Chapter 27

Chemical Recycling of PET: Methods and Products

T. Spychaj

1. Introduction Poly(ethylene terephthalate) (PET) is a polymer used in large amounts by the textile industry, for the production of audio and video tapes and transparent films, as well as in the manufacture of various types of packaging, mainly bottles for soft drinks. An annual rise of the polymer consumption, in the immediate future, is evaluated on ca. 10% [I]. The increasing worldwide usage of PET, along with economic and ecological pressures, has caused post-consumer or waste polymer recycling to be the subject of continuous interest for many scientists and industrial companies for ude as a valuable feedstock for chemical processes. PET can be recycled by practically all known recycling methods. Among these, chemical recycling is of great interest because of the wide spectrum of degrading (depolymerizing) agents and the large variety of products (Table 1). Chemical recycling can result in total polymer degradation to monomers or in a partial chain cleavage to oligomers. The molecular weight of the post-consumer PET, more commonly represented by its equivalent intrinsic viscosity, may vary in a range of 0.600.85 dL/g; the highest values stand for the material from bottles for carbonated drinks or industrial type cord while the lowest ones are characteristic of recording tapes [2]. It is also worth mentioning that the bottle grade PET is in fact a polyester modified by low levels (total up to ca. 3 wt% [3]) of other glycols

Handbook of Thermoplastic Polymers: Homopolymers, Copolymers, Blends, and Composites Edited by Stoyko Fakirov Copyright 2002 WILEY-VCH Verlag GmbH, Weinheim ISBN: 3-527-30113-5

Chemical Recycling of PET: Methods and Products

1253

(such as diethylene glycol or 1,4 bis(hydroxymethyl) cyclohexane) or diacids (usually isophthalic acid) rather than a homopolyester of terephthalic acid (TA) and ethylene glycol (EG). This fact is important because the product of post-consumer bottle PET recycling may contain, in addition to TA and EG, some other monomers. Compared to the homopolymer of TA and EG, modified PET exhibits lower crystallinity, improved ductility, better processability, and increased transparency. In this chapter, chemical recycling methods of post-consumer or waste PET are discussed together with applications of the obtained products. Compared to our earlier work [4], this presentation is a more comprehensive review of the state of the art in the field of polyester chemical recycling. Greater emphasis is placed on recent developments and industrially important techniques. The reader should also consult the specialized chapters in recent monographs [2,5,6] and Chapters 26 and 28, related to polyester recycling, or should consider reactive modification (Chapter 18). Poly (ethylene terephthalate), like other polyesters, can undergo various degradation processes [6]: (i) thermal degradation under the influence of heat alone, (ii) oxidative (oxygen and heat) and photo-oxidative (oxygen and light) degradation, (iii) hydrolytic degradation in the presence of moisture, (iv) radiochemical degradation under the action of ionizing radiation, and (v) chemical degradation in the presence of various solvolytic agents. 2. Theoretical basis of ester bond cleavage PET and other polyesters are polymers synthesized in reversible reactions. In the forward direction polymerization occurs and in the reverse direction polymer degradation (depolymerization) takes place by hydrolysis or by other solvolytic reactions. C-OH + nHOCH2CH2OH ;=
O
HO+C(( ))- COCH2CH2O^H + (2n-l)H2O
M

solvolysis

The solvolytic reactions of polyesters consist of the cleavage of C-O bonds of the polymer backbone. The polymer chain is degraded according to Scheme 2

Il

I ]OC wv + Y Z

I OZ +Y-CWV
O

Il

9 (2)

/\

1254

T. Spychaj

where YZ is the solvolytic agent molecule, e.g., water, alcohol, acid, alkali, or amine. The moisture content, temperature, and type of solvolytic agent are the factors affecting most strongly the rate of solvolysis of ester bonds in the PET chain. Moisture content as low as 0.02wt% still causes PET molecular weight reduction by hydrolysis [7]. The rate of hydrolysis is higher by several orders of magnitude than that of thermal breakdown. Heating of PET at elevated temperatures in the absence of moisture can lead to the formation of carboxylic acid groups; terminal carboxylic groups can catalyze hydrolysis [5]. COCH 2 CH 2 OH
O

C-OH +CH 3 CHO

(3)

Poly(ethylene terephthalate) is quite prone to chemical degradation. Depending on the type of the solvolytic agent, the PET degradation reactions are as follows: Hydrolysis
COCH2 CH2 O^/v O
COH + ^OCH 2 CH 2 OH
H2O

Alcoholysis with monohydroxylic compounds

COCH2 CH2 O^/v +ROH O
vVS^C

Il

\^/

^OCH 2 CH 2 OH (5)

with glycols or polyhydroxylic compounds (glycolysis)

COCH2 CH2 O^/v +HOROH O
COROH+ ^OCH 2 CH 2 OH (6)

Chemical Recycling of PET: Methods and Products Acidolysis with monocarboxylic or polycarboxylic compounds COCH 2 CH 2 OWVV +ACOOH
O

1255

COH +WVVOCH 2 CH 2 OC-A (7)

O O

Ammonolysis with ammonia under anhydrous conditions COCH 2 CH 2 OWVV +NHs

O

Aminolysis with primary or secondary amines

/R 1 - COCH 2 CH 2 OWVv +HN
\
R2

WVVOCH 2 CH 2 OH

(9) V '

O O The hydrolysis of PET can obey various mechanisms of polyester chain degradation in alkaline, neutral, or acidic media [8].
pH < 7

:ovw
O +
OH+

I OH

(10)

OWV + H 2 O ^^ ws/vC=O + H+ + HOvw

OH OH

OH
P

H>7
OH~

/vC OVW

Il O

I 0~

OVW ^^

OH +

0
(U)

-O" + HOvw
O

1256

T. Spychaj

In practice, the chemical degradation processes in post-consumer bottles or polyester waste are associated with mixed chemical mechanisms, depending on the PET additives or contaminants and on the reaction conditions (see also Chapter 1). 3. Methanolysis This process consists in the degradation of PET by methanol at high temperatures under high pressures. Methanolysis of PET results in the stoichiometric formation of dimethyl terephthalate (DMT) and EG that are raw materials for the production of this polymer.
COCH2 CH2 O^/v + CH3OH > COCH3 + HOCH 2 CH 2 OH

(12)

DMT
0

EG

The process is performed at temperatures of 160-30O C [4,5] and pressures up to 7MPa [5], in the presence of transesterification catalysts, and usually involves two stages: methanolysis itself to give DMT and EG and purification of the resulting raw DMT by crystallization and distillation. Distillation removes all physical impurities and yields a high purity product. Methanolysis is currently applied to PET waste, arising in the production cycle, as well as to the polymer scrap. Typical feedstocks for methanolysis include used films, plant waste, fiber waste, and post-consumer bottles. Methanolysis of PET was first reported in patents issued in the late 1950s [9-11]. The process is used by the principal PET manufacturers, such as Hoechst [12], Eastman-Kodak [13], and DuPont [14], as well as by smaller-scale manufacturers [4]. The monomers recovered are used in the production of a full value polymer. A schematic representation of the installation for PET methanolysis is shown in Figure 1. The reaction is conducted most frequently at pressures of 2-4 MPa and temperatures of 180-28O0C for ca. I h [15-20], and is usually catalyzed by typical transesterification catalysts, such as zinc acetate (most commonly used), magnesium acetate, or cobalt acetate. Examples are known of using arylsulfonic acid salts as catalysts for the methanolytic degradation of PET [1O]. After the completion of the reaction, the catalyst should be deactivated; otherwise, in subsequent stages of the process, possible DMT losses could result from transesterification with EG. The DMT obtained is precipitated from the cooled post-reaction mixture and is then centrifuged, crystallized and, optionally, distilled. Both continuous and batch methods can be applied in methanolysis. The principal elements of the installation used in the batch method are

Chemical Recycling of PET: Methods and Products

PET

1257

Methanol
l

Methanol tank
A i.

EG tank A^ Methanol

PET production A ^

PE]T ^r wa ste Depolymerization A [ ~

Separation PET waste

DMT ^,

DMT tank ^

Figure 1. Flowchart of the methanolysis process [4]

autoclave, crystallizer, centrifuge, and a system for the melting and distillation of the DMT obtained [15]. The continuous method requires a much more complex apparatus because of the necessity to continuously supply a pressurized reactor with raw materials. In a two-stage continuous process developed for Hoechst [16], PET waste, melted at 265-2850C, is collected in the liquid state in a tank and then fed to a first reactor. Methanol, preheated to the reaction temperature, e.g., 190-21O0C, is introduced into the autoclave, equipped with a mixer, at a weight ratio to PET of 4:1. The average residence time of the reagents in the first reactor is 7-13 min and the conversion is 70-90%. The reaction mixture is then fed to the bottom part of the second autoclave at a slightly lower temperature and is slowly raised toward the outlet placed at the top of the reactor. The denser impurities settle at the bottom and are removed, the reaction stream leaves the second autoclave, and its pressure is reduced to 0.3MPa. It is then directed to a mixer where it is cooled to about 10O0C. After further pressure reduction and cooling, DMT is precipitated and then purified. In accordance with another continuous depolymerization technology, premelted (by superheated steam) PET waste is solidified and sputtered into dust of 1 mm particle size. The dust is introduced into the reactor in the form of an aerosol with an inert gas (e.g., nitrogen) and methanol vapors [17]. The temperature of the reactor is maintained at 250-30O0C. It is important for the reaction to proceed in an oxygen-free atmosphere and the turbulent flow of the substrate through the reactor should be maintained. Eastman-Kodak Co. is the owner of patents describing improved methanolysis processes [21,22]. According to [21], the PET methanolysis is realized in a three-stage installation, consisting of a dissolver, a depolymerization reactor, and a rectifying column. The polyester stream is directed into the dissolver where, under the action of the molten polymer from the reactor and the liquid from the rectifying column, the polyester chain length

1258

T. Spychaj

is reduced. PET is then degraded in the reactor by superheated methanol. The degradation products are divided by rectification into a gaseous phase containing the monomer components and a liquid oligomerized phase. The second method [22] is based on mixed glycolytic/methanolytic PET degradation. This process, as well as the mixed chemical recycling by successive methanolysis and hydrolysis [19], are described in Section 9 where examples of the hybrid chemical recycling methods of PET are also given. A combination of high-temperature PET methanolysis with the esterification of TA or with the products of para-xylene oxidation is proposed in [U]. Polyester waste is introduced at a weight fraction of 20-30% (based on TA) which results in an increased process yield. Because of the increased interest in the production of polymer blends containing PET, the need to develop methods for the chemical recycling of such systems appeared. This is particularly justified in the case of polycondensation polymer blends. Sato and Sumitani [23] have patented a method of methanolysis of polymer blends containing the segment alkylene2,6-naphthalene dicarboxylate and the segment alkylene terephthalate. Dimethyl esters of the corresponding dicarboxylic acid and glycol are thus recovered. The reaction products of methanolysis of post-consumer PET comprise a complex mixture of glycols, alcohols, and phthalate derivatives. For this reason, the yield of DMT usually does not exceed 90% [15]. It has been found that after methanolysis and DMT separation, dissolved methyl(hydroxyethyl) terephthalate (MHET) remains in the filtrate. Depending on the reaction parameters, the filtrate usually contains 11-22 wt% MHET [15]. This TA derivative can be almost quantitatively transformed into DMT. The presence of MHET is disadvantageous during subsequent distillation of the EG formed. Substantial amounts of waste EG usually contaminated by degraded polyester are formed during PET depolymerization and may be recovered by distillation in recycling installations and fed back into the system. The greasy and environmentally harmful residue from the glycol rectification contains about 80wt% BHET, 5wt% EG, diethylene glycol, and poly(ethylene glycol)s, as well as other derivatives of TA and EG. A method has been developed for the utilization of this residue in PET methanolysis processes [24] through its introduction into the reactor along with an appropriate transesterification catalyst. This method causes an increase by about 10% in the yield of the PET methanolysis process and significantly increases the size of the DMT crystals, thus facilitating the separation of the latter from the reaction mixture. The essential features of methanolysis as a process for the chemical recycling of PET are: (i) it allows the use of lower quality PET feed than glycolysis because of the easier purification of the final DMT product; (ii) it is a more expensive than glycolysis, but tolerates higher levels of contamination so that higher chemical processing costs are offset by relatively low feed-stock costs [2]; (iii) it is rather sensi-

Chemical Recycling of PET: Methods and Products

1259

tive to the presence of water and causes problems associated with catalyst poisoning, formation of azeotropes, etc. [25]; (iv) the costs of DMT recovery are usually higher than that of virgin DMT [25], but new technologies, developed by Eastman-Kodak and DuPont, are economically more advantageous than conventional processes [2]. 4. Glycolysis 4.1. Process characteristics The degradation of high molecular weight PET to short-chain oligomeric or even low molecular weight, hydroxy-terminated products can be achieved by glycolysis. These products are valuable raw materials for the preparation of unsaturated polyester resins, polyurethanes (especially rigid foams) or bis(hydroxyalkyl) terephthalates, which are the substrates for PET and poly(butylene terephthalate) (PBT) syntheses. Glycolysis is performed by heating PET waste with a glycol (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4butanediol, etc.) under normal or higher pressure at 180-25O0C in the presence of a catalyst. Typical catalysts are amines, alkoxides, BHET, or metal salts of acetic acid. Usually, glycolysis proceeds for 3-8 h (depending on the glycol applied) at ca. 20O0C under reflux, the PET/glycol weight ratio ranging from 1:2 to 1:3. The reaction is carried out under a continuous nitrogen purge to inhibit degradation of the resulting polyols. Number-average molecular weight, M n , and hydroxyl number characterize the polyol products.
PET glycolysis products with ethylene glycol

with 1,4-butanediol

HOCH 2 CH 2 O-C
.O

COCH 2 CH 2 0+H

(13)

BHET for n = I
HOCH 2 CH 2 CH 2 CH 2 0--C.0

- COCH 2 CH 2 CH 2 CH 2 O-^H
O

BHBT for n = I

Glycolysis of PET was first described in Polish and US patents in 1964 and 1965 respectively [26,27]. Since then, this method of waste polyester

1260

T. Spychaj

recycling has been a subject of permanent interest from both a scientific and an applied viewpoint. PET degradation is often carried out with EG [28-41]. The result of deep polymer glycolysis by EG is primarily BHET, which, similarly to DMT, is a substrate for PET synthesis. Some oligomers (with n = 2 10) are obtained in parallel [2,41]. Since BHET is a waxy solid with a relatively high melting point, it cannot be easily purified by distillation. Purification of BHET is generally achieved by melt filtration under pressure to remove physical impurities. An additional treatment with activated carbon is usually conducted to remove impurities responsible for oxidative degradation/discoloration. Glycolysis of PET with 1,4-butanediol is performed in order to obtain bis(4-hydroxybutyl) terephthalate, which is a substrate for the production of PBT [2]. Zimmer AG has developed a two-stage process PET glycolysis takes place in an extruder where bis(4-hydroxybutyl) terephthalate is formed and then PBT is synthesized in a polycondensation reactor. Commercial grade EG and tetrahydrofuran (by-product from 1,4-butanediol) are recovered by distillation [2]. Other frequently used glycolytic agents include diethylene glycol (DEG) [34,35,37,42], propylene glycol (PG) [5,39,40,43,44,], and dipropylene glycol [37,44]. The variables affecting the rate of PET glycolysis with various glycols have been studied by Baliga and Wong [32], Johnson and Teeters [36], Campanelli et al. [38], Vaidya and Nadkarni [43], and Lee et al. [45]. Souza et al. [46] have investigated PET glycolysis products, using EG oligomers (PEG) and PG oligomers (PPG), as solvolytic agents. By means of proton nuclear magnetic resonance (1H NMR) analysis, these authors have found that the products obtained in the process carried out at 19(K270C contain incorporated oligomers Jn the range 77-91% for PEG of Mn - 400g/mol, 80-99% for PPG of Mn ~ 220g/mol, and 39-50% for PPG of Mn ~ 1000g/mol. Research on the glycolysis process has been mainly conducted from the point of view of the utilization of the oligomeric products. The reactions performed to obtain polyols designated for unsaturated polyesters and polyurethanes are widely described in the literature [32,35,40,42,43,47-5O]. A new method of PET glycolysis in xylene using EG or PG has been recently developed [39]. The process performed in the temperature range 1702450C is characteristic in that it initially proceeds in PET/glycol droplets suspended in xylene. PET dissolves in EG at the reaction temperature, whereas EG is almost immiscible with the solvent. The reaction products (oligomeric diols) are gradually transferred into the xylene phase. The process has some advantages over conventional glycolysis, such as shorter duration, improved stirring, and higher purity products. Another extremely efficient method of polyester glycolysis has been developed by Krzan [51,52]. By microwave irradiation, complete PET degradation with glycols takes place in a few minutes, depending on the radiation power and the amount and type of the energy-absorbing additive. The cumulative parallel wave action and heating are responsible for the high

Chemical Recycling of PET: Methods and Products

1261

effects of the process. Glycolysis is widely used on a commercial scale by large, medium and small enterprises to produce unsaturated polyester resins (e.g., Ashland Chemical, USA, Chemical Works Pustkow and Chemical Works Organika-Sarzyna, both from Poland) and polyurethane/polyisocyanurate rigid foams (e.g.. The Chardonol Division of Cook Composites and Polymers, USA). 4.2. Unsaturated polyesters from PET-derived polyols PET glycolyzates find application in the manufacture of unsaturated polyester resins [26,40,42-44,47,50,53-59]. For unsaturated polyester resins (UPR), PG is preferred over EG or DEG as a glycolytic agent. The reason is that PET/PG-derived UPRs are compatible with styrene, whereas those based on PET/EG or PET/DEG glycolysis products are not fully compatible [50]. In the preparation of UPR, glycolysis and polyesterification can proceed in the same reactor by a two-stage reaction. A schematic diagram of PET glycolysis and use of the glycolyzate for UPR production is given in Figure 2. One of the first methods for the synthesis of UPRs, using a product of partial PET glycolysis, was developed by Ostrysz et al. [26]. After dissolving the synthesized polyester alkyd in styrene, UPR was obtained. Later, the Industrial Chemistry Research Institute in Warsaw developed a tech-

PET waste Propylene glycol (First stage) Partial glycolysis (First stage) 18O0C Polycondensation (Second stage) 15O0C Maleic anhydride (Second stage) Unsaturated polyester resin Styrene

Figure 2. Scheme of PET glycolysis and use of the glycolyzate as a substrate for unsaturated polyester resin

1262

T. Spychaj

nology for the production of UPR with built-in segments of oligo(ethylene terephthalate) by partial PET waste glycolysis at PG/PET molar ratios of 0.25-1.0, 20O0C, using a reaction time of 2h [42,47]. Because of difficulties in producing a glycolyzate with reproducible properties, a new type of unsaturated polyester has been prepared, containing ethylene-diethylene diester obtained as a result of PET degradation by DEG as its terephthalic part. This resin was used in the production of polyester molding compounds [59]. Generally, glycolysis occurs at a temperature higher than that of polyesterification ca. 18O0C vs. ca. 15O0C (Figure 2). After cooling, the PET-based polyol and residual EG are treated with maleic anhydride to form a polyester. The esterification step may also include phthalic anhydride and/or isophthalic acid [5]. The reaction of maleic anhydride with PG and PET-based polyols is faster than that with PG and phthalic anhydride or isophthalic acid. The PET-derived resins require about 12 h to form an unsaturated polyester alkyd with a number-aver age molecular weight of 2000-2500 g/mol and acid value of 25-30 mg KOH/g [5]. Conventional resins require production times of ca. 20 h. The kinetics of polyesterification have been reported by Vaidya and Nadkarni [33,43]. The growing interest in the manufacture and usage of UPRs, utilizing PET waste, results from the comparable or higher strength, stiffness, and toughness offered by terephthalic acid-based resins in comparison with conventional unsaturated polyesters [54-57]. UPRs derived from PET-based polyols offer various application opportunities, e.g., for gel coat, polymer concretes and mortars, sheet molding compounds (SMC) used in the automotive industry, etc.

4.3. Polyurethane/polyisocyanurate polyols

foams from

PET-derived

The methods of synthesis of saturated (sometimes branched) polyesters or rather oligomeric estrodiols based on PET glycolyzates as substrates for polyurethanes (PUR) developed in the last two decades have been reviewed recently [60,61]. Rigid polyurethane foams are the most important materials produced on this basis because the insulation is invisible to the consumer. Milgrom [5] has evaluated that more than 50% of all rigid polyurethane/polyisocyanurate (PUR/PIR) insulation boards in the USA (in 1990-1992) used polyols made from waste X-ray and lithographic films or PET soft drink bottles. The leading American company (Cook Composites and Polymers, Port Washington, WI) converted 11.3-11.5 thousand tons of waste PET (especially colored) into aromatic polyols designated for PUR/PIR insulations [5]. PET-based polyols can also be used in flexible PUR elastomers and foams, typically as modifiers combined with other commercial polyols. The

Chemical Recycling of PET: Methods and Products

1263

addition of PET-derived polyols provides significant improvements in tear strength, elongation, and indentation-load deflection of flexible PUR foams [5]. Probably the first patents claiming PET-based polyols designated for the synthesis of polyurethanes were those of Ostrysz and Penczek [62,63]. PET was reacted with polyhydroxylic alcohols and a saturated polycarboxylic acid (or its anhydrides, or hydroxy acids) at temperatures in the range 120-16O0C. The oligoestrols formed had hydroxyl number values of 50-200 mg KOH/g and viscosities of 500-700 mPa-s at 550C [62]. These polyols were used for PUR foam synthesis [63]. In the 1980s, numerous methods for the synthesis of PET-derived saturated polyols and their usage for PUR/PIR materials have been reported, e.g., [28,29,32-34,49,64-73]. Research on the application of PET-based polyols for PUR synthesis has been continued during the last decade (see, e.g., [35-37,45,74-77]). In order to get polyols designated for PUR/PIR syntheses, the following hydroxyl group-bearing solvolytic agents are used for PET glycolysis: DEG [5,36,64,72,73,77], PG [36,72,73], tri- and polyhydroxylic compounds, such as glycerol, sorbitol, saccharose [68], mixtures of glycols with eri-alkanolamines [69] or with the products of oxyalkenylation of alkylphenols [71], amines and/or amides [70], or PET-derived polyols [65]. However, the products of PET glycolysis with DEG are the most important for this purpose. Adipic acid most often serves as an acidic component in the synthesis of saturated oligoestrols [4]. Compared to other methods of polyester chemical recycling, the main features of glycolysis are: (i) it does not lead to the formation of well defined chemical species (as in the cases of methanolysis or hydrolysis) and the mixture of glycolysis products is difficult to separate by conventional techniques of crystallization and distillation; (ii) it can be easily adapted to the required scale of PET-derived polyols production, but it cannot provide the removal of dyes, copolymers, and other contaminants from the final products; (iii) the application options for the final glycolysis products are numerous. 5. Other transesterification methods In recent years, numerous processes have been developed based on new, specific trends of PET waste chemical recycling. Most of these processes are for low-tonnage production of substrates for the plastics and coatings industry. It is possible to obtain valuable products with prices that are competitive to their equivalents manufactured through conventional synthesis methods. These technologies are safe, low-waste or practically waste-free, and sometimes less complex than the traditional ones.

1264 5.1. Plasticizers

T. Spychaj

The degradative transesterification of PET may be realized with long-chain aliphatic alcohols [78-82], and the respective products serve as plasticizers of poly (vinyl chloride) (PVC). PET alcoholysis, aiming at obtaining dioctyl terephthalate (DOTP), is most often carried out using 2-ethylhexanol [7881]. The actual product is a mixture of DOTP and small amounts of 2-ethylhexyl-2-(hydroxyethyl) terephthalate and terephthalate oligoesters [81]. The plasticizer obtained in this way is at least as good as a commercial DOPT from direct synthesis [80] and can replace the most commonly used dioctyl phthalate [80,81]. Bathe [82] described a method of synthesis of a plasticizer of PVC in the reaction of PET waste with a poly(ester-ether) synthesized from trimellitic acid, Ci2-Cis fatty acids, and a mixture of DEC and EG oligomers. 5.2. Coating materials The use of PET chemical recycling products for the manufacture of coating materials is reported more and more frequently. Polyester-based paints have excellent properties, such as hardness, tensile strength, and chemical resistance [2]. PET degradation products can be used for alkyd resin syntheses; polyhydroxylie alcohols or esters serve as solvolytic agents. PET transesterification can be performed by esters of higher glycols and carboxylic acids as well as by esters of polyhydroxylic compounds and fatty acids. The first technology to obtain coating materials using the PET degradative transesterification products was claimed in 1985 by Dainippon Toyo Co. [83]. The polymer waste was dissolved in the reaction product of pentaerythritol with fatty acids at temperatures of 200-30O0C and the intermediate was esterified with polycarboxylic acids; the final product with Mn = 2000-8000 g/mol was dissolved in a mixture of organic solvents (xylene/butanol). The lacquer obtained had an outstanding shelf-life stability and gave a glossy coating after drying [83]. PET waste can be used in the production of terephthalic electroinsulating lacquers [84]. For this purpose, PET is heated in a mixture of triol and glycol at temperatures of 230-26O0C to obtain a homogeneous solution. The process is continued under reflux until the polyester softening temperature is established below 6O0C (l-4h). The next stage consists of the addition of a transesterification catalyst, e.g., zinc chloride, heating at 220-25O0C, and distilling off the low molecular weight products of degradation, until the required softening temperature of the polyester (60-10O0C) is achieved. The products of transesterification of PET or PBT waste with alkanediol esters or dicarboxylic acids at 30O0C are low-melting polyesters, finding application as adhesives or coating materials [85]. For instance, a mixture of PET and PBT waste was subjected to a reaction with the product of polycondensation of adipic acid and 1,4-butanediol at 28O0C. The polyester

Chemical Recycling of PET: Methods and Products

1265

obtained was applied as a powder coating for steel plates, using a fluidized bed technique at 35O0C. The coating exhibited excellent adhesion to the metal substrate [85]. In the patent specification [86], a hot-melt adhesive based on PET is claimed. It is designated for paper, aluminum, and polyethylene foils. PET waste is subjected to degradative transesterification using the product of the reaction of trimellitic anhydride and poly(ethylene glycol) at temperatures of 230-25O0C, under pressures of 0.1-0.3MPa. Khan and Chandra [87] described PET degradation with glycerol or monoglycerides to obtain intermediates for alkyd resins designated for coatings. A mixture of PET waste and glycerol (1:1 by wt) refluxed at 23O0C for 12 h yielded a clear solution that could be used for alkyd resin production. The polyol prepared in the first stage of reaction is capable of reacting with acidic species such as phthalic anhydride and unsaturated fatty acids according to Schemes 14 and 15.

(14)
COCH 2 CH 2 OWv+HOCH 2 - CH-CH2OH

O PET
Glycerol

OH I COCH 2 CH 2 OH + HOCH2-CH-CH2 OCO O

cOCH 2 CH 2 Ow

Polyols

^ Phthalic anhydride

Unsaturated fatty acid

= CVWCH 3 Oil-modified alkyd resin

(15)

Alternatively, polyester waste can be processed with monoglycerides prepared from glycerol and linseed oil. The costs of the surface coatings

1266

T. Spychaj

based on PET-derived polyols are reduced by up to 25% as compared to the conventional glycerol/phthalate-based type [2]. The products of PET degradation by trimethylolpropane and pentaerythritol can be used in the manufacture of high-solids paints [88] . In the first stage, PET waste is depolymerized by trimethylolpropane and pentaerythritol at temperatures of 230-24O0C for 45 min. The final paint compositions contain 30-50 wt% of PET degradation products. PET waste was used in the manufacture of alkyd resins for waterthinnable paints. The products obtained from the reaction of PET with a mixture of fatty acids, linoleic acid, and trimethylolethane were used in the preparation of water-dispersible coating compounds [89]. As described in [90], trimethylolpropane was reacted with PET at 23O0C for 45 min. The resulting mixture of oligomers was subjected to a reaction with isophthalic and fatty acids and then with trimellitic anhydride. The reaction took place without the addition of a catalyst since the catalysts present in commercial PET ensured a satisfactory reaction rate [9O]. 6. Hydrolysis The hydrolysis of PET relies on the use of aqueous systems at elevated temperatures and pressures to obtain terephthalic acid and ethylene glycol.

COH + HOCH 2 CH 2 OH

O
TA EG

Each cleavage of the polymer chain consumes one molecule of water and creates two functional groups, carboxylic and hydroxylic, at the scission place. The growing interest in this method is associated with the development of the PET synthesis directly from EG and TA, which eliminates toxic methanol from the technological cycle. Hydrolysis of PET waste can be performed as an acid-catalyzed, base-catalyzed, or neutral process, and is used on a commercial scale. However, this method is not as widely applied as methanolysis and glycolysis since the cost associated with the purification of the recycled TA is rather high [2] . PET hydrolysis was first described in patents issued in the years 1959-1962 [91-93]. 6.1. Acid hydrolysis Acid hydrolysis of PET is performed most frequently using concentrated sulfuric acid [94-97] although the application of other concentrated mineral

Chemical Recycling of PET: Methods and Products

1267

acids, e.g., phosphoric [98] or nitric acid [99], is possible. If concentrated sulfuric acid (at least 87wt%) is used, PET degradation can be performed under normal pressure at temperatures below 10O0C for times shorter than 30 min [94-96]. The process can be carried out without an external energy supply [95] or may require heating of the reaction mixture [94,96]. The reaction takes place for up to 5 min under atmospheric pressure. In the first stage, PET waste is mixed with sulfuric acid of a concentration of at least 87wt% at temperatures of 85-9O0C [96], 60-930C [94], or at room temperature [95]. As a result of dissolution and PET degradation to TA and EG, an oily viscous liquid is obtained. It is introduced into an aqueous solution of sodium hydroxide in order to neutralize TA and raise the pH to 7.5-8 [94]. According to Pusztaszeri [95], the post-reaction mixture was first diluted with cool water, and then alkali was added to obtain a pH level of 11. The solution had a dark coloration and contained TA in the form of its water-soluble sodium salt, sodium sulfate, EG, and sodium hydroxide, as well as a small amount of insoluble impurities which were filtered off by conventional methods. The coloration of the filtrate could be removed by means of ion-exchange columns. The next stage of the process was the acidification of the solution to pH 0-3 [95], 2.5-3 [94], or 6-6.5 [96], using an acid (e.g., sulfuric or hydrochloric) in order to reprecipitate TA. After filtering, washing with water, and drying, TA of purity > 99% was obtained. EG was recovered from the remaining filtrate through extraction with organic solvents, e.g., trichloroethylene [94]. Another method for EG recovery is based on the introduction of sodium sulfate into the filtrate so as to obtain a saturated solution; EG salting-out takes place, forming a separate organic layer. Calcium oxide in quantities equivalent to the sodium sulfate/sulfuric acid content is added and simultaneously mixed into the aqueous layer obtained in the first variant. The precipitated calcium sulfate is separated by filtration or centrifugation, and the remaining aqueous solution of sodium hydroxide can be reused. A flowchart of the installation based on this concept is shown in Figure 3. Substantial drawbacks of PET hydrolysis by concentrated sulfuric acid are the high corrosivity of the reaction system and the generation of large quantities of waste inorganic salts and aqueous wastes. Yoshioka et al. [97] tried to minimize the last two inconveniences. Dilute solutions of ^SO4 (< 67.7wt%) were used to this purpose; the sulfuric acid can be recovered and reused in the process. However, this requires prolonged reaction times of 1-6 h and much higher temperatures (~ 15O0C); also, the pressurized apparatus used should have a large volume because of the necessity of using an excess of dilute acid. After the reaction, PET residue and TA were filtered off, the deposit obtained was treated with 5M NH4OH in order to transform TA into a soluble salt and then PET was filtered off. TA was precipitated with the previously obtained filtrate containing ^SO4. A hydrolysis process in which PET soft-drink bottles are digested in nitric acid (7-13M) at temperatures in the range 70-10O0C, at atmospheric

1268

T. Spychaj

NaOH solution
Reaction mixer
^

-+ Filtration

Hydrolysis

Neutralization

NaOH solution for the cycle

Lime

Calcium sulfate

Figure 3. Flowchart of an installation for acidic hydrolysis of PET [94]

pressure for 72 h, was described by Yoshioka et al. [99]. The reaction products were TA and EG, and the EG was simultaneously partially oxidized to oxalic acid. This approach allows one to obtain a product (i.e., oxalic acid) which is more expensive than TA and EG. The yield of oxalic acid was 40% at 7O0C after 72 h and the yield of EG was 60.8%. TA was formed quantitatively since it is stable to oxidation by nitric acid [99]. As already mentioned, corrosion of the equipment and the separation of EG from the waste acid are the critical problems in the acidic processes. 6.2. Alkaline hydrolysis Alkaline hydrolysis of PET is usually carried out by the use of an aqueous solution of sodium hydroxide [91,100-106] or potassium hydroxide [100,104,107,108], or with an aqueous ammonia solution [109,11O]. According to literature data, PET waste containing impurities up to 40wt% can be processed by hydrolysis with NaOH solutions [2]. Sodium hydroxide-catalyzed hydrolysis processes are performed in alkaline solutions of a concentration of 3-20 wt% under pressures of 1-2MPa (or under atmospheric pressure) at temperatures of 100-25O0C. However, in order to obtain reaction rates applicable to industrial processes, hydrolysis should be conducted at a temperature above the polymer melting point [111,112]. Catalysts may also be used in the alkaline hydrolysis of PET, e.g., amines with dissociation constant K > 10~5 [113]. Representative examples of PET hydrolysis using alkaline solutions are given below. Pitat et al. [91] have patented a method of PET alkaline hydrolysis in an 18 wt% solution of NaOH. The most advantageous results are achieved at a PET/NaOH weight ratio of 1:20 at about 10O0C for 2h. The sodium

Chemical Recycling of PET: Methods and Products

1269

salt of TA formed has relatively good solublility in aqueous solutions of alkaline hydroxides; however, by maintaining the NaOH concentration at a constant level of 18 wt%, it is possible to achieve its complete precipitation. After separation, the salt is dissolved in a small amount of water so as to obtain a nearly saturated solution. After acidification, TA is precipitated from the solution, filtered off, rinsed, and dried. EG formed during the reaction remains in the aqueous phase and is fed back into the process after addition of NaOH. The EG content in the solution increases and, therefore, its recovery by vacuum distillation becomes feasible. The process can be run under either high or atmospheric pressure as well as under conditions using lower hydroxide concentrations [91]. Lazarus et al. [100] described a process allowing the recovery of TA and other monomeric components from PET/polyamide-6 blends. In the first stage, the mixture is heated in an aqueous solution of sodium or potassium hydroxide; most favorable results are achieved at temperatures of 21025O0C under autogenic pressure. Weight ratios of the polymer blend to water of 1:2 to 1:3 are technologically most advantageous. When hydroxide solutions of concentrations of 3-10 wt% are used, the reaction time amounts to 3-5 h. The quantity of alkalies used depends on the polyester content of the polymer blend. After the completion of the reaction, the mixture is filtered in order to remove the insoluble residue and a strong mineral acid is added in order to separate the dicarboxylic acid formed. The generated caprolactam and EG are separated by distillation or are salted-out using NaCl. Another relatively simple process has been developed in which PET containing up to 40 wt% of impurities can be recycled to starting monomers [2]. High pressure equipment is not required and the process uses just a rotary kiln, a condenser, and a centrifuge, thus being less capital intensive and less costly to run than methanolysis. After degradation of the PET waste in aqueous NaOH solution to EG and disodium terephthalate, the mixture is heated up to 34O0C to evaporate and recover EG by distillation. This treatment also reduces the organic impurities to C2 and water. TA is isolated and purified under normal pressure at 10O0C. The process was commercialized in the USA under the trade name UnPET and in France under the trade name RECOPET [2]. An interesting approach is the alkaline hydrolysis of a mixture of PET waste and methyl benzoate formed as a by-product of the oxidation of para-xylene to TA [102]. In the first stage, PET is treated with methyl benzoate at temperatures of 190-20O0C. The mixture obtained undergoes hydrolysis by an aqueous solution of alkali-metal hydroxide with a concentration of 2-7 wt% for 30 min at temperatures of 95-10O0C. The process allows the recovery of TA and benzoic acid in yields of 87-95% and 84-89%, respectively. Yoshioka et al. [105] described an alkaline hydrolysis process, involving the conversion of post-consumer PET to TA and oxalic acid in a con-

1270

T. Spychaj

centrated NaOH solution. The optimal conditions for this base-catalyzed oxidation were determined to be NaOH concentration of 27 M, temperature of 25O0C, reaction time of 5h, and oxygen partial pressure of 5MPa. The process can effectively oxidize even green PET waste, giving a colorless product mixture. A concept of EG oxidation in the mixture with disodium terephthalate (which is stable to oxidation under the reaction conditions) has also been used in the acidic PET hydrolysis method [99]. In a kinetic study of PET alkaline hydrolysis by thermal methods, Kao et al. [107] have found that potassium hydroxide is more active than sodium hydroxide. Experiments performed with KOH solutions (molar ratio of PET repeat units to KOH of 1:4) under autogenic pressure at 16O0C for 30min showed complete polymer disintegration [108]. Using ammonium hydroxide instead of sodium hydroxide solutions for PET hydrolysis, it is possible to eliminate the impurities present in postconsumer PET bottles. Ammonium hydroxide is more expensive than alkali-metal hydroxides or carbonates used in typical alkaline degradation processes. However, the maximum obtainable pH of the reaction medium is below the level at which aluminum bottle cups or other extraneous materials are attacked, thereby eliminating the need to remove the cups or labels before processing. The process according to Lamparter et al. [110] is performed preferably at temperatures of 190-23O0C under pressures of 1.4-3.1 MPa for maximum 3h, with the amount of NH4OH being higher by a factor of about 3 than the stoichiometric amount with respect to the formed terephthalic acid diammonium salt. The reaction mixture containing water-soluble diammonium terephthalate is filtered while still hot. The filtrate is then acidified with sulfuric acid to precipitate TA. The latter is isolated by filtration, washed with water, and dried. The secondary residual filtrate contains EG and ammonium sulfate. Ammonium sulfate is reacted with calcium oxide (or hydroxide) to remove gaseous ammonia; gypsum is formed as a byproduct [UO]. EG is separated from the aqueous solution by distillation (as a bottom residue). A similar process was reported by Datye et al in their review article [109]. Namboori and Haith [101] have compared reactivities of PET with various solutions, namely aqueous NaOH, sodium tert-butoxide in eri-butanol, sodium isopropoxide in isopropanol, sodium methoxide in methanol, and sodium ethoxide in ethanol. It has been demonstrated that sodium ethoxide in ethanol is the most reactive solution and an aqueous solution of sodium hydroxide is the least reactive. Treatments based on partial PET alkaline hydrolysis are widely used in the polyester fiber industry. The effect of such processes on the mechanical properties of fibers [101,114,115], oligomer content, and change in the molecular weight distribution [103,115], or loss of fiber mass [103,114] has been investigated. Collins and Zeronian [103] have demonstrated that NaOH solutions in methanol react with PET significantly faster than anal-

Chemical Recycling of PET: Methods and Products Neutral hydrolysis [122]: 30O0C, H2O/PET weight ratio 1:1, conversion 18.5% pET flakes Melting zone
:

1271

(B)

Reaction zone

t
Solid NaOH Basic hydrolysis [118]: 100-20O0C, conversion 97%
(A)

Qi CO

TA+ EG

TA/Na salt + EG

Figure 4. Hydrolytic PET degradation in extruder

ogous aqueous solutions. Tindall et al. [116,117] have claimed methods of PET hydrolysis using substantially anhydrous three-component mixtures comprising a hydroxide (or alkoxide), alcohol or glycol, and a polar aprotic solvent. The most effective reaction conditions are as follows: sodium or potassium hydroxide (or the alkoxide tetralkylammonium hydroxide), methanol or EG, dimethylsulfoxide or N-methyl-pyrrolidone as polar aprotic solvents, at temperatures of 90-15O0C and pressures from atmospheric to 1.5MPa. In the recycling of PET to terephthalates of alkali metals or alkalineearth metals, the process described by Benzaria et al. [118] may be crucial. The depolymerization is carried out in a mixer-extruder with the use of solid NaOH at temperatures of 100-20O0C. After distillation of EG from the post-reaction mixture under reduced pressure, the respective salt of TA is obtained in powder form. Here, the necessity of separating the glycol and water mixture is eliminated, which is undoubtedly the essential advantage of the process. The degree of polyester saponification reaches ca. 97%. Figure 4A shows a scheme of the extruder system used for PET waste degradation according to this concept. 6.3. Neutral hydrolysis During the last decade, the hydrolysis of PET with water at neutral pH and temperatures of 200-30O0C has been intensively studied [119-124], although the first reports on such degradative polyester reactions have been known since the 1960s [92,93]. Despite the fact that the process is conducted in the absence of acidic or alkaline catalysts, the pH of the reaction mixture

1272

T. Spychaj

reaches values of 3.5-4.0, which, according to Michalski [120], is because of the formation of TA monoglycol ester. The process is usually carried out at pressures of 1-4MPa and temperatures of 200-30O0C [112,119-121,123126]. The weight ratios of PET to water vary from 1:2 to 1:12. It has been confirmed that PET hydrolysis proceeds significantly faster in the molten state than in the solid state [111,112]; therefore, it is advantageous for the recycling to be carried out at temperatures higher than 2450C. The application of common transesterification catalysts is possible, but the recommended ones are alkali-metal acetates [102]. Michalski [127] has studied the influence of the catalysts contained in commercial PET, i.e., acetates of calcium, manganese or zinc used in the first stage of PET synthesis (transesterification), antimony trioxide added in the second stage (polycondensation), and the effect of the stabilizers blocking transesterification (added between the first and second stage), i.e., phosphorus compounds. Michalski's investigations have proved the accelerating action of the transesterification catalysts. No inhibition by stabilizers was observed and in some cases they had an accelerating effect. Campanelli et al. [112,121] have described the catalytic effect of zinc catalysts at temperatures of 2502650C. The rate constant was found to be higher by about 20% than in the uncatalyzed system. The catalytic effect of zinc and sodium salts is attributed to the electrolytic destabilization of the polymer/water interface in the hydrolysis process. During PET hydrolysis, a monoester of glycol and terephthalic acid is formed as a by-product. It dissolves well in water at 95-10O0C; at these temperatures TA is practically insoluble and its separation from the postreaction mixture does not create any problems [127]. It has been proved that the appropriate control of the process parameters limits the amount of monoester formed to less than 2% [127,128]. An effective five-stage process of neutral hydrolysis of PET to EG and TA of purity required for the synthesis of this polymer has been patented by Tustin et al. [123]. PET is hydrolyzed at temperatures of 200-28O0C. After cooling the post-reaction mixture to 70-10O0C, the solid product is filtered and dried at temperatures of 25-1990C. EG is recovered from the filtrate as a result of two-stage distillation. The solid product of hydrolysis is heated with water at temperatures of 310-37O0C and, after cooling, TA is obtained. The purity of the recovered TA and EG allows their application in the production of high quality homo- and copolymers and does not exclude their use in the manufacture of bottles and fibers. The neutral hydrolysis method lacks the primary drawbacks characteristic of acid or alkaline hydrolysis. The formation of substantial quantities of inorganic salts that are hard to dispose of is avoided; corrosion problems due to the use of concentrated acids and alkalies are also avoided. Another undoubted advantage of neutral hydrolysis is that the process is environmentally friendly and, therefore, growing interest in this technology can be expected. Its main drawback is that all mechanical impurities present in

Chemical Recycling of PET: Methods and Products

1273

the polymer are left in the TA and, consequently, a much more sophisticated purification process is required. Possible product contaminations are removed by filtration of the caprolactam solution of TA or of its aqueous sodium hydroxide solution [127]. The crystallization of TA from caprolactam makes it possible to obtain a product with purity of at least 99% [129]. During the hydrolysis of PET, a substantial volume of diluted EG is generated, which can be recovered through extraction or by distillation. Kamal et al [122] have presented an efficient process of continuous hydrolysis, using a twin-screw extruder as a reactor and resulting in PET oligomers containing 2-3 repeat units. The products with carboxyl endgroups have higher melting temperatures than virgin PET, while those with one carboxyl and one hydroxyl group or with two hydroxyl groups have lower melting points. It has been demonstrated that the utilization of cold or even hot water in the process does not give a satisfactory degree of depolymerization. The situation changes when high-pressure saturated steam of temperatures close to that of molten PET is injected into the reaction zone of the extruder. The maintenance of adequate high pressures requires the application of suitable throttling systems, allowing the control of back- leakage of the post-reaction mixture from the extruder. A scheme of the extruder setup for neutral hydrolysis of PET waste is shown in Figure 4B. 7. Ammonolysis and aminolysis 7.1. Ammonolysis The action of anhydrous ammonia on PET causes degradation of the polymer, resulting in terephthalamide [130,131]. Terephthalamide can be converted into terephthalic acid nitrile and further to para-xylylene diamine or l,4-bis(aminomethyl) cyclohexane [13O].
COCH 2 CH 2 OVX, I, O

-EG

Terephthalamide H 2 NH 2 Cp-Xylylene diamine N=C-(( ))-C=N

100-20O 0 C catalysts

'

52

,.
v \ . . (18)

Terephthalonitrile

H 2 NH 2 C-(^J-CH 2 NH 2 l,4-Bis(aminomethyl) cyclohexane

1274

T. Spychaj

Very good results were obtained during the ammonolysis of PET waste from post-consumer bottles; the process was carried out under a pressure of about 1 MPa in a temperature range of 120-18O0C for 1-7 h [13O]. After the reaction was completed, the amide product was filtered, rinsed with water, and dried at a temperature of 8O0C. The product had a purity of at least 99%, in a yield of more than 90%. A low-pressure method of PET ammonolysis, in which the degradation agent is ammonia in ethylene glycol medium is also reported [131]. The process, conducted at a temperature of 7O0C and a ratio of PET/NH3 of 1:6, is catalyzed by zinc acetate in a quantity of 0.05 wt%. Terephthalamide is produced in a yield of about 87%.

7.2. Aminolysis
The processes of a partial surface modification of PET fibers or powders by aminolysis have been the subject of extensive research [114,132-139] and find industrial-scale application. Such modification processes improve the dyeability and other technical and end-use parameters of the fibers. In most cases, the aminolytic modification of PET fiber surfaces is conducted using primary amines in aqueous solutions [114,132-139] or, less frequently, in gaseous form [138]. Most frequently used are methylamine [133-136], ethylamine [114,136], and butylamine [114,137]. Ethanolamine [136], ethylene diamine [139], and triethylene tetramine [138] are also used. The purpose of this aminolytic PET fiber modification is a selective degradation, allowing control of the fiber morphology. The amorphous regions of a semicrystalline polymer undergo rapid degradation, whereas the crystalline regions are much more resistant to attack by amines [132]. Popoola [135] put forward the mechanism of aminolytic degradation of PET, based on the example of n-butylamine. Carduner et al. [140] have investigated the PET fiber degradation mechanism caused by sulfonamides and thiurams present in nitrile rubber composites used for cord tyres. These rubber additives (applied in curing compositions) diffused into the PET fiber, resulting in a uniform aminolytic degradation of the polymer surface. There is one earlier report on deep aminolytic PET degradation [141]. Other references concerning this process and the respective reaction products have started to appear over the last few years [142-147]. Aminolytic degradation of PET waste with allylamine [142,143] produced ,'-bisallyl terephthalamide. The degradation occurred at a temperature of 17O0C under pressures of 1.5-2.OMPa for 2 h with the amine in excess. After removing the residual allylamine by distillation and EG by 0 washing with water, a high purity powdery product, melting at 217-219 C, was obtained [142]. The product may be considered as a high-temperature solid crosslinking agent for unsaturated polyesters. Sulkowski et al. [144] have recently investigated products of PET

Chemical Recycling of PET: Methods and Products

1275

aminolysis with morpholine and hydrazine. Conditions of the degradation reaction were not given. These authors found that morpholine-degraded PET contains practically exclusively N-bismorpholine terephthalamide, whereas the product of aminolysis with hydrazine contains a mixture of hydrazides of TA and hydrazide derivatives of /EG oligomers. Polyamines (diethylenetriamine and triethylenetetramine (TETA)) have been applied for PET aminolysis in order to obtain aminoamide derivatives of TA, designated for epoxy resin hardening [145-147]. The chemical degradation of PET with polyamines, at a molar ratio of the recurrent polymer unit to polyamine of 1:2, results mainly in low molecular weight products and oligomers.
COCH 2 CH 2 OVW +H 2 NCH 2 CH 2 (NHCH 2 CH 2 ) 2 NH 2
20

-210c-EG

O
H 2 N(CH 2 CH 2 NH) 2 CH 2 CH 2 HNC-/QV CNHCH 2 CH 2 (NHCH 2 CH 2 ) 2 NH 2

O O Symmetrical TA amide
I y /CH 2 CH 2 NH 2 H 2 N(CH 2 CH 2 NH) 2 CH 2 CH 2 HNC- (C))- CN Il v^V Il X (CH 2 CH 2 NH) 2 H (19) Asymmetrical TA amide/imide i /CH 2 CH 2 NH 2 / N C ^ O ) V - CN H(HNCH 2 CH 2 )/ Il V^y Il N (CH 2 CH 2 NH) 2 H Symmetrical TA imide H 2 NCH 2 CH 2

NMR spectra of the PET/TETA aminolysis products showed the presence of symmetrical terephthalamide (47%), symmetrical terephthalimide (21%), and asymetrical amide/imide TA derivatives (32%) [146]. The PET/TETA product is a viscous liquid (~ 5Pa-s at 6O0C) that is compatible with liquid epoxy resins. Some characteristics of the epoxy materials hardened with PET/polyamine aminolysis products have been reported [145-147]. 8. Aminoglycolysis This process concerns the solvolytic reactions performed by alkanolamines with tert-nitrogen atom. In addition to alkali solutions [113] or glycols [70], solvolysis of the ester bond in polyesters is sometimes realized in the presence of amines. Primary and secondary amines in such reaction systems can act either as catalysts or as active aminolytic agents. Examples of mixtures

1276

T. Spychaj

of glycols and aminoalcohols used in PET solvolytic degradations can be found, e.g., in [69]. Similar mixed substances are applied in the chemical recycling of PUR/PIR foams [148]. Research on PET chemical degradation with triethanolamine (TEA) was undertaken in the author's laboratory [142,145-147,149]. The chemical degradation of PET with TEA is considered to be glycolysis catalyzed by a tertiary amine. For this reason, the process is termed "aminoglycolysis". The solvolytic activity of eri-N-alkanolamines with respect to PET ester bonds is a function of the hydroxyl group content and of the amine basicity [146]. Aminoester derivatives of TA and TEA are formed during the PET degradation with TEA in excess (molar ratio of 1:2).
/CH 2 CH 2 OH COCH 2 CH 2 OVW +HOCH 2 CH 2 N
X

CH 2 CH 2 OH

CH 2 CH 2 OH COCH 2 CH 2 N 'CH 2 CH 2 OH (20) CH 2 CH 2 OH COCH 2 CH 2 NCH 2 CH 2 OC

O O

The product of PET aminoglycolysis with TEA (PET/TEA) at a temperature of 2050C is a multicomponent mixture of TA ester derivatives [146]. This product is a viscous liquid (~ 13mPa-s at 6O0C) with hydroxyl number in the range of 100-400 mg KOH/g, depending on the reaction conditions [60,146,149]. It is miscible with epoxy resins, polyols designated for rigid polyurethane foams, and water. Results of the application of PET/TEA as a polyol component for rigid polyurethane foams are described in [60,149]. However, the most promising results have been obtained with the PET/TEA product used as epoxy resin hardener [145-147,15O]. The main features of the product obtained by PET degradation with triethanolamine and applied as epoxy resin hardener are: (i) advantageous technological properties, i.e., low viscosity in the compositions with liquid epoxy resins at elevated temperatures, long pot-life at ambient temperature and at 8O0C [146,147]; (ii) relatively wide range of the epoxy resin/hardener weight ratios [147]; (iii) high values of the mechanical properties; the simultaneously demonstrated flexural, tensile and impact strengths of the PET/TEA-hardened epoxy materials [146,147] place them on the level of epoxy materials modified with special additives, i.e., rubber or thermoplas-

Chemical Recycling of PET: Methods and Products

1277

tic resin modifiers [151-153]; (iv) ability to emulsify liquid epoxy resins in water and to be used in water-thinnable paints [15O]. Research on PET aminoglycolysis with other alkanolamines is in progress, and some new degradation products are considered as promising additives to reactive polymeric systems [154]. 9. Hybrid chemical recycling methods Some hybrid solvolytic methods of PET degradation are described in the literature, e.g., [2,19,22,155]. The combined processes of methanolysis/hydrolysis and glycolysis/hydrolysis are most important, and some industrially relevant examples are described below. A continuous process for the recovery of TA and EG from PET waste by hybrid methanolysis/hydrolysis, resulting in the production of fibergrade terephthalic acid, was claimed by Socrate and Vosa [19]. The process comprises the following steps: (i) decomposition of the polymer to its constituent monomers with superheated methanol (230-25O0C) introduced to the molten PET (26O0C) at atmospheric pressure; (ii) continuous removal of methanol and monomer vapors and condensation of EG and DMT mixture; (iii) removal of EG from the mixture of condensed monomers by distillation; (iv) hydrolysis of the distillation residue at a temperature above 15O0C (e.g., 27O0C) under pressure (e.g., 8MPa) for a certain time (e.g., 30min); (v) recovery of TA by filtration; (vi) optionally, crystallization of TA. A two-step hybrid glycolysis/methanolysis process [22] involves glycolysis as a first stage to obtain bis(hydroxyethyl) terephthalate (BHET) and higher /EG oligomers. As a result of methanolysis of these products, DMT is obtained. The method allows inconveniences associated with highpressure methanolysis to be minimized. The PET feed is dissolved in a glycolyzed PET product to achieve considerable energy savings. Next, the superheated methanol vapor is added. The reaction mixture is held at pressures lower than that necessary to keep methanol in the liquid state because the DMT formed is removed as a vapor. The removal of esters and alcohols as vapors allows the use of more contaminated PET than that accepted by conventional liquid-phase methanolysis. The process developed by West [2] allows the conversion of significantly contaminated plastics by a combination of glycolysis and hydrolysis into high-quality substrates for PET synthesis. This technology was used for TA and EG recovery by Innovations in PET, West Footscray, Victoria, Australia. The scheme of the production line is shown in Figure 5 [2], and the process includes several steps: (i) shredding of the PET bottles at the collection point; (ii) washing of the flakes in a "float/sink" water tank to separate paper and polyolefins; (iii) drying of the PET flakes; (iv) partial glycolysis with boiling EG to obtain PET in a brittle state (performed

1278
PET bottles

T. Spychaj

EG & contaminants

Granulation Drier Glycolysis EG Hindered settling Screening

EG, water

J Waste

| Adsorbents

paper fiber

PVC, PE, PP, PaPer> metal

Figure 5. Scheme of hybrid glycolysis/hydrolysis process for recycling contaminated post-consumer PET bottles [2] in a screw conveyor for ca. 50min); (v) crushing of the brittle flakes to particles of less than 1 mm in size; (vi) screening (to < 700 ) to remove uncrushed paper, PVC, aluminum fragments, etc., and hindered settling to eliminate the remaining small particles, such as paper fibers and glue; (vii) glycolysis of PET crumb to BHET and adsorption of other organic compounds, pigments, etc., on activated carbon or clays; (viii) filtration in order to eliminate submicron particles; (ix) BHET hydrolysis at 20O0C; (x) recovery of TA from the boiling water (impurities remain dissolved); (xi) distillation of EG. With the exception of the aforementioned impurities, the modifiers and pigments added to commercial PET are also effectively removed in this hybrid process. PET produced using TA and EG obtained from the process is of similar purity to that of the parent polyester [2]. Penczek and Ostrysz [155] have developed a process, combining partial hydrolysis of PET with subsequent condensation of the product into phenol/formaldehyde resins, that can also be considered as a chemical recycling method. Unlike the typical hydrolysis processes, only the first stage of the solvolytic reaction is carried out in order to achieve partial PET degradation. PET waste is dissolved in phenol, and a polymer solution of high viscosity is obtained. In order to reduce the viscosity, a small amount of water and a catalyst are added to the system, and subsequent heating results in partial PET hydrolysis. The next step consists in the condensation of phenol with formalin, under conditions characteristic of standard novolac resin synthesis. PET waste contaminants, including the mechanical impurities, do not pose problems because powdery fillers are subsequently

Chemical Recycling of PET: Methods and Products

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added into the final resin for use in the production of molding compounds [155].
10. Other methods

There are known processes of chemical degradation of PET waste which do not belong to the methods described so far (see Chapters 26 and 28). Wang et al [156] have investigated the kinetics of PET degradation using bisphenol A (phenolysis?) as the solvolytic agent. The reaction was performed at temperatures of 190-23O0C under autoclave conditions. The influence of the process parameters and the reaction mechanisms of this process were investigated. An interesting method of recycling PET waste is based on polymer degradation in a coal-tar pitch environment, and the products obtained are utilized in the manufacture of polyurethane of an inferior quality, designated for the production of putties and sealing compounds for construction [157]. Pulverized foil waste or PET fibers are mixed in batches with coal-tar pitch and heated at temperatures of 130-33O0C. The most advantageous effects are obtained in the case of mixtures containing at least 30 wt% of coal-tar pitch. Products with softening temperatures within the range 30-23O0C are obtained. Post-polymerization of PET waste, after a special treatment, can be considered as a separate method of chemical recycling. This process leads to higher molecular weight PET. For instance [158,159], PET waste is dissolved in a suitable organic solvent or solvent mixture (benzyl alcohol, phenol/tetrachloroethane 60/40 by wt, ort/io-chlorophenol, trifluoroacetic acid, trifluoroacetic acid/dichloromethane 50/50 by vol, or nitrobenzene) and then precipitated with methanol so as to develop a large surface area in the material. The latter is subjected to solid-state polycondensation under reduced pressure at 23O0C for 8h. A molecular weight of about 60000g/mol is achieved, i.e., threefold higher than the starting one (Mn = 20300g/mol). Chemical reactions during blend preparation are described in Chapters 17, 20, and 28, and chain extension is discussed in Chapter 18.
11. Summary and conclusions

PET waste originates from various sources (soft-drink bottles, photographic and X-ray films after removal of the silver compounds, spent textile materials, industrial wastes), differing in shape (flakes, pellets), color, and degree of contamination. It is considered as a feed-stock for chemical processing. PET waste recycling represents the most successful and widespread example of polymer reuse. The chemical recycling of PET can be performed with various solvolytic agents, and useful products for many appli-

1280

T. Spychaj

cations may be obtained. The important advantages of the chemical recycling methods related to post-consumer and waste PET are: (i) removal of any impurities associated (physically or chemically) to the polymer chain by purification of the monomers and oligomers; (ii) the selection of the most appropriate recycling method depends on the quality of the available feed-stock and on the type of the targeted product. However, some drawbacks of the PET chemical recycling processes should also be listed: (i) necessity to operate with well-sorted feed-stocks; (ii) consistency of the batch-to-batch quality; (iii) separation of colored PET wastes is often required; (iv) contaminants, such as PVC, paper, glue, should be reduced to a minimum; (v) in addition to TA and EG, the recycled PET product contains a number of comonomers that increase its chemical heterogeneity. Among the chemical methods of polyester recycling, glycolysis, methanolysis, and hydrolysis are commercially important. In addition to monomers for PET or PBT synthesis, the former can also offer polyol substrates for various applications, especially for unsaturated polyester resins and foamed polyurethanes. The products of methanolysis and hydrolysis are monomers for virgin PET synthesis. A comparative evaluation of the three most commercially important chemical recycling methods is given in Table 2. Some hybrid methods, i.e., combinations of the aforementioned important chemical degradation processes, find industrial-scale applications. These recycling techniques are economically viable at a facility throughput of at least 15000 tons per year [2]. In recent years, an increasing tendency to use less common chemicals for PET degradation is observed. These trends relate to the special transesterification reactions, ammonolysis, aminolysis, or aminoglycolysis methods used in order to obtain the components or additives for polymeric or resinous materials. The economic viability of a given method of chemical recycling is decisive for its application. This is related to the following factors: (i) processing capability of the installation; (ii) specific parameters of the technology used (temperature, pressure); (iii) nature of the agents used for solvolysis and as auxiliary solvents, neutralizers, etc. (corrosive and/or toxic); special labor safety requirements associated with the above chemical agents; (iv) methods of the products separation (if necessary); (v) purity and further application of the products; (vi) waste generation; (vii) contamination of the recycled PET; (viii) cost of the recycled polymer; (ix) continuity of the PET recycled material supply. All these factors influence the final price of the product obtained from PET recycling. It seems, however, that chemical recycling processes offering medium or low tonnage specialized products for paints, adhesives, plasticizers, hardeners, etc., are economically plausible with a throughput limit substantially lower than that given above for large-scale methods.

Chemical Recycling of PET: Methods and Products

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Acknowledgement This work was supported by the State Committee for Scientific Research (KBN), Poland. References
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