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PET modification with MPDiol glycol

S.A. Schwartz, P.M. Puckett, Lyondell Chemical Company, Houston, TX/USA A.W. Saraf, M. Bridges, Equistar Chemicals, Houston, TX/USA Polyethylene terephthalate (PET) is the most widely used polymer for the formation of synthetic fibers. Typically, PET is melt spun to produce POY that is subsequently processed to make fully drawn, flat or textured yarns (FDY). Although the PET homopolymer has many outstanding properties, it has limitations related to its processability and properties. To overcome these limitations, several new polyesters, copolyesters, and blends have been introduced into the market. For example, polytrimethylene terephthalate (PTT) and blends between PTT and PET have been recently reported to show unique improvements in fiber characteristics [1, 2]. Chemical modification via addition of a small amount of a third component, typically a glycol or a diacid (e.g. DEG or IPA), is also practiced in order to improve polyester textile features [3]. While fibers converted from random copolymers containing third components often provide targeted processing or property advantages, these can be at the expense of other important characteristics such as its ease of use, polymerization rate, melt strength, fiber convertibility, mechanical properties, or cost. A successful commercial product seeks to economically achieve a good balance of the above properties. To achieve this, the copolymer formulation must be processable on existing commercial PET resin manufacturing and product conversion processes without substantial modification. Glycol modification of PET through copolymerization with 2-methyl-1,3propanediol (MPDiol Glycol, MPDiol) is an attractive technique to differentiate the properties of PET. Copolymerization leads to PET property enhancements without sacrificing existing PET advantages [4]. The objective of this paper is to highlight particular advantages related to processability and properties of MPDiolsubstituted PET (MPDiol-co-PET, Fig. 1). Melt phase copolymerization MPDiol-co-PET copolyesters were batch-polymerized using conventional polyethylene terephthalate reaction conditions. Homogeneous, stable slurries of EG, MPDiol, and TPA were polymerized to nominal intrinsic viscosities (IV) of 0.62 to yield copolymer compositions containing 4, 7, and 10 mole-% substitutions for ethylene glycol (EG). A twostage ester interchange process from purified terephthalic acid (TPA) and the diol mixture included a high pressure, low temperature esterification to form the bis-hydroxyalkyl-terephthalate. This was followed by a low pressure, high temperature (melt) polymerization to achieve the melt-phase MPDiol-co-PET with the elimination of glycol that is readily volatilized and removed from the system. A typical catalyst/stabilizer (antimony trioxide/phosphoric acid) combination was used. Increasing concentrations of MPDiol slightly decreased the polymerization rate, but the decrease was not significant below 10 mole-% MPDiol substitution. Solid state polymerization It is well known that some glycol-modified melt-phase copolyesters exhibit lower melt strength at equivalent IV values to PET homopolymer, resulting in poor processability in fiber spinning and do not have sufficient melt viscosity to spin filaments [5]. By introducing a solid state polymerization step, the molecular weight increase facilitates the spinning process. While this has not been observed with MPDiol-co-PET at the levels of MPDiol that was studied, it is recognized that spinnability and properties can be optimized as a function of copolymer molecular weight. For this reason, the solid state polymerization behavior of the melt-phase copolymers was studied. MPDiol-co-PET at 4, 7, and 10 mole-% MPDiol substitution levels were solidstate polymerized on a bench scale unit at temperatures of 195, 205, and 215 C. This temperature range is typical for solid state polymerizations of standard PET. Solid state polymerization times were 3, 6, 9, and 16 hours for each material at each temperature. A typical rate profile is shown in Fig. 2 for 7 mole-% MPDiol-co-PET at 215 C. The solid state polymerization rates between

Fig. 1 MPDiol-co-PET Fig. 3 Effect of MPDiol on thermal transitions (quench-cooled pellets)

Fig. 2 I.V. vs. Solid state polymerization time

Fig. 4 Effect of MPDiol on melting endotherm (quench-cooled pellets)

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the copolymer and PET homopolymer are equivalent. This was also the case for the 4 and 10 mole-% MPDiol-co-PET samples over the temperature range studied. Resin properties The DSC heating trace of meltquenched pellets of PET and MPDiol-coPET exhibit an exotherm as a result of thermally induced crystallization. With increasing MPDiol comonomer incorporation, more energy and time is needed for the molecular rearrangement that is required to sort through the polymer segments, exclude MPDiol, and promote homogeneous nucleation and crystal growth. The effect is an increase in Tcc. Crystal lamellae are thinner than those that would result from PET homopolymer due to comonomer exclusion, and this accounts for a decrease in Tm. One of the earliest theories that explains the effects of comonomer units on the melt temperature was provided by Flory [6]. He developed an equation to examine the melting point depression as a function of comonomer concentration. This model was used to test the MPDiol-coPET copolymers in this study, and it supports that claim that MPDiol units are excluded from the parent PET homopolymer crystal. X(t) = 1 - exp(-ktn) where X(t) is the weight fraction of crystallized material at time t, k is the temperature dependent rate constant for crystallization, and n is the Avrami exponent that represents that dimensionality of the crystallite growth. As would be expected, increasing the isothermal crystallization temperature resulted in a decrease in the isothermal crystallization rate. Furthermore, the introduction of MPDiol decreases the crystallization rate constant, k, at the same temperatures. These behaviors are summarized in Fig. 5. The lower crystallization rate of MPDiolco-PET relative to the homopolymer reduces the tendency of stress-induced crystallization during fiber spinning. As a result, higher spinning speeds are accessible and lower denier fibers are achievable. POY properties

- Thermal analysis The incorporation of MPDiol into the PET chain lowers both the glass transition temperature (Tg) and the melting temperature (Tm) and it raises the coldcrystallization temperature (Tcc) relative to PET homopolymer. The sensitivity of these transitions to MPDiol incorporation level is shown in Fig. 3. MPDiol also affects the copolymer crystallinity (Fig. 4). For fibers, these shifts affect both processability and properties. The more flexible MPDiol comonomer unit imparts a "kink" to the linear structure of PET and causes a reduction in Tg. The secondary methyl group promotes main chain bond rotation, and it acts like a chain end. It is also theorized that the methyl group increases the free volume of the amorphous phase relative to PET homopolymer. The combined effects on the structure and mobility of the amorphous phase of MPDiol-co-PET are believed to account for the dramatic improvements in disperse dyeability with low levels of MPDiol substitution into the copolymer.

- Crystallization kinetics It is well known that the presence of random branching drastically changes the crystallization behavior of linear polymers. The expression that is most often used for the analysis of isothermal crystallization kinetics is the Avrami equation [7]

- Spinnability Monofilaments were extruded in laboratories at the University of Tennessee [8] at a mass throughput rate of 6.5 g/min. The maximum spinning speed was determined as a function of MPDiol content. As shown in Fig. 6 below, the maximum spinning speeds increase until the MPDiol reaches a concentration of 7 mole-% and then decrease slightly with further increase in MPDiol content. We hypothesize that the slower development

Fig. 5 Isothermal crystallization rate constant vs. Temperature (quenchcooled pellets) Fig. 7 Denier reduction vs. MPDiol content (3,000 m/min; 72 round hole spinneret)

Fig. 6 Maximum Spinning Speed vs. MPDiol Content in MPDiol-co-PET (IV= 0.62)

Fig. 8 Elongation vs. Spinning speed (12 hole spinneret, dtex 36 POY)

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of crystallinity initially allows a greater draw-down and higher spinning speed before reaching the critical stress for spinline fracture to occur. At some concentration of MPDiol (above 7 mole-%), the crystallization rate is insufficient to provide the deformation strengthening needed to further increase the drawdown without fracture. In another trial, copolymers were meltspun at 3,000 m/min through a 72 round hole spinneret. The mass throughput rate was incrementally decreased resulting in finer denier POY. Relative spinnability is defined as the finest denier (lowest mass throughput rate) that could be sustained. The results for these tests are shown in Fig. 7. Spinnability was superior to the PET homopolymer control. It is interesting that in these experiments, the spinnability of the 10 mole-% MPDiol-co-PET was better than the 7 mole-% MPDiol-co-PET. Moreover, the ultimate denier reduction was not observed for the 10 mole-% MPDiol-coPET material due to winder equipment limitations. "wind-up speed suppression". Wind-up speed suppression leads to yarns which, when spun at high spinning speeds, exhibit properties like those spun at lower spinning speeds. MPDiol-co-PET provides this advantage over PET homopolymer because the latter, when melt spun above a certain speed (typically about 3500 m/min), tends to crystallize in the spin line. This drastically limits the mechanical properties, in this case % elongation, at higher spinning speeds. MPDiol delays the onset of stress-induced crystallization to higher levels of stress that is higher spinning speeds. Therefore, higher elongation values are observed at higher spinning speeds. (Note that line breaks for PET homopolymer were encountered at 4500 m/min, and therefore no elongation data was obtained.). Furthermore, the majority of the other PET physical properties are maintained such as modulus and tenacity. Figs. 9 and 10 show the boiling water shrinkage behaviors of PET and MPDiolco-PET as a function of yarn denier at constant spinning speed (Fig. 9) and as a function of spinning speed at constant mass throughput, 2.1 g/min (Fig. 10). Shrinkage occurs above the glass transition temperature due to the entropic driving force to relax the molecular orientation of polymers in the amorphous phase. For PET and PET copolymers, the crystalline phase acts as anchoring points that prevent this relaxation. The reduced tendency of MPDiol-co-PET to undergo oriented crystallization during yarn spinning, therefore allows for greater shrinkage at equivalent spinning conditions. Note in Fig. 9 that with decreasing denier, data is only available for MPDiol-co-PET with higher MPDiol content. This is an indication of improved fiber spinnability as a function of MPDiol copolymer incorporation. Disperse dyeability Enhanced disperse dyeability is one important improvement of MPDiol-co-PET over PET homopolymer. MPDiol-co-PET can be successfully dyed with disperse dyes at temperatures below 100 C (atmospheric rather than pressure dyeing becks) in the absence of dye carriers. This behavior is particularly valuable in light of the growth of low denier fibers. The use of MPDiol diol to improve dyeability is generally advantageous with respect to costs associated with dyestuff, carriers, energy consumption, and environmental control. An illustration of this behavior is shown in Fig. 11. Dye bath exhaustion between fibers composed of PET homopolymer and 10 mole-% MPDiol-co-PET is compared. The dye bath concentrations were 2 wt.-% (on weight of fiber) disperse dye (Dianix Blue AD-R from Dystar). No carriers were used, and the dye bath temperature was 100 C. The total dyeing cycle time (including 2 C/min ramps to and from 100 C) was 105 min

- Mechanical properties Fig. 8 shows the elongation values for dtex 36 (33 denier) POY that was extruded through a 12 round hole spinneret as a function of spinning speed. This data provides an example of a processability advantage derived from low levels of MPDiol substitution. This is known as

Fig. 9 Boiling water shrinkage vs. Denier (3,000 m/min, 72 round hole spinneret)

Fig. 11 Absorbance of exhausted dye baths

Fig. 10 Boiling water shrinkage vs. Spinning speed (monofilament)

Fig. 12 Competitive pressure dyebath (130 C) to exhaustion (no carrier)

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(45 min at 100 C). The tests were conducted in separate dye baths and were driven to equilibrium at the dyeing temperature. The data in Fig. 11 shows that the visible light absorbency from the exhausted dye bath of PET homopolymer is significantly greater than that of 10 mole-% MPDiol-co-PET. Therefore, MPDiol-co-PET more efficiently absorbs the available dye in the bath than a PET homopolymer. Fig. 12 is another illustration of the enhanced disperse dyeability of MPDiolco-PET. In this test, a knit yarn sock with both yarns knitted in different sections was dyed in a "competitive" condition in a carrier-free, pressure dyeing process. The dyeing was carried to exhaustion at 130 C. It is evident from the photograph that the 7 mole-% MPDiol-co-PET dyes significantly deeper with a higher rate of dyeability. The Kubelka-Munk (K/S) reflectance values, which are proportional to the colorant concentration in the materials, also validate the greatly enhanced dyeing characteristics associated with small MPDiol comonomer incorporation. Conclusion MPDiol-co-PET broadens the potential for PET fibers through both processing efficiencies and improved properties. The decrease in the thermal transitions and crystallinity when MPDiol is used to modify PET present opportunities for new and innovative low melt/high shrink fibers that can be converted into both woven and non-woven textiles. MPDiol is compatible with existing PET melt phase polymerization schemes. It mixes easily into a stable slurry with EG and displays equivalent polycondensation reactions to produce random copolymers using conventional PET formulations, pressures, and temperatures. The lower crystallization kinetics of MPDiol-co-PET relative to PET homopolymer reduces the tendency of stress-induced crystallization during fiber spinning. As a result, higher spinning speeds and lower denier fibers are achievable. Moreover, MPDiol-co-PET yarns have properties that are equivalent to those of PET homopolymer that were spun at lower take-up velocities. Thus, wind-up speed suppression is a distinct advantage of MPDiol-co-PET over PET homopolymer. It has also been observed, though not reported here, that filaments of MPDiol-co-PET can be drawn to give mechanical properties similar to PET homopolymer. Soft feel has also been observed for MPDiol-co-PET yarns. For draw-textured yarns, the dyeability of MPDiol-co-PET copolyester is improved due the reduction of the Tg, the change in crystalline fraction, and the free volume in the amorphous phase. The copolyester fibers have a high exhaustion rate, which translates to reduced dye costs and fewer environmental issues. A particular advantage of MPDiolco-PET is that fibers may be dyed at low temperatures and atmospheric pressure without the use of carriers.
MPDiol = registered trademark References [1] Chuah, H.H., Werny, F., Langley, T., IC&E, American Association of Textile Chemists and C o l orists, 1995; 98-106 [2] Yang, Y., Brown, H. Shiqi, L., J. Appl. Polym. Sci. 86 (2002) 223 [3] Nichols, C.S., Humelsine, B.M., US Patent 6,485,829 B2 (Nov. 26, 2002) [4] a) Toga, Y., Shimada, T., Okamoto, I., US patent 4,415,727 (1983) b) Chen, S.C., Lin, F.S., Chou, J.-Y., Wang, H.Y., Lee, M.S., Chen, M.-S., Huang, Y.J., Sun, H.S., US Patent 5,916,677 (1999) [5] Branum, J.B., Nichols, C.S., Carnes, K.J., US Patent 6,509,091 (Jan. 21, 2003) [6] Flory, P.J.., J. Chem. Phys. 15, 684 (1947); Trans. Farady Soc. 51 (1955) 848 [7] Avrami, M., J. Chem. Phys. 7, (1939) 1939, 8 (1940) 212, 9 (1941) 17 [8] Suh, J., Spruiell, J.E., Schwartz, S.A., J. Appl. Polym. Sci. 88 (2003) 2598

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