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Preparation of polyacrylic dyes.

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Die Angewandte Makromolekulare Ghemie 25 (1972) 97-103 ( N r . 339)
From the Chemical Laboratory of Textile Fibers, Kyoto University of Industrial
Arts and Textile Fibers, Matsugasaki, Sakyo-ku, Kyoto, Japan
Preparation of Polyacrylic Dyes*
By SEISHIMACHIDA,HIROSHINARITA,and KAZUO
KATO
(Eingegangen am 16. Dezember 1971)
SUMMARY:
Polyacrylic chloride was reacted with aminonaphthol sulfonic acid to give a
polymeric intermediate, from which the corresponding dyestuff was prepared by
coupling with an aromatic diazonium salt. The water-solubility of the polymeric
azo dye was found to depend mainly on the number of sulfonic groups in the molecular chain, and the colouring of dye was comparatively rich in variety. A copolymer of acrylic chloride with methyl methacrylate was directly reacted with a
dyestuff containing amino groups to give a polymeric dye. I n the molecular chain
of those polymeric dyes, the functional structure of the dyestuff was kept by its
incorporation t o the acrylic polymer chain.
ZUSAMMENFASSUNG :
I’olyacrylsiiurechlorid wurde mit Aminonaphtholsulfonsiiure umgesetzt, urn
ein polymeres Zwischenprodukt zu ergeben, woraus durch Kupplung mit einem
aromatischen Diazoniumsalz der entsprechende Azofarbstoff hergestellt wurde.
Die Loslichkeit der polymeren Azofarbstoffe in Wasser hiingt hauptsiichlich von
der Zahl der Sulfonsiiuregruppen in der Polymerkette ab. Die Farbe der polymeren
Azofarbstoffe war verhaltnisrniiljig mannigfaltig. Copolymere am Acrylsiiurechlorid und Methylmethacrylat wurden mit aminogruppenhaltigen Farbstoffen
zu polymeren Farbstoffen umgesetzt. Die funktionelle Farbstoffgruppe wird so
durch Einbau in die Makromolekule der Acrylpolymeren festgehalten.
Introduction
The synthesis of polymeric dyes is a n interesting theme with regard not
only t o the reactivity of polymer1 b u t also fastness of organic colourz.
In the previous papers39 4, vinyl monomers having a n aromatic substituent
were copolymerized with water-soluble comonomers, and the resulting copolymers were converted t o the polymeric dyes by some polymer reactions. As for
the copolymer of styrene, diazonium salts were formed on the phenyl groups
*
Stxdies of the water-soluble polymers, part 26.
97
S. MACHIDA,H. NARITA,
and K . KATO
in the polymer chain, and the polymeric azo dyes were synthesized by coupling
with other aromatic amines or naphthol$. On the other hand, the copolymer
of 2-methyl-N-vinyl-imidazole
which serves as a coupling component was
directly converted into the polymeric azo dyes by coupling with aromatic
diazonium compounds4.
The present paper deals with the synthesis of polymeric dyes by introducing
an intermediate or a dyestuff into the acrylic polymer chain.
Materials and Measurements
Acrylic acid and methyl methacrylate were purified and distilled.
Aminonaphthol sulfonic acids and amino group-containing dyestuffs were
obtained commercially.
All other chemicals used were of a guaranteed reagent grade.
UV and visible absorption spectra were taken with a Hitachi 124 type double
beam spectrophotometer.
Potentiometric titration was carried out with a Shimazu CT-2 type Potentiometric titration apparatus.
Preparation of Polyacrylic Chloride
Acrylic chloride was prepared by the reaction of acrylic acid with benzoyl
chloride in the presence of hydroquinone using the technique of sTEMPEL5.
The polymerization of acrylic chloride was carried out in dioxane solution
under nitrogen in a sealed glass tube a t 50 "C for 48 hrs. using azobisisobutyronitrile as an initiator. The conversion was determined by the titration of
polymer isolated as precipitation in water according to the method of SCHULZ~,
and the value of 84yo was obtained by averaging data. For the determination
of molecular weight of the polyacrylic chloride, the polymer was converted
to polymethyl acrylate by the polymer-analogous substitution with methanol
in the presence of triethyl amine a t 68°C for 12 hrs., followed by further
esterification with diazomethane. The viscosity of the polymethyl acrylate
in chloroform solution was determined a t 30"C,and the mean molecular weight
was calculated to be 4.3 x 104 by using the following equation7 :
rrll = 0.49 x 10-4 ~
0 ~ 8 2
The mean degree of polymerization, accordingly, is 530.
Preparation of Polymeric Intermediates
Polyacrylic chloride was reacted with J-acid (5-amino-2-naphthol-7-sulfonic acid), H-acid (l-amino-8-naphthol-3,6-disulfonic
acid) and SS-acid
(l-amino-8-naphthol-2,4-disulfonic
acid) respectively. As t o the reaction with
98
Polyacrylic Dyes
H-acid, for example, 0.027 mole of H-acid was suspended in about 100 ml of
water, and sodium hydroxide was added to the suspension to adjust the pH
to 8 - 9 and dissolve the H-acid completely. The solution was heated to
60 65 "C and 6.15 mole of polyacrylic chloride dissolved in 100 ml of dioxane
was dropped into the solution with stirring. At the same time, 0.033 mole of
sodium carbonate in 50 ml of water was also dropped. The reaction started
with generation of hydrogen chloride gas, and the solution became turbid.
After the dropping, the reaction mixture was heated for about 4 hrs. to extinguish the turbidity. The solution was then evaporated to about 50ml and
poured into 70 yo aqueous methanol. The polymeric intermediate precipitated
wats filtered, washed with methanol and dried. Yield 7 g. For the analysis, the
sample was purified by dialysis in running water for about two weeks. All the
polymeric intermediates thus prepared were of usually brownish colour but
soluble in water.
-
Practionution of Polymeric Intermediate by Gel-filtration Method
!Che polymeric intermediate obtained from the reaction of polyacrylic
chloride with H-acid, for instance, was fractionated by means of gel-filtration.
Sixty five mg of the sample were dissolved in one ml of water, and the solution
was poured into a column consisting of a glass tube of three cm diameter and
30 cm length, packed with about 50 g of Sephadex G-25 (50 100 mesh).
Eluant water was then run through the column with the constant flow rate of
80 ml/hr, and the eluates were collected in a fraction collector. Each fraction
was analyzed by visible spectrophotometry, and the weight of the fraction
was determined after freeze-drying. The relation between the absorbance a t
400 mp and weight of fraction and the volume of effluent is shown in Fig. 1.
The absorbance a t 400 m,u (elution diagram in Fig. 1 ) shows that the polymer chain carries aminonaphthol sulfonic acid groups as side chains.
-
0
Fig. 1.
50
I00
Effluent
I50
200
(ml)
Gel-filtration elution diagram of polymeric intermediate obtained from
reaction of polyacrylic chloride with H-acid (Sephadex G-25).
99
S. MACHIDA,H. NARITA,
and K. KATO
Preparation of Polymeric Dyes by Coupling Reaction
Sulfanilic acid, aniline, m-nitro-p-anisidine, m-nitro-o-toluidine, benzidine
and o-dianisidine were diazotized respectively and coupled with the polymeric
intermediate according to the procedure described in the previous papefi. The
dyestuffs prepared from the polymeric intermediates contained H-acid or SSacid as a side chain were generally soluble in water, except those coupled with
benzidine and o-dianisidine diazonium salts.
The dyestuff prepared from the intermediate containing J-acid residue,
however, was soluble in water only when it was coupled with sulfanilic acid
diazonium salt.
Other than those were generally insoluble in both water and most organic
solvents. The colours ofthe polymeric dyes prepared are summarized in Table 1.
Table 1. Colours of polymeric dyes.
Coupling
Diazo
J-acid
H-acid
SS-acid
component
Sulfanilic acid
red
orange-red
red
Aniline
red
red
reddish
m-Nitro-p-anisidine
violet
red
violet
reddish
m-Nitro-o-toluidine
reddish
violet
violet
Benzidine
violet
brownish
violet
brownish
violet
brownish
o-Dianisidine
brownish
brownish
brownish
violet
violet
violet
violet
violet
Preparation of Polymeric Dyes by Reaction of Copolymer of Acrylic Chloride
and Methyl Methacrylate with Dyestug
Acrylic chloride was copolymerized with methyl methacrylate in dioxane
solution under nitrogen a t 70°C for 6 hrs. using azobisisobutyronitde as an
initiator. The copolymer was isolated by pouring the reaction mixture into
water. The conversion was found t o be 39.1 yo,and the copolymer was analysed
to be composed of 21.2 mole-% of acrylic chloride units and 78.8 mole-% of
methyl methacrylate units by potentiometric titrationg. The copolymer was
reacted with the dyestuff containing amino groups in the molecule. The dyestuffs
100
Polyacrylic Dyes
used were Diacelliton Fast Orange GLFlo, Diacelliton Fast Pink BF", Celliton
Fast Blue FFB12 and Diacelliton Fast Violet 5RF13.
The reaction was carried out in a mixture of dioxane and acetone ( 2 : l )
a t room temperature for 24 hrs. The polymeric dye was isolated by pouring
the reaction mixture into water and purified, if desired, by extraction with
petroleum ether. The polymeric dyes were soluble in methanol, isopropyl
alcohol, acetone, ether and benzene, but insoluble in water and petroleum
ether. The acrylic chloride residue unreacted was hydrolyzed to acrylic acid
residue during the reaction, which was proved by IR spectrophotometry.
Frmtionution of Polymeric Dyes
The polymeric dyes obtained by the reaction of the copolymer with Diacelliton
Fast Blue FFB, for instance, was dissolved in dioxane and fractionated by a
column of Sephadex LH-29 as described above. The elution diagram is shown
in Fig. 2.
0
50
I00
Effluent
Fig. 2.
I50
(rnl)
200
Fractionation of polymeric dye obtained by reaction of acrylic chloride
methyl methamylate copolymer with Diacelliton Fast Blue FFB
(Sephadex LH-20).
I Polymeric dye (535 m p ) ,
I1 Oligomeric dye (670 mp),
I11 Oligomeric dye (510 mp),
IV Monomeric dye (490 mp),
V Unreacted dye (580 mp).
-
By the fractionation with gel-filtration, the fractions are effused in their
order of molecular weight; the polymeric dye is effused a t firsts. From the
fraction I in Fig. 2, the desired polymeric dye was isolated in a 83.6% yield.
The fractions 11, I11 and IV were by-products, and the fraction V was unreacted dyestuff. Absorption spectra of the fractions are shown in Fig. 3.
A s the fraction IV was assumed to be monomeric dye, a calibration curve
for the absorbance of the dye component was depicted in order to determine
101
S. MACHIDA,H. NARITA,
and K. KATO
L
400
500
Wave length
Fig. 3.
700
600
(mv)
Absorption spectrophotometry of the fractions of polymeric dye. Fig. 3
corresponds t o Fig. 2.
the content of the component in the molecular chain of polymeric dye of fraction I. It was thus found that the polymeric dye contains 2.2 yo of dye component. The structure of the polymeric dye was thus proposed to be a linear
copolymer chain composed of 78.8 mole-% of methyl methacrylate and 21.2
mole-% of acrylate units with, on the average, every a hundred units carring
a dyestuff residue. Accordingly, about 5 yo of the acrylic chloride residues in
the original copolymer were found to be reacted with the dyestuff.
Discussion
The polymerization of acrylic chloride was previously investigated in detail
and co-worker&. The polyacrylic chloride is considerably unstable
by SCHULZ
in isolated condition, and it is convenient to use the polymer for the subsequent reaction without purification. SCHULZ~
determined the molecular weight
of the polymer by converting it into polyacrylamide. But a conversion of the
polymer into polymethyl acrylate was used since, in our hand, it gave more
satisfactory results.
I n the preparation of the polymeric intermediate, the acid chloride group
of polyacrylic chloride is considered t o react with the amino group rather than
with the hydroxyl group of the aminonaphthol sulfonic acid, because the reaction is carried out under alkaline condition. A part of the acid chloride
groups is hydrolyzed to carboxylate groups. The polymeric intermediate fractionated by gel-filtration was shown to have the structure in which the functional portion of the aminonaphthol sulfonic acid is kept unchanged by its
bonding to acrylic polymer chain. By the use of fractionation with gel-filtra-
Polyacrylic Dyes
tion, monomeric and oligomeric intermediates can be removed to adjust the
chain length of the polymeric intermediate. The coupling reaction of the polymeric intermediate with an aromatic diazonium salt produces readily a polymeric azo dye. The water-solubility of the dye is mainly dependent on the
number of sulfonic groups in the molecular chain, and the carboxylic groups
and bulkiness of aryl side chains are also related to the solubility. The colouring of the polymeric azo dye is rather rich in variety, compared with those
reported previously3.
It was also found that the copolymer of acrylic chloride with other comonomer such as methyl methacrylate is directly reacted with a dyestuff
containing amino groups to give a polymeric dye, in which the functional
portion of the dyestuff is kept by its incorporation to vinyl polymer. The
polymer which is carrying, on the average, one dyestuff residue per one hundred
monomer units along the chain was prepared. The water-soluble polymeric
dyes will be useful €or the dyeing of textile fibres, and the water-insoluble dyes
will be available as organic pigments for blending with plastics. Those applications of the polymeric dyes will be published elsewhere.
1
2
3
4
5
W. KERNand R. C. SCHULZ,
Angew. Chem. 69 (1957) 157; W. KERN,H. HOLLANDER,
TH. HUCHE,
and R. SCHNEIDER,
Makromol. Chem. 22 (1957) 39.
H. KAMOGAWA,
J. Polymer Sci. A-1 7 (1969) 2458; G. MANECKEand G. KossMEHL,
Makromol. Chem. 80 (1964) 22.
S. MACHIDA,
K. AMATATSU,
N. MURATA,
and Y . SHIMURA,
J. SOC.org. synth.
Chem., Japan (YGki Gosei Kagaku Kyokai Shi) 23 (1965) 336; S. MACHIDAand
J. SANO,
J. SOC. Fiber Sci. Tech. Japan (Sen-iGakkaishi) 22 (1966) 173.
S. MACHIDA,
M. &=I,
and K. MATSUO,
J. appl. Polymer Sci. 12 (1968) 325.
G. H. STEMPEL,
R. P. CROSS,
and R. P. MARIELLA,
J. h e r . Chem. SOC.72 (1950)
2299.
6
7
8
9
10
11
l2
l3
R. C. SCHULZ,
P. ELZER,and W. KERN,Makromol. Chem. 42 (1960) 189,
197.
A. KATCHALSKY
and H. EISENBERG,
J. Polym. Sci. 6 (1950) 159.
P. FLODIN,
J. Chromatogr. (Amsterdam)5 (1961) 103.
S. SIGGIA,Quantitative Organic Analysis via Functional Groups, 3rd ed.,
#JohnWiley & Sons, New York 1963, p. 179.
Colour Index No. 11005.
Colour Index No. 60710.
Colour Index No. 62035.
Colour Index No. 61100.
103
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