Fiber, polyester

TP polyester offers a low density, high tenacity fiber with good impact resistance but low modulus. It is used in areas where high stiffiiess is not required, but where low cost, lightweight, and high impact or 

Polyesters are the most important class of synthetic fibers. In general, polyesters are produced by an esterification reaction of a diol and a diacid. Carothers (1930) was the first to try to synthesize a polyester fiber by reacting an aliphatic diacid with a diol. The polymers were not suitable because of their low melting points. However, he was successful in preparing the first synthetic fiber (nylon 66). In 1946, Whinfield and Dickson prepared the first polyester polymer by using terephthalic acid (an aromatic diacid) and ethylene glycol. 

Polyesters can be produced by an esterification of a dicarboxylic acid and a diol, a transesterification of an ester of a dicarboxylic acid and a diol, or by the reaction between an acid dichloride and a diol. 

The polymerization reaction could be generally represented by the esterification of a dicarboxylic acid and a diol as  

Less important methods are the self condensation of w-hydroxy acid and the ring opening of lactones and cyclic esters. In self condensation of w-hydroxy acids, cyclization might compete seriously with linear polymerization, especially when the hydroxyl group is in a position to give five or six membered lactones. 

Using excess ethylene glycol is the usual practice because it drives the equilihrium to near completion and terminates the acid end groups. This results in a polymer with terminal -OH. When the free acid is used (esterification), the reaction is self catalyzed. However, an acid catalyst is used to compensate for the decrease in terephthalic acid as the esterification nears completion. In addition to the catalyst and terminator, other additives are used such as color improvers and dulling agents. For example, PET is delustred hy the addition of titanium dioxide. 

Azoic dyes and pigment-binder systems have also found limited use on polyesters. Polyester modified with appropriate comonomeis can be (fyed at lower temperatures or with acid or basic dyes depending on the nature of the modifying groups. 

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Dyes polyester fibers fast blue, brown, and red shades... 

Gives blue and violet shades on polyester fibers... 

ETHYLENE We discussed ethylene production in an earlier boxed essay (Section 5 1) where it was pointed out that the output of the U S petrochemi cal industry exceeds 5 x 10 ° Ib/year Approximately 90% of this material is used for the preparation of four compounds (polyethylene ethylene oxide vinyl chloride and styrene) with polymerization to poly ethylene accounting for half the total Both vinyl chloride and styrene are polymerized to give poly(vinyl chloride) and polystyrene respectively (see Table 6 5) Ethylene oxide is a starting material for the preparation of ethylene glycol for use as an an tifreeze in automobile radiators and in the produc tion of polyester fibers (see the boxed essay Condensation Polymers Polyamides and Polyesters in Chapter 20)... 

The carboxylic acid produced m the greatest amounts is 1 4 benzenedicarboxylic acid (terephthahc acid) About 5 X 10 Ib/year is produced m the United States as a starting material for the preparation of polyester fibers One important process converts p xylene to terephthahc acid by oxidation with nitric acid... 

The production of polyester fibers leads that of all other types Annual United States production of poly ester fibers is 1 6 million tons versus 1 4 million tons for cotton and 1 0 million tons for nylon Wool and silk trail far behind at 0 04 and 0 01 million tons re spectively... 

The Textile Eiber Product Identification Act (TEPIA) requires that the fiber content of textile articles be labeled (16). The Eederal Trade Commission estabhshed and periodically refines the generic fiber definitions. The current definition for a polyester fiber is "A manufactured fiber ia which the fiber-forming substance is any long-chain synthetic polymer composed of at least 85% by weight of an ester of a substituted aromatic carboxyUc acid, including but not restricted to terephthalate units, and para substituted hydroxyben2oate units."... 

In the late 1980s, new fully aromatic polyester fibers were iatroduced for use ia composites and stmctural materials (18,19). In general, these materials are thermotropic Hquid crystal polymers that are melt-processible to give fibers with tensile properties and temperature resistance considerably higher than conventional polyester textile fibers. Vectran (Hoechst-Celanese and Kuraray) is a thermotropic Hquid crystal aromatic copolyester fiber composed of -hydroxyben2oic acid [99-96-7] and 6-hydroxy-2-naphthoic acid. Other fully aromatic polyester fiber composites have been iatroduced under various tradenames (19). 

Standard polyester fibers contain no reactive dye sites. PET fibers are typically dyed by diffusiag dispersed dyestuffs iato the amorphous regions ia the fibers. Copolyesters from a variety of copolymeri2able glycol or diacid comonomers open the fiber stmcture to achieve deep dyeabiHty (7,28—30). This approach is useful when the attendant effects on the copolyester thermal or physical properties are not of concern (31,32). The addition of anionic sites to polyester usiag sodium dimethyl 5-sulfoisophthalate [3965-55-7] has been practiced to make fibers receptive to cationic dyes (33). Yams and fabrics made from mixtures of disperse and cationicaHy dyeable PET show a visual range from subde heather tones to striking contrasts (see Dyes, application and evaluation). 

Mechanical Properties. Polyester fibers are formed by melt spinning generally followed by hot drawing and heat setting to the final fiber form. The molecular orientation and crystalline fine stmcture developed depend on key process parameters in all fiber formation steps and are critical to the end use appHcation of the fibers. 

Polyester fibers have exceUent resistance to soap, detergent, bleach, and other oxidiziag agents. PET fibers are generally iasoluble ia organic solvents, including cleaning fluids, but are soluble ia some phenoHc compounds, eg, (9-chlorophenol. 

Other Properties. Polyester fibers have good resistance to uv radiation although prolonged exposure weakens the fibers (47,51). PET is not affected by iasects or microorganisms and can be designed to kill bacteria by the iacorporation of antimicrobial agents (19). The oleophilic surface of PET fibers attracts and holds oils. Other PET fiber properties can be found ia the Hterature (47,49). 

Physical testing appHcations and methods for fibrous materials are reviewed in the Hterature (101—103) and are generally appHcable to polyester fibers. Microscopic analyses by optical or scanning electron microscopy are useful for evaluating fiber parameters including size, shape, uniformity, and surface characteristics. Computerized image analysis is often used to quantify and evaluate these parameters for quaUty control. 

Woddwide, the production capacity for polyester fiber is approximately 11 million tons about 55% of the capacity is staple. Annual production capacity iu the United States is approximately 1.2 million tons of staple and 0.4 million tons of filament. Capacity utilization values of about 85% for staple and about 93% for filament show a good balance of domestic production vs capacity (105). However, polyester has become a woddwide market with over half of the production capacity located iu the Asia/Pacific region (106). The top ranked PET fiber-produciug countries are as follows Taiwan, 16% United States, 15% People s RepubHc of China, 11% Korea, 9% and Japan, 7% (107—109). Woddwide, the top produciug companies of PET fibers are shown iu Table 3 (107-109). 

PET is based on petroleum and the price of polyester fiber fluctuates with the price of -xylene and ethylene raw materials as well as with the energy costs for production. With the abiUty to interchange with other fibers, especially cotton iu cotton blends, the price of polyester is affected by the price and avadabihty of cotton as well as the supply and demand of polyester. 

Polyester Fibers Containing Phosphorus. Numerous patents describe poly(ethylene terephthalate) (PET) flame-retarded with phosphoms-containing diftmctional reactants. At least two of these appear to be commercial. 

Antlblaze 19. Antiblaze 19 (Mobil), a flame retardant for polyester fibers (134), is a nontoxic mixture of cycHc phosphonate esters. Antiblaze 19 is 100% active, whereas Antiblaze 19T is a 93% active, low viscosity formulation for textile use. Both are miscible with water and are compatible with wetting agents, thickeners, buffers, and most disperse dye formulations. Antiblaze 19 or 19T can be diffused into 100% polyester fabrics by the Thermosol process for disperse dyeing and printing. This requires heating at 170—220°C for 30—60 s. 

Phenylstilben-4-yl)benzoxazoles are prepared by means of the anil synthesis from 2-(4-methylphenyl)benzoxazoles and 4-biphenylcarboxaldehyde anil, and used for brightening polyester fibers (24,25). An example is (3) [16143-18-3]. 

The pyrene derivative (17) [3271-22-5] is obtainable by the Friedel-Crafts reaction of pyrene with 2,4-dimethoxy-6-chloro-j -triazine, and is used for brightening polyester fibers (75). 

Cydohexanedimethanol, 1,4- dim ethyl o1 cycl oh exa n e, or 1,4-bis (hydroxymethyl) cyclohexane (8), is a white, waxy soHd. The commercial product consists of a mixture of cis and trans isomers (6). This diol is used in the manufacture of polyester fibers (qv) (64), high performance coatings, and unsaturated polyester molding and laminating resins (5). 

Fig. 2. Ultrafine fibers are produced by spinning bicomponent or biconstituent polymer mixtures, highly stretching such products to ultrafine deniers, and extracting or otherwise removing the undesked matrix carrier to release the desked ultrafine fibers (30). For example, spinning polyester islands in a matrix of polystyrene and then, after stretching, dissolving the polystyrene to leave the polyester fibers cospinning polyester with polyamides, then stretching,...

Correlation with markets for other products is particularly useful for a new product. For example, market growth history of an older product, eg, nylon, can be plotted on a graph to predict the probable growth for a newer product, eg, polyester fibers. Data for both products may be plotted on the same chart, though not necessarily to the same scale and with the time scale shifted to bring the respective curves in parallel. 

A review covers the preparation and properties of both MABS and MBS polymers (75). Literature is available on the grafting of methacrylates onto a wide variety of other substrates (76,77). Typical examples include the grafting of methyl methacrylate onto mbbers by a variety of methods chemical (78,79), photochemical (80), radiation (80,81), and mastication (82). Methyl methacrylate has been grafted onto such substrates as cellulose (83), poly(vinyl alcohol) (84), polyester fibers (85), polyethylene (86), poly(styrene) (87), poly(vinyl chloride) (88), and other alkyl methacrylates (89). 

Xylene Isomeri tion. The objective of C-8-aromatics processing is the conversion of the usual four-component feedstream (ethylbenzene and the three xylenes) into an isomerically pure xylene. Although the bulk of current demand is for xylene isomer for polyester fiber manufacture, significant markets for the other isomers exist. The primary problem is separation of the 8—40% ethylbenzene that is present in the usual feedstocks, a task that is compHcated by the closeness of the boiling points of ethylbenzene and -xylene. In addition, the equiUbrium concentrations of the xylenes present in the isomer separation train raffinate have to be reestabUshed to maximize the yield of the desired isomer. 

Naphthalenedicarboxylic Acid. This dicarboxyhc acid, a potential monomer in the production of polyester fibers and plastics with superior properties (105), and of thermotropic Hquid crystal polymers (106), is manufactured by the oxidation of 2,6-dialkylnaphthalenes (107,108). 

One of the limitations of the curtain/slot draw process is that the amount of fiber attenuation is constrained due to the short distance generally allowed between the spinnerette and the venturi slot and the use of relatively low pressure air for drawing so as not to induce high turbulence in the area of the laydown. In practical terms this has made the process difficult to adapt for the production of polyester fabrics which inherently require much higher fiber acceleration to attain the desired polyester fiber properties. 

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

Some time earlier, Eastman-Kodak has been working on a novel polyester as an entry into the important polyester fiber market and had devised a new ahcychc diol, 1,4-cydohexanedimethanol [105-08-5] effectively made by exhaustive hydrogenation of dimethyl terephthalate. Reaction of the new diol with dimethyl terephthalate gave a crystalline polyester with a higher melting point than PET and it was introduced in the United States in 1954 as a new polyester fiber under the trade name Kodel (5). Much later the same polyester, now called PCT, and a cyclohexanedimethanol—terephthalate/isophthalate copolymer were introduced as mol ding resins and thermoforming materials (6). More recentiy stiU, copolymers of PET with CHDM units have been introduced for blow molded bottie resins (7). 

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