeings which comprises applying to the fibrous material in combination with the vat dyestutf as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula GHQ-CH5 /N-CH OH -NH GET-GHQ and of (b) about 1 mol of adipic acid, the average condensation degree being at least 2 and at most 3.
- a process for the production of level vat dyeings which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent the quaternary ammonium compound from dimethyl sulfate and a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula and of (b) about 1 mol of adipic acid.
- a process for the production of level vat dyeings which comprises applying to the fibrous material in combination with the vat dyestuif as a levelling agent the quaternary ammonium compound from glycolchlorohydrin and a low molecular polyamide obtained from condensation of (a) about l mol of a polyamine of the formula CH2CHz I HN N-CHECHr-NH GHQ-CH2 and of (b) about 1 mol of adipic acid.
- a process for the production of level vat'dyeings which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent the quaternary ammonium compound from chloracetic acid amide and a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CHz-CH:
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Description
Un d St t s Pat n 3,404,941 VAT DYEING WITH AN AMINOETHYL-PIPER- AZINE-DICARBOXYLIC ACID POLYAMIDE LEVELLER Alfred Berger, Basel, Switzerland, assignor -to Ciba Limited, Basel," Switzerland, a Swiss 1 39) No Drawing. Filed June 8,. 1962, Ser. No. 200,955 Claims priori ,.-application Switzerland,
6 Claims. (Cl. 8-34) ABSTRACT OF THE DISCLOSURE The invention is vat dyeing with a polyamide made from a water soluble condensate of N-aminoethyl piperazine and adipic acid. Other diamines and dibasic acids are also shown-The amide can be quaternized with dimethyl sulfate, ethylene chlorohydrin, 'glycolchlorohydrin or chloroacetic acid.
The present invention relates to a process for the production of level vat dyeings, wherein polyamides are allowed to act on the fibrous material either during or after dyeing with vat dyestuffs, the said polyamides consisting mainly of:
(a) Structural elements of polyamides that contain at least one tertiary or quaternary nitrogen atom and at least two nitrogen atoms bound to hydrogen, and
(b) Structural elements of dicarboxylic acids.
The polyamides can be prepared in the usual manner by polycondensation of the polyamines defined under (a) with dicarboxylic acids. The said polyamines contain at least three nitrogen atoms, of which at least one must be a tertiary or quaternary atom. In general, it is advantageous to start with polyamines having tertiary nitrogen atoms and then to quaternate the polyamide, so far as a levelling agent with quaternary nitrogen atoms is desired. It is advantageous tofchoose aliphatic polyamides, or polyamides which, in addition to another radical, for example, an alicyclic or heterocyclic radical, contain at least one 'alkylene radical.
There are used, for example, polyamines of the formula group may form a heterocyclic ring. Preference is given to derivatives of dipropylenetriamine, that is to say, polyamines of the Formula 1 whose N-alkylene-N-alkylene-N radical has the formula There may also be used derivatives of triethylene tetraamine. The dialkylene triamines of the Formula 1 contain one (m!=1; n'=1) to three (m=2; n=2) aliphatic substituents, for example, cyano-alkyl radicals, such as cyano-ethyl, or advantageously alkyl radicals, such as methyl, ethyl, isopropyl and n-butyl. The substituents R June 12, 1961,
Patented Oct. 8, 1968 R and R can be identical or dilferent from one another. Two such substituents can also be joined together so that, together with an N-alkylene-N group, they form a heterocyclic ring The polyamines are advantageously condensed with aliphatic dicarboxylic acids; There are used for this purpose more especially the simple aliphatic acids that: contain at least 5 carbon atoms and that have the formula (4) HOOCC H COOH and more especially those of the formula (5) HOOC (CH COOH in which k represents a whole number of a value of at least 3, but preferably not more than 8. Examples are glutaric acid, suben'c acid, azelaic acid, sebacic acid and especially adipic acid.
As starting materials for certain polyamides of the constitution defined above there can also be used poly: amines such as the dialkylenetriamine of the formula that do not contain a tertiary nitrogen atom, the secondary basic nitrogen atoms present being converted into tertiary atoms after polycondensation, for example, withthe aid of alkylatin'g or hydroxyalkylating agents, such as dimethyl sulfate or ethylenechlorohydrin. As already mentioned, the procedure can be taken a step further and the tertiary nitrogen atoms quaternated, for example,
with the agents just mentioned.
The polyamides can be manufactured by a method in itself known, advantageously by heating the two reaction components in a molecular ratio of 1:1, if necessary in the presence of inert solvents and/or agents that split off water, such as toluene sulfonic acid. It is of advantage to WOIk in such a manner that only a low degree of condensation is achieved. Thus, in the reaction of 1 mol of a dicarboylic acid with 1 mol of polyamine, the amount of reaction water should be at least 20 cc., advantageously about 25 cc. Thiscorresponds to an average degree ofcondensation of 2, that is to say, the linkage of 2 dicarboxylic acid molecules with 2 polyamine molecules. If con densation is taken further until approximately 29 cc. of water are split off, which corresponds to an average linkage of 3 dicarboxylic acid molecules with 3 polyamine molecules, the levelling action is generally not improved, but remains approximately the same.
Some polyamides of the constitution defined above are known. These polyamides are new that consist princi-,
pally of (a) Structural elements of polamines that contain at in which at least one of the nitrogen atoms is a tertiary atom, n represents a whole number of a value not greater than 2, and R R and R represent aliphatic radicals, whereby two such radicals, together with an group, can also form a heterocyclic ring. The alkylene groups are for example, n-propylene groups or advantageously ethylene groups.
Also in the case of the new polyamides there are primarily used as structural elements of dicarboxylic acids, those which have already been mentioned above as being specially valuable.
In accordance with the invention, the polyamides of the aforesaid constitution are used as levelling agents for vat dyeings. They are specially suitable for cellulosic fibers and can be used in all cases where the dyestuii used and/ or the material dyed are expected to give rise to unlevel dyeings or have already given rise to unlevel dyeing. For example, the polyamides can be added to the dyebaths so that they exert a levelling action during the dyeing process. On the other hand, unlevel vat dyeings can subsequently be levelled up with the assistance of the polyamides in an alkaline bath that contains hydrosulfite. The quantity of polyamide that can be added to the treatment baths can vary between fairly wide limits; the quantity used is advanageously 0.25 to 5 parts of polyamide per 1000 parts by volume of water.
Unless otherwise stated, the parts and percentages in the following examples are by weight, and the temperatures are given in degrees centigrade.
Example 1 A dyebath is prepared from 1000 parts of water, 16 parts of sodium hydroxide solution of 30% strength, 2 parts of sodium hydrosulfite, 0.1 part of the dyestuif of the formula Qggb (--01),
and 1 part of a 50% solution of a polyamide, the manufacture of which is described below. 100 parts of cotton yarn on cheeses are dyed for one hour at 50 to 60 C. in the bath so prepared. The dyeings are then oxidised and finished in the usual manner. The yarn 0n the cheeses is dyed violet and is very well penetrated by the dyestuif, which is in contrast to a dyeing carried out in the same manner but without the addition of the polyamide.
The polyamide is manufactured as follows: A reaction mixture consisting of 146 parts of adipic acid (1 mol), 126 parts of N-amino-ethylpiperazine of Formula 3 (1 mol), 1.5 parts of para-toluene-sulfonic acid and 500 parts of xylene is allowed to boil for hours while a current of nitrogen is passed through it, and the water that is formed is continually removed with the assistance of a suitable separator. After this period, there are about parts of water in the separator. The xylene is then distilled off in vacuo. A highly viscous mass remains which is dissolved in the same amount by weight of water, thus giving a solution of the polyamide. g
In place of this polyamide, when dyeing according to the instructions given in the first paragraph of this example, a polyamide can be used that is obtained by maintaining the aforesaid reaction components at 160 to 165 C. for about 7 hours, without a solvent andwith a descending condenser until 29 parts of water have collected .inmthe receiver which is. cooled with ice, and. then dissolving the reaction product so obtained in water in the same manner.
A good levelling action is also obtained with the following dyestuffs just as well as withvthe dyestuit of the Formula 8 f 1 Q- n I violet I NH 0 t 0 blue I NH 0 01 blue H II 0 blue EN l o t? 2 blue black (14) Polyanthrimide derived from:
1 mol of tetrabromo-pyranthrone 2 mols 0f l-amino-anthraquinone black 2 mols of amino-dibenzanthrone Example 2 The same procedure is adopted as described in Example 1, but one of the polyamides described below under A, B and C is used. A levelling action is likewise obtained.
(A) 146 parts of adipic acid (1 mol), 208 parts of the compound of the Formula 6 (1 mol), which is obtained by the additive combination of 2 molecules of acrylonitrile with 1 molecule of diethylene-triamine, and 1.5 parts of para-toluenesulfonic acid are heated to 160 C. in a reaction vessel equipped with a stirrer and descending condenser. The mixture becomes viscous after A to 1 hour, but can still be stirred easily. The mixture is cooled to C., 10 parts of ethylene glycol are added,
and the mixture is further cooled to 120 C. The descending'condenser is then replaced by a reflux condenser, whereupon 126 parts of dimethylsulfate (1 mol) are slowly added dropwise, and the mixture is maintained at 120 to 130 C. for a further 1 to 2 hours. The heating bath is then removed, and 240 parts of water are slowly added, the saidwater being immediately taken up by the reaction product. After cooling there are obtained about 694 parts of a solution with a polyamide content of about 50%.
(B) 146 parts of adipic acid (1 mol), 126 parts of amino-ethylpiperazine of the Formula 3 (1 mol) and 1.5 parts of para-toluenesulfonic acid are maintained at 160 to 165 C.. for 3 to 4 hours in a reaction vessel with a descending condenser while stirring. After this period, there are 26 parts of water in the receiver, which is cooled with ice. The reaction mixture is then cooled to 130 to 140 C. and, after the addition of 20 parts of ethylene glycol, it is cooled to 120 C. 126 parts of dimethyl sulfate (1 mol) are then allowed to run in slowly at that temperature, and stirring is continued for a further 2 hours at 120 to 130 C. 120 parts of water are then added. After cooling, there are obtained about 504 parts of a clear, viscous solution that contains about 50% of polyamide.
(C) 132 parts of glutaric acid (1 mol), 126 parts of amino-ethylpiperazine of the Formula 3 (1 mol) and 1.5 parts of para-toluenesulfonic acid are maintained at about 160 C. for 4 hours in a reaction vessel with a descending condenser while stirring. The reaction mixture is then allowed to cool to 140 C., whereupon 20 parts of ethylene glycol are added, and the mixture is allowed to cool further to 130 C. After 210 parts of water have been added and the mixture has cooled to room temperature, there is obtained a clear, viscous solution (460 parts) that contains about 50% of polyamide.
Example 3 An unlevel dyeing on cotton tricot produced with 0.5% of the green dyestutf of the formula is treated for 1 hour at 60 C. in a goods-to-liquor ratio (1 mol), 1.5 parts of para-toluenesulfonic acid and 500 parts of xylene is maintained at the boil for 20 hours while a current of nitrogen is passed through, and the water that is formed is continually removed with the aid of a suitable separator. After this period, there are about 20 parts of water in the separator. Xylene is distilled away from the polyamide so formed, which is insoluble in xylene, and the residue is maintained at about 160 C. for 5 hours under a reduced pressure of about 50 mm. Hg. The viscous product so obtained is then dissolved in the same amount by weight (about 250 parts) of water.
An unlevel dyeing produced with the blue dyestuff of the Formula 9 can also be levelled up in the same manner.
Example 4 10 parts of cotton satin are dyed for 1 hour at 60 C. in a dyebath prepared from 800 parts of water, 13 parts by volume of a sodium hydroxide solution of 30% strength, 1.6 parts of sodium hydrosulfite, 0.3 part of a concentrated aqueous paste of a dyestuff that is obtained from methyl benzanthrone by sulfur fusion, and 0.8 part of one of the preparations described below under D, E or F. The dyeing is then oxidized and finished in the usual manner. A level blue dyeing is obtained.
The preparations mentioned above are obtained in the following manner:
(D) 174 parts of su-beric acid (1 mol), 126 parts of N-amino-ethyl-piperazine (1 mol) and 1.5 parts of paratoluenesulfonic acid are maintained at 160 to 165 C. for 4 to 5 hours in a reaction vessel with a descending condenser while stirring. After the reaction mixture has cooled to 140 C., 10 parts of ethylene glycol are added, after which 260 parts of water are added, when the reaction mixture has cooled to 130 C.
There is obtained a clear, viscous solution that contains about 50% of polyamide.
(E) 188 parts of azel-aic acid (1 mol) and 126 parts of N-amino-ethyl-piperazine (1 mol) are reacted in the presence of 1.5 parts of para-toluenesulfonic acid in the same manner as in the manufacture of preparation D. 26 parts of water collect in the receiver. 10 parts of ethylene glycol are added at C., and then 275 parts of water are added at 130 C., whereupon a clear solution is obtained.
(F) 202 parts of sebacic acid (1 mol), 252 parts (1 mol) of the reaction product of 1 part of triethylenetetramine and 2 moles of acrylonitrile and 1.5- parts of para-toluenesulfonic acid are maintained at 160 C. with a descending condenser while stirring until the reaction mixture becomes viscous, but is still easily stirred. 252 parts of dimethyl sulfate (2 mols) are added dropwise at 140 to C., and the reaction mixture is then maintained at 120 to 130 C. for 2 hours. After dissolving in 240 parts of water there is obtained a preparation that contains about 50% of polyamide.
Example 5 Dyeing is carried out by the method described in Example 4, but there is used 0.05 part of a dyestuff (obtained by the alkaline fusion of benzanthrone with subsequent bromination) in the form of a finely dispersed powder, or 0.05 part of the dyestuff of the formula likewise in the form of a finely dispersed powder, and, as levelling agent, there is used 0.8 part of one of the preparations G or H described below. The dyeings obtained are level.
The preparations G and H are prepared in the following manner:
(G) 146 parts of adipic acid (1 mol), 126 parts of N-amino-ethyl-piperazine (1 mol) and 1.5 parts of paratoluenesulfonic acid are maintained at to C. for 3 to 4 hours in a reaction vessel with a descending condenser until 26 parts of water have collected in the receiver. The reaction mixture is then allowed to cool to 130 C., whereupon 247 parts of butylene glycol are added, in which the reaction mixture dissolves.
After cooling, there are obtained 492 parts of a paste that contains 50% of polyamide (preparation G 49.2 parts (1 mol) of the preparation G 50 obtained are heated to 100 C. in a vessel equipped with stirrer and refiux condenser, and 8.8 parts (1.1 mol) of glycolchlorohydrin are then added dropwise. The reaction mixture is maintained at 110 to 115 C. for 6 hours. There is obtained a preparation of which a considerable proportion comprises the quaternation product of the polyamide used.
(H) 49.2 parts (1 mol) of the preparation G described in the manufacture of preparation G are quaternated with 10 parts (1.05 mol) of chloracetic acid amide for 4 hours at 60 to 65 C. and then for 2 hours at 90 to 95 C.
What is claimed is:
1. A process for the production of level vat dyeings, which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CH -CH,
HN N-CH CHg--NH1 CHrCHz and of (b) about 1 mol of a dicarboxylic acid of the formula HOOC-(CH COOH in which k represents a whole number of at least 3 and at the most 8.
2. A process for the production of level vat dyeings, which comprises applying to the fibrous material in com: bination with the vat dyestuff as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CH -CH: HN\ N-GHr-CHz-NI-Iz GHQ-H2 and of (b) about 1 mol of adipic acid.
3. A process for the production of level vat dyeings, which comprises applying to the fibrous material in combination with the vat dyestutf as a levelling agent a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula GHQ-CH5 /N-CH OH -NH GET-GHQ and of (b) about 1 mol of adipic acid, the average condensation degree being at least 2 and at most 3.
4. A process for the production of level vat dyeings, which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent the quaternary ammonium compound from dimethyl sulfate and a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula and of (b) about 1 mol of adipic acid.
5. A process for the production of level vat dyeings, which comprises applying to the fibrous material in combination with the vat dyestuif as a levelling agent the quaternary ammonium compound from glycolchlorohydrin and a low molecular polyamide obtained from condensation of (a) about l mol of a polyamine of the formula CH2CHz I HN N-CHECHr-NH GHQ-CH2 and of (b) about 1 mol of adipic acid.
6. A process for the production of level vat'dyeings, which comprises applying to the fibrous material in combination with the vat dyestuff as a levelling agent the quaternary ammonium compound from chloracetic acid amide and a low molecular polyamide obtained from condensation of (a) about 1 mol of a polyamine of the formula CHz-CH:
and of (b) about 1 mol of adipic acid.
References Cited UNITED STATES PATENTS 2,091,105 8/1937 Piggott 8-34 2,931,272 4/1960 Haas 8-100X 2,984,539 5/1961 Matter 83 2,487,197 11/1949 Stott et al. 834 2,541,839 2/ 1951 Sharkey 260268 2,958,693 11/ 1960 Phillips 260-268 2,958,694 11/ 1960 Janssen 260-268 FOREIGN PATENTS 536,686 5/ 1941 Great Britain.
834,393 5/1960 Great Britain.
784,191 10/1951 Great Britain.
NORMAN G. TORCHIN, Primary Examiner.
D. LEVY, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,404,941 October 8, 1968 Alfred Berger I It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 7, lines 47 to 50, the right-hand portion of the formula should read -CH -CH -NH Signed and sealed this 24th day of February 1970.
(SEAL) Attest:
Edward M. Fletcher, Jr.
Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH689161A CH380078A (en) | 1961-06-12 | 1961-06-12 | Use of polyamides as leveling agents for vat dyeing |
Publications (1)
Publication Number | Publication Date |
---|---|
US3404941A true US3404941A (en) | 1968-10-08 |
Family
ID=4316680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US200955A Expired - Lifetime US3404941A (en) | 1961-06-12 | 1962-06-08 | Vat dyeing with an aminoethyl-piperazine-dicarboxylic acid polyamide leveller |
Country Status (4)
Country | Link |
---|---|
US (1) | US3404941A (en) |
CH (1) | CH380078A (en) |
ES (1) | ES278193A1 (en) |
GB (1) | GB970564A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10550227B2 (en) | 2014-07-01 | 2020-02-04 | Arkema France | Polyamides based on aminoalkylpiperazine or aminoarylpiperazine for hot-melt adhesives |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2091105A (en) * | 1933-02-15 | 1937-08-24 | Ici Ltd | Textile assistants and process for preparing the same |
GB536686A (en) * | 1939-11-22 | 1941-05-23 | Courtaulds Ltd | Improvements in or relating to the treatment of cellulosic textile materials |
US2487197A (en) * | 1944-03-11 | 1949-11-08 | Du Pont | Process for dyeing textile fibers with vat dyes |
US2541839A (en) * | 1949-07-22 | 1951-02-13 | Du Pont | Process for improving vat dyed nylon fibers |
GB784191A (en) * | 1954-12-08 | 1957-10-02 | Rhodiaceta | Improvements in or relating to the dyeing of mixed textile materials |
US2931272A (en) * | 1955-08-03 | 1960-04-05 | Polaroid Corp | Sheet stock for dichroic dye light-polarizing means |
GB834393A (en) * | 1957-07-10 | 1960-05-04 | Basf Ag | Dyeing textiles with vat or sulphur dyestuffs |
US2958694A (en) * | 1959-06-22 | 1960-11-01 | Janssen Paul Adriaan Jan | 1-(aroylalkyl)-4-(2'-pyridyl) piperazines |
US2958693A (en) * | 1957-10-31 | 1960-11-01 | Burroughs Wellcome Co | C-substituted piperazine derivatives and method |
US2984539A (en) * | 1957-01-14 | 1961-05-16 | Ciba Ltd | Process for dyeing polyacrylonitrile material |
-
1961
- 1961-06-12 CH CH689161A patent/CH380078A/en unknown
-
1962
- 1962-06-06 GB GB21969/62A patent/GB970564A/en not_active Expired
- 1962-06-08 US US200955A patent/US3404941A/en not_active Expired - Lifetime
- 1962-06-11 ES ES278193A patent/ES278193A1/en not_active Expired
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2091105A (en) * | 1933-02-15 | 1937-08-24 | Ici Ltd | Textile assistants and process for preparing the same |
GB536686A (en) * | 1939-11-22 | 1941-05-23 | Courtaulds Ltd | Improvements in or relating to the treatment of cellulosic textile materials |
US2487197A (en) * | 1944-03-11 | 1949-11-08 | Du Pont | Process for dyeing textile fibers with vat dyes |
US2541839A (en) * | 1949-07-22 | 1951-02-13 | Du Pont | Process for improving vat dyed nylon fibers |
GB784191A (en) * | 1954-12-08 | 1957-10-02 | Rhodiaceta | Improvements in or relating to the dyeing of mixed textile materials |
US2931272A (en) * | 1955-08-03 | 1960-04-05 | Polaroid Corp | Sheet stock for dichroic dye light-polarizing means |
US2984539A (en) * | 1957-01-14 | 1961-05-16 | Ciba Ltd | Process for dyeing polyacrylonitrile material |
GB834393A (en) * | 1957-07-10 | 1960-05-04 | Basf Ag | Dyeing textiles with vat or sulphur dyestuffs |
US2958693A (en) * | 1957-10-31 | 1960-11-01 | Burroughs Wellcome Co | C-substituted piperazine derivatives and method |
US2958694A (en) * | 1959-06-22 | 1960-11-01 | Janssen Paul Adriaan Jan | 1-(aroylalkyl)-4-(2'-pyridyl) piperazines |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10550227B2 (en) | 2014-07-01 | 2020-02-04 | Arkema France | Polyamides based on aminoalkylpiperazine or aminoarylpiperazine for hot-melt adhesives |
Also Published As
Publication number | Publication date |
---|---|
ES278193A1 (en) | 1963-01-16 |
CH380078A (en) | 1962-12-29 |
GB970564A (en) | 1964-09-23 |
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