PTTA New Member in n Polyester Family

(A New Fibre)

By : Piyush Takkar
[Pick the date]

Table of Contents

1. Introduction 1 2. Polymerization.. 2 2.1 1,3-PROPANEDIOL MONOMER. 3 2.2 THE POLYMERIZATION STAGE 3 2.3 SIDE REACTIONS AND PRODUCTS 8 2.4 Environmental benefits of PTT fibre.. 10 3. PTT as a Textile Fibre 10 3.1 FIBRE STRUCTURE 10 3.2 FIBRE CHARACTERISTICS 11 3.3 Comparison with different fibre. 12 4. CHEMICAL PROCESSING OF PTT.. 15 4.1. TECHNOLOGY OF DYEING 16 5. APPLICATIONS 20 6. PTT for nonwovens. 22 7. HEALTH AND SAFETY.. 23 8. CONCLUSION 24

1. INTRODUCTION
Poly(trimethylene terephthalate) (also referred to as 3GT or PTT or PTMT) is a futuristic synthetic fibre with its unique spring -like molecular structure possessing the favourable properties of both polyester and nylon, while having its own stretchiness. It is also readily compatible with natural and synthetic fibres thanks to its unique soft texture. It is a newly commercialized aromatic polyester and has recently received much attention as a polymer for use in textiles, flooring, packaging and other end uses. It was rst synthesized by Whineld and Dickson nearly 60 years ago. PTT has remained an obscure polymer until recent times because one of its monomers, 1,3-propanediol (PDO), was not readily available and was therefore not suitable as a raw material for commercial polymers. For a long time, the ber industry had been aware of PTT having desirable properties for ber applications. In a 1971, Fiber Industries found PTT ber have a lower modulus, better bending and work recoveries than PET, and was therefore more suitable than PET for making berll and carpets. They compared the mechanical properties of the three polyester bers(PET, PBT and PTT), and found PTT indeed had a better tensile elastic recovery and a lower modulus than both PET and PBT. These two properties are very desirable and are valued for making soft, stretch-fabrics with good hand and touch, and for resilient carpets. Thus, it was a challenge for chemical and ber companies to develop breakthrough technologies to lower PDO cost and to commercialize PTT. In the early 1970s, the Shell Chemical Company, a producer of PDO via the acrolein route, explored the commercial potential of PDO and PTT by sampling PDO with several ber companies. This led to a period of active research in PTT polymerization and applications. Despite making signicant progress in lowering PDO manufacturing cost, PTT was still an unfavorable polyester for business atmosphere at that time so further development of PTT was stopped. Shell later exited the PDO business and Degussa assumed its manufacturing. Interest in PTT revived in the late 1980s when both Shell and Degussa made breakthroughs in two different PDO manufacturing technologies. Degussa was able

to lower the cost of manufacturing PDO via the acrolein route and improve its purity to levels suitable for polymerization. Shell developed an alternate synthesis route by hydroformylating ethylene oxide (EO) with a combination of CO and H2 synthesis gas, leveraging their core competencies in hydroformylation technology and EO feedstock. In 1995, Shell announced the commercialization of PTT, and built a 160 mm lb PDO plant in Geismar, Louisiana. This was followed by DuPont announcing the retrotting of an existing polyester plant in Kinston, North Carolina, to produce PTT using PDO obtained from Degussa while they and Genecore International collaborated to develop a potentially cheaper biological route for making PDO through glycerol fermentation. More than half a century after its synthesis, PTT nally joined PET and PBT, and became a commercial reality.

2. POLYMERIZATION

PTT is made by the melt polycondensation of PDO with either terephthalic acid or dimethyl terephthalate. It is also called 3GT in the polyester industry, with G and T standing for glycol and terephthalate, respectively. The number preceding G stands for the number of methylene units in the glycol moiety.

The chemical structure of Poly(trimethylene terephthalate) Shell Chemical Companys PTT is trademarked as Corterra polymer,while DuPonts trademark is Sorona 3GT.

2.1 1,3-PROPANEDIOL MONOMER PDO also called trimethylene glycol, is a colorless, clear liquid with a boiling point of 214C. There are two commercial synthesis routes The rst of these is the traditional route, via the hydration of acrolein under pressure at 50C into 3-hydroxypropanal (3-HPA) using an acid catalyst. The 3-HPA intermediate is then hydrogenated into PDO by using Raney nickel catalyst. In the second process, Shell uses EO as a starting raw material. EO is rst hydroformylated into 3-HPA by using a combination of CO and H2 synthesis gas with cobalt catalysts. The aqueous 3-HPA solution is then concentrated and hydrogenated to produce PDO.

A new route with the potential of further lowering PDO cost is the enzymatic fermentation of glycerol and alcohol. This process is still under development by Du Pont and Genecore International. With advances in biogenetic engineering, new strains of engineered bacteria have improved the yield and selectivity of the process to the point where this route is ready for pilot plant scale-up.

2.2 THE POLYMERIZATION STAGE

PTT is melt polymerized by either the transesterication of PDO with dimethyl terephthalate (DMT) or by the direct esterication of PDO with puried terephthalic acid (PTA).

The process is similar to that for PET but with major differences, as follows: 1. Because of PDOs lower reactivity, more active catalysts based on titanium and tin, which would discolor PET, are used to polymerize PTT. 2. PTT has different side reaction products. Instead of the acetaldehyde produced with PET, acrolein and allyl alcohol are the volatile byproducts of PTT production. The generation of acrolein is to be expected since it is one of the starting raw materials for making PDO. Acrolein is toxic and is a very strong lachrymator, and requires special handling and treatment.

3. Instead of cyclic trimer, PTT produces a lower-melting cyclic dimer by-product.

4. Compared to 1,4-butanediol, which forms tetrahydrofuran byproduct in PBT polymerization, PDO is difcult to cyclize into oxetane because of the high ring strain. Oxetane was not found in the byproduct analysis. 5. PTT is polymerized at a much lower temperature between 250 and 275C. Because of its higher melt degradation rate and a faster crystallization rate, it requires special consideration in polymerization, pelletizing and solid state treatment. Direct esterication of PDO with TPA is a more economical route than transesterication with DMT. However, it is also more difcult technology to implement. Table 1 summarizes the reaction conditions, catalysts and additives for both the DMT and TPA processes, while Fig.2 shows the direct esterication reaction scheme. Only the TPA process will be described below. Because TPA has a melting point of >300C and poor solubility in PDO, direct esterication is preferably carried out in the presence of a heel under a pressure of 70150 kPa and at 250270C for 100140 min. A heel is an oligomeric PTT melt with a degree of polymerization (DP) of 3 to 7, purposely left in the reaction vessel from a previous batch to

improve TPA solubility and to serve as a reaction medium. The esterication step is self-catalyzed by TPA.

Polymerization of PTT by direct esterication of PDO with TPA using the heel process

After reaching the desired DP, 4050% of the oligomeric melt is transferred to the polymerization vessel. Titanium butoxide (50150 ppm) or dibutyl tin oxide catalyst (100250 ppm), or some combinations of the two catalysts, is added to catalyze polymerization at 260275C. A vacuum of <0.15 kPa is applied to remove the condensed water so as to drive the reaction until the polymer reaches an intrinsic viscosity (IV) of 0.70.9 dL/g. To obtain higher-molecularweight PTT with an IV >1.0 dL/g, melt-polymerized chips are solid-state polymerized at 180210C under nitrogen. The solid-state treatment prevents the polymer from becoming yellow or degraded by prolonged melt polymerization to reach the high IV. This post-condensation process also helps drive off volatile byproducts, thus reducing the amount of residual acrolein and cyclic dimer in the nal polymer; however, the molecular weight distribution is broadened. The reduction of cyclic dimer during post condensation is through sublimation. The chips are also more crystalline and tend to be more brittle. 2.3 SIDE REACTIONS AND PRODUCTS PTT melt undergoes several side reactions during polymerization and melt processing. Under an inert atmosphere, PTT has a similar thermogravimetric weight loss prole to that of PET with one main decomposition step. A thermogravimetric analysis (TGA) scan of PTT does not show signicant weight loss up to 280C. Degradation in air is, however, different and involves two mechanisms. At about 300C, degradation was decomposition-controlled. At higher temperatures, the rate increases and decomposition changes to a diffusion-controlled process. PTT shares several similar thermo-oxidation degradation mechanisms with PET. Some of the more important ones are as follows: McClafferty rearrangement of the ester moiety (Figure 11.3). The carbonyl unit abstracts a -methylene hydrogen through a six-member cyclic transition state, and the chains fragment with carboxyl and vinyl ester end groups. Further scission of the vinyl ester group generates allyl alcohol, which in the presence of oxygen is oxidized to acrolein.

 Back-biting of the growing polymer chain generates cyclic oligomers. Instead of cyclic trimer, PTT forms its cyclic dimer, which has a melting point of 254C. The amount of cyclic dimer in the nal polymer is preferably below 3 wt% because it tends to sublime and deposit as needle-like crystals on the spinnerette die face, so interfering with ber spinning process. During polymerization, PDO dimerizes into dipropylene ether glycol (DPG) which incorporates into the PTT chains as a copolymer. DPG formation is more severe in the acidic TPA process. The incorporated DPG lowers the polymers melting point and affects ber dye uptake.

Proposed PTT thermal degradation mechanism through the Mc-Clafferty rearrangement and the formation of acrolein and allyl alcohol.

The above side reactions can be suppressed to various extents by adding antioxidants and phosphites, using higher purity PDO and controlling the polymerization conditions .

2.4. Environmental benefits of PTT fibre Producing PTT fibre uses 30 per cent less energy and reduces green house gas emissions by 63 percent compared to the production of an equal amount of nylon 6. Further, there are no additional chemical treatments used for stain resistance. Less energy, lower emissions, no added chemical treatments. Energy savings is also part of the environmental story with PTT offering a 30 percent savings over nylon 6 and a 40 percent savings over nylon 6,6.

3. PTT as a Textile Fibre 3.1. FIBRE STRUCTURE PTT is crystalline, hard, strong, and extremely tough. If we analyze macromolecular structure of PTT, we can notice the structural and substantial differences with the fibers of PET.

The unique molecular structure of PTT features a pronounced kink as shown above, which gives serious beneficial properties to PTT compared with PET. The molecular structure of a zigzag shape can translate tensile or compressive forces at a molecular level to bending and twisting of bonds rather than simply stretching, which is analogous to the tensile behavior of a coiled spring compared with a straight wire. This is reason for better stretch recovery characteristics than other traditional polymer. 3.2. PTT FIBRE CHARACTERISTICS PTT is an advanced polymer that can be spun into fibres. The fibres and yarns have a unique combination of properties including stretch and recovery, softness, bulk. Fabrics produced from PTT fibres and yarns clean easily and have superior durability. As regards to other synthetic fibres, PTT ones are easier to be dyed, keep vivid colours longer, lose their shape easier and as easier go back to their original shape. They also are better dirty-resistant, are easier to be cleaned and dry quickly. PTT has a very desirable property set, combining the rigidity, strength and heat resistance of poly(ethylene terephthalate)(PET) with the good processability of poly(butylene terephthalate)(PBT). PTT is also resistant to strong oxidizing bleaches, such as sodium hypochlorite, even in concentrated form (6 percent). In fact, it is said to resist bleaching even better than polyester PET. Colour fastness of PTT is superior to polyester and Type 6 nylon and comparable to Type 6, 6 nylon when subjected to a wide range of tests including high concentrations of ozone, nitrogen dioxide, and light and sun fading. PTT is oleophilic, and performs similarly to polyester PET and olefin, and it easily removes oily spots and soils (petroleum, animal, vegetable) using dry solvent spotters and cleaning additives (e.g., propylene glycol). PTTs hand, while a some what subjective evaluation, is achieved by the polymer itself, and is noticeably softer than polyester, and comparable to nylon fibre.

3.3.

Comparison with different fibre

PTT fibre combines the best properties of nylon and polyester. Whether used in carpet, garments, home furnishings or automotive fabrics, PTT fibres look better longer. Compared with other synthetic fibres like nylon and acrylic, PTT fibres feel softer, dye easier, retain vibrant colours longer, stretch and recover better. More important, PTT fibres resist staining, clean easily and dry quickly. Properties of poly(triethylene terephthalate)

PTT

PET

PBT

Tensile strength (cN/dtex) 3.4-3.7 Elongation at break (%) 36-42 Initial modulus (cN/dtex) 23 Elastic recovery at 20% elongation 88 3 Density (g/cm ) 1.34 Moisture regain(%) 0.4 Shrinkage at boiling (%) 14 Melting point (C) 230 Heat distortion temperature at MPa(C) 65 Specific gravity 1.35 Glass transition point 51

3.7-4.4 30-38 97 29 1.38 0.4 7 254 59 1.40 69

3.5 38 23 40 1.31 0.4 15 230 54 1.34 25

Carpets made from PTT fibres combine luxurious feel inherent stain resistance excellent wear performance anti-static performance, and most importantly, easy care.

Carpets have nylon-like wear performance without the need of chemicals stain treatments and complicated cleaning procedure. Comparsion of Stain Analysis on different carpets :

PTT Polymer chemical resistance :

4. CHEMICAL PROCESSING OF PTT

Like normal polyester fabrics, sizing, desizing and scouring may be generally required for the woven PTT fabrics. In addition, preheat set and softening are optional and final heat-set is deemed necessary. For knitted fabrics, generally, desizing and scouring may not be needed. Relaxation and preheat set on fabrics may or may not be applied. In order to obtain a power stretch fabric, a heat-set process at an identified temperature is required. A fiber softening process and a fabric softener may be applied to the dyed and heat-set fabric and thereafter, a final heat-set (at temperature lower than or equal to

previous heat-set one) is used. The resulting fabrics should have good stretch and soft hand-touch and may be better than the greige fabrics. KNITTED FABRICS Scouring
(optional)

Mecerization
(optional)

Preset (T1)

Dyeing

Heat Set (T2)

Final Heat Set(T3)

Softening

An outline of the dyeing and finishing procedure for PTT knitted fabrics

WOVEN FABRICS Scouring Mecerization

(optional)

Preset (T1)
(optional)

Dyeing

Heat Set (T2)

Final Heat Set(T3)

Softening

An outline of the dyeing and finishing procedure for PTT woven fabrics Note : Conditions for scouring were as follow Na2CO3(2 g/l), detergent LS (2 g/l) temperature 90-100C, time 20 min.

4.1. TECHNOLOGY OF DYEING Because of the low Tg, PTT bers and fabrics are dyed at atmospheric boil without the need of a carrier. PTT is therefore a more environmentally friendly polymer than PET in this regard, although the later is now dyed under pressure at 130C to avoid using carrier. Poly(triethylene terephthalate) combines properties of both, PET and nylon in terms of dyeability. It gives excellent colourfastness and also possesses natural stain resistance. No pH adjustment, carrier or high pressure is required in the case of dyeing of PTT fibre.

PTT is dyeable without a carrier at boiling temperatures under atmospheric conditions because of the open molecular structure, providing colour fastness comparable to nylon with to nylon with select dyes. PTT allows for additional tonal shades with pressure dyeing, giving designers more choices for textile colors. Disperse dyes work best on PTT fibres, yielding a uniform colour with good fastness. It is known that various dyeing and finishing procedures have been employed in the textile industry. The procedures depend on the equipment used and types and materials of fabrics.

Sample dyeing cycle and temperatures for PTT fibers using low energy disperse dye

95-100C

20-40 min

1C/min
60C

2-3C/min

3-5C/min Drop-Rinse-Scour-Rinse
Ambient

For PTT, the temperature that affects the levelness starts at 60 C, which is 10-20C higher in the case of PET. In the holding time indicated in the graph, majority of the dye uptake takes place within 20 minutes. Higher holding time does not increase the dye uptake value. But lower K/S values have been obtained due to opaqueness of the fabric. Better dye penetration results in better colour-fastness properties like washing rubbing fastness. Exact holding time used during the dyeing depends on temperature profiles used in the production, shade depth and dyeing temperature.

 Effect of dyeing temperature on PTT and PET ber shade depth.

Some results and comparsion:

For colorant C.I. disperse blue 139, the variation in absorption of colorant with coloring temperature for PTMT and PET

 The variation in depth of penetration of colorant C.I. disperse blue 139 with coloring temperature for PTMT and PET

For colorant C.I. disperse red 60, the variation in absorption of colorant with coloring temperature for PTMT and PET

Main achieved environmental benefits: The following environmental benefits are achieved in the dyeing pocess compared to standard polyester fibres (PET type):

emissions of carriers in the workplace and in the environment are completely avoided. a lower amount of energy is consumed compared with PET dyed under high-pressure-high-temperature (HT) conditions (PTT is dyed atmospherically at 100C with excellent dye exhaustion and colourfastness).

5. APPLICATIONS

Fabrics made from PTT fibres not only offer easy-care and stretch, but a combination of features that include inherent stain resistance, lasting durability for longer wear, remarkable softness, beautiful fluid drape and rich brilliant colours. There also are benefits for textile manufacturers i.e. PTT fibres dye well at low temperatures, blend well with other fibres, and are less expensive and much easier to work with than spandex. The application of PTT in the textile industry include filament yarns, staple fibre, and bulked continuous filament yarns(BCF) for carpets. PTT fibres can be used in apparel as well as home furnishing. In apparel it can be used in casual, swimwear, active wear and inner wear and on the other hand in home furnishing carpets, draperies, sheets and pillow cases, wall coverings and upholstery can be made by PTT fibres. However, PTT fibres are best to manufacture the carpets. Carpets made with PTT fibres offer a breakthrough in the combination of stain resistance and durability. They have nylon-like wear performance without the need for chemical

stain treatments and complicated cleaning procedures. Most stains, including mustard, iodine and hot coffee, can bere moved with hot water and are dry within a few hours. Moreover, PTT fibre's stain resistance offers an ease of maintenance and reduced need for replacement. ready-to-wear, active wear, intimate apparels, and inner linings where stretch-recovery, softness, hand and drape are the key attributes; carpets where resiliency, newness retention, stain resistance and low static generation provide values over currently used materials in some market segments; automotive and home upholstery, utilizing the easy dyeing, stain resistance, and stretch-recovery properties. One of the most recent applications is sewing thread which will endow clothing products with added values by appropriate extensibility, recovery, and dimensional stability. Within a short period of time since the polymers commercialization, PTT ready-towear stretch apparels and resilient oor coverings have already appeared in the market. some of these commercial products:

(a) Solo soft, stretch casual wear by Asahi; (b) cut-pile carpet marketed by Shaw Industries.

Other potential applications of PTT are in monolaments, non-wovens, lms, engineering thermoplastics and molded goods. Fabrics made with PTT monolaments are use in papermaking machines because this combines the chemical resistance of a polyester and the resiliency of the less chemical resistant nylon. PTT non-woven fabric shows better dimensional stability and is softer than PP. Other applications include synthetic leathers, exible transparent lm for packagings and zip fasteners.

6. PTT for nonwovens From staple fibers Blends of PTT staple with other fibers such as PET, nylon and polypropylene have been or may be made into nonwovens through needle punch and hydroentanglement. The soft hand-touch and high bulk are the features of the PTT based nonwovens.

From spunbonds PTT based spunbond nonwovens have been made using either the higher speed machine made by Hills/Ason process, or the slower speed machines by Reifenhuser. The Reifenhuser line (slower speed) gives a very dimensionally stable fabric if processed with the correct calender settings. Shell is developing the spunbond as carpet backing for PTT. The benefit is to have an all PTT based carpet system for easiness in recycle stream. Fabrics made from the higher speed process are soft and drapeable, while retaining the outstanding resistance to gamma radiation. Damage from gamma radiation is a major problem with the use of

polypropylene in medical fabrics, while softness and extrusion in a spunbond process is a major weakness of PET. From meltblown A melt temperature between 260 and 275C was used to produce PTT fabric samples from the meltblown process. The fabric was characterized by random and uniform web formation. The basis weight was 12.2 g/m2, a relatively thin nonwoven. When thicker structures were formed, they were somewhat boardy, and not at all soft. This may be due to the heat in the fibers still present when they fibers are packed onto the collection drum. The PTT meltblown sample was somewhat different in nature from PP meltblown. It does not appear to form the same kind of web as PP, forming more of an unbounded spunbond sort of structure. The 12.2 g/ m2 meltblown sample is quite soft and drapable.

From bicomponent (conjugated) fibers PTT based sheath core and side-by-side spunbonds have been produced. PTT may be used as the binder for the PET-PTT conjugated spunbond or meltblown web in nonwoven application. One may get a more bulky web because of the differential shrinkage during web forming. The PTT based sea-and-island fibers may be made into ultra-fine denier fibers for application such as artificial leathers. Conjugated PTT-PET side-by-side SDY may exhibit high bulk due to the difference in shrinkage after stretch in the solid state for the two materials. Conjugated fibers from PTT with other materials such as nylon, PP and PE are being studied.

7. HEALTH AND SAFETY

Since PTT is a new commercial product, the Shell Chemical Company, as the company which rst introduced it to the market, took the responsibility of product stewardship, and registered the polymer on the chemical inventory lists in several

countries. As a high molecular weight polymer, PTT is biologically inactive and requires safe handling like many other commercial polymers. When PTT is exposed to high heat such as during drying and melt processing, it releases acrolein, allyl alcohol and cyclic dimer by-products. Among these, acrolein is of special concern because it is a very strong lachrymator. It can also irritate lung and respiratory tracts, and affect breathing. The effects are acute and do not have cumulative long-term effects. The US Occupational Safety and Health Agency industrial hygiene guidelines gave the time-weighted exposure limit of acrolein over a period of 8 h as 0.1 ppm, while the short-term exposure limit for 15min is 0.3 ppm. Therefore, adequate ventilation must be provided to avoid acrolein exposure.

8. Conclusion

The PTT fibre is considered to be the most important fibre of the after-polyester period. It is the first significant new material in the textile and carpet industry for some time. Fabrics made with PTT fibres have great appeal in the fast-growing stretch market. It provides manufacturers with a wider range of options for new products than they have now. At this point, PTT does not hold a significant carpet market share; however, promotion by major industry players, such as Mohawk, Shaw and DuPont, may change that. As far as long-term performance is concerned, no other fibre can beat PTT. PTT polymer is also a good candidate as a fiber in nonwoven applications. PTT based nonwovens can be produced from staple fibers (pure or blends) through the techniques of needle punch and hydroentanglement. The PTT based nonwovens can also be made from spun-bond and meltblown. Ultra micro-denier artificial leather based on PTT polymer is also possible. Again, the resistance to gamma radiation and softness are the two major benefits in nonwoven articles based on PTT polymers.

The mantra of Performance PLUS environmental benefits is evident for PTT fibre in carpet applications. In todays competitive environment, beauty is simply not enough. Designers, architects, and facility managers demand more in terms of performance, environment and value when it comes to products. Todays market demands beauty, performance and sustainable solutions. PTT fibre in commercial carpet applications provides what designers, architects and managers are looking for

References

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.

www.freepatentsonline.com/6495254 www.intota.com/multisearch.asp www.technica.net/NF/NF1/eptt.html sciencelinks.jp/j-east/article www.fbi.gov/hq/lab/fsc/backissu/july2001/houck.html www.wipo.int/pctdb/en/wo.jsp www.swicofil.com/polytrimethyleneterephthalate.html en.wikipedia.org/wiki/Polyethylene_terephthalate www.springerlink.com/index/AV1DWAWEDCQPHTC3.pdf jit.sagepub.com/cgi/content/refs/31/3/159 http://www.scribd.com/doc/78810135/New-Fibres-for-Home-Textile-PTTTriexta-Fibre# 12. Modern polyesters 2003 (www.isotextile.blogspot.com).pdf 13. http://www.indiantextilejournal.com/articles/FAdetails.asp?id=1240 14. http://www.swicofil.com/ptt.html 15. www.ftc.gov/os/statutes/textile/info/PTTGenAppRev8-30-06.pdf