Polymer Degradation and Stability 94 (2009) 604–609

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Chemical recycling of PET waste into hydrophobic textile dyestuffs

S.R. Shukla*, Ajay M. Harad, Laxmikant S. Jawale
Department of Fibers and Textile Processing Technology, Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, Maharashtra, India

a r t i c l e i n f o a b s t r a c t

Article history: The paper aims at effective chemical recycling of poly(ethylene terephthalate) (PET) fiber waste into
Received 11 December 2008 useful products, such as hydrophobic disperse dyes for synthetic textiles. For this, PET fiber waste was
Received in revised form glycolytically depolymerized using excess of ethylene glycol in the presence of sodium sulfate as catalyst.
6 January 2009
The product, pure bis(2-hydroxyethylene terephthalate) (BHET) was obtained with >60% yield by
Accepted 9 January 2009
successive recrystallization. In order to synthesize hydrophobic disperse dyes, applicable to synthetic
Available online 18 January 2009
textile fibers, BHET was converted to bis(2-chloroethylene terephthalate), reacted with the p-nitro
benzoic acid, reduced and then reacted with bromine and potassium thiocyanate to get benzothiazole
Keywords:
PET fiber waste derivative. Coupling with N,N-diethylaniline produced a bright yellow disperse dye (Dye A). Similarly,
Glycolysis coupling of p-amino benzoic ester with N,N-diethylaniline led to an orange colored disperse dye (Dye B).
BHET These dyes were applied onto polyester fabric by conventional method. Results in terms of depth of
Benzothiazole dyeing, evenness and the performance characteristics were found to be promising.
Disperse dye Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction high purity virtual monomer BHET [8,9] having a potential of

conversion into chemicals of utility.
Poly(ethylene terephthalate) (PET) is a semi-crystalline ther- Literature indicates that the product of PET waste depolymer-
moplastic polyester widely used in the manufacture of apparel ization can be made use of in various applications such as unsat-
fibers, disposable soft-drink bottles, photographic films, etc. It is urated polyesters [10,11], polyurethane foam [12], copolyesters
used largely in the production of textile fibers since mid-1940s. The [13], polyurethane coatings [14], alkyd resins [15], low temperature
world production of PET in 2002 was 26 million tons which is curable resins [16], UV curable resins [17], etc. We have reported
expected to rise to 55 million ton in 2010 [1]. In 1980s, PET also the synthesis of a cationic softener for cotton fabric from BHET
began to be used popularly for the production of disposable soft- obtained through glycolysis of PET fiber waste [18].
drink bottles with a high growth rate [2]. Although the nontoxic The hydrophobic disperse dyes are the only ones that can impart
nature, durability and crystal clear transparency of PET during use color to polyester textiles that cover about 40% of apparel market.
are major advantages, its nonbiodegradability is the serious cause They can also be used on nylon, cellulose acetate and acrylic fiber
of concern to the environmentalists. PET accounts for more than 8% materials [19]. They are sparingly water soluble and applied from
by weight and 12% by volume of the world’s solid waste [3]. Since their aqueous dispersion. About 70% of these dyes contain azo
land filling of such nonbiodegradable waste has severe limitations, chromophore which is obtained through azo coupling reactions.
chemical recycling is the best possible alternative. The major The present communication deals with the recycling of PET fiber
sources of PET fiber waste generation are the manufacturing waste waste through glycolytic depolymerization to obtain pure BHET and
and the post-consumer waste. then converting it into disperse dyes useful for coloration of poly-
One of the chemical recycling techniques comprises of glycolytic ester fabric.
depolymerization of PET waste, conventionally carried out in
boiling ethylene glycol under atmospheric pressure using metal
acetate catalyst to obtain the virtual monomer bis(2-hydroxy- 2. Experimental
ethylene terephthalate) (BHET) [4–7]. Our studies have shown that
simple and ecofriendly chemicals may be used as catalyst to obtain 2.1. Materials

2.1.1. Fiber waste

* Corresponding author. Tel.: þ91 22 24145616; fax: þ91 22 24145614. PET fiber manufacture waste of 1.44 denier and various lengths
E-mail address: [email protected] (S.R. Shukla). up to 5 mm was obtained from Reliance Industries (Mumbai, India).

0141-3910/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2009.01.007
 S.R. Shukla et al. / Polymer Degradation and Stability 94 (2009) 604–609 605

O O O
COOH COCl C O CH2CH2OH C O CH2CH2OC NO2

SOCl2 Pyridine
+

NO2 NO2 C O CH2CH2OH C O CH2CH2OC NO2

O O O
Compound 1 Compound 2

10% Pd/C
Reduction
3.52 kg/cm2

S NH2
O O O O
C O CH2CH2OC N C O CH2CH2OC NH2
KSCN / Br2

C O CH2CH2OC N C O CH2CH2OC NH2

O O O O
S NH2
Compound 4 Compound 3

Scheme 1. Preparation of benzothiazole from BHET.

2.1.2. Chemicals added as a catalyst. The reaction was monitored on TLC using ethyl
Ethylene glycol, sodium sulfate, p-nitro benzoic acid, thionyl acetate:hexane (6:4) as mobile phase. The excess solvent was
chloride, dimethyl formamide, potassium thiocyanate, bromine, recovered using vacuum distillation. The compound 4-nitro
pyridine, N,N-diethylamine, toluene, ethyl acetate, hexane, acetic benzoyl chloride (compound 1) obtained was slightly yellowish
acid, liq. ammonia, sulfuric acid, sodium nitrate, sodium hydroxide, solid with 95% yield.
sodium dithionite were all of LR grade.
3.2.2. Reaction of p-nitro benzoyl chloride with BHET
3. Methods Accurately weighed BHET and compound 1 were dissolved in
toluene and taken in a three-necked round bottom flask fitted
3.1. Glycolysis of PET with a stirrer and condenser. Molar ratio of BHET:compound 1
was adjusted to 1:2. Pyridine was added as a catalyst to the
The glycolysis of PET was carried out by the method reported reaction (0.5%). The reaction was monitored on TLC using the
earlier [18]. By using 0.3–1% (w/w) sodium sulfate catalyst and 1:6, mobile phase ethyl acetate:hexane (4:6). After completion of
PET:ethylene glycol ratio, the glycolysis was carried out at 197  C the reaction, excess solvent was collected via vacuum distillation.
under reflux for 8 h to get 60% yield of pure BHET through repeated The reaction mixture obtained was dissolved in dichloromethane
crystallization. (MDC) and aqueous washes were given. MDC was then distilled
off to get the product bis(2-(4-nitrobenzoyloxy)ethyl) tere-
3.2. Synthesis of dyes phthalate (compound 2).

3.2.1. Preparation of p-nitro benzoyl chloride 3.2.3. Reduction of nitro to amino

Accurately weighed p-nitro benzoic acid was dissolved in A suspension of compound 2 in glacial acetic acid was hydro-
toluene and taken in a three-necked round bottom flask fitted with genated at room temperature in the presence of 10% Pd/C as
a dropping funnel, stirrer and condenser. Accurately weighed thi- a catalyst (initial hydrogen pressure: 0.345 MPa). After 10 min, the
onyl chloride was taken in a dropping funnel for continuous product was isolated by dilution with water. Recrystallization
dropwise addition. Molar ratio of p-nitro benzoic acid to thionyl through aqueous ethanol gave pale yellow compound bis(2-(4-
chloride was adjusted to 1:1.2 and dimethyl formamide (0.5%) was aminobenzoyloxy)ethyl) terephthalate (compound 3).

S NH2 S N N N
O O O O
C O CH2CH2OC N C O CH2CH2OC N
Diazotization
p-N,N-diethylaniline
C O CH2CH2OC N C O CH2CH2OC N
O O O O
S NH2 S N N N
Compound 4
Dye A

Scheme 2. Synthesis of Dye A.

606 S.R. Shukla et al. / Polymer Degradation and Stability 94 (2009) 604–609

O O O O
C O CH2CH2OC NH2 C O CH2CH2OC N N N
Diazotization
p-N,N-diethylaniline

C O CH2CH2OC NH2 C O CH2CH2OC N N N

O O O O
Compound 3 Dye B

Scheme 3. Synthesis of Dye B.

3.2.4. Preparation of benzothiazole from ester 3.2.6. Coupling reaction of compound 3 with N,N-diethylaniline
Accurately weighed compound 3 was dissolved in acetic acid Compound 3 was dissolved in glacial acetic acid and then cooled
and taken in a three-necked round bottom flask fitted with a stirrer, to 5  C. The reaction with N,N-diethylaniline was carried out as
a dropping funnel and condenser. Potassium thiocyanate was mentioned above, to obtain a disperse dye, orange in color (Dye B).
added (1:3) and mixed thoroughly for 2 h at room temperature.
Bromine dissolved in glacial acetic acid was then added at 10  C 3.3. Characterization of dyes
dropwise by maintaining temperature and then the reaction was
continued further for 12 h at room temperature. At the end, the Elemental analysis was carried out by using Heraus Combustion
reaction mixture was dumped in crushed ice. The solution was Apparatus. Nuclear Magnetic Resonance (NMR) of the Dye A and
filtered and the residue was discarded. The product obtained by Dye B were recorded on JEOL, FT-NMR (60 MHz). UV–visible spectra
neutralizing the filtrate with liq. ammonia was the precipitate of were recorded with a UV–vis Spectrophotometer, 8500, TECH-
benzothiazole of ester i.e. bis(2-(2-aminobenzo[d]thiazole-6-car- COMP, Hong Kong using acetone as solvent. The FT-IR spectra were
bonyloxy)ethyl) terephthalate (compound 4). It was then filtered recoded using Shimadzu 8400S FT-IR.
and dried at room temperature.
3.4. Dyeing of polyester with disperse dye
3.2.5. Coupling reaction of compound 4 with N,N-diethylaniline
Sodium nitrite (30 ml, 2 mol) was added slowly to 50 ml of Polyester being thermoplastic, the textile fabric made out of it
magnetically stirred concentrated hydrochloric acid at <10  C. The can be dyed suitably at a high temperature of 130  C in a pressure
temperature of reaction was increased to 65  C and the solution vessel. High temperature laboratory dyeing machine (R.B. Electronic
was then cooled to 5  C; the diazo solution was slowly added to and Engineering Ltd., Mumbai, India) was used for this purpose.
a beaker containing compound 4 dissolved in glacial acetic acid Stock solution of a dye was prepared by dissolving the required
while maintaining the temperature of the whole system below amount of dye in a small quantity of dimethyl formamide and rep-
5  C and reaction continued for 3 h with stirring. The resulting recipitating it under continuous stirring, as a dispersion in water
clear diazonium salt solution was used immediately in the containing a dispersing agent. The dyebath was set up for dyeing (2%
coupling reaction with N,N-diethylaniline. The diazonium salt was dye on weight of fabric) using dispersing agent (1 g/l) and acetic acid
added to a solution of N,N-diethylaniline dissolved in glacial acetic to maintain pH about 5.5. Fabric piece (2 g) was entered in the dye
acid and stirred for 1 h at <10  C. The pH was maintained dispersion in a SS beaker of the dyeing machine, lid closed tightly
between 4 and 5 by adding aqueous sodium acetate solution. and machine started with rotation of beakers and heating to 130  C
Stirring was continued for 3 h at that temperature and bright at the rate of 2  C/min. The dyeing was continued at this tempera-
yellow colored dye (Dye A) obtained was filtered, washed with hot ture for 1 h. The bath was cooled, fabric was taken out and treated
water and dried. with a solution containing 2 g/l sodium hydroxide and 2 g/l sodium

Table 1
Structure and analysis of synthesized dyes.

Dye A Dye B

S N N N O O
O O
C O CH2CH 2OC N C O CH2 CH2 OC N N N

Structure

C O CH2CH 2OC N C O CH2 CH2 OC N N N

O O O O
S N N N

Formula C48H46N8O8S2 C46H48N6O8

Mol. wt. 927.06 812.91

Elemental analysis (%) Calculated (Found)

C 62.19 (61.92) 67.96 (67.57)
H 5.00 (4.94) 5.95 (5.83)
N 12.09 (12.05) 10.34 (10.27)
S 6.92 (6.90) –
 S.R. Shukla et al. / Polymer Degradation and Stability 94 (2009) 604–609 607

Dye A Dye B

Fig. 1. Color photographs of polyester fabric dyed with synthesized dyes.

dithionite at 75  C for 20 min to remove any dye adhering to fabric 3.5.3. Dye build-up properties
surface. The dyed fabric was then rinsed and dried. Relative color values (L*, a*, b*, C*, H*, K/S) of each dyed fabric
were measured in a Spectrascan 5100þ Spectrophotometer, India
using Premier Colorscan Colorlab Color Matching Software.
3.5. Evaluation of the dyed polyester samples

3.5.1. Color fastness to light

Color fastness of the dyed polyester fabric to light was measured 4. Results and discussion
according to the AATCC Test Method 16, Option E, using Q-Sun
Xenon Test Chamber Xe-3, U.S.A. [20]. As per the law of sustainable development, chemical recycling of
PET is the best recycling option leading to basic reactants that can
3.5.2. Fastness to heat (sublimation) be used again in the synthesis of original polymer or some other
Dyed polyester samples were placed against a piece of adjacent useful products.
plain polyester. ‘‘Rossari Labtech Sublimation Fastness Tester’’ Although, methanolysis and hydrolysis lead to the basic reac-
(Mumbai, India) was used to conduct the test. The adjacent poly- tants useful in the synthesis of PET itself, the requirement of high
ester samples were visually assessed for staining using AATCC grey temperature and pressure adds to the cost of the process. In
scales for staining [21]. contrast, glycolysis can be carried out under atmospheric pressure
and that too in an environmentally friendly manner to give BHET as
a virtual monomer, which can be obtained in pure crystalline form
with sufficiently high yields to employ it in some chemical reac-
Table 2
1 tions [18].
H NMR values of Dye A.
The product BHET possesses two hydroxyl groups at the
g h i j
terminal positions. These being reactive, may be converted into
N
O O d N N N more reactive intermediates via simple chemical reactions. It was,
b c
C CH2 CH2 O S
therefore, thought possible to reuse BHET in the synthesis of
O C g i j
h
chemicals useful in different fields of application. The present
e f communication reports synthesis of two hydrophobic disperse
g h i j
a a dyes using various reactions on BHET as shown in Schemes 1–3.
N
d N N N Synthetic fibers like PET are much hydrophobic, compact and
C O CH2 CH2 O C S j devoid of any polar groups. These characteristics do not allow any
g h i
b c ionic water soluble dyes to be applied for coloration. Only nonionic
O O
e f hydrophobic disperse dye (named so because they form dispersion
d Value and not solution in water) can be applied through hydrophobic
a 8.00 (m, 4H, Ar-H) interaction.
b 4.40 (t, 4H, –CH2) Reaction Scheme 1 shows the synthesis of benzothiazole
c 4.00 (t, 4H, –CH2–O–) derivative of BHET; initially p-nitro benzoic acid was converted to
d 8.10 (d, J ¼ 8.2 Hz, Ar-H)
p-nitro benzoyl chloride (compound 1) using dimethyl formamide
e 8.70 (d, J ¼ 9.2 Hz, Ar-H)
f 8.30 (d, J ¼ 8.8 Hz, Ar-H) as a catalyst. Virtual monomer BHET was then reacted with p-nitro
g 7.10 (d, J ¼ 8.4 Hz, Ar-H) benzoyl chloride in the presence of pyridine as a catalyst to get
h 7.40 (d, J ¼ 8.4 Hz, Ar-H) bis(2-(4-nitrobenzoyloxy)ethyl) terephthalate (compound 2). This
i 3.39 (q, 6H, –CH3) was further reduced to p-amino benzoic ester (compound 3).
j 1.13 (t, 4H, –CH3)
Finally the benzothiazole derivative of BHET (compound 4) was
608 S.R. Shukla et al. / Polymer Degradation and Stability 94 (2009) 604–609

Table 3 samples are darker with redder and yellower tone [22]. In
1
H NMR values of Dye B. comparison to Dye B, the dyeing with Dye A is deeper and the tone
d e f g
O O h i is much yellower. The differences in redder tone, although existent
b c
C O CH2 CH2 O C N N N
are not very high, thereby giving distinctly bright yellow color to
sample dyed with Dye A. By virtue of the dyeing mechanism of
d e h i
f g disperse dyes on polyester (viz., solid solution theory), the wash
a a fastness of the dyed textile was found to be good [23]. The light
d e f g
h i
fastness of polyester dyed with Dye A was found to be good (rating
6 on the scale of 1–8; 8 being excellent) as compared to that of
C O CH2 CH2 O C N N N
sample dyed with Dye B (rating 4–5), while reverse was the case for
b c
O O d e f g h i sublimation fastness (rating 4–5 for Dye B, on the scale of 1–5; 5
d Value being excellent and rating 2–3 for Dye A).
a 8.10 (m, 4H, Ar-H)
b 4.46 (t, 4H, –CH2)
5. Conclusion
c 4.13 (t, 4H, –CH2–O–)
d 8.15 (d, J ¼ 8.2 Hz, Ar-H)
e 8.66 (d, J ¼ 8.4 Hz, Ar-H) In the present communication, the PET fiber waste was depo-
f 7.46 (d, J ¼ 8.8 Hz, Ar-H) lymerized and the resulting monomer was converted into disperse
g 7.60 (d, J ¼ 9.0 Hz, Ar-H) dyes successfully. The application of these dyes on polyester fabric
h 3.41 (q, 6H, –CH3)
i 1.15 (t, 4H, –CH3)
showed good coloration characteristics with satisfactory perfor-
mance properties. Among the two synthesized dyes, Dye A gave
a bright yellow color whereas Dye B gave orange color. These dyes
show a potential to be used for coloration of polyester textiles.

obtained by reacting compound 3 with bromine and potassium Acknowledgment

thiocyanate.
Reaction Scheme 2 is the coupling of compound 4 with N,N- The authors are grateful to Council of Scientific and Industrial
diethylaniline to get a bright yellow disperse dye (Dye A) whereas, Research, Govt. of India, New Delhi for funding this project.
reaction Scheme 3 shows the synthesis of an orange colored
disperse dye (Dye B) through the coupling of compound 3 with the
coupler N,N-diethylaniline. References
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