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, yak, guanaco, beaver, otter, followed or not by the name 'wool' or 'hair' (1) Fibre description Fibre from sheep's or lambs' fleeces (Ovis aries) Hair of the following animals: alpaca, llama, cammel, kashmir goat, angora goat, angora rabbit, vicuna, yak, guanaco, beaver, otter
animal or horsehair, with or without an indication of the kind of animal (e.g. cattle hair, common goat hair, horsehair) silk cotton kapok
Hair of the various animals not mentioned under 1 or 2
4 5 6
Fibre obtained exclusively from silksecreting insects Fibre obtained from the bolls of the cotton plant Fibre obtained from the inside of the kapok fruit (Ceiba pentandra) Fibre obtained from the bast of the flax plant (Linum usitatissimum) Fibre obtained from the bast of hemp (Cannabis sativa) Fibre obtained from the bast of Corchorus olitorius and of Corchorus capsularis. For the purposes of this Directive, bast fibres obtained from the following species shall be treated in the same way as jute: Hibiscus cannabinus, Hibiscus sabdariffa,
true hemp jute
Abultilon avicennae, Urena lobata, Urena sinuata 10 11 12 13 14 abaca (Manila hemp) alfa coir (coconut) broom ramie Fibre obtained from the sheating leaf of Musa textilis Fibre obtained from the leaves of Stipa tenacissima Fibre obtained from the fruit of Cocos nucifera Fibre obtained from the bast of Cytisus scoparius and/or Spartium junceum Fibre obtained from the bast of Bohemeria nivea and Bohemeria tenacissima Fibre obtained from the leaves of Agave sisalana Fibre from the bast of Crotalaria juncea Fibre from the bast of Agave Fourcroydes Fibre from the bast of Agave Cantala Cellulose acetate fibre wherein less than 92% but at least 74% of hydroxyl groups are acetylated Fibre obtained from metallic salts of alginic acid Regenerated cellulose fibre obtained by the cuprammonium process A fibre of regenerated cellulose having a high breaking force and high wet modulus. The breaking force (BC) in the conditioned state and the force (BM) required to produce an elongation of 5% in the wet state are: BC (centinewton)>=1,3 sqr(T) + 2T BM (centinewton) >= 0,5 sqr(T) where T is the mean linear density in decitex
15 16 17 18 19
sisal Sunn Henequen Maguey acetate
20 21 22
alginate cupro (cuprammonium rayon) modal
Fibre obtained from natural protein substances regenerated and stabilized through the action of chemical agents Cellulose acetate fibre wherein at least 92% of the hydroxyl groups are acetylated Regenerated cellulose fibre obtained by the viscose process for filament and discontinuos fibre Fibre formed of linear macromolecules comprising at least 85% (by mass) in the chain of the acrylonitrilic pattern Fibre formed of linear macromolecules having in their chain more than 50% by mass of chlorinated vinyl or chlorinated vinylidene monomeric units Fibre formed of linear macromolecules made from fluorocarbon aliphatic monomers Fibre formed of linear macromolecules having in their chain more than 50% and less than 85% (by mass) of the acrylonitrilic pattern Fibre formed of linear macromolecules having in their chain the recurring amide functional group Fibre formed of linear macromolecules having in their chain at least 85% (by mass) of an ester of a diol and terephthalic acid Fibre formed of un-substituted aliphatic saturated hydrocarbon linear macromolecules Fibre formed of an aliphatic saturated hydrocarbon linear macromolecule where one carbon atom in two carriers a methyl side chain in an isotactic disposition and
polyamide or nylon (2)
or composed of one or more dienes polymerized with or without one or more vinyl monomers. recovers rapidly and substantially to its initial length Fibre made of glass Fibres obtained from miscellaneous or new materials not listed above 35 polyurethane (2) 36 vinylal (m) 37 trivinyl (2) 38 elastodiene (2) 39 elastane 40 41 glass fibre name corresponding to the material of which the fibres are composed. and which. asbestos. followed or not by the word 'yarn' or 'fibre' . and which. metallized). paper. none of which represents as much as 50% of the total mass Elastofibre composed of natural or synthetic polyisoprene. recovers rapidly and substantially to its initial length Elastofibre composed of at least 85% (by mass) of a segmented polyurethane. when stretched to three times its original length and released. a chlorinated vynil monomer and a third vinyl monomer.g. when stretched to three times its original length and released. metal (metallic.without further substituition 34 polycarbamide (2) Fibre formed of linear macromolecules having in their chain the recurring ureylene (NH-CO-NH) functional group Fibre formed of linear macromolecules composed of chains with the recurring urethane finctional group Fibre formed of linear macromolecules whose chain is constituted by poly(vinyl alcohol) with differing levels of acetilization Fibre formed of acrylonitrile terpolymer. e.
(1) The name 'wool' in item 1 of this Annex may also be used to indicate a mixture of fibres from sheep's or lambs' fleeces and the hairs listed in the third column of item 2. This provision is applicable to the textile products listed in Articles 4 and 5 and to those referred to in Article 6. (2) The 'word' fibre is understood. . provided that the latter are partly composed of the fibres listed in items 1 and 2.
their solutions. thus a monomer is a “single part”. higher molecular weights lead to higher strength. are among the most plentiful . Proteins and Carbohydrates Life as we know it could not exist without polymers. meaning “many”. Since a polymeric material contains many chains with the same repeating units. or they may be branched. meaning “parts” — thus polymers are substances made of “many parts”. with small chains extending out from the molecular “backbone”. A polymer made entirely from molecules of one monomer is referred to as a “homopolymer”. perform a wide variety of vital roles in plants and animals. As with the molecules themselves. and “mer”. three-dimensional matrix. A molecule used in producing a polymer is a “monomer” — mono is Greek for single. The size of polymer molecules is important. average molecular weight must be used. this technical pursuit is diverse and complicated. But as polymer chains get bigger. In general. or millions of times. but with different chain lengths. with chains made up of repeating units derived from simple sugars. Variants of these molecular shapes are among the most important factors in determining the properties of the polymers created. with large numbers of amino acids joined by amide linkages. The resulting molecules may be long.Essential Requirements Of Fibre Forming Polymers Polymer Fundamentals: Fiber Applications Polymer science addresses the chemistry and physics of large. The following discussion provides an introduction to the manufacture and use of synthetic organic polymers for those with some knowledge of basic science. straight chains. Carbohydrates. This is usually expressed in terms of molecular weight. The branches also may grow until they join with other branches to form a huge. In most cases the parts are small molecules which react together hundreds. Chains that contain two or more different repeating monomers are “copolymers”. or thousands. become more viscous and difficult to process. More advanced tutorial information on polymers is contained in the links displayed at the end. Proteins. or melts. What is a Polymer? The term “polymer” is derived from the Greek “poly”. chain-like molecules.
Many of these polymers are capable of dissolving or melting. Synthetic Polymers Synthetic polymers offer more possibilities. starches. Both of these natural polymers are important for fibers. or step-growth polymerization. cellulose is a good fiber-former. Bullet-proof vests are made from synthetic fibers. Thus. a characteristic that gives filaments good strength. silk and other animalderived filaments. but natural polymers tend to be very difficult to work with and form into fibers or other useful structures. Cellulose as a carbohydrate occurs as cotton. . are difficult to isolate from their sources. which contain the same basic sugar units. There are. Thus. then “trimers” (three “parts”). However. It has few side chains or linkages between the sugar units forcing its chains into extended configurations. natural polymers usually have melting points that are so high that they degrade before they liquefy. The properties of these fibers are limited by the form provided in their natural state. Some. linen and other vegetable fibers. The inter-chain forces tend to be strong because of the large number of polar groups in the molecular chains. The most useful molecules for fibers are long chains with few branches and a very regular. or chain-growth polymerization. do not form useful fibers because their chains are branched and coiled into almost spherical configurations.compounds in plants and animals. of course. since they can be designed with molecular structures that impart properties for desired end uses. which makes them scarce and expensive. Synthetic polymer fibers can be made with regular structures that allow the chains to pack together tightly. monomers with two reactive ends join to form dimers (two “parts” joined together). extended structure. There are two basic chemical processes for the creation of synthetic polymers from small molecules (1) condensation. like linen and silk. Step-Growth Polymerization In step-growth polymerization. such as wood pulp. Proteins are the basis for wool. filaments can be made from some synthetic polymers that are much lighter and stronger than steel. and (2) addition. thin filaments needed to make most textile products. Thus. many other sources of proteins and cellulose. allowing them to be extruded into the long.
that is. the material is dimensionally stable and it resists changes in shape. and polyester. Thus. polyamide (commonly known as nylon). Another important property of PET is its Tg. or wrinkle resistance to the fabric. This property is very important for textile applications because it allows some fibers. and countless other products. and the fabrics made from them. the reactive functions are acids and amines. it does not soften or melt at temperatures normally encountered in laundering or drying. Because its chains are closely packed and its ester groups do not form good hydrogen bonds. This form of step-growth polymerization is used for the manufacture of two of the most important classes of polymers used for textile fibers. When a polymer is above its glass transition temperature.e. Antimony oxide is usually added as a catalyst. which is formed by reacting ethylene glycol with either terephthalic acid or dimethyl terephthalate. so a dimer and a trimer would form a pentamer (five repeating “parts”). they can join together. or PET. it is easy to change its shape.. Below its Tg. This can provide bulk to the yarn. nylon 6. PET is a “thermoplastic” material. Since its melting point is high. There are also many important classes of synthetic polyamides (nylons) and they have a wide variety of commercial uses. The monomers used may have their two reactive functions of the same chemical type (both acids. Thus. Here. and to keep the resultant polymer in a molten state. to be texturized or heat-set into a given shape. films. polyamides are formed by stepgrowth polymerization of monomers possessing two reactive groups. and high vacuum is used to remove the water or methanol byproducts. This property also requires special dyeing techniques. or “glass transition temperature”. The polymer usually used for textile fibers is poly(ethylene terephthalate). coatings. In this way the chains may quickly great length achieve large size. they do not absorb water). or of different types. polyesters are also hydrophobic (i. since each of the newly formed oligomers (short chains containing only a few parts) also has two reactive ends. it can be melted and then solidified to form specific products. so their inter-chain forces are strong — but not strong enough to prevent melting. These set-in shapes remain permanent as long as the polymer is not heated above its Tg.6 — a very common fiber polymer — is made by reacting molecules of adipic acid (containing six . However. including plastics. paints. These are usually distinguished from each other by names based on the number of carbon atoms contained in their monomer units. High temperature (>250oC) is necessary to provide the energy for the reaction. or both amines). As with polyesters.and so on. PET molecules are regular and straight. There are many different commercial versions of polyester in a wide variety of applications.
and the ratio of flexible to rigid segments controls the amount of stretch. and they carry an intrinsic color that ranges from light yellow to deep gold. and the other flexible.10. This allows them to be dyed from aqueous media. the aramids are characterized by exceptionally high strength and thermal stability. The flexible segments stretch. Their usefulness for common textile applications is limited by their high melting points and by their insolubility in common solvents. Other step-growth polymers — the polyurethanes — are produced by the reaction of polyols and polyisocyanates.carbons in a chain.6 have melting points similar to PET but they have a lower Tg Also. nylons have regular structures to allow good interchain forces that impart high strength. with an acid function at each end) with hexamethylene diamine (also six carbon atoms. which contain aromatic rings as part of their polymer chain backbone. with amine functions at each end). Fibers made in this way are classified as spandex and they are used widely in apparel where stretch is desirable. there is another commercially important group of synthetic polyamides. These are the aramids. As with the polyesters. nylons can be penetrated by water molecules. They are expensive to fabricate. The other common polyamide fiber polymer is nylon 6. Due to the stability of their aromatic structures and their conjugated amide linkages. this class of linear polymers is formed from glycols and diisocyanates. In another variant the diamine contains ten carbons atoms. with an amine at one end and an acid at the other. unlike their polyester counterparts. Its monomer has six carbons in the chain. while the rigid sections act as molecular anchors to allow the material to recover its original shape when the stretching force is removed. Commercial production of nylon 6 makes use of caprolactam. Thus only one form of monomer is needed to conduct the reaction. For fiber purposes. a derivative which provides the same result. Usually. In addition to nylon. since the amide functions in nylon chains are good at hydrogen bonding. . the reactions are carried out to form block copolymers containing at least two different chemical structures — one rigid. Both nylon 6 and nylon 6. the product designated nylon 6. Varying the properties of the segments.
Thus. The breakthrough in making chain-growth polymers useful for fibers and for most commercial plastics came with the development of special selective catalysts that drive the production of long. The process may be repeated thousands. but several stereoselective catalysts are now available. these polyolefins must rely on close contact between the molecular chains for strength. Since these branches prevent the molecules from forming regular structures with other molecules. This also makes them virtually undyeable. such as a free radical or ion. producing a new bond and a new by activated location. the physical characteristics of polyethylene are very sensitive to even a small number of chain branches. or millions. . and a regular alternating structure is “syndiotactic”. Even without chain branching. to produce very large molecules. except when the dye is applied to the polymer in its molten state — a process know as “solution dyeing”. Synthesis of these polymers was a major challenge. they also may attack other chains. The arrangement of these side groups is described as the “tacticity” of the polymer. adds to a double bond. and a new reactive end. or without tacticity. Since their polymer chains contain no polar groups.Chain-Growth Polymerization Chain-growth polymerization occurs when an activated site on a chemical. Very straight chains of polyethylene can form strong crystalline structures which exhibit exceptional strength. A random arrangement is considered “atactic”. each monomer unit adds one methyl group pendant to the chain. Regular arrangement with all side groups on one side of the chain is “isotactic”. adding another unit to the chain. hydrophobic and highly crystalline. their inter-chain forces are weak. Ethylene and propylene form the simplest chain-growth polymers. Polypropylene is more complicated. Fibers made from it are lightweight. That location then attacks another double bond. Their resistance to wetting gives them good moisture wicking and anti-staining properties. producing highly branched structures. The resulting polymers tend to be low-melting and waxy. and high-density polypropylene has become a commodity product. This is usually a high energy process and the intermediate species are so reactive that. Protective fabrics made from this type of highly structured polyethylene are virtually impossible to penetrate or cut. Polypropylene molecules can only pack closely in an isotactic arrangement. straight polymer chains from monomers containing basic carbon-to-carbon double bonds. of times. in addition to attacking available monomer.
. the hair of the sheep (Ovis ales). Wool Wool – The most important of the fibres of animal origin is wool. They include (polybenzimidazole)and Their chemistry is beyond the scope of this introductory discussion. Pure homopolymers from acrylonitrile are non-thermoplastic and difficult to dissolve or dye. for most commercial acrylonitrile polymers. electrical conductivity. Wool. vinyl acetate. thermal stability. These materials are occasionally used in high performance materials where the complex structures impart exceptional strength. acrylic acid. It’s scaly structure led in the past to unwanted felting(matting of fibres) and shrinkage in laundering but modern finishing treatments have now overcome these difficulties. and others desirable properties. similarly.By contrast. the hair of various breeds of sheep. the pendant nitrile functions in polyacrylonitrile are sufficiently polar to produce very strong inter-chain forces. and methyl acrylate. The characteristics of wool fibres differ depending on the breed and general condition of the sheep. to reduce the inter-chain forces. specialty fiber polymers with methods of synthesis that are not easily classified. small amounts of other monomers with bulky side chains are introduced to force the chains apart. is a warm springy fibre. Thus. Specialty fiber polymers There are also a number of complex. Common co-monomers for these fiber applications include vinyl chloride. attack by the clothes moth is no longer a problem.
the fibre swells anisotropically (unequally). or fineness. the diameter. Staple length generally increases with increasing fibre diameter. When wool fibres have been processed it is not possible to say with confidence from what breed of sheep or country they have originated because wool fibres from several breeds have the same microscopical appearance. . this characteristic is extremely important.5 to 13 cN/tex. There are four main types of wool fibre: fine. Upon uptake of water . It is determined to a large extent by the grade assigned to a lot.5%. especially in numerous processing steps. or batch. Staple length is lower than mean fibre length because of the crimp that results in a helical configuration in an individual fibre and an uni-planar wave in the staple. ranging from four to eight centimetres for fine Merino up to 35 centimetres for coarse Cotswold wool. Technologically. Its strength when wet is less than when it is dry. creaseresistance and durability. Important properties of wool are a dry strength of 11.Relative humidity in the processing plants must be controlled for optimum processing conditions. a breaking elongation of 30 to 40% and a moisture regain of 16 to 18%. combing. including carding. bulk. which gives it good elasticity. The ability of wool fibres to absorb and release moisture contributes to wearing comfort in garments made of wool. Because most fibres are dependent on moisture content. of the wool fibre is probably the most important property. absorbing water from a moist atmosphere in a reversible way.Wool has a natural crimpiness. In the UK alone there are 34 main breeds of sheep and a further 43 rare breeds and hybrids. Wool fibres are hygroscopic. of wool. spinning and weaving. increasing up to 16% in diameter while the change in length is only about 1. Diameters range from 16 microns in the finest Merinos to over 40 microns in the coarsest long-wool types.2 to 1.
An important aspect of the environmental impact of wool processing is the use of pesticides on sheep. this is still a major concern since these toxic chemicals make their way into rivers. Methane is a powerfulgreenhouse gas and contributes to the effect of global warming. Each type has a characteristic scale pattern so that it is possible to distinguish between types. another pesticide. Although the problem has been minimised over recent years with the introduction of tighter restrictions or even bans on the use of some formulations. as with cotton there is also the effect of transporting huge quantities of textiles across the globe with the associated fuel usage and fume generation problems. is added to the yarn that goes into making contract carpets. Kemp fibres are usually chalky white in appearance. is the methane generated globally by the many hundreds of millions of sheep. Another impact at this early stage which is maybe less obvious. The effluent from this process must therefore be treated and continually monitored. The scouring of the raw wool. with a long tapering tip and a taper over a short distance to the root end. with the finer fibres having a circular cross section and the coarse fibres being more irregular in contour. The discharge of chromium is strictly controlled and so companies are being forced into using alternatives or consider on-site effluent treatment. Wool fibres are generally white. outercoat and kemps. In the carpet industry permethrin.coarse. although it is not possible to assign a type to a breed of sheep. this is a quality requirement to protect the wool from moth attack. the next stage. is a process which produces a liquid effluent with a very high organic load and solids content and varying levels of pesticide contamination. . very coarse and brittle. Again. The highly polluting nature of this waste and the strict discharge consents associated with the process means that scourers have to treat their effluent on-site. Another environmental problem is that many of the dyestuffs available for obtaining good dark shades on woollen fabric or yarn are mordant dyes containing chromium.
a period of 25 to 30 days. the Chinese. Eri. Silk has a long and fascinating history. meaning the people from Eastern Asia i. On average 75% of the fresh ‘green’ cocoon.25 kg of fresh cocoons are necessary.Silk Silk – In Old English. which are found mainly in India and Asia. During this time it eats some 22g of leaves and converts more than 70% of its intake of nitrogenous material into silk. From the day it hatches to the time it stops feeding.000 times. while for raising 6. demand has been considerably more variable than for many other fibres. Tussah and Muga. There are several species of silk producing worms but most of the world’s silk results from the worm of the mothBombyx mori which lives exclusively on the leaves ofMorus alba the white mulberry tree.25 kg of cocoons about 104 kg of mulberry leaves containing 26 kg of solid matter are required. To produce 1kg of raw silk about 6. because its main uses have been in very expensive apparel and other luxury goods. such as Atlas. The name is thought to have originated from the Greek seres.e. by weight is chrysalis. The outer layer of floss and the inner layer are collected as silk waste and used in spun silk manufacture. Wild silks such as Tussah are also generally used for spun silk as the cocoons are seldom in a reelable condition. . silk was sioloc. Other silkworms include the wild or semi-wild varieties. Since that time silk has remained highly valued for its luxurious qualities but. where plantations of bush-like mulberry trees are cultivated to provide leaves which are fed to the worms in special rearing rooms. The term sericulture derives from this Greek root. starting over 4000 years ago with the development by the Chinese of the art of rearing silkworms to make a textile fibre. the worm gains in weight about 10. The silkworms are reared in large numbers at silk farms.
Silk is a fairly strong fibre and although it does not compare with nylon and polyester in this respect its strength makes it suitable for use in sewing thread in high quality articles. which is lower than that of mulberry silk. but the cocoon shell is thinner.3%. Tussah Moth The Tussah chrysalis and cocoon are larger than those of the mulberry silkworm. and transmitted through the material and into the atmosphere. while the mulberry cocoon is white. particularly those made from silk. comes in two varieties monovoltine and bivoltine. has a lower layer ratio and yields less silk. Silk absorbs more moisture from the surrounding air than do most of the synthetic fibres. Quercus serrata. and this property confers considerable advantages.7% and is composed of 15 amino acid residues. Attempts to improve on this and also to apply easy-care treatments have not been very successful. rubber trees or Chinese toon trees are available. The fibroin. accounts for the remaining 86. Tussah silk’s seracin or protein content. There is one main type of tussah silkworm. a kind of wild silkworm. It lives and multiplies wherever oak trees or leaves of the Mongolian oak. since moisture can be absorbed without the fibre becoming noticeably damp. it prevents a clammy feeling where fabric is in contact with the skin.Tussah. Antheraea pernyi. or feel. is 13. . Silk has a fairly high natural resistance to creasing. as they impair the unique handle. and one general type of oak tree on which it feeds. The Tussah cocoon is reddish-brown in colour. or fibre itself. of silk which is one of its most valuable properties.
Cotton Cotton – Cotton fibres are the seed hairs of the plantGossypium. weaving. Egypt. Under a microscope . a cotton fibre appears as a very fine.The environmental impact of silk processing is relatively minor in its initial stages when compared to cotton or wool. Almost half of the world’s requirements for textile fibres are met by cotton. These twists are called convolutions. India. . through spinning. the former USSR. They are usually off-white in colour although some varieties have been bred to incorporate a natural colour. China.> Subsequent processing. dyeing and finishing have an impact on the environment similar to most of the other fibres. Africa and South America. Each fibre is formed by the elongation of a single cell from the surface of the seed. qutn or qutan depending on the dialect. the main producers being USA. The cocoons are cooked to kill off the insects and then the fibre is washed in synthetic detergents to remove most of the sericin (gum) in readiness for dyeing. Noise and dust is produced in weaving and a complex effluent with variable BOD/COD. regular fibre. looking like a twisted ribbon or a collapsed and twisted tube. It is grown in many parts of the world where a hot dry climate is to be found. The word cotton is derived from it’s Arabic name pronounced kutan. pH and solids content is produced in finishing.
Synthetic fibres have largely replaced its use in industrial textiles. After scouring and bleaching. The ginning or separation of the seed from the fibre is a dusty process that has serious health implications on cotton workers in developing countries. These pesticides also have an effect on people living in the viscinity of cotton fields.g. noise and waste fibre and is also a relatively large consumer of electricity (as much as 2½ tonnes of oil per tonne of yarn). The fibres are weakened and destroyed by acids but are resistant to alkalis. The environmental impact of the cotton manufacturing process starts in the field with the fertilisers and insecticides used in the growing of the cotton plant.Cotton consists typically of between 88 to 96% cellulose with the rest being protein.000 people came from a pesticide used in the spraying of cotton crops. Relative humidity in the processing plant must also be controlled to minimise breakages. India which killed over 3. Cotton is a relatively strong fibre with a strength of 25 to 35 cN/tex and a breaking elongation of 7 to 9%. another consumer of energy. ash and wax. It is also interesting to note that the gas leak at Bhopal . The US alone spends about 500 million dollars a year on pesticides for protection against the bollworm and other harmful bugs. which makes cotton clothes comfortable to wear in warm weather (water retention of 50%. Despite these shortcomings cotton has a good wear life. Nausea. It is stronger when wet. The fibre is then packaged and transported across the globe. Cotton also absorbs moisture readily. The production of natural fibres is conducted in many separate locations. and biodegradation. crease resistance and flame resistance. pectic substances (congealed gum-like carbohydrates). The spinning process introduces another set of significant impacts. These have a direct impact on the land and the local flora and fauna. Its properties can also be readily modified by chemical finishes which provide enhanced performance. as well as acids. The fibre length varies with the type and quality. It is used in both 100% form and in blends with other fibres for household textiles and apparel. cotton is then about 99% cellulose. within the range 10 to 65mm. transportation of the cotton bales has therefore a significant impact on the environment. Weaving creates a similar set of impacts plus . diarrhoea and throat irritation being the most common complaints. where the separation is carried out using traditional methods. producing more dust. e. the fibre diameter ranges from 11 to 22 ¼m. moisture regain of 7%). Cotton fibre burns readily and is not inherently resistant to oxidising agents.
the added effect of using size and biocides has to be considered on the aqueous environment. Sizes are either natural, like starches or synthetic such as polyvinyl alcohol. The new sizes make weaving on the faster modern machinery a lot easier, but they have the drawback of being harder to biodegrade from the waste water. Cotton preparation, that is singeing, desizing, scouring, bleaching and mercerising impacts on both the air and water. Singeing produces a dusty odorous emission, whilst the other preparative processes are the major contributors to BOD/COD in a textile effluent. There is also the problem of pentachlorophenol (pcp) on imported fabric which is washed out during preparation. This is an eco-toxic rot-proofing chemical with a very low discharge consent (maximum allowable concentration). Cotton is by far the most popular fibre in use today, at least in terms of volume of production. The most widely used class of dyestuff on cotton are reactive dyes, which unfortunately are also the most poorly exhausted, producing a more coloured effluent. Colour consents on discharges have therefore been enforced in certain areas where there are significant numbers of cotton dyers. The main pollution problem associated with cotton finishing processes is that of formaldehyde emissions from resin and other finishes. Low formaldehyde formulations have improved over the past few years but not far enough to eliminate the need for abatement on many stenters. Attempts have been made to reduce the impact of cotton growing by eliminating pesticide use and by growing coloured strains of cotton so that the preparation and dyeing of the cotton is minimised. The bollworm can be eliminated by imposing a three month fallow period at the end of the growing season, and certain short fibre coloured cottons used by Indians in Central America have been cross bred with long fibre strains by a company in the US called Foxfibre. However, the amount of organic cotton grown in the US is still only a tiny fraction of the global output ( by the mid-1990’s, 80 cotton growing countries were producing about 85 million bales of cotton).
Bast fibre Bast fibre (fiber) or skin fibre is fibre collected from the Phloem (the "inner bark" or the skin) or bast surrounding the stem of a certain, mainly
dicotyledonic, plants. Most of the technically important bast fibers are obtained from herbs cultivated in agriculture, as for instance flax, hemp or rhamie, but also bast fibers from wild plants, as stinging nettle, and trees as the lime tree, have been used to some extent. Since the valuable fibers are located in the phloem, they must often be separated from the xylem material ("woody core"), and sometimes also from epidermis. The process for this is called retting, and can be performed by microoganisms either on land (nowadays the most important) or in water, or by chemicals (for instance high pH and chelating agents) or by pectinolytic enzymes. In the phloem bast fibers occur in bundles that are glued together by pectin and calcium ions. More intense retting separate the fiber bundles into elementary fibers, that can be several cm long. The bast fibres have often higher tensile strength than other kinds, and are therefore used for textiles (not seldom very exclusive textiles, sometimes in blends with cotton or synthetic fibers) ropes, yarn, paper, composites and burlap. A special property of bast fibers are that the fiber contain a special structure, the fiber node, that represents a weak point. Fiber nodes seems not to be present in seed hairs as cotton. Examples are:
• • • • • • • • • • •
Jute Industrial hemp Flax (Linen) Ramie Kenaf Roselle Hemp Rattan Soybean fibre Okra fibre Vine fibre Banana fibre
Use of bast fibre Bast fibres are processed for use in carpet yarn, rope, geotextile (netting or matting), traditional carpets, hessian or burlap, paper, sacks, etc. Bast fibers are also used in the non-woven, moulding, and composite technology industries for the manufacturing of non-woven mats and carpets, composite boards as furniture materials, automobile door pannels and headliners, etc. From prehistoric times through at least the early 20th century, Bast shoes were woven from bast strips in the forest areas of Eastern Europe.
Process of viscose Viscose is a viscous organic liquid used to make rayon andcellophane. Cellulose from wood or cotton fibres is treated with sodium hydroxide, then mixed with carbon disulfide to form cellulose xanthate, which is dissolved in more sodium hydroxide. The resulting viscose is extruded into an acid bath either through a slit to make cellophane, or through a spinneret to make rayon. The acid converts the viscose back into cellulose.
Cellulose is treated with alkali and carbon disulfide to yield viscose. Viscose was created by French scientist and industrialist Hilaire de Chardonnet (1838-1924), inventor of the first artificial textile fiber, artificial silk) in Échirolles in 1884, then the process for manufacturing viscose was patented by three British scientists, Charles Frederick Cross, Edward John Bevan and Clayton Beadle, in 1891. Industrial applications Viscose was first used for coating fabrics, a purpose for which it is quite suitable. However, when Cross and his partners tried to make solid objects like umbrella handles they were found to be much too brittle.
used in mostly tops. Its novel . By 1913 C. Ten years later DuPont Cellophane Co. and finally rayon in 1924. Before synthetic fibrers were developed. which comes from plants. just in time for World War II rationing.Somerset. providing the staple for towels and table-cloths and was being made into high tenacity yarn for tires. Viscose is currently becoming less common because of the polluting effects of carbon disulfide and other by-products of the process. but not truly synthetic. had taken over in 1904. known as artificial silk from 1855 onwards. By the twenties and thirties it had almost completely replaced the traditional cotton and wool for women’s stockings and underwear. established La Cellophane SA. fiber forming materials through holes (called spinnerets) into the air. being made from wood. the first synthetic fiber. became known as viscose around 1894. forcing the Bridgwater factory to close in 2005 Synthetic Fibre Synthetic fibers are the result of extensive research by scientists to improve upon naturally occurring animal and plant. made its debut in the United States as a replacement for silk. too. artificial (manufactured) fibers were made from cellulose. In general. Viscose manufacture became big business. after Samuel Courtauld & Co. usually through extrusion. successful modern manufacture began much later (see the dates below).Further development led to viscose being spun into thread for embroidery and trimmings.T. coats and jackets. Making viscose film had been tried by Cross in the 1890s but it was in Switzerland and France that major successes were achieved. Similar changes occurred in the US and in Europe. The first artificial fiber. Yet other uses included the manufacture of sponges and absorbent cloths. synthetic (manmade) fibers are created by forcing. forming a thread. Viscose was also being used for linings and furnishing fabrics. Viscose is a soft material. was set up in the USA and in 1935 British Cellophane Ltd was established in Bridgwater. Rayon and acetate are both artificial fibers.A. Eventually. Although these artificial fibers were discovered in the midnineteenth century. Nylon. A similar product known as cellulose acetate was discovered in 1865.
known as Nomex. Common synthetic fibers include: • • • • • • • • Rayon (1910) (artificial. such as a replacement for the silk in parachutes and other military uses. Kevlar and Twaron Modal (1960's) PBI (Polybenzimidazole fibre) (1983) Sulfar (1983) Lyocell (1992) Dyneema/Spectra (1979) M-5 (PIPD fibre) Orlon Zylon (PBO fibre) Vectran (TLCP fiber) made from Vectra LCP polymer Other synthetic materials used in fibers include: • Acrylonitrile rubber (1930) Modern fibers that are made from older artificial materials include: • Glass Fiber is used for: o industrial. not synthetic) Nylon (1939) Modacrylic (1949) Olefin (1949) Acrylic (1950) Polyester (1953) PLA (2002) Specialty synthetic fibers include: • • • • • • • • • • • • • • Vinyon (1939) Saran (1941) Spandex (1959) Vinalon (1939) Aramids (1961) . and home insulation (Fiberglass) o reinforcement of composite and plastics o specialty papers in battery separators and filtration . not synthetic) Acetate (1924) (artificial. automotive.use as a material for women's stockings overshadowed more practical uses.
exampes are expanded polystyrene flakes urea-formaldehyde foam resin polyurethane foam phenolic resin foam Spinning Processes .• Metallic fiber (1946) is used for: o adding metallic properties to clothing for the purpose of fashion (usually made with composite plastic and metal foils) o elimination and prevention of static charge build-up o conducting electricity to transmit information o conduction of heat in the horticulture industry synthetics are often used in soils to help the plants grow better.
the small fluid molecules are mixed and reacted to form the otherwise intractable polymers during the extrusion process (if you are interested in the latest information on extrusion. if the polymers are thermoplastic synthetics (i. A spinneret may have from one to several hundred holes. or form appropriate derivatives.. in some cases.Synthetic and Cellulosic Fiber Formation Technology Most synthetic and cellulosic manufactured fibers are created by “extrusion” — forcing a thick. they soften and melt when heated). For these materials. The tiny openings are very sensitive to impurities and corrosion. corrosion-resistant metals. viscous liquid (about the consistency of cold honey) through the tiny holes of a device called a spinneret to form continuous filaments of semi-solid polymer. .e. This is usually achieved by melting. dissolve. or by dissolving them in a suitable solvent if they are non-thermoplastic cellulosics. Recent technologies have been developed for some specialty fibers made of polymers that do not melt. The Spinneret The spinnerets used in the production of most manufactured fibers are similar. In their initial state. in principle. The liquid feeding them must be carefully filtered (not an easy task with very viscous materials) and. to a bathroom shower head. If they cannot be dissolved or melted directly. the spinneret must be made from very expensive. they must be chemically treated to form soluble or thermoplastic derivatives. the fiber-forming polymers are solids and therefore must be first converted into a fluid state for extrusion.
and gel spinning. where short pieces of staple fiber are twisted into yarn. modacrylic and spandex can be produced by this process. Acrylic. rayon. The spinnerets are submerged in a chemical bath and as the filaments emerge they precipitate from solution and solidify. This process may be used for the production of acetate. The filaments do not come in contact with a precipitating liquid. acrylic. eliminating the need for drying and easing solvent recovery. this process for making fibers is called wet spinning. Melt Spinning . spandex. aramid. not to be confused with the textile operation of the same name. triacetate. This process of extrusion and solidification of endless filaments is called spinning. There are four methods of spinning filaments of manufactured fibers: wet. the liquid polymer is converted first to a rubbery state and then solidified. PBI. modacrylic. and vinyon. melt. It is used for fiber-forming substances that have been dissolved in a solvent. Wet Spinning Wet spinning is the oldest process. instead of precipitating the polymer by dilution or chemical reaction. Because the solution is extruded directly into the precipitating liquid.Maintenance is also critical. and spinnerets must be removed and cleaned on a regular basis to prevent clogging. However. dry. solidification is achieved by evaporating the solvent in a stream of air or inert gas. As the filaments emerge from the holes in the spinneret. Dry Spinning Dry spinning is also used for fiber-forming substances in solution.
pentagonal. Nylon. octagonal. saran and sulfar are produced in this manner. trilobal. the fiber-forming substance is melted for extrusion through the spinneret and then directly solidified by cooling. olefin. Melt spun fibers can be extruded from the spinneret in different crosssectional shapes (round. . and others). polyester.In melt spinning.
Not completely separated. creating a considerably stronger yarn. the filaments may be drawn to impart strength. down. Detailed production flowcharts: • Acrylic • Nylon(Polyamide) • Polyester Gel Spinning Gel spinning is a special process used to obtain high strength or other special fiber properties. Drawing pulls the molecular chains together and orients them along the fiber axis. or better than. The filaments emerge with an unusually high degree of orientation relative to each other. . Octagonal-shaped fibers offer glitter-free effects. when used in carpet.Trilobal-shaped fibers reflect more light and give an attractive sparkle to textiles. since the filaments first pass through air and then are cooled further in a liquid bath. as they would be in a true solution. Hollow fibers trap air. In addition. Some high-strength polyethylene and aramid fibers are produced by gel spinning. or in some cases even after they have hardened. Pentagonal-shaped and hollow fibers. further enhancing strength. creating insulation and provide loft characteristics equal to. The polymer is not in a true liquid state during extrusion. the liquid crystals are aligned along the fiber axis by the shear forces during extrusion. the polymer chains are bound together at various points in liquid crystal form. Stretching and Orientation While extruded fibers are solidifying. The process can also be described as dry-wet spinning. This produces strong inter-chain forces in the resulting filaments that can significantly increase the tensile strength of the fibers. show less soil and dirt.
So how do you grow crystals? Let's consider an example that is fairly easy to envision. In Figure 1. In order for crystallization to take place a solution must be "supersaturated". Crystal shapes can include cubic. Continue adding salt until no more salt will .Cryatallization Crystals are grown in many shapes. which are dependent upon downstream processing or final product requirements. tetragonal. The number of hydrate molecules shown in Figure 1 is strictly arbitrary and will vary for each substance. orthorhombic. As with any separation method. monoclinic. Take a pot of boiling water and add table salt while stirring to make a water-salt solution. X may be any solid that can form hydrates such as Na 2S2O3. Below is a general solubility curve for a solid that forms hydrate (a compound that has one or more water molecules attached) as it cools. triclinic. hexagonal. equilibrium plays an important role. Supersaturation refers to a state in which the liquid (solvent) contains more dissolved solids (solute) than can ordinarily be accomodated at that temperature. and trigonal.
it's the growth of a new crystalA On an industrial scale. The . once primary nucleation has begun. cooling will be gradual so we need to provide a "seed" for the crystals to grow on. In continuous crystallization. the crystal size distribution begins to take shape. You can think of the supersaturation driving force as being created by a combination of high solute concentration and rapid cooling. the instantaneous formation of many nuclei can be observed "crashing out" of the solution. Simply defined. Usually. a large supersaturation driving force is necessary to initiate primary nucleation. as you look at Figure 2 describing the progression of crystallization. Figure 2: Progression of Crystallization The second chief mechanism in crystallization is called secondary nucleation. The salt that will not dissolve will help the first step in crystallization begin. The initiation of primary nucleation via this driving force is not fully understood which makes it difficult to model (experiments are the best guide). crystal growth is initiated with contact. This first step is called "nucleation" or primary nucleation. In the salt example. The salt resting at the bottom of the pot will provide a site for nucleation to occur. Primary nucleation is the first step in crystallization. Think about our salty water. In this phase of crystallization.dissolve in the solution (this is a saturated solution). Now add one final teaspoon of salt.
we bypassed primary nucleation by "seeding" the solution with a final teaspoon of salt. only preliminary data measurements are truly necessary. Cooling is one of the four most common methods of achieving supersaturation.contact can be between the solution and other crystals. Although this is nearly always the case. . Mathematic relationships do exist to correlate experimental data. Secondary nucleation requires "seeds" or existing crystals to perpetuate crystal growth. but how do we reach supersaturation? We have already covered one such method in our salt crystallization example. We've discussed how crystallization occurs once supersaturation is reached. Secondary nucleation can be thought of as the workhorse of crystallization. For batch operations. no complete theory is available to model secondary nucleation and it's behavior can only be anticipated by experimentation. In Figure 3. as the solution cools. etc. It should be noted that cooling will only help reach supersaturation in systems where solubility and temperature are directly related. correlating experimental data to model crystallization is time consuming and often considered extreme for batch operations. However. its saturation increases until it reaches supersaturation and crystallization begins (Figure 3). but can easily be justified for continuous processes where larger capital expenditures are necessary. Since the solubility of salt in water decreases with decreasing temperature. a vessel wall. Again. a mixer blade. you'll note that Ce2(SO4)3 actually becomes less soluble in water at higher temperatures. there are exceptions. This phase of crystallization occurs at lower supersaturation (than primary nucleation) where crystal growth is optimal. a pipe. In our salt example.
4.Figure 3: Solubilities of Several Solids The four most common methods of reaching supersaturation in industrial processes are: 1. Equipment Used in Crystallization 1. rapid crystallization where the mixing mechanism can exert significant influence on the product characteristics. Each method of achieving supersaturation has its own benefits. the solute-solvent mixture is commonly referred to as the "mother liquor". Drowning describes the addition of a nonsolvent to the solution which decreases the solubility of the solid. supersaturation can be generated near a heat transfer surface and usually at moderate rates. Drowning or reactive crystallization allows for localized. For cooling and evaporative crystallization.Tank Crystallizers . thus working toward supersaturation. A chemical reaction can be used to alter the dissolved solid to decrease its solubility in the solvent. 3. Chemical Reaction (with Solvent some exceptions) Evaporation Drowning In an industrial setting. Cooling 2.
the mother liquor is drained and the crystals are collected. saturated solutions are allowed to cool in open tanks. Labor costs are high. The outside is jacketed with cooling coils and an agitator blade gently passes close to the trough wall removing crystals that grow on the vessel wall. After crystallization. The crystallization is essentially just "allowed to happen". then up through a fluidized area of crystals and liquor where crystallization takes place via secondary nucleation. flash evaporation occurs. these crystallizers combine crystallization and evaporation. the "pot of salt water" is a good example of tank crystallization. In fact. 3.Forced Circulating Liquid Evaporator-Crystallizer Just as the name implies. thus driving the mother liquor towards supersaturation. reducing the amount of solvent in the solution (increasing solute concentration). The supersaturated liquor flows down through a tube. and reheated.This is probably the oldest and most basic method of crystallization. Here. Controlling nucleation and the size of the crystals is difficult. Heat transfer coils and agitation can be used. thus the driving forces toward supersaturation. Hot. The heated liquid flows into the vapor space of the crystallization vessel. Larger product crystals are withdrawn while the liquor is recycled. The circulating liquid is forced through the tubeside of a steam heater. mixed with the feed. 2. thus this type of crystallization is typically used only in the fine chemical or pharmaceutical industries where the product value and preservation can justify the high operating costs.Scraped Surface Crystallizers An example may be the Swenson-Walker crystallizer consisting of a trough about 2 feet wide with a semi-circular bottom. .
Circulating Magma Vacuum Crystallizer In this type of crystallizer. A vacuum in the vapor space causes boiling at the surface of the liquid. The evaporation causes crystallization and the crystals are drawn off near the bottom of the vessel body.4. the crystal/solution mixture (magma) is circulated out of the vessel body. The magma is heated gently and mixed back into the vessel. .
Glass Transition Have you ever left a plastic bucket or some other plastic object outside during the winter. it becomes hard and brittle. They will move . The Snake Pit Now. and become a disordered liquid. The glass transition is a transition which happens to amorphouspolymers. When the polymer is cooled below this temperature. When it's warm. Amorphous and Crystalline Polymers We have to make something clear at this point. that is. This transition is something that only happens to polymers. But you should know that the amorphous portion undergoes the glass transition only. and some are used below. and is one of the things that make polymers unique. This is why the same sample of a polymer can have both a glass transition temperature and a melting temperature. the snakes are happy. The glass transition is pretty much what it sounds like. and found that it cracks or breaks more easily than it would in the summer time? What you experienced was the phenomenon known as the glass transition. The glass transition is not the same thing as melting. even though they are in the solid state. that is. where they are soft and flexible. polymers whose chains are not arranged in ordered crystals. like glass. Melting happens when the polymer chains fall out of their crystal structures. are used above their Tg's. Rubber elastomers like polyisoprene and polyisobutylene. are used below their glass transition temperatures. snakes are cold blooded animals. so all their body heat has to come from their surroundings. Now as you may remember. to understand just why polymers with no order to them are hard and brittle below a certain temperature and soft and pliable above it. Some polymers are used above their glass transition temperatures. or Tg for short. in therubbery state. Melting is a transition which occurs in crystalline polymers. but are just strewn around in any old fashion. This portion usually makes up 40-70% of the polymer sample. Each snake is a polymer chain. and the crystalline portion undergoes melting only. and can go on about their business of slithering and sliding with no trouble at all. Hard plastics like polystyrene and poly(methyl methacrylate). it can help to think of a polymer in the amorphous state as a big room full of slithering snakes. that is in their glassy state TheirTg's are well above room temperature. There is a certain temperature(different for each polymer) called the glass transition temperature. both at around 100oC. But even crystalline polymers will have a some amorphous portion.
and being unable to move around to relieve the stress. and they slither hither and thither. and the bulldozer won't get through. still not moving anywhere. Now the exact temperature at which the polymer chains undergo this big change in mobility depends on the structure of the polymer. the polymer chains can move around easily. and tend to just sit still. snakes don't move too much. and the bulldozer moves through the room. have no trouble moving into new positions to relieve the stress you have placed on them. or as good a time as snakes ever have. one of two things will happen to the motionless snakes. they can quickly slither out of your way. causing a minimal amount of snake damage. just having a great time. But when it gets cold. When the temperature is warm. and the snakes will stay put. If it's warm.all about randomly. Now imagine trying to drive a bulldozer through this room full of snakes. it just doesn't happen. being in motion already. that is. or (B) the bulldozer will be stronger than the snakes. and the sample won't bend. one of two things will happen. Things are "hot" when their molecules have lots of kinetic energy and move around very fast. the polymer sample will break or shatter in your hands. Either (A) the chains are strong enough to resist the force you apply. the polymer chains won't be able to move into new positions to relieve the stress which you have placed on them. It is actually an effect of random motion of molecules. and the snakes are moving. when you take a piece of the polymer and bend it. the energy of objects in motion. but as far as motion is concerned. or not at all. So just like in the example of a room full of cold snakes. take a look at the difference between poly(methyl acrylate) and poly(methyl methacrylate) on the acrylate page. Either (A) the snakes will be stronger than the bulldozer. But if it's cold. Polymers are the same way. To see how a small change in structure can mean a big change in Tg. and they'll get squashed. But if you try to bend sample of a polymer below its Tg. They slow down without any heat. the molecules. whether they are polymer molecules or small molecules. over. Now they're still all wrapped around. Things are "cold" when their molecules lack kinetic energy and move around slowly. and under each other. . This change in mobility with temperature happens because the phenomenon we call "heat" is really a form of kinetic energy. So. over and around each other. or (B) the force you apply will be too much for the motionless polymer chains to resist.
we made a little movie showing what happens to the polymer chains at the glass transition temperature. because you could get frostbite if you try to touch it with your fingers) and it will shatter! Neato. An individual snake is not only wiggling around. and the long-range segmental motion grinds to a halt. to move any distance in one direction. much like little kids in church. While polymers are not incapable of such motion. mostly they are not undergoing translational motion. like rubber bands or plastic wrap. The motion that allows a polymer above its glass transition temperature to be pliable is not usually translational motion. and whatnot are changing position a lot. being nippy as it is. tangled up in each other as they are. will cool the objects below their glass transition temperatures. you are undergoing translational motion. and drop in some household objects made from polymers. See for yourself Now to make sure this is all clear.Twistin' the Night Away There is a difference between polymers and snakes that we probably should discuss at this point. and turn like a giant corkscrew. and the polymer changes from being soft and pliable to being hard and brittle. Then put some in a styrofoam cup. for polymers the party's over. Try This! Want to have some fun? First. but what is known in the business aslongrange segmental motion. When this long-range motion ceases. various arms. get your teacher to bring some liquid nitrogen to class. but actually moving from one side of the room to the other. Measuring the Tg . Try to bend your rubber band (hold it with a pair of pliers. huh? The rubber band will shatter because it's below its glass transition temperature. The polymer samples may be thought of as a crowd of people on a dance floor. When you walk down the street. it is already too cold for the polymer molecules. The liquid nitrogen. by the time we get down to the glass transition temperature. But they are still moving around. To be sure. While the polymer chain as a whole may not be going anywhere. When the temperature drops below the Tg. While each whole body tends to stay in the same spot. segments of the chain can wiggle around. legs. presuming you're not like most Americans who never walk anywhere. wiggling this way and that. This is called translational motion. the glass transition occurs. swing to and fro.
and easier to work with. If you're wondering what kind of small molecule we're talking about. now there's a wonderful page to tell you all about a technique called differential scanning calorimetry. We call this increasing the free volume.If you want to know how we measure both melting points and Tg's. When this happens they can slide past each other more easily. we just put something in it called a plasticizer. This is a small molecule which will get in between the polymer chains. Melting What Becomes the High Tg Polymer? Messing Around with the Glass Transition Sometimes. and space them out from each other. plus latent heats of melting. In this way. they can move around at lower temperatures than they would without the plasticizer. That's ok. the Tg of a polymer can be lowered. and changes in heat capacity. Go visit it! Where Next? Want to know more about the wonderful glass transition? Read these little segments! Messing Around with the Tg The Tg vs. When they slide past each other more easily. to make a polymer more pliable. here are some that are used as plasticizers: . a polymer has a Tg that is higher than we'd like.
It will hold steady until the polymer has completely melted.) . even though you're adding heat to the polymer. second order transition It's tempting to think of the glass transition as a kind of melting of the polymer. and none of it goes into raising the temperature. But the chains that melt are not the chains that undergo the glass transition. and the dashboard will become brittle and crack. This heat is called the latent heat of melting. so the same sample can often show a melting point and a Tg. if enough of it evaporates. Melting Keywords: first order transition. All the energy you add to a crystalline polymer at its melting point goes into melting. TheTg of the polymers in your dashboard will rise above room temperature. When you heat a crystalline polymer at a constant rate. while the glass transition happens only to polymers in the amorphous state. but that smell is the plasticizer evaporating from the plastic parts on the inside of your car. Now the temperature will continue to increase until the polymer reaches its melting point. There are a lot of important differences between the glass transition and melting. (The word latentmeans hidden. A given polymer will often have both amorphous and crystalline domains within it. Like I said earlier. Then the temperature of the polymer will begin to increase once again. heat capacity. your dashboard will no longer be plasticized. The temperature rising stops because melting requires energy. The Glass Transition vs. When this happens. There is another big difference between melting and the glass transition. After many years. The heat amount of heat required to raise the temperature of one gram of the polymer one degree Celsius is called the heat capacity. the temperature will hold steady for awhile.Have you ever smelled "that new car smell"? It's not something I smell too often on the money I make. melting is something that happens to a crystalline polymer. the temperature will increase at a constant rate. But this is an inaccurate way of looking at things.
is called a first order transition. so it can absorb more heat with a smaller increase in temperature. and it undergoes a change in its heat capacity. But the temperature doesn't go up at the same rate above the Tg as below it. First you heat it. It may help to look at some nifty pictures. the temperature begins to rise again. which has a change in heat capacity. The temperature doesn't stop rising. or boiling or condensation. something different happens. It goes up at a rate determined by the polymer's heat capacity. and a latent heat involved. The polymer does undergo an increase in its heat capacity when it undergoes the glass transition. but now it rises at a slower rate. Because the glass transition involves change in heat capacity. two things happen when a crystalline polymer melts: It absorbs a certain amount of heat. The plots show the amount of heat added to the polymer on the y-axis and the temperature that you'd get with a given amount of heat on the x-axis. this transition is called a second order transition. and the temperature goes up. . whether it is melting or freezing. The temperature keeps going up. but it doesn't involve a latent heat. just like before. So. the latent heat of melting. Any change brought about by heat.Now once the polymer has melted. The molten polymer has a higher heat capacity than the solid crystalline polymer. Only something funny happens when you reach the Tg. There is no latent heat of glass transition. But when you heat an amorphous polymer to its Tg.
right before your eyes. That's the latent heat of melting. As I said before. which means. is the difference between a first order transition like melting. we know at this point that some polymers have highTg's. so this increase in steepness corresponds to our increase in heat capacity above the melting point. We see the slope getting steeper on the high side of the break. At that break. We can see a heat capacity change at the Tg. What makes one polymer move more easily than another? I'm glad you asked that. while one that doesn't move so well will have a high one. The slope of this kind of plot is equal to the heat capacity.. There are several things that affect the mobility of a polymer chain. but no break. that we have an increase in heat capacity. This makes sense. What Becomes the High Tg Polymer? Ok. But in the plot on the right. my friends. And this. You can look at it and see that it's discontinuous.The plot on the left shows what happens when you heat a 100% crystalline polymer. which shows what happens to a 100% amorphous polymer when you heat it. of course. See that break? That's the melting temperature. The question we haven't bothered to ask yet is this: why? What makes one polymer glass transition at 100 oC and another at 500 oC? The very simple answer is this: How easily the chains move. we don't have a break. and some have low Tg's. like we do in the plot for the crystalline polymer. The only change we see at the glass transition temperature is an increase in the slope. there is no latent heat involved with the glass transition. So then I suppose we've brought ourselves to another question. A polymer chain that can move around fairly easily will have a very low Tg. Go look at each one! Backbone Flexibility Pendant Groups Part I: Fish Hooks and Boat Anchors Pendant Groups Part II: Elbow Room . a lot of heat is added without any temperature increase at all. The more easily a polymer can move. and a second order transition like the glass transition. the less heat it takes for the chains to commence wiggling and break out of the rigid glassy state and into the soft rubbery state..
The most dramatic one is that of silicones. Ether groups work nicely. It's so rigid that it doesn't have a Tg! You can heat this thing to over 500 oC and it will still stay in the glassy state. Let's look at some examples. The more flexible the backbone chain is. This polymer's backbone is just plain stiff. and those flexible ether groups bring the Tg of this one down to a more manageable 190 oC. Polymers like this are called poly(ether sulfones). poly(phenylene sulfone). and the lower its Tg will be. This backbone is so flexible that polydimethylsiloxane has aTg way down at -127 oC! This chain is so flexible that it's a liquid at room temperature. Now we'll look at another extreme. and it's even used to thicken shampoos and conditioners. the better the polymer will move.Backbone Flexibility This is the biggest and most important one to remember. Let's take a look at one called polydimethylsiloxane. . It will decompose from all the heat before it lets itself undergo a glass transition! In order to make a polymer that's at all processable we have to put some flexible groups in the backbone chain.
Even a small pendant group can act as a fish hook that will catch on any nearby molecule when the polymer chain tries to move like corkscrew. It's a downright boat anchor. just take a look at two poly(ether ketones). one with an adamantane pendant group and one without. To see how much this affects the Tg.Pendant Groups Part I: Fish Hooks and Boat Anchors Pendant groups have a big effect on chain mobility. An adamantyl group is derived from a compound called adamantane. Not only does it get caught on nearby polymer chains. One of the best pendant groups for getting a high Tg is the big bulky adamantyl group. Click on the adamantane to see it in 3-D! A big group like this does more than just act like a hook that catches on nearby molecules and keeps the polymer from moving. Pendant groups also catch on each other when chains try to slither past each other. . its sheer mass is such a load for its polymer chain to move that it makes the polymer chain move much more slowly.
The further they are from each other. This lowers the Tg. the big pendant groups limit how closely the polymer chains can pack together. We can see this with a series of methacrylate polymers: . The more free volume. You see. Pendant Groups Part II: Elbow Room But big bulky pendant groups can lower the Tg. to 225 oC. but the adamantyl group raises even higher. too. in the same way a plasticizer does.The Tg of the polymer on the top is already decent at 119oC. The fancy way to say that there is more room between the polymer chains is to say there is more free volume in the polymer. the lower the Tg generally. the more easily they can move around.
Nylon-6 .You can see a big drop each time we make that pendant alkyl chain one carbon longer. pretty close to room temperature. but by the time we get to poly(butyl methacrylate) the Tg has dropped to only 20oC. We start out at 120 oC for poly(methyl methacrylate).
So what happens to caprolactam when there's water around? The carbonyl oxygen looks around. You can look at the picture if you don't believe me. a little thing like this that seem harmless enough can grow into something much bigger. and sees how easy it would be to steal one of the water's hydrogen atoms. .6.Nylon 6 is an awful lot like our friend nylon 6. Let's get on with the business of turning caprolactam into nylon 6. Nylon 6 is made by heating caprolactam to about 250 oC with about 5-10% water thrown in. If you watch. nylon 6 is only made from one kind of monomer. Nylon 6. If you want to see caprolactam in 3-D. you'll see that caprolactam's greed is going to get the better of it. a monomer called caprolactam.6 is made from two monomers.6. Now as is often the case. First of all. But making nylon 6 is lot different from nylon 6. and sees a water molecule. But enough small talk. adipoyl chloride and hexamethylene diamine.
because it is going to come back to haunt greedy ol' caprolactam.The carbonyl oxygen donates a pair of electrons to the hydrogen atom of water. But first. so it swipes a pair of electrons from the carbonyl double bond. This gives us a protonated carbonyl. But carbocations are not happy critters. let's remember that the carbonyl oxygen now has a positive charge. Putting a carbocation in a molecule is just begging for some nucleophile to come along and attack it. It's that old hydroxide ion that was left when caprolactam stole the proton from the water molecule. and a free hydroxyl group. leaving the positive charge on the carbonyl carbon atom. Nucleophile? Did someone say nucleophile? I think there's one nearby. . Keep this hydroxyl group in mind. it attacks the carbocation. Still harboring a lot of hostility. It doesn't like this. This little hydroxide ion never really worked through the negative emotions of having lost its proton to caprolactam. thus stealing the hydrogen from the water.
a lot like the water molecule did. . stealing it away from the amino acid. that linear amino acid can react with a caprolactam molecule. severing the carbon-nitrogen bond. the circle is broken. What we're left with is a linear amino acid. But our story is far from over. The electrons that the hydrogen shared with its oxygen shift to form a double bond between the oxygen and the carbon atom.The molecule formed is now an unstable gem diol. Alas. stealing it away. Didn't I tell you that caprolactam's greed would be its undoing? A mad reshuffling of electrons happens next. the electrons shared by the carbon and the nitrogen shift completely to the nitrogen. Witnessing one of their own destroyed by greed doesn't make them any less greedy. Caprolactam molecules aren't very bright. The nitrogen atom donates a pair of electrons to a hydrogen atom on one of the hydroxyl groups. They just try to steal what they can from their fallen sibling. a caprolactam molecule will steal the acid hydrogen form the linear amino acid. And lastly. and caprolactam is no more! Like many junk bond dealers in the eighties. Ever avaricious. You see. like greedy little buzzards. The carbonyl oxygen donates a pair of electrons to that hydrogen. it has paid dearly for its greed. Unstable? Of course.
That's the amino acid that just lost its acid hydrogen. the electrons rearrange to form the carbocation. but this time.And as expected. just as before: This carbocation is still an open invitation to any nucleophile around. It too has a lot of hostility towards the thieving caprolactam. and attacks just like we saw the hydroxide ion attack earlier. there's a new nucleophile on the block. .
opening the ring. the ring nitrogen steals a hydrogen from the ammonium nitrogen. Another greedy caprolactam molecule bites the dust. . and this particular one is very unstable. Showing no elemental loyalty. In addition. The electrons play musical chairs.This gives us an ammonium species. the bond joining the carbon and the nitrogen is severed. That carboxylate group at the end of the molecule is going to sweep around and steal the alcohol hydrogen. But we're not through yet.
They might happen in the reverse order. (Remember. (Here's a little secret: No one really knows the order of the last two steps.) Now that we have an acid again. it is sure to react with another avaricious caprolactam molecule. . We just know that both of them happen before everything is over.This makes a new carbonyl group in the middle of the molecule. and then another. and regenerates the carboxylic acid.) If you want to see a movie of the whole propagation process. and another. until we get long chains of nylon 6. . this is a step growth polymerization.
then it's made out of some copolymer of polyacrylonitrile. and even fiber reinforced concrete.Polyacrylonitrile Polyacrylonitrileis used for very few products an average consumer would be familiar with. except to make another polymer. . sometimes we make copolymers of acrylonitrile and vinyl chloride. If the label of some piece of clothing says "acrylic". sails for yachts. carbon fiber. But mostly copolymers containing polyacrylonitrile are used as fibers to make knitted clothing. like socks and sweaters. or acrylonitrile and methyl methacrylate: Also. and the fibers made from them are called modacrylic fibers. These copolymers are flame-retardant. outdoor awnings. as well as outdoor products like tents and such. Usually they're copolymers of acrylonitrile and methyl acrylate. Homopolymers of polyacrylonitrile have been uses as fibers in hot gas filtration systems.
which can polymerize. Poly(styreneco-acrylonitrile) (SAN) and poly(acrylonitrile-co-butadiene-co--styrene) (ABS). Polybutadiene has carbon-carbon double bonds in it. like you see below. but it is so light that Wassana can lift this front bumper fascia over her head with only hand! Using plastics like ABS makes automobiles lighter. It is strong enough to be used to make automobile body parts.But the slew of copolymers of acrylonitrile doesn't stop there. So we end up with a polybutadiene chain with SAN chains grafted onto it. are used as plastics. . But ABS is more complicated. too. and therefore they pollute less. ABS is very strong and lightweight. It's made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. SAN is a simple random copolymer of styrene and acrylonitrile. so they use less fuel.
PETE. Also the rubbery polybutadiene makes ABS tougher than polystyrene. and a derivative of the acrylate familyof polymers. food and other liquid containers. or the obsolete PETP or PET-P). beverage. so they are attracted to each other. It is made from the monomer acrylonitrile by free radical vinyl polymerization. This allows opposite charges on the nitrile groups to stabilize each other like you see in the picture on the left. Depending on its processing and thermal history. It is one of the most important raw materials used in manmade fibers. Its monomer can be synthesized by the esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct. Polymerization is through a polycondensation reaction of the monomers (done immediately after esterification/transesterification) with ethylene glycol as the byproduct (the ethylene glycol is recycled in production). or the transesterification reaction between ethylene glycol and dimethyl terephthalate with methanol as a byproduct. Poly (ethylene terephthalate) Polyethylene terephthalate (sometimes written poly(ethylene terephthalate).ABS is a stronger plastic than polystyrene because of the nitrile groups of its acrylonitrile units. it may exist both as an amorphous (transparent) and as a semi-crystalline (opaque and white) material. and engineering resins often in combination with glass fiber. commonly abbreviated PET. thermoforming applications. The nitrile groups are very polar. making the material stronger. . is a thermoplastic polymer resin of the polyester family and is used in synthetic fibers. This strong attraction holds ABS chains together tightly. Polyacrylonitrile is a vinyl polymer.
Chemical structure of polyethylene terephthalate Contents • • • • • • • • • • • • 1 Uses 2 Intrinsic viscosity 3 Drying 4 Copolymers 5 Crystals 6 Degradation 7 Antimony 8 Re-crystallization 9 Processing equipment 10 See also 11 References 12 External links Uses .Rynite and Valox injection molding resins. Impet.The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting for around 30% of global demand. andTrevira fibers. and Arnite. Ertalyte. and Mylar films. Terylene. In discussing textile applications. elinex. The polyester Industry makes up about 18% of world polymer production and is third after polyethylene (PE) and polypropylene (PP). PET is generally referred to as simply "polyester" while "PET" is used most often to refer to packaging applications. Some of the trade names of PET products are Dacron. Hostaphan. Diolen. Cleartuf. Eastman PET and Polyclear bottle resins.
When filled with glass particles or fibers. and Crastin. depending on its thickness. It makes a good gas and fair moisture barrier. When produced as a thin film (often known by the tradename Mylar). PET sandwiches an additional polyvinyl alcohol to further reduce its oxygen permeability. PET or Dacron is also used as a thermal insulation layer on the outside of the International Space Station as seen in an episode of Modern Marvels "Sub Zero".soft drink bottle PET can be semi-rigid to rigid. PET bottles are excellent barrier materials and are widely used for soft drinks. It is naturally colorless with high transparency. It is strong and impact-resistant. as well as a good barrier to alcohol (requires additional "Barrier" treatment) and solvents. in a semi-crystalline formulation. and to make it reflective and opaque. Hostadur. . PET is often coated with aluminium to reduce its permeability. it becomes significantly stiffer and more durable. Arnite. This glass-filled plastic. is sold under the tradename Rynite. (see carbonation). For certain specialty bottles. and is very lightweight.
(intrinsic viscosity). The longer the chains. of about: 0.V. Intrinsic viscosity One of the most important characteristics of PET is referred to as I. PET has a resin identification code of 1.60 dl/g: Would be appropriate for fibre . is also an excellent candidate for thermal recycling (incineration) as it is composed of carbon. a brand of PET fiber.V.Sails are usually made of Dacron. PET. The I.V. The primary reason is that plastic carbonated soft drink bottles and water bottles are almost exclusively PET which makes them more easily identifiable in a recycle stream. PET bottle recycling is more practical than many other plastic applications. and therefore the higher the I.V. the stiffer the material. measured in deciliters per gram (dl/g) is dependent upon the length of its polymer chains. colorful lightweight spinnakers are usually made of nylon. hydrogen and oxygen with only trace amounts of catalyst elements (no sulphur) and has the energy content of soft coal. While most thermoplastics can. One of the uses for a recycled PET bottle is for the manufacture of polar fleece material. The average chain length of a particular batch of resin can be controlled during polymerization. as with many plastics. The PET bottle was patented in 1973. PET was patented in 1941 by the Calico Printers' Association of Manchester. It can also make fiber for polyester products. be recycled. in principle. An I. of the material.
Typically residual moisture levels in the resin must be less than 40 parts per million (parts of water per million parts of resin. Dryer residence time should not be shorter than about four hours. hot dry air is pumped into the bottom of the hopper containing the resin so that it flows up through the pellets. the modified properties of copolymer are more desirable for a particular application. PET modified by copolymerization is also available. In some cases. However. removing moisture on its way. Such PET is generally known as PETG (EastmanChemical and SKchemicals are the only two manufacturers). Inside the dryer.84 dl/g: Bottles 0. The resulting cool wet air is then passed through a desiccant bed.0. as much moisture as possible must be removed from the resin.65 dl/g: Film 0. This is achieved through the use of a desiccant or dryers before the PET is fed into the processing equipment. The hot wet air leaves the top of the hopper and is first run through an after-cooler. Copolymers In addition to pure (homopolymer) PET. This means that before the resin can be processed in a molding machine. This is because drying the material in less than 4 hours would require a temperature above 160 °C. it does not fit in with the neighbouring chains the way an ethylene glycol unit would.76-0. . by weight) before processing.85 dl/g: Tire cord Drying PET is hygroscopic. at which level hydrolysis would begin inside the pellets before they could be dried out. For example. This interferes with crystallization and lowers the polymer's melting temperature. Since this building block is much larger (6 additional carbon atoms) than the ethylene glycol unit it replaces. when this 'damp' PET is then heated a chemical reaction known as hydrolysis takes place between the water and the PET which reduces its molecular weight (IV) and its physical properties. because it is easier to remove moisture from cold air than hot air. meaning that it naturally absorbs water from its surroundings. Finally the cool dry air leaving the desiccant bed is re-heated in a process heater and sent back through the same processes in a closed loop. cyclohexane dimethanol (CHDM) can be added to the polymer backbone in place of ethylene glycol.
This procedure is known as solid-state crystallization. rather than forming one large single crystal. they begin to move again. such as carbon dioxide in carbonated beverages. For PET bottles. which also disturbs crystallinity. which is used for example to make tray or blister packagings from PETG film. but if enough heat energy is put back into them. As a result. such as seat belts. symmetrical pattern. Such copolymers are advantageous for certain moulding applications. which are both clear and crystalline enough to be an adequate barrier to aromas and even gases. allowing crystals to nucleate and grow. PET is no exception to this rule. Like most materials. Light tends to scatter as it crosses the boundaries between crystallites and the amorphous regions between them.Replacing terephthalic acid (right) with isophthalic acid (center) creates a kink in the PET chain. At room temperature the molecules are frozen in place. such as thermoforming. Long polymer chains tend to become entangled on themselves.4(para-) linked terephthalate units.2-(ortho-) or 1. Like glass. crystallization is important in other applications where mechanical and dimensional stability are important. or PETG sheet. interfering with crystallization and lowering the polymer's melting point. Clear products can be produced by rapidly cooling molten polymer to form an amorphous solid. 60% crystallization is the upper limit for commercial products. crystallization is slowed but not prevented entirely. replacing some of the 1. Crystals Crystallization occurs when polymer chains fold up on themselves in a repeating.3-(meta-) linkage produces an angle in the chain. On the other hand. bottles are obtainable via stretch blow molding ("SBM"). with the exception of polyester fibers. The 1. This scattering means . amorphous PET forms when its molecules are not given enough time to arrange themselves in an orderly fashion as the melt is cooled. PET tends to produce many small crystallites when crystallized from an amorphous solid. Another common modifier is isophthalic acid. which prevents full crystallization in all but the most carefully controlled circumstances. the use of small amounts of CHDM or other comonomers can be useful: if only small amounts of comonomers are used. PET in its natural state is a crystalline resin.
Acetaldehyde forms in PET through the "abuse" of the material. This helps to prevent degradation. such as soft drinks.that crystalline PET is opaque and white in most cases. for fruit juices. This becomes a problem when the optical requirements of the polymer are very high like for example in packaging applications. When acetaldehyde is produced. Degradation PET is subject to various types of degradations during processing. When PET degrades. Acetaldehyde is normally a colorless gas with a fruity smell. chain scissions resulting in reduced molecular weight. Recently. extruder speeds (excessive shear flow raises temperature) and long barrel residence times all contribute to the production of acetaldehyde. altering the taste and aroma. Antimony . The main degradations that can occur are hydrolytic. mainly antioxidants such as phosphites. by weight) of acetaldehyde can produce an off-taste. This is not such a problem for nonconsumables such as shampoo. several things happen: discoloration. Fiber drawing is among the few industrial processes that produces a nearly single-crystal product. because if nothing masks the aroma. but it can cause an off-taste in bottled water. unnoticeable) level. which already contain acetaldehyde or for strong-tasting drinks. high pressures. reducing the acetaldehyde content of the finished product to an acceptable (that is. molecular level stabilization of the material using nanostructured chemicals has also been considered. It forms naturally in fruit. For bottled water. formation of acetaldehyde and cross-links ("gel" or "fish-eye" formation). low acetaldehyde content is quite important. See copolymers. some of it remains dissolved in the walls of a container and then diffuses into the product stored inside. thermal and probably most important thermal oxidation. High temperatures (PET decomposes above 300 °C or 570 °F). The thermal and thermooxidative degradation results in poor processability characteristics and performance of the material. even extremely low concentrations (10-20 parts per billion parts of resin. One way to alleviate this is to use a copolymer. Discoloration is due to the formation of various chromophoric systems following prolonged thermal treatment at elevated temperatures. Thus the resin can be plastically formed at lower temperatures and/or with lower force. Other ways to improve the stability of the polymer is by using stabilizers. Comonomers such as CHDM or isophthalic acid lower the melting temperature and reduces the degree of crystallinity of PET (especially important when the material is used for bottle manufacturing). above.
 (report available in German and French only) The Swiss Federal Office of Public Health concluded that small amounts of antimony migrate from the PET into bottled water. It remains in the material and can thus in principle migrate out into food and drinks. part of the material will visibly change. but still well below the allowed maximal concentrations. Although antimony trioxide is of low toxicity. its presence is still of concern. The Swiss Federal Office of Public Health investigated the amount of antimony migration. This releases the . The resin identification code can be used to verify the type of plastic it is made of: many plastic beverage bottles have the letters PET or PETE and a code of 1 on the bottom. The most recent WHO risk assessment for antimony in drinking water can be found here:  Re-crystallization PETE has SPI resin ID code 1 Recrystallized PET PET can be used to explore the crystallization of amorphous solids. A later (2006) but more widely publicized study by a group of geochemists at the University of Heidelberg headed by William Shotyk found similar amounts of antimony in water in PET bottles. comparing waters bottled in PET and glass: the antimony concentrations of the water in PET bottles was higher. This happens because high temperatures melt the PET. When a flame is held several inches below the bottle and slowly brought closer.Antimony trioxide (Sb2O3) is a catalyst that is often used in the production of PET. near the center. but that the health risk of the resulting low concentrations is negligible (1% of the "tolerable daily intake" determined by the WHO).
Because of the decreased order of the polymer chains. and far higher visual quality than can be achieved by the two-step system. In one-step machines. Because the new crystallites are larger than the wave length of light. If you want to see what adipic acid and hexamethylene diamine look like in 3-D. giving the material an opaque white appearance. The preform looks like a test tube. The first machine injection molds the preform. Nylons are made from diacids and diamines. the preforms are heated rapidly and then inflated against a two-part mold to form them into the final shape of the bottle. the entire process from raw material to finished container is conducted within one machine. when the crystallites re-form upon cooling they grow larger than the original crystallites in the bottle wall. including jars. To start off. which results in shrinkage of the softened area. making it especially suitable for molding non-standard shapes (custom molding). The bottle-cap threads are already molded into place. . In two-step molding.tension that was frozen in during the blow molding process and the polymer chains will shift to a more relaxed and disordered state. one-step and two-step. two separate machines are used. Nylon-66 This page is all about how to make nylon. Processing equipment There are two basic molding methods. and a condensation polymerization. they will now cause light to scatter. In the second process. product handling and energy. . flask shapes etc. Preforms (uninflated bottles) are now also used as containers for candy. Its greatest merit is the reduction in space. and the body of the tube is significantly thicker. nylon is made by a reaction which is a step-growth polymerization. We're telling you this as if you can't read the title for yourself. Consequently. there are now fewer crystal nuclei. flat oval. as it will be inflated into its final shape in the second step using stretch-blow molding.
To make nylon 6. there are a few more details to the reaction than you see up there in that little picture. This happens because our protonated oxygen bears a positive charge. one of the monomers is itself an acid.6 on doesn't need a catalyst. but acids do catalyze the reaction. A little reaction happens between two adipic acid molecules. So it pulls the electrons it shares with the carbonyl . and wouldn't you know it. Oxygen does not like to have a positive charge. When this oxygen is protonated the carbonyl oxygen becomes much more vulnerable to attack by the nitrogen of our diamine. One will donate a proton to a the carbonyl oxygen of another.Of course.
toward itself. . One of the electron pairs form the carbonyl double bond shifts entirely to the oxygen. taking care of the problem of the positive charge at that atom. This leaves the carbonyl carbon lacking electrons. and ready for the amine nitrogen to donate a pair to it: Then the electrons play musical chairs. but now our nitrogen has a positive charge.
or a molecule of the diamine. and gets rid of the positive charge on that nitrogen. and an amine group at the other. As it now shares a pair of electrons with the oxygen. you get a trimer. The oxygen of the hydroxyl group decides to do a little bit of electron shuffling of its own. regenerating the carbonyl double bond. so it lets go of that pair. severing the bond between it and the carbon. this isn't enough.So then we get an even more elaborate game of electron musical chairs. it sees no need to keep the pair it shares with the nitrogen. This means that it can react with a molecule of the diacid. and you'll see that it has an acid group at one end. So what does this dimer do? Look close. freeing the proton. giving it over to the nitrogen. regenerating the acid catalyst. That gets this hydrogen thinking. . Then the carbonyl oxygen shares its newly regained electrons with the carbon atoms. It then donates a pair of electrons to a hydrogen connected to the nitrogen. Either way. The electrons from the hydrogen oxygen bond go back to the oxygen. It splits off H2O. This shift of electrons breaks the bond between the hydrogen and the nitrogen. and generates the amidecontaining dimer. It takes the pair it shares with the carbon and hogs them to itself. Of course.
This keeps happening until they become big enough to be called polymers. to form even bigger oligomers. and bigger oligomers. to make a tetramer if it wants to. dimers will grow into trimers. and these big oligomers will react with each other.Wanna know a little secret? Our dimer can also react with other dimers. tetramers. and it can also react with bigger oligomers. . Or it can react with a trimer to form a pentamer. when this happens. Eventually.
You see. the reaction still goes on.) Also. If you want to see a movie of this method . high molecular weight nylon 66 could not be made without an external catalyst. it produces HCl gas as a byproduct rather than water. the amine can react with the unprotonated carboxylic acids.For the molecules to grow big enough to be called polymers. when there aren't many acid groups left to be catalysts. we have to do this reaction under a vacuum. adipic acid acts as the catalyst. all that by-product water will evaporate and get sucked away. because the reaction would stop at higher conversions. If this were not so. When we do this. but you need to add a little bit of acid to act as a catalyst. Wanna know something else? Nylons can also be made from a diamine and a diacid chloride: This reaction goes by the same mechanism. when there aren't many acid groups left to be catalysts. Now remember how at the beginning of this little lesson I said that the reaction doesn't need an acid catalyst to take place? The reason we know this is that near the end of the polymerization. (When you make nylon the other way. We need to get rid of the water because of a little rule called Le Chatelier's Principle.
Polypropylene can be made from the monomer propylene by ZieglerNatta polymerization and by metallocene catalysis polymerization. Polypropylene can be made with different tacticities. Most polypropylene we use is isotactic.Polypropylene Polypropylene is one of those rather versatile polymers out there. and because polypropylenedoesn't absorb water. This is what the monomer propylene really looks like: Wanna know more? Research is being conducted on using metallocene catalysis polymerization to synthesize polypropylene. Metallocene catalysis polymerization can do some pretty amazing things for polypropylene. As a fiber. will anneal at around 100oC. a more common plastic. It serves double duty. like this: But sometimes we use atactic polypropylene. As a plastic it's used to make things like dishwasher-safefood containers. or 320oF. This means that all the methyl groups are on the same side of the chain. Atactic means that the methyl groups are placed randomly on both sides of the chain like this: . which means that polyethylenedishes will warp in the dishwasher. like nylon does. and is similar topolyethylene. polypropyleneis used to make indoor-outdoor carpeting. both as a plastic and as a fiber. it's a vinyl polymer. Polyethylene. Structurally. only that on every other carbon atom in the backbone chain has a methyl group attached to it. It can do this because it doesn't melt below 160oC. the kind that you always find around swimming pools and miniature golf courses. It works well for outdoor carpet because it is easy to make colored polypropylene.
The hard isotactic blocks hold the rubbery isotactic material together. as is shown in the picture: This polymer is rubbery. But because the isotactic blocks are joined to the atactic blocks. but it wouldn't be very strong. by using special metallocene catalysts. To be honest. atactic polypropylene would be rubbery without help from the isotactic blocks. This is because the isotactic blocks will form crystals by themselves. but notpolypropylene elastomers.However. and makes a good elastomer. Most kinds of rubber have to be crosslinked to give them strength. to give the material more strength. it's believed that we can make polymers that contain blocks of isotacticpolypropylene and blocks of atactic polypropylene in the same polymer chain. as you can see in the picture on the right. the little hard clumps of crystalline isotactic polypropylene are tied together by soft rubbery tethers of atactic polypropylene. .
is a kind of thermoplastic elastomer. as this copolymer is called. but this is too much for it to behave as an elastomer.Elastomeric polypropylene. until the research is completed. . this type of polypropylene will not be commercially available.60% crystallinity. The polypropylene that you can buy off the shelf at the storetoday has about 50 . However.
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