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Organic fibres impregnated with polymerized aminotriazole complexes with transition metals
February
ELSEZIER
1997
Materials Letters 30 (1997) 249-25 1
Organic fibres impregnated with polymerized aminotriazole complexes with transition metals A. Lukasiewicz
*,
L. Walib
Institute of Nuclear Chemistry and Technology. Dorodna 16, 03-195 Warsaw, Poland
Received 23 May 1996; revised 4 September 1996, accepted 5 September 1996
Abstract Cellulose and polypropylene fibres were stably impregnated with polymerized aminotriazole complexes with transition metals. Impregnated fibres were effectively dyed with both anionic and basic dyes. These novel fibre materials are interesting for the textile industry and other uses. Keywords:
Organic
fibres; Polymerized
aminotriazole
complexes;
Transition
metals
1. Introduction
2. Polymerized aminotriazole complexes (MAXpI
In a previous paper [l], the impregnation of mineral supports with polymerized aminotriazole complexes with transition metals, denoted by MAXp, has been described. It was established that to attach MAXp to the support, anionic or acidic centres on its surface are necessary. Elevated temperature favours the impregnation, pointing out a coagulation mechanism of the impregnation process. We found in a further study that by using suitable procedures all kinds of fibres can be permanently impregnated with the MAXp complexes [2]. In this paper polypropylene and cellulose fibres impregnated with MAXp are described. Bath-dye ability, obtained due to impregnation with MAXp complexes, is a novel property of polypropylene fibres.
Preparation and properties of MAXp complexes have been described previously [ll. The complexes have the general formula MA, X?(p), where M is a transition metal (CL?+, Co2’, Ni”) or two different metals, A is the acetate anion, X stands for the 3-amino-1,2,4-triazole ligand (atr) and p for the complex polycondensed with formaldehyde. For impregnation of the fibres the copper complex (M = Cu2+ ) was used. The ligand atr has four nitrogen atoms:
* Corresponding
author.
00167-577X/97/$17.00 Copyright PII SOl67-577X(96)00205-4
According to literature data for solid 1,2,4-triazole and 4-amino- 1,2,4-triazole complexes with 0 1997 Elsevier Science B.V. All rights reserved.
250
A. tukusirwk,
L. Wali~/Materiuls
copper, the nitrogen atoms I and 2 are the ligand atoms in complexing metals [3-51. Two remaining nitrogen atoms of the atr ligand are certainly involved in the polycondensation of the MAX complex with formaldehyde.
3. Impregnation 3.1. Impregnation
of the fibres of cellulose fibres
When impregnating silica, clays and zeolites with MAXp, anionic (acidic for SiO,) centres initiate coagulation of the complex on the support surface. Cellulose contains always some amount of carboxyl groups [6], which can be able to initiate the coagulation of the MAXp complex. Binding of the CuAXp complex to cellulose fibres was examined. Commercial cotton wool was used as model cellulose fibre. A CuAXp concentrate [I] was diluted 100 X with water to a working solution, containing 2.5 mmol of the complexed copper in 1 litre. A cotton sample (1 g> was dipped into the CuAXp solution at room temperature for 15 min or at 80°C for 3 min. Complete binding of the complex by the fibre (disappearing of the complex from the solution) occurred, when 10 and 20 cm3 were used, at room temperature and at 80°C respectively. This corresponds to 25 and 50 moles of copper in the MAXp complex, bound by 1 g of the fibre. The green coloured cotton was washed with water and dried in air. High stability of the CuAXp layer bound to the fibre was demonstrated by dying of the impregnated cotton with anionic dyes, according to the procedures described below for polypropylene fibres. 3.2. Impregnation
of the polypropylene Jibre f PP)
PP fibre has no groups which can be able to initiate coagulation of the MAXp complex on its surface. In our experiments coagulation was initiated by addition of a coagulating substance to the CuAXp complex before impregnation of the fibre. Many anionic or acidic compounds can be used as coagulation additive in impregnation of the fibres with MAXp [2]. In our experiments poly(sodium-4styrenesulfonate) and polyacrylic acid (Aldrich) were used. A PP fibre (continuous filament) received from ‘ ‘Anilana’ ’ was used for impregnation.
Letteu 30 (1997) 249-253
A fibre sample (1 g) was heated in 10 cm3 of the diluted CuAXp complex, containing 0.2 cm3 of 1% aqueous solution of the coagulating compound, for 10 min at 80-90°C. Almost complete binding of the complex by the fibre occurred for both coagulating compounds, The greenish coloured fibre was washed with water and dried in air. The coagulating substances did not participate to a significant degree as constituents in the formation of the MAXp layer on the fibre (they were found in the post-impregnation liquid).
4. Dying of the impregnated
PP fibres
Several anionic compounds show affinity to MAXp complexes exchanging their acetate (A) anions [7]. The affinity of anionic compounds to impregnated fibres was investigated by using synthetic dyes. PP fibre has no dyeability in bath-dying procedures with anionic (and most other) dyes [8]. Dying of the impregnated fibre with anionic dyes should be ascribed, therefore, exclusively to a property of the MAXp layer. The dyes used (Aldrich) are listed in Table 1. The dying was carried out by heating on impregnated PP sample in 0.05% aqueous solution of a dye (commercial dyes were treated as 100% compounds) at 80°C for 3 min. Another procedure consisting in dying the fibre at room temperature in a bath containing 1% of acetic acid (I 0 min) was also used. In the latter procedure the colour was stabilized by dipping the dyed fibre (after washing it with water) in diluted CuAXp and then in hot water
Table I Anionic dyes used for dying impregnated No.
Commercial of the dye
I
Acid Red 88 Acid Red 97 Amaranth Acid Orange 8 Acid Orange 63 Acid Yellow 34 Chrysophenine Eriochrome Black T Acid Black 24
2 3 4 5 6
7 8 9
name
PP fibres
Amount of anionic (SO,Na) groups 1 2 3
1 2
I 2
I 2
A. tukasiewicz, Table 2 Relative dying efficiency of impregnated cationic and anionic dyes
L. WaliS/Materials
PP fibres with salts of
Cationic dye
Anionic dye (No.)
Dying efficiency
Methylene Blue
1,3,6 2, 5, 7 1, 374, 6 2, 5, I 1. 3.4, 6 2, 5, 7
+ ++ + ++ + ++ + ++
Maximilon Yoracryl
Blau 5G Black VSN
Yoracryl Yellow RL
8 9
a. b
’ + slight change of the colour of the anionic dye. b + + distinct change of the colour of the anionic dye.
(SO’C, 2 min). This procedure gave as a rule more intense colours than the first one. The dyed fibre samples were washed with warm synthetic washing agents. All the dyes listed in Table 1 gave stable to washing and relatively intense colours. The trianionic dye No. 3 was less effective. The impregnated PP fibre has no affinity for cationic dyes such as Methylene Blue and of Yoracryl or Maximilon type (used for dying acrylic fibres). However, salts of these dyes formed with anionic dyes are effective in dying impregnated PP fibre. The relative dying efficiency obtained when using these salts is shown in Table 2. The salts were prepared by mixing cationic and anionic dyes (0.05% solutions) in the proportion 1: 1. The dying was carried out on heating (SO’C, 3 min). Most effective were the salts formed by di-anionic dyes (with two SO,Na groups). They behave as typical anionic dyes in dying of the impregnated PP fibres. It was observed that several amines form combinations with MAXp, evidently by complexing metal M together with the ligand atr. The expected affinity of impregnated PP fibre to basic dyes was confirmed by effective dying with Mordant Brown 4 and Brilliant Green (80°C 3 min). The active sites in the MAXp complex are different for basic (by complexing the metal) and anionic (by exchanging A anions) compounds. Therefore a double dying of the impregnated fibres is possible.
Letters 30 (19971 249-251
251
Dying of the impregnated PP fibre with Brilliant Green followed by dying with anionic dyes listed in Table 1 confirmed the double dyeability of the fibres impregnated with MAXp. In all cases new, intense and stable colours were obtained. The results of the dying obtained for PP fibre are valid for all fibres impregnated with the CuAXp complex.
5. Conclusions Organic fibres are permanently impregnated with polymerized aminotriazole complexes with transition metals. Cellulose is impregnated by simple dipping in a MAXp solution at room or elevated temperature, whereas for impregnation of PP fibre addition of an anionic or acidic compound on heating is necessary. The impregnated fibres are effectively dyed with anionic as well as basic dyes. The effective surface dying of polypropylene fibre can be competitive to conventional methods of melt-dying. The presence of regions in the MAXp layer on the impregnated fibre, in which binding of anionic and basic compounds occurs, makes it possible to obtain fibres of novel properties, useful for diverse applications.
References Ill A. Lukasiewicz,
L. WaliS, J. Michalik and J. Sadlo, Mater. Lett., in press. I21 A. tukasiewicz, J. Panasiewicz and R. Szymilewicz, P. 3 11855 (12.1995). 131M. Inone and M. Kubo, Coor. Chem. Rev. 21 (1976) 1. [41J.A.J. Jarvis, Acta Crystallogr. 15 (1962) 964. I51J.G. Haasnoot, G. Vos and W.L. Groeneveld, 2. Naturforsch. 32b (1977) 1421. Ullmann’s Encyclopaedia of Industrial Chemistry, Vol. A5 ['51 (1987) p. 377. J. Michalik, J. Sadlo, T. Wasowicz and L. [71A. tukasiewicz WaliS, Report of the Institute of Nuclear Chemistry and Technology, Warsaw, INCT- l/94. of Industrial Chemistry, Vol. A10 k31Ullmann’s Encyclopaedia (Fibers) (1987).
ELSEZIER
1997
Materials Letters 30 (1997) 249-25 1
Organic fibres impregnated with polymerized aminotriazole complexes with transition metals A. Lukasiewicz
*,
L. Walib
Institute of Nuclear Chemistry and Technology. Dorodna 16, 03-195 Warsaw, Poland
Received 23 May 1996; revised 4 September 1996, accepted 5 September 1996
Abstract Cellulose and polypropylene fibres were stably impregnated with polymerized aminotriazole complexes with transition metals. Impregnated fibres were effectively dyed with both anionic and basic dyes. These novel fibre materials are interesting for the textile industry and other uses. Keywords:
Organic
fibres; Polymerized
aminotriazole
complexes;
Transition
metals
1. Introduction
2. Polymerized aminotriazole complexes (MAXpI
In a previous paper [l], the impregnation of mineral supports with polymerized aminotriazole complexes with transition metals, denoted by MAXp, has been described. It was established that to attach MAXp to the support, anionic or acidic centres on its surface are necessary. Elevated temperature favours the impregnation, pointing out a coagulation mechanism of the impregnation process. We found in a further study that by using suitable procedures all kinds of fibres can be permanently impregnated with the MAXp complexes [2]. In this paper polypropylene and cellulose fibres impregnated with MAXp are described. Bath-dye ability, obtained due to impregnation with MAXp complexes, is a novel property of polypropylene fibres.
Preparation and properties of MAXp complexes have been described previously [ll. The complexes have the general formula MA, X?(p), where M is a transition metal (CL?+, Co2’, Ni”) or two different metals, A is the acetate anion, X stands for the 3-amino-1,2,4-triazole ligand (atr) and p for the complex polycondensed with formaldehyde. For impregnation of the fibres the copper complex (M = Cu2+ ) was used. The ligand atr has four nitrogen atoms:
* Corresponding
author.
00167-577X/97/$17.00 Copyright PII SOl67-577X(96)00205-4
According to literature data for solid 1,2,4-triazole and 4-amino- 1,2,4-triazole complexes with 0 1997 Elsevier Science B.V. All rights reserved.
250
A. tukusirwk,
L. Wali~/Materiuls
copper, the nitrogen atoms I and 2 are the ligand atoms in complexing metals [3-51. Two remaining nitrogen atoms of the atr ligand are certainly involved in the polycondensation of the MAX complex with formaldehyde.
3. Impregnation 3.1. Impregnation
of the fibres of cellulose fibres
When impregnating silica, clays and zeolites with MAXp, anionic (acidic for SiO,) centres initiate coagulation of the complex on the support surface. Cellulose contains always some amount of carboxyl groups [6], which can be able to initiate the coagulation of the MAXp complex. Binding of the CuAXp complex to cellulose fibres was examined. Commercial cotton wool was used as model cellulose fibre. A CuAXp concentrate [I] was diluted 100 X with water to a working solution, containing 2.5 mmol of the complexed copper in 1 litre. A cotton sample (1 g> was dipped into the CuAXp solution at room temperature for 15 min or at 80°C for 3 min. Complete binding of the complex by the fibre (disappearing of the complex from the solution) occurred, when 10 and 20 cm3 were used, at room temperature and at 80°C respectively. This corresponds to 25 and 50 moles of copper in the MAXp complex, bound by 1 g of the fibre. The green coloured cotton was washed with water and dried in air. High stability of the CuAXp layer bound to the fibre was demonstrated by dying of the impregnated cotton with anionic dyes, according to the procedures described below for polypropylene fibres. 3.2. Impregnation
of the polypropylene Jibre f PP)
PP fibre has no groups which can be able to initiate coagulation of the MAXp complex on its surface. In our experiments coagulation was initiated by addition of a coagulating substance to the CuAXp complex before impregnation of the fibre. Many anionic or acidic compounds can be used as coagulation additive in impregnation of the fibres with MAXp [2]. In our experiments poly(sodium-4styrenesulfonate) and polyacrylic acid (Aldrich) were used. A PP fibre (continuous filament) received from ‘ ‘Anilana’ ’ was used for impregnation.
Letteu 30 (1997) 249-253
A fibre sample (1 g) was heated in 10 cm3 of the diluted CuAXp complex, containing 0.2 cm3 of 1% aqueous solution of the coagulating compound, for 10 min at 80-90°C. Almost complete binding of the complex by the fibre occurred for both coagulating compounds, The greenish coloured fibre was washed with water and dried in air. The coagulating substances did not participate to a significant degree as constituents in the formation of the MAXp layer on the fibre (they were found in the post-impregnation liquid).
4. Dying of the impregnated
PP fibres
Several anionic compounds show affinity to MAXp complexes exchanging their acetate (A) anions [7]. The affinity of anionic compounds to impregnated fibres was investigated by using synthetic dyes. PP fibre has no dyeability in bath-dying procedures with anionic (and most other) dyes [8]. Dying of the impregnated fibre with anionic dyes should be ascribed, therefore, exclusively to a property of the MAXp layer. The dyes used (Aldrich) are listed in Table 1. The dying was carried out by heating on impregnated PP sample in 0.05% aqueous solution of a dye (commercial dyes were treated as 100% compounds) at 80°C for 3 min. Another procedure consisting in dying the fibre at room temperature in a bath containing 1% of acetic acid (I 0 min) was also used. In the latter procedure the colour was stabilized by dipping the dyed fibre (after washing it with water) in diluted CuAXp and then in hot water
Table I Anionic dyes used for dying impregnated No.
Commercial of the dye
I
Acid Red 88 Acid Red 97 Amaranth Acid Orange 8 Acid Orange 63 Acid Yellow 34 Chrysophenine Eriochrome Black T Acid Black 24
2 3 4 5 6
7 8 9
name
PP fibres
Amount of anionic (SO,Na) groups 1 2 3
1 2
I 2
I 2
A. tukasiewicz, Table 2 Relative dying efficiency of impregnated cationic and anionic dyes
L. WaliS/Materials
PP fibres with salts of
Cationic dye
Anionic dye (No.)
Dying efficiency
Methylene Blue
1,3,6 2, 5, 7 1, 374, 6 2, 5, I 1. 3.4, 6 2, 5, 7
+ ++ + ++ + ++ + ++
Maximilon Yoracryl
Blau 5G Black VSN
Yoracryl Yellow RL
8 9
a. b
’ + slight change of the colour of the anionic dye. b + + distinct change of the colour of the anionic dye.
(SO’C, 2 min). This procedure gave as a rule more intense colours than the first one. The dyed fibre samples were washed with warm synthetic washing agents. All the dyes listed in Table 1 gave stable to washing and relatively intense colours. The trianionic dye No. 3 was less effective. The impregnated PP fibre has no affinity for cationic dyes such as Methylene Blue and of Yoracryl or Maximilon type (used for dying acrylic fibres). However, salts of these dyes formed with anionic dyes are effective in dying impregnated PP fibre. The relative dying efficiency obtained when using these salts is shown in Table 2. The salts were prepared by mixing cationic and anionic dyes (0.05% solutions) in the proportion 1: 1. The dying was carried out on heating (SO’C, 3 min). Most effective were the salts formed by di-anionic dyes (with two SO,Na groups). They behave as typical anionic dyes in dying of the impregnated PP fibres. It was observed that several amines form combinations with MAXp, evidently by complexing metal M together with the ligand atr. The expected affinity of impregnated PP fibre to basic dyes was confirmed by effective dying with Mordant Brown 4 and Brilliant Green (80°C 3 min). The active sites in the MAXp complex are different for basic (by complexing the metal) and anionic (by exchanging A anions) compounds. Therefore a double dying of the impregnated fibres is possible.
Letters 30 (19971 249-251
251
Dying of the impregnated PP fibre with Brilliant Green followed by dying with anionic dyes listed in Table 1 confirmed the double dyeability of the fibres impregnated with MAXp. In all cases new, intense and stable colours were obtained. The results of the dying obtained for PP fibre are valid for all fibres impregnated with the CuAXp complex.
5. Conclusions Organic fibres are permanently impregnated with polymerized aminotriazole complexes with transition metals. Cellulose is impregnated by simple dipping in a MAXp solution at room or elevated temperature, whereas for impregnation of PP fibre addition of an anionic or acidic compound on heating is necessary. The impregnated fibres are effectively dyed with anionic as well as basic dyes. The effective surface dying of polypropylene fibre can be competitive to conventional methods of melt-dying. The presence of regions in the MAXp layer on the impregnated fibre, in which binding of anionic and basic compounds occurs, makes it possible to obtain fibres of novel properties, useful for diverse applications.
References Ill A. Lukasiewicz,
L. WaliS, J. Michalik and J. Sadlo, Mater. Lett., in press. I21 A. tukasiewicz, J. Panasiewicz and R. Szymilewicz, P. 3 11855 (12.1995). 131M. Inone and M. Kubo, Coor. Chem. Rev. 21 (1976) 1. [41J.A.J. Jarvis, Acta Crystallogr. 15 (1962) 964. I51J.G. Haasnoot, G. Vos and W.L. Groeneveld, 2. Naturforsch. 32b (1977) 1421. Ullmann’s Encyclopaedia of Industrial Chemistry, Vol. A5 ['51 (1987) p. 377. J. Michalik, J. Sadlo, T. Wasowicz and L. [71A. tukasiewicz WaliS, Report of the Institute of Nuclear Chemistry and Technology, Warsaw, INCT- l/94. of Industrial Chemistry, Vol. A10 k31Ullmann’s Encyclopaedia (Fibers) (1987).