Chapter II

Literature Review

2.1

Raw Materials:

This section describes the technical preparation of the main raw materials required to produce polyethylene terephthalate and their specifications.

2.1.1

Terephthalic acid:

Polyethylene terephthalate is increasingly produced from very pure terephthalic acid. Terephthalic acid has some advantages over dimethyl. terephthalate for the production of PET [1]. lower price does not need catalyst like transesterification higher polycondensation speed no recovery of methanol necessary Because of these benefits, the world production of terephthalic acid has been increasing, the world capacity for 1994 is 10.8 million tons compared to 5.3 million tons for dimethyl terephthalate [1]. Terephthalic acid is produced mainly by the Amoco process, then the raw terephthalic acid, containing 4-carboxybenzaldehyde as the main contaminant, is purified by hydrogenation and crystallization. The final terephthalic acid has a purity of 99.99 wt% [1]. To produce light-colored and high molecular weight PET, the following demand, incorporating values established by the American Public Health Association (APHA), are made on terephthalic acid as shown in Table (2.2) with a typical particle size distribution lies between 50 and 600 m [1].

Table (2.1) Purified terephthalic acid specifications for PET production [1].
Ash content Metals Fe, Ca, Al, Na, K Co, Mo, Cr, Ni, Ti, Mg 4- Carboxybenzaldehyde Water content 15 ppm 10 ppm 2 ppm 1 ppm 25 ppm 0.05 %

Table (2.2) Physical properties of purified terephthalic acid [2].

Property Molecular weight, g/mol Melting point, oC Triple point, oC Specific gravity at 25 oC, g/mL Specific heat J/(kg.K) Sublimation point, oC Heat of combustion at 25 oC, kJ/mol Heat of formation at 25 oC, kJ/mol Heat of sublimation, kJ/mol Value 166.14 427 427 1.522 1202 404 -3198 -816 142

2.1.2

Ethylene Glycol:

Ethylene glycol is produced industrially by the reaction of ethylene oxide with excess water. The typical product distribution between the products of this reaction, which are ethylene glycol, diethylene glycol, and triethylene glycol, is a mass relation of 30:4:1 respectively [1]. The glycols are separated by purification under vacuum in distillation columns connected in series. To produce light-colored, high molecular weight PET, demands are made on ethylene glycol as shown in Table (2.3).

Table (2.3) Ethylene glycol specifications for PET production [1].

Purity Water content Diethylene glycol content Ash content Iron content Acid content as acetic acid Acetaldehyde content Density at 20 oC UV permeability at 220 nm at 275 nm at 350 nm 99.9 wt% 0.05% 0.03 0.04% 0.005 g/100 ml 0.05 ppm 0.005% 7 ppm 1.1151 1.116g/cm3 70% 90% 98%

Table (2.4) includes some important physical properties of ethylene glycol.

Table (2.4) Physical properties of ethylene glycol [3,4]. Property

Molecular weight, g/mol Specific gravity at 20 oC, g/ml Heat of vaporization at 101.3 kPa, kJ/mol Specific heat, J/(g.K) as liquid, 19.8 oC as ideal gas, 25 oC Autoignition temperature, oC Heat of combustion at 25 oC, kJ/mol Heat of formation at 25 oC, kJ/mol Heat of fusion, kJ/mol Critical constants temperature, oC pressure, kPa volume, L/mol compression factor Viscosity, mPa.s (cP) at 0 oC at 40 oC

Value
62.07 1.1135 52.24 2.406 1.565 400 -1189.595 -392.878 11.63 446.55 6515.73 0.186 0.2671 51.37 9.20

2.2

Product:

The main product in this process is the Polyethylene terephthalate. However, water is produced as a polycondensation by-product with no important economical value. Polyethylene terephthalate (PET) is a polycondensation polymer. It is most commonly produced from a reaction of ethylene glycol (EG) with either purified terephthalic acid (TPA) , using a continuous melt-phase polymerization process. This polymer is the most common thermoplastic polyester. It is often called just polyester, which often causes confusion. PET is a hard, stiff, strong , dimensionally stable material that absorbs very little water. It has good gas barrier properties and good chemical resistance except to alkalis (which hydrolyze it). Its crystallinity varies from amorphous to fairly high crystalline. It can be highly transparent and colorless but thicker sections are usually opaque and off-white (Salaeh A. Jabarin, 1996). PET is widely known in the form of thermally stabilized films used for capacitors, graphics, film base and recording tapes etc. It is also used for fibres for a very wide range of textile and industrial uses. Other applications include bottles and electrical components. Many analysts estimate PET growth at an annual rate of 7% through 2003. According to purchasing survey data, PET spot pricing currently average about 59 /Ib. Prices have risen steadily in 1999, when PET spot prices averaged about 51 /Ib. Since the third quarter 1999, PET prices have risen an average of 8 /Ib (Buyers News, Sep 2000).

2.3

Chemical fundamental of PET production:

The two most important synthesis of PET are based on the reaction of ethylene glycol (EG) with either purified terephthalic acid (TPA) or its ester dimethyl terephthalate (DMT). Early PET production was based solely on the ester, but, with the advent of purified terephthalic acid on a commercial scale in 1964 [5], it became possible to implement processes based on the acid. Using pure acid as a raw material has a lot of advantages over using its ester. The first step of the two routes, known respectively as transesterification (ester interchange) and direct esterification, both produce a mixture of ethylene glycol ester of terephthalic acid. In the second step the obtained BHET undergoes polycondensation at higher temperature to form the polyester PET, while glycol is removed. An advanced polycondensation in the solid state just below the melting temperature of the polyester is necessary to obtain very high molecular weights [1].

2.3.1

Esterification process:

As an equilibrium reaction, esterification is always accompanied by the reverse reaction being hydrolysis[6]. The esterification process involves three phases, i.e. solid TPA, a homogeneous liquid phase and the gas phaseThe esterification of TPA with EG is a reaction between two bifunctional molecules which leads to a number of reactions occurring simultaneously. Since TPA has a very low solubility in boiling glycol at atmospheric pressure, it is necessary to raise the reaction temperature and pressure in order to obtain an adequate reaction rate. Adequate rates are obtained at 240-260 C and above atmospheric pressure, usually 4 atm. The reaction is self-catalyzed by the carboxylic acid groups. Usually, the glycol: terephthalic acid molar ratio is 1.1 to 1.3:1 [5], The initial reaction product is a mixture of linear oligomers, mostly BHET, in addition to water as by product according to this reaction [1].
HOOC-C6H6-COOH + 2 HOCH2CH2O 2 H20 + HOCH2CH2OOC-C6H6-COOCH2CH2OH

(2.1) The volatile product of direct esterification is water, which is distilled out of the reactor to force the reversible reaction toward completion.

2.3.2

Polycondensation process :

With polycondensation polymerization, two monomers join to produce dimers, trimers, tetramers, and higher oligomers; and finally polymers, plus a by-product which is usually H2O[2].The second step in PET synthesis is similar for both the ester interchange and direct esterification routes. A further catalyst is to be added to the mixture of linear oligomers, free glycol is distilled out according to reaction (2.2) [1] , and the temperature is raised until it reaches 260- 290. The pressure is reduced as rapidly as possible without causing carry-over due to foaming, and polymerization is carried out finally at a pressure below 1 mbar (100 Pa) until the required molecular weight is attained [5,6].
n HOCH2CH2OOC n COOCH2CH2OH (n-1) HOCH2CH2OH +

[ OCH2CH2OOC

CO OCH2CH2OH (2.2)

The most popular catalyst for this stage is antimony trioxide, although antimony pentoxide and germanium dioxide has also been used. The polycondensation reaction is reversible as it is shown in reaction (2.2), so it is

important to remove the glycol produced from the system as quickly as possible. In most polymerization reactors, the rate of attainment of high molecular weight is diffusion-controlled rather than chemically controlled, and it is useful to minimize the diffusion path by maximizing the surface: volume ratio and the rate of generation of free surface. There are two types of polycondensation, the melt and the solid polycondensation. The melt polycondensation of PET, carried under common industrial conditions, leads to products with a molecular weight of 15,000-25,000 [1]. Bottle-grade PET appears glass-clear in the amorphous state. Special requirements for bottle-grade PET are a brilliant white colour and a composition fulfilling the regulations for food packaging. The average molecular weight ranges from 24 000 to 36 000 g/mol, which refers to an IV of between 0.75 and 1.00 dL/g. The standard bottle grade has an IV of 0.80 dL/g. Etherification of EG to form DEG is an important side reaction in PET synthesis. Most of the DEG is generated during the initial stages of polycondensation in the preheating stage (up to 50% of total DEG) and in the low-vacuum stage (up to 90% of total DEG). In the final high-vacuum stage, approximately 10% of the total DEG is formed[0]. the total DEG is formed . Most of the DEG is already formed during the esterification stage[6].

2.4

Constraints in PET production :

The polycondensation process is accompanied with many constraints which should be consider during the processing of PET.

2.4.1

Reactions with Co-monomers:

The properties of PET can be modified by the incorporation of co-monomers. Typical examples of these are isophthalic acid (IPA) (influences stress cracking resistance and melting temperature), 2,6-naphthalene dicarboxylic acid (NDC) (improves mechanical properties and reduces gas permeability), cyclohexane dimethanol (CHDM) (influences rate of crystallization and melting temperature), diethylene glycol (DEG) (improves dyeability of fibre grades and lowers melting temperature) and bisphenol A (improves melt stiffness).

2.4.2

Formation of short chain oligomers:

PET contains about 23% of short chain oligomers, which cause problems in the processing of the polymer. Oligomers can occur as linear or cyclic molecules and can be extracted by suitable solvents. In a thorough study on oligomers in recycled PET, found that the oligomer formation depended on the reaction temperature and the type of thermal treatment. During vacuum treatment of solid PET at 150220 C, the oligomer concentration decreased with increasing reaction temperature.

2.4.3

Formation of diethylene glycol and dioxane :

Etherification of EG to form DEG is an important side reaction in PET synthesis. Most of the DEG is generated during the initial stages of polycondensation in the preheating stage (up to 50% of total DEG) and in the low-vacuum stage (up to 90% of total DEG). In the final high-vacuum stage, approximately 10% of the total DEG is formed found that most of the DEG is already formed during the esterification stage. Nevertheless, DEG contents should be as low as possible in other PET grades, because DEG decreases the melting point and the thermal stability of the polymer.

2.4.4 Thermal degradation of diester groups and formation of acetaldehyde:

Thermal degradation of PET is a major problem at temperatures above the melting point and inevitably occurs in polymer melts during synthesis and processing. Major consequences for the PET quality are an IV drop, the formation of carboxyl end groups and acetaldehyde, and the yellowing of the polymer. Carboxyl end groups reduce the hydrolytic and thermal stability, and in standard PET grades their concentration should not exceed 25 mmol/kg. Acetaldehyde migrates into the contents of food packaging, so causing flavour problems of the products. For bottle-grade PET, often an acetaldehyde content below 1 ppm is specified. By-products of thermal degradation are light gases, being mainly CO, CO2, ethene, methane, and benzene, together with TPA, HET and short-chain oligomers.

2.4.5

Yellowing:

The polymer colour is regarded as a quality parameter, and low-quality PET grades show yellow colouring. Yellowing of the polymer can be caused by thermal as well as by oxidative degradation and is a severe problem in PET synthesis, especially in the production of bottle grades. Oxidative degradation can be minimized by careful operation under an inert gas atmosphere, but thermal degradation can only be avoided by reducing the reaction temperature which also reduces the polycondensation rate [6].

References:
1. Ludwig Bottenbruch, Engineering Thermoplastics: Polycarbonates, Polyacetals Polyesters, and Cellulose Esters, 1996, Hanser/Grander Publications, Inc. 2. Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, Volume 18, 1994, John Wiley & Sons, Inc. 3. Beaton and Hewitt, Physical Property Data for the Design Engineer, 1989, Hemisphere Publishing Corporation. 4. Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, Volume 12, 1994, John Wiley & Sons, Inc. 5. Menachem Lewin and Eli. Pearce, Handbook of Fiber Chemistry, Second Edition, 1998, Marcel Dekker, Inc. 6. Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters. Edited by J. Scheirs and T. E. Long 2003 John Wiley & Sons, Ltd ISBN: 0-471-49856-4.