Modern Plastics Handbook 2011 Part 5 ppt

Lubricants represent a broad class of materials that are used to improve the flow characteristics of plastics during processing.Besides this primary task of improving flow properties, lu

The growth of heat stabilizers is dependent on PVC growth RigidPVC applications are expected to grow at a faster rate than flexiblePVC applications worldwide This indicates organotins will experiencehigher growth than mixed metals Over the next 5 years, heat stabi-lizers are expected to grow at a rate of 6%/year paced by theAsia/Pacific and the developing regions of the world.

4.11 Impact Modifiers

4.11.1 Description

Impact modifiers are used in a wide variety of thermoplastic resins to

absorb the energy generated by impact and dissipate it in a structive fashion The behavior and definition of impact modifiers arecomplex The selection of an impact modifier is dependent on compat-ibility, physical solubility, impact performance, and cost

nonde-Impact modifiers are primarily used in PVC, engineering resins, andpolyolefins The use levels of impact modifiers vary widely dependingupon the modifiers, matrix type, and properties desired The majortypes are shown in Table 4.15 along with the resins in which they areprimarily used

TABLE 4.14 Selected Heat Stabilizer Suppliers

TABLE 4.15 Major Types of Impact Modifiers by Resin

Resin

MABS

EPDM (ethylene propylene

Methacrylate-butadiene-styrene (MBS). Methacrylate-butadiene-styrene

represents the highest volume of the styrenic type impact modifiers.This modifier is used in transparent packaging applications due to itsclarity Rigid applications include film, sheet, bottles, credit cards,and interior profiles MBS has limited use in exterior applications due

to poor ultraviolet (UV) stability ene-styrene (MABS) is closely related to MBS, but has minor use inthe industry and has been completely replaced by MBS in NorthAmerica

Methacrylate/acrylonitrile-butadi-Acrylonitrile-butadiene-styrene (ABS). Acrylonitrile-butadiene-styrene

is used in a variety of resins, with about 60% in PVC The primaryABS applications are in automotive parts, credit cards, and packag-ing ABS, like MBS, is not suitable for outdoor applications unless it

is protected by a UV-resistant cap ABS, although compatible withMBS, suffers from the disadvantage of not being regarded as anindustry standard

Acrylics. Acrylics are similar to MBS and ABS but have butyl acrylate

or 2-ethyl-hexyl acrylate graft phases Acrylics offer greater resistance

to UV degradation and are used primarily in PVC siding, window files, and other applications calling for weather resistance Due togrowth in the building and construction industry, acrylics are experi-encing the highest growth rate

pro-Chlorinated polyethylene (CPE). Chlorinated polyethylene modifiers

are most commonly used in pipe, fittings, siding, and weatherableprofiles CPE modifiers compete primarily with acrylics in sidingapplications CPE can be used in resins other than PVC, for example,

PE and PP

Ethylene vinyl acetate (EVA). Ethylene vinyl acetate modifiers have

minor usage compared to other types of impact modifiers EVA findsuse in limited segments of the flexible PVC sheet business

Ethylene propylene diene monomer (EPDM). Ethylene propylene diene monomer is used in thermoplastic olefin (TPO) for automotive

bumpers and parts as well as scattered consumer durable markets

Maleic anhydride grafted EPDM. Maleic anhydride grafted EPDM reacts

with the matrix resin, typically nylon, to become its own compatibilizer.This type of modifier provides for excellent balance in impact, hardness,modulus, and tensile strength and is the major additive component of

“super tough” nylon

4.11.2 Suppliers

There are over 30 suppliers of impact modifiers worldwide Most centrate their efforts in one type of modifier as a result of their devel-oped technologies and backward integration Selected suppliers resellother producers’ technologies in their home regions to broaden theirproduct lines

con-Rohm and Haas, Kaneka, and Atochem are the leading suppliers ofimpact modifiers worldwide Each has strong positions in both theacrylic and MBS-related modifiers Elf Atochem is stronger in acrylics,while Kaneka is stronger in MBS types Rohm and Haas, including itsjoint venture with Kureha in the Asia/Pacific region, has a more bal-anced position Table 4.16 presents the major global suppliers ofimpact modifiers by type

4.11.3 Trends and forecasts

The need for cost-effective materials that are strong, stiff, and ductilewill continue to increase In many cases the key to success will be thedevelopment of tailored impact modifier systems for specific resins.The EPDM market will probably see a decline over the next couple

of years due to the advent of reactor-generated polypropylene Thismaterial incorporates the impact modifier in the polymer chain anddoes not require a secondary compounding operation

The MBS market is decreasing partially due to PVC bottles beingreplaced by PET This trend is more evident in Europe due to wide-spread use of water bottles In contrast, the film and sheet marketremain strong Overall, MBS sales are heavily dependent on thefuture of PVC, particularly flexible PVC Flexible PVC, comprising15% of the total PVC market, is vulnerable to penetration by metal-locene catalyzed polyolefins (for example, “super soft polypropylene”).Acrylic impact modifiers will continue to grow with the growth ofrigid PVC in the construction market Product development in thismarket will target improved low-temperature impact properties toreduce failures, lengthen the installation season, and lower cost

A significant area for product development is the impact tion of engineering plastics The replacement of such conventionalmaterials as metal, glass, and wood by plastics has been underway foryears The applications are typically converted to engineering plasticsand then lost to lower-cost polyolefins and/or vinyl type materials.Most of the “easy” applications have already converted to plastic Theremaining ones, particularly in durable goods, require new levels ofstrength and impact performance

modifica-Consumption of impact modifiers worldwide is projected to grow at5%/year over the next 5 years

TABLE 4.16 Selected Impact Modifier Suppliers

4.12 Light Stabilizers

4.12.1 Description

Light stabilizers are used to protect plastics, particularly polyolefins,

from discoloration, embrittlement, and eventual degradation by UVlight The three major classes of light stabilizers are UV absorbers,excited state quenchers, and free-radical terminators Each class isnamed for the mechanism by which it prevents degradation Themajor types included in each light stabilizer class may be categorized

by their chemistries, as shown in Table 4.17

Benzophenone. Benzophenone UV absorbers are mature products and

have been used for many years in polyolefins, PVC, and other resins.These products also have wide use in cosmetic preparations as sun-screens and protectants

Benzotriazole. Benzotriazole UV absorbers are highly effective in

high-temperature resins such as acrylics and polycarbonate They also findextensive use in areas outside plastics such as coatings

Benzoates and salicylates. Benzoates and salicylates such as

3,5-di-t-butyl-4hydroxybenzoic acid n-hexadecyl ester, function by

rearrang-ing to 2-hydroxybenzophenone analogs when exposed to UV light toperform as UV absorbers

Nickel organic complexes. Nickel organic complexes protect against

degradation caused by UV light via excited state quenching Thesedeactivating metal ion quenchers stop the energy before it can breakany molecular bonds and generate free radicals Nickel complexes areprimarily used in polyolefin fiber applications Some examples of nick-

el complexes are nickel dibutyldithiocarbamate and 2,2′ thiobis

(4-octylphenolato)-n-butylamine nickel II which are also used in

agricultural film because of their resistance to pesticides

Hindered amine light stabilizers (HALS). Hindered amine light ers are the newest type of UV light stabilizer They were introduced in

stabiliz-1975 by Ciba and Sankyo HALS do not screen ultraviolet light, butstabilize the resin via free-radical termination HALS are used at low-

er levels than benzophenones and benzotriazoles, and are widely used

in polyolefins for their cost-effectiveness and performance The cessful growth of HALS has been directly related to their substitutionfor benzophenones and benzotriazoles in many applications as well astheir blending with benzophenones

4.12.3 Trends and forecasts

The entrance of Great Lakes into the European light stabilizer marketwith a series of acquisitions has been the most significant restructur-ing that has occurred in the light stabilizer market This move hasaccelerated the trend toward a more competitive market in thesematerials

Growth in the light stabilizer business is strongly dependent on thegrowth of the polyolefin applications Polyolefins account for aboutthree-quarters of the total global consumption of light stabilizers inplastics Polyolefins, particularly PP, are replacing metals, engineer-

TABLE 4.17 Major Types of Light Stabilizers

UV light absorbers

2-hydroxy-4-n-octoxybenzophenone 2,4-dihydroxy-4-n-dodecycloxybenzophenone

Benzotriazole 2,2-(2-hydroxy-5-tert-octylphenyl) benzotriazole

2-(3 chlorobenzotriazole

′-tert-butyl-2-hydroxy-5-methylphenyl)-5-2-(3 chlorobenzotriazole

′,5′-di-tert-butyl-2′-hydroxyphenyl)-5′-2-(2 ′hydroxy-3′-5′-di-tert amyl phenyl) benzotriazole

2-(2-hydroxy-5-methylphenyl) benzotriazole Phenyl esters 3,5-di-t-butyl-4hydroxybenzoic acid

N-hexadecyl ester

Diphenylacrylates Ethyl-2-cyano-3,3-diphenyl acrylate

2-ethylhexyl-2-cyano-3,3-diphenyl acrylate Excited state quenchers

2,2′-thiobis (4-octylphenolato)-n-butylamine

nickel II Free-radical terminators

Hindered amine light stabilizers Bis (2,2,6,6-tetramethyl-4-piperidinyl)

N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexane diamine polymer with 1,3,5 triazine and 2,4,4-trimethyl-

2,4,6-trichloro-1,2-pentanamine

TABLE 4.18 Selected Light Stabilizer Suppliers

ing plastics, and styrenics in automotive and other applications, ther increasing the volume of stabilizers consumed.

fur-The use of nickel-containing stabilizers is decreasing in the place, particularly in North America, due to potential toxicity concerns

market-In Europe, nickel continues to be used in agricultural film applications.Design efforts are focusing on down-gauging of exterior plastic partsfor weight and cost reduction This will place increased value on lightstabilization to maintain adequate performance at thinner wall sections.HALS will experience the strongest growth due to their widespreaduse in polyolefins and their cost-effectiveness and performance.Benzotriazoles and benzophenones, however, are more effective thanHALS in vinyl and engineering plastics

Significant product development work is being done in HALS nology to produce higher-performance products in polyolefin systems.Low molecular weight alkoxy substituted amine systems and highermolecular weight HALS stabilizers significantly improve the perfor-mance of pigmented TPO parts with regard to color and gloss retention.HALS are being promoted by selected suppliers as effective lightstabilizer with excellent capabilities as antioxidants In some cases,these materials are comparable to well-established antioxidant prod-ucts such as Ciba’s IRGANOX 1010

tech-Suppliers continue to improve on the physical forms of light lizers For example, Cytec is introducing a flake form light stabilizerwhich reduces dusting and increases the shelf life of the products.Consolidation is expected to continue due to margin pressurescaused by regulatory issues such as FDA compliance, toxicologicaltesting, environmental compliance, and the continual need for capitalinvestment This trend may be most apparent in the Asia/Pacificregion where there are a large number of small suppliers

stabi-Globally, light stabilizers should grow at a rate of 7%/year over the next

5 years, with the less developed regions in Asia/Pacific, Latin America,and Africa leading the way This robust growth parallels the growth ofpolyolefins, particularly polypropylene/TPO, and engineering resins intomore exterior applications replacing metal and painted plastic

4.13 Lubricants and Mold Release Agents

4.13.1 Description

Lubricants. Lubricants represent a broad class of materials that are

used to improve the flow characteristics of plastics during processing.Besides this primary task of improving flow properties, lubricants canact as melt promoters, antiblock, antitack, and antistatic agents aswell as color and impact improvers They can be used in conjunctionwith metal release agents and heat stabilizers Lubricants are widely

used in packaging film to prevent sticking to the metal processingequipment Lubricants can improve efficiency by lowering the resinmelt viscosity, resulting in reduced shear and equipment wear,increased rate of production, and decreased energy consumption.Selection of lubricants is dependent upon the type of polymer as well

as the process by which it is manufactured The method of selection iseasier when the manufacturing process is fully developed Lubricantchoices for new processes require careful experimentation

The selection process is driven by the lubricant’s compatibility withthe hot resin, lack of adverse effects on polymer properties, good trans-parency, regulatory approval, and the balance of other additives in thepolymer The amount of lubricant used can also affect the final poly-mer properties Overlubrication can cause excessive slippage andunderlubrication can cause degradation and higher melt viscosities.The two general classifications of lubricants are internal and exter-

nal External lubricants do not interact with the polymer but function

at the surface of the molten polymer between the polymer and the face of the processing equipment and are generally incompatible withthe polymer itself These lubricants function by coating the processequipment and reducing friction at the point of interface They delayfusion and give melt control and the desired polymer flow to suchapplications as rigid PVC pipe, siding, and window frames

sur-Internal lubricants are usually chemically compatible with the

poly-mer and act by reducing friction between polypoly-mer molecules Theyreduce van der Waals forces, leading to lower melt viscosity and low-ering energy input needed for processing

Several chemicals are used as both internal and external lubricantssince lubricants can function at several different points during poly-mer processing When used during the blending portion of processing,they are usually waxy substances that coat the surface of resin pelletsallowing easier movement through the cold portions of the processingequipment As the polymer mix is heated, the lubricant softens, melts,and penetrates the polymer The rate of penetration is dependent uponthe solubility of the particular lubricant in the specific polymer

Metallic stearates. Metallic stearates are the most widely used

lubri-cants They are utilized predominantly in PVC, but also find use inpolyolefins, ABS, polyesters, and phenolics The primary disadvantage

of metallic stearates is their lack of clarity Calcium stearate, the mostcommon metallic stearate, is primarily used as an internal lubricant,but in PVC applications, it provides external lubricant and metalrelease characteristics while also acting as a heat stabilizer

Esters. Esters, including fatty esters, polyol esters, and even wax

esters, are reasonably compatible with PVC They are also used in

polystyrene and acrylic polymers High molecular weight esters areused as external lubricants; conversely, low molecular weight estersare used as internal lubricants, although they are somewhat ineffi-cient as either.

Fatty amides. Fatty amides possess unique mold release properties.

Simple primary fatty amides are used as slip and mold release agentsprimarily in polyolefins but also in a variety of other polymers Themore complex bis-amides, such as ethylene bis-stearamide, offer moldrelease as well as internal and external lubricity functions in materi-als such as PVC and ABS

Fatty alcohols. Fatty alcohols are used primarily in rigid PVC Because

of their compatibility and internal and external lubricant capabilities,they are chosen where clarity is important

Waxes. Waxes are nonpolar and are, therefore, very incompatible with

PVC which makes them excellent external lubricants for this

materi-al Partially oxidized PE wax works well as an external lubricant forPVC by delaying fusion and is almost always combined with calciumstearate for melt flow control Although the primary function of wax-

es, as well as metallic soaps, fatty acid esters, and amides is tion, they are in fact multifunctional, as noted previously, providingslip, antiblock, and mold release properties

lubrica-Mold release agents. When a plastic part tends to stick in the mold, a

mold release agent is applied as an interfacial coating to lower the

fric-tion Improper mold release can lead to long cycle times, distortedparts, and damaged tooling The two types of mold release agents areinternal and external

Internal mold release agents are mixed directly into the polymer.

These materials have minimal compatibility with the polymer Theadditive either migrates to the surface of the polymer and sets up athin barrier coating between the resin and mold cavity or is present in

a sufficient quantity on the surface of the polymer to reduce adhesion

to the mold cavity

Traditionally, external release agents are applied by spraying or

painting the surface of the mold with an aerosol, liquid, or by applying

a paste The solvent or water carrier then evaporates leaving a layer

of release agent on the mold

Mold release agents are used in a variety of applications, includingfiber-reinforced plastics, castings, polyurethane foams and elastomers,injection-molded thermoplastics, vacuum-formed sheets, and extrudedprofiles Because each application has its own plastic, mold material,cycle time, temperature, and final product use, there is no universal

release agent Mold release selection is dependent upon all of theseconditions.

Release agents should ideally have high tensile strength so they arenot worn by abrasive mineral fillers or glass fiber reinforcements Theagents should also be chemically resistant to decomposition andshould stick to the mold to prevent interference with the final product.The major types of materials used as mold release agents are fatty acidesters and amides, fluoropolymers, silicones, and waxes

Fatty acid esters and amides. Fatty acid esters and amides do not usually

interfere with the secondary finishing operations and some have temperature stability making them well-suited for rotational moldresins and engineering plastics

high-Fluoropolymers. Fluoropolymers form a monolayer providing easy

appli-cation but are expensive

Silicones. Although silicones are used as both external and internal

mold release agents, the primary application is as the active ingredient

in external release agents The silicone is in a solution or aqueous persion that is sprayed intermittently into the mold cavity betweenshots A disadvantage of silicones as internal release agents is their pos-sible interference with painting and contamination of finish surfaces

dis-4.13.2 Suppliers

There are numerous suppliers of lubricants and mold release agents as

a result of the variety of chemistries that perform the function of nal and external lubrication The suppliers are generally large spe-cialty chemical companies that sell the particular chemistry to a widevariety of end-use applications The amount of material sold to func-tion as a lubricant or mold release agent for plastics is typically small

inter-in comparison to each company’s total sales Table 4.19 shows themajor global suppliers of lubricants and mold release agents by type

4.13.3 Trends and forecasts

Other than plasticizers, lubricants come closest to being a commoditybusiness within the plastic additives market Since over 70% of lubri-cant consumption is directed at PVC for applications such as pipe, sid-ing, and windows, demand will be highly dependent on the constructionindustry

The use of lubricants with heat stabilizers, particularly lead types,

in “one-pack” systems has not taken off in North America as it has inEurope North America has focused more on the tin-based stabilizersystems, and customers still prefer buying the additives separately

Type

Key technology trends in lubricants include the development ofhigh-temperature lubricants and the continuing work on lubricantsthat are compatible with other additives and colors in the plastic.Mold release agents are actually a different business than lubri-cants although there are some related chemistries at the lower end.These products are typically higher-priced formulations and are usedprimarily in thermoset urethanes, polyesters, and epoxies The activeingredients are sold by silicone and fluorochemical producers such asDow Corning, GE Silicones, Wacker, DuPont, and ICI.

Overall, the lubricant and mold release businesses are growing at 4

to 5%/year worldwide

4.14 Nucleating Agents

4.14.1 Description

Nucleating agents are used in polymer systems to increase the rate of

crystallization These agents are added to partly crystalline polymersand change the polymer’s crystallization temperature, crystalspherulite size, density, clarity, impact, and tensile properties Theseintentional contaminates achieve these functions by acting as sites forcrystalline formation

Nucleating agents are typically added postreactor and are used marily in injection molding applications However, they can also befound in blow molding, sheet extrusion, and thermoforming They areincorporated into materials such as nylon, PP, crystalline polyethyleneterephthalate (CPET), and thermoplastic PET molding compounds atuse levels typically below 1%, although CPET uses higher levels Theincorporation of these nucleating agents can be done in several ways,including powder mixtures, suspensions, solutions, or in the form of amasterbatch Whichever method is used, good dispersion of the nucle-ating agent throughout the polymer must be achieved to provide theoptimal effect The addition of nucleating agents into polymers yieldsbenefits such as higher productivity and improved optical properties.Nucleating agents can shorten cycle time by reducing set-up time inthe mold Care must be taken to ensure that shrinkage and impactproperties are not negatively affected With some difficult-to-crystal-lize thermoplastics, such as partially aromatic polyamides or PET,nucleants are needed to obtain useful parts with reasonable cycletimes and mold temperatures

pri-The optical benefits of nucleating agents are increased clarity andimproved gloss These properties improve because of an increase in thenumber of fine crystals When crystals are smaller than the wave-length of visible light, the light is scattered at smaller angles, decreas-ing the hazy effect seen when nucleating agents are not used When

utilized to improve transparency in materials such as PP, these

mate-rials are referred to as clarifiers or clarifying agents An example of

how clarifiers work is depicted in Fig 4.1

Types. Several different types of nucleating agents are used in

specif-ic polymers, as shown in Table 4.20 The four major categories of ical nucleating agents are substituted sorbitols, low molecular weightpolyolefins, sodium benzoate, and ionomer resins In addition, a vari-ety of mineral fillers, reinforcements, and pigments are used in nylonand other polymers These nonchemical nucleating agents are easilydispersed, inexpensive, and typically available “on-site” since they arecommonly used for their primary reinforcing and filling function

chem-Substituted sorbitols. Substituted sorbitols are used in polyolefins,

par-ticularly PP, for nucleation and clarification purposes They have ing degrees of miscibility in PP and different melting points andprocess temperatures as well as odor Both homopolymers and randomcopolymers of PP use sorbitols Use levels range from 0.1 to 0.3% onthe polymer The FDA has regulated the use of substituted sorbitols,but has given its approval for their use in PP These materials are used

vary-in vary-injection molded housewares, medical devices, and protective aging Smaller amounts are used in blow-molded bottles

pack-Low molecular weight polyolefins. Low molecular weight polyolefins are

pri-marily used in CPET for rapid crystallization of otherwise amorphousmaterial These products are typically sold by the CPET suppliers in apackage along with the base resin Use levels are higher than with thesorbitols and average 1 to 3% of the resin The major application is in

Figure 4.1 How clarifiers work: Conventional homopolymer PP (a) consists of large

uneven “crystal” microstructures that refract light and increase opacity Sorbitol

clari-fiers, (b) generate smaller, highly dispersed crystallites which are smaller than the

wavelength of light The result is a clarified PP in which the haze percentage falls;

clar-ity and surface gloss are boosted (Courtesy Ciba Specialty Chemicals.)

thermoformed dual-purpose food trays for conventional and microwaveovens The nucleating agent promotes fast crystallization during thetray thermoforming process.

Sodium benzoate. Sodium benzoate is an inexpensive traditional

nucle-ating agent used predominantly in nylon and PP homopolymer.Sodium benzoate has full FDA approval in PP and is used in foodapplications and pharmaceutical synthesis Typical use levels of sodi-

um benzoate as a nucleating agent in PP are lower than the sorbitols.The major application is in injection-molded packaging closures

Ionomer resins. Ionomer resins are metal salts of ethylene/methacrylic

acid copolymers and have a long chain semicrystalline structure.DuPont’s SURLYN is the representative material Ionomers are used

as nucleating agents to control crystallization in PET molding resins.PET is processed at high mold temperatures The ionomer providesfaster crystallinity, more rapid cycle time, and good dimensional sta-bility at elevated temperatures The improvement rate in crystalliza-tion at lower temperatures allows the use of water-cooled molds.Typical use levels are below 1%

4.14.2 Suppliers

Milliken is the leading producer of substituted sorbitol clarifiers inNorth America and Europe under the MILLAD trademark Ciba hasrecently reached a joint market agreement with Roquette This willenable the formidable Ciba marketing organization to increase sig-nificantly the market exposure of Roquette’s sorbitol-based clarifiers.Significant amounts of sodium benzoate are sold to the plasticsindustry through distributors, who purchase from basic suppliers

TABLE 4.20 Nucleating Agents Used in Specific Polymers

Polyethylene terephthalate Inert mineral fillers, chalk, clay, talc,

Organic compounds, carboxylic acids, diphenylamine Polymers, mainly polyolefins, PE, PP, ethylene and styrene copolymers, ionomers

Polyamides (nylon) Highly dispersed silica

Sodium benzoate Talc

Titanium dioxide

Bis-benzylidene sorbitol

Nucleated PE or higher polyolefins

such as Kalama Chemical The suppliers of low molecular weightpolyolefins are the CPET resin producers such as Shell, Eastman,and ICI AlliedSignal also offers related compounds DuPont and oth-ers supply ionomer resins A list of selected global suppliers can beseen in Table 4.21.

4.14.3 Trends and forecasts

PP, CPET, and PET molding resins, and, to some extent, nylon, accountfor most of the nucleating agent consumption Approximately 10% ofall PP and nearly 50% of the injection molding category is nucleated.Smaller percentages of the PP blow molding and extrusion categoriesuse nucleating agents

Improved clarity of PP has provided the ability for replacement of PVCwith PP in applications such as blisterpacks for hardware In addition,new PP resins are being developed that use single-site metallocene cata-lysts (mPP) While virtually no difference exists in the processing behav-ior or finished product properties between conventional PP and mPP,these new materials are easier to nucleate The use of nucleated mPPprovides for a product with the higher physical properties of PPhomopolymer and the clarity of nucleated random PP copolymer.There is continuing growth of nucleated PP, particularly in the blowmolding and extrusion markets CPET continues to expand in ther-moforming applications, and PET molding compounds continue to pen-

TABLE 4.21 Selected Suppliers of Nucleating Agents

Type Sodium LMW Supplier Sorbitols benzoates polyolefins Other

etrate electrical uses Based on this activity, consumption of ing agents is likely to increase at a rate of about 6%/year globally overthe next 5 years.

nucleat-4.15 Organic Peroxides

4.15.1 Description

Organic peroxide initiators serve as sources of free radicals in the

preparation of a variety of resins for plastics, elastomers, and coatings.Their usage in plastics processing can be divided into four functions:

■ Polymerization of thermoplastic resins

■ Curing for unsaturated polyester thermoset resins

■ Cross-linking of polyethylene and various elastomers

■ Visbreaking (rheology modification) of polypropylene

The peroxide group (—O—O—) contained in all organic peroxides ishighly unstable This instability eventually leads to homolytic cleavage.When the bond is broken between the two oxygen molecules, the perox-ide decomposes and two free radicals are formed The general formulafor such compounds is R1—O—O—R2, whereby R1 and R2 either sym-bolize organic radicals or an organic radical and hydrogen atom

Types. Organic peroxide initiators can be further classified by tional groups into seven major classes as follows:

es of these organic peroxides

Dialkyl peroxides. Dialkyl peroxides can be further categorized

depend-ing on the two substituent groups This class may contain two organic

radicals which are wholly or partially aliphatic Depending on thissubstitution, further categorizing may occur For example, when bothgroups are aliphatic, it is known as a dialkyl peroxide When both sub-

stituent groups are aromatic, the peroxide is known as a diarylalkyl

peroxide When the substituent groups are alkyl and aromatic, the

per-oxide is known as an alkylaryl perper-oxide The workhorse product among the dialkyl peroxides is dicumyl peroxide which accounts for one-third

of the worldwide volume for dialkyls

Figure 4.2 General chemical structures of organic peroxides by major class.

Diacyl peroxides. Diacyl peroxides can be subdivided similarly to dialkyls,

depending on the composition of the organic groups R1 and R2:

■ Dialkanoyl peroxides

■ Alkanoyl-aroyl peroxides

■ Diaroyl peroxides

Benzoyl peroxide is the most common of the diacyl peroxides

Hydroperoxides. Hydroperoxides are generally unsuitable for cross-linking

and polymerization reactions since the possibility of a side reaction, such

as ionic decomposition, is too great They are used as a raw material tomanufacture other organic peroxides The most common hydroperoxides

include cumene hydroperoxide and t-butyl hydroperoxide.

Ketone peroxides. Ketone peroxides are mixtures of peroxides and

hydroperoxides that are commonly used during the room temperaturecuring of polyester Methyl ethyl ketone peroxide (MEKP) is the majorproduct

Peroxydicarbonates. Peroxydicarbonates, such as di-(n-propyl)

peroxydi-carbonate and di-(sec-butyl) peroxydiperoxydi-carbonate, are relatively sive products used largely to initiate polymerization of PVC

expen-Peroxyesters. Peroxyesters, such as t-butyl peroxybenzoate and t-octyl

peroxyester, are made from the reaction of an alkyl hydroperoxide,

such as t-butyl hydroperoxide, with an acid chloride.

Peroxyketals. Peroxyketals, such as n-butyl-4,4-di-(t-butylperoxy)

valer-ate and 1,1-di-(t-butyl peroxy)-3,3,5-trimethylcyclohexane, are

high-temperature peroxides used in selective applications for PE andelastomer cross-linking and in the curing of unsaturated polyester.Peroxyesters, ketones, and dialkyls are the largest volume organicperoxides used in the world The peroxyesters and dialkyls are used in

a broad range of resins, while the ketones are the highest volume uct used in the large unsaturated polyester market Others, such asperoxydicarbonate types, are used in only one resin, in this case, PVC.The largest application globally for organic peroxides, based on ton-nage, is in glass-reinforced unsaturated polyester resins These resinsrepresent about one-third of the total global organic peroxide con-sumption in plastics Traditional high-pressure LDPE resins and PVCtogether account for another one-third of the tonnage, with ABS, cross-linked HDPE, PP, PS, and solid acrylics making up most of theremainder Peroxides are also used in applications outside of plastics

prod-in elastomers and emulsion acrylics for coatprod-ings A summary of

organ-ic peroxide types with primary uses is provided in Table 4.22

Raw materials. The major raw materials for the organic peroxides arebasic petrochemicals (propylene, benzene, and isobutane), organicintermediates (such as acid chlorides), and, in some cases, hydrogenperoxide or an inorganic peroxide salt Diacyl peroxides may be man-ufactured by reacting hydrogen peroxide, or an alkali metal peroxide,with an acid chloride Hydrogen peroxide is used to make ketone per-oxides Peroxyesters are made by reacting an alkyl hydroperoxide with

an acylating agent such as acid chloride A major class of peroxyesters

is the t-butyl peroxyesters The starting material, t-butyl ide, is produced as an intermediate to manufacture t-butyl alcohol and

hydroperox-propylene oxide from isobutane and hydroperox-propylene Dicumyl peroxide, animportant dialkyl peroxide, can be made from cumene hydroperoxideobtained from the oxidation of cumene

4.15.2 Suppliers

There are about 30 major worldwide suppliers of organic peroxides.Most of these companies serve the plastics industry, and others producehydroperoxides that are used as raw materials to produce other perox-ides Some of these companies also produce other plastics additives such

as antioxidants, light stabilizers, PVC heat stabilizers, and flame dants Only three companies, namely, Akzo Nobel, Elf Atochem, and, tosome extent, LaPorte, are significant suppliers of organic peroxides tothe plastics industry in every region of the world Important regionalsuppliers include Witco (North America) and Nippon Oil and Fats(Asia/Pacific) In North America, Hercules supplies dicumyl peroxide,while Aristech and Arco supply hydroperoxide raw materials Noracmakes a variety of peroxides for use in unsaturated polyesters Selectedglobal suppliers of organic peroxides are given in Table 4.23

retar-TABLE 4.22 Organic Peroxides Types and Functions

Dialkyl peroxides Polyethylene cross-linking

Initiator for polystyrene polymerization Polypropylene rheology modification Diacyl peroxides Initiator for polystyrene polymerization

Unsaturated polyester curing Hydroperoxides Initiator for ABS polymerization

Raw material for other organic peroxides Ketone peroxides Unsaturated polyester curing

Peroxydicarbonates Initiator for PVC polymerization

Peroxyesters Initiator for ABS polymerization

Initiator for polystyrene polymerization Unsaturated polyester curing

Peroxyketals Polyethylene cross-linking

Unsaturated polyester curing

4.15.3 Trends and forecasts

The development of completely new organic peroxide chemicals tinues to be limited by regulatory consent degrees, safety and healthtesting, and by threats from new technologies for manufacturing andmodifying plastics

con-The global producers of organic peroxides have been focusing on thefollowing areas to solidify and expand their existing product offerings:

■ Research and development efforts directed at formulation, blending,and mixing known peroxide components rather than developing newchemicals

■ Focus on reduction of safety and handling issues, including tion of solvent-based carrying systems which generate emissions ofvolatile organic compounds (VOC)

reduc-■ Development of new recyclable and returnable packaging systems

■ Continuing efforts on newer alternate technologies, such as site metallocene catalysis which have the potential of replacingorganic peroxides in some polyolefin systems

single-Concerns with VOCs and a consent decree relating to carcinogenityhave limited development and, in most cases, changed the order of pref-erence for organic peroxide products For example, government regula-tions on styrene emissions from unsaturated polyester operations haveincreased the trend toward elevated closed molding operations and awayfrom traditional open molding This favors the use of peroxyester andperoxyketal types versus diacyl types in these operations

The organic peroxide business historically has followed the growthpatterns of the major resins Over the next 5 years, the global market

is expected to grow at 4%/year, paced by the Asia/Pacific and otherdeveloping regions, especially in the latter half of the period

From a competitive standpoint, there will be continued efforts at solidation, through joint ventures, alliances, and acquisitions as themajors look to the growing markets in Asia/Pacific, outside of Japan,and the developing countries The remaining independent and regionalproducers of organic peroxides are largely located in countries such asKorea, Taiwan, China, and India, and this is where the action will be

con-4.16 Plasticizers

4.16.1 Description

Plasticizers are the largest volume additives in the plastic industry.

They are largely used to make PVC resin flexible and are generallyregarded as commodity chemicals, although significant specialty nich-

es exist The primary role of a plasticizer is to impart flexibility, ness, and extensibility to inherently rigid thermoplastic and ther-moset resins Secondary benefits of plasticizers include improvedprocessability, greater impact resistance, and a depressed brittle point.Plasticizers can also function as vehicles for plastisols (liquid disper-sions of resins which solidify upon heating) and as carriers for pig-ments and other additives Some plasticizers offer the synergisticbenefits of heat and light stabilization as well as flame retardancy.Plasticizers are typically di- and triesters of aromatic or aliphaticacids and anhydrides Epoxidized oil, phosphate esters, hydrocarbonoils, and some other materials also function as plasticizers In somecases, it is difficult to discern if a particular polymer additive functions

soft-as a plsoft-asticizer, a lubricant, or a flame retardant

The major types of plasticizers are

Phthalate esters. The most commonly used plasticizer types are

phtha-late esters They are manufactured by reacting phthalic anhydride

(PA) with 2 moles of alcohol to produce the diester The most often usedalcohols vary in chain length from 6 to 13 carbons Lower-alcoholphthalate esters are also manufactured for special purposes The alco-hols may be either highly branched or linear in configuration The mol-ecular weight and geometry of the alcohol influences plasticizerfunctionality The most frequently used alcohol is 2-ethylhexanol (2-EH) Other plasticizer alcohols include isooctanol, isononanol, isode-canol, tridecanol, and a variety of linear alcohols The three majordiester phthalate plasticizers are as follows:

■ Dioctylphthalate or di-2-ethylhexyl phthalate (DOP or DEHP)

■ Diisononyl phthalate (DINP)

■ Diisodecyl phthalate (DIDP)

Aliphatic esters. Aliphatic esters are generally diesters of adipic acid,

although sebacic and azelaic acid esters are also used Alcoholsemployed in these esters are usually either 2-EH or isononanol.Higher esters of these acids are used in synthetic lubricants and oth-

er nonplasticizer materials Lower esters are used as solvents in ing and other applications Adipates and related diesters offerimproved low-temperature properties compared with phthalates

coat-Epoxy ester. Epoxy ester plasticizers have limited compatibility with

PVC Therefore, they are used at low levels Epoxidized soybean oil(ESO), the most widely used epoxy plasticizer, is also used as a sec-ondary heat stabilizer As a plasticizer, it provides excellent resistance

to extraction by soapy water and low migration into adjoining als that tend to absorb plasticizers Other epoxy plasticizers includeepoxidized linseed oil and epoxidized tall oils Tall oils are preparedfrom tall oil fatty acids and C5–C8alcohols

materi-Phosphate triesters. Phosphorous oxychloride can be reacted with

var-ious aliphatic and aromatic alcohols and phenols to yield phosphate

triesters Commercially, the trioctyl (from 2-EH) and triphenyl (from

phenol) phosphates are often seen Mixed esters are frequentlyencountered as well Phosphate esters are considered to be both sec-ondary plasticizers as well as flame retardants

Trimellitates. Trimellitates, the esters of trimellitic anhydride

(1,2,4-ben-zenetricarboxylic acid anhydride), are characterized by low volatility.This property increases the service life of a PVC compound subjected toelevated temperatures for long periods of time and reduces fogging Themost important trimellitates are trioctyl trimellitate (TOTM) and tri-isononyl trimelliate (TINTM) Trimellitates are most commonly used forPVC wire insulation, often in conjunction with phthalates

Polymer plasticizers. Esterification of diols with dibasic acids yields

high molecular weight (1000 to 3000) polymeric plasticizers that can

plasticize PVC and other polymers These polymerics are used in junction with phthalates to provide improved permanence andreduced volatility

con-Other plasticizers. A number of other chemical compounds areemployed in special cases to plasticize PVC and other polymers Theseinclude benzoates, citrates, and secondary plasticizers

Benzoates are esters of benzoic acid and various polyhydric alcohols

and glycols They are most often used in vinyl floor covering productsbecause of their resistance to staining

Citrates are plasticizer alcohol esters of citric acid They are used in

food-contact and medical applications due to their perceived low toxicity

Other secondary plasticizers include various liquid aromatic and

aliphatic hydrocarbons, oils, and esters They are used in conjunctionwith such primary plasticizers as phthalates While some offer partic-ular functional benefits, secondaries are often chosen to lower formu-lation cost at the expense of other properties

4.16.2 Suppliers

The general trend in plasticizer supply has been a consolidation amongthe leading plasticizer suppliers Smaller suppliers are either vacatingthe business or focusing on selected specialty products Although thereare still a large number of suppliers, the majority of the market is held

by the leading petrochemical companies of the world The top three

glob-al plasticizer producers are Exxon, BASF, and Eastman, respectively.Table 4.24 lists selected global suppliers of plasticizers by type

4.16.3 Trends and forecasts

Environmental concerns with PVC seem to have abated, although issueshave arisen concerning alleged “hormone mimicking” properties ofphthalate plasticizers The industry has rigorously disputed these claims,but research into test materials is still going on Although the industry isconfident that there is no problem with the safety of phthalate plasticiz-ers, alternatives to these materials are being developed All in all, plasti-cizer usage is likely to follow flexible PVC growth with consumptionincreasing at about a 4%/year growth rate over the next 5 years

4.17 Polyurethane Catalysts

4.17.1 Description

Polyurethanes are versatile polymers typically composed of

polyiso-cyanates and polyols By varying constituents, a broad range of mosets and thermoplastics can be produced and used in differentapplications Possible systems include high-strength, high-modulus,structural composites; soft rubbers; elastic fibers; and rigid or flexiblefoams Although isocyanates have the ability to form many differentpolymers, very few types are used in actual production The most com-mon diisocyanates are methylene diphenylene diisocyanate (MDI) andtoluene diisocyanate (TDI) Of these, TDI is the most commerciallyimportant dimer

ther-While polyurethanes can be formed without the aid of catalysts, thereaction rate increases rapidly when a suitable catalyst is selected A

well-chosen catalyst also secures the attainment of the desired ular weight, strength, and, in the case of foams, the proper cellularstructure In some applications catalysts are used to lower the tem-perature of the polymerization reaction.

molec-The major applications for polyurethane catalysts are in flexible andrigid foam, which account for over 80% of the catalyst consumption.Other applications are in microcellular reaction injection-molded(RIM) urethanes for automobile bumpers and a variety of noncellularend uses such as solid elastomers, coatings, and adhesives

There are more than 30 different polyurethane catalyst compounds.The two most frequently used catalyst types are tertiary amines andorganometallic salts which account for about equal shares of the mar-ket The tertiary amine-catalyzed reaction causes branching andcross-linking and is used primarily for polyurethane foam formation.Organometallic salts, such as organotin catalysts, encourage linearchain extension and are used in flexible slabstock, rigid foam, and in avariety of noncellular elastomer and coating applications

Tertiary aliphatic amines. The most common of the amine catalysts are

tertiary aliphatic amines, and they are used to accelerate the

isocyanate-TABLE 4.24 Selected Suppliers of Plasticizers

Type Supplier Phthalate Trimellitate Polymeric Adipate Other

hydroxyl reaction and give off carbon dioxide Triethylenediamine, alsoknown as diazabicyclooctane (DABCO), is the most prevalent of the ter-tiary amine catalysts used for polyurethane manufacture due to its highbasicity and low steric hindrance which yields high catalytic activity Itshould be noted that tertiary aliphatic amines can be discharged fromfresh foams, causing unpleasant odor and potential skin irritation.Safety precautions are necessary when working with these materials toproduce polyurethane foam.

Organometallic compounds. While organometallic compounds make

excellent polyurethane catalysts, they affect the aging characteristics

of the polymer to a higher degree than tertiary amines Stannousoctoate is the most broadly accepted catalyst of this type ofpolyurethane formation, although other organotins and potassiumsalts are also used While minute quantities of the inorganic portion ofthese substances speed up polyurethane reactions during processing,residual amounts of metal from these catalysts can cause side reac-tions or change properties of the final product

Different catalyst types can also be combined to obtain a desired effect.For example, polyurethane foam production can use both organotin andamine catalysts for a balance of chain extension and cross-linking

4.17.2 Suppliers

Air Products is the major supplier of polyurethane catalysts in NorthAmerica and one of the largest in Europe, making both amine andorganometallic types BASF is also active in both regions with aminetypes Witco and Huntsman in North America and Goldschmidt inEurope are major regional suppliers The Asia/Pacific market is served

by a number of regional suppliers largely out of Japan Selected globalsuppliers of polyurethane catalysts by type are listed in Table 4.25

4.17.3 Trends and forecasts

As the guidelines for environmental safety become more stringent andchlorofluorocarbons (CFCs) gradually phase out as blowing agents forpolyurethane foams, the demand for urethane catalysts will rise.Alternative blowing agents, such as methylene chloride, acetone,hydrochlorofluorocarbons, and carbon dioxide, are being introducedand, as a result, new catalyst technology is required to rectify prob-lems caused by these new procedures In addition, volatile organiccompound (VOC) emissions are raising new concerns which are likely

to propagate additional changes to adjust the viscosity and control thebehavior of the polyurethane foam as well as its final properties

The global market for urethane catalysts is growing at a rate ofapproximately 4%/year Growth is tied closely to the flexible and rigidfoam markets Rigid foam is growing at slightly above the average andflexible foam is growing at slightly below the average The smallerautomotive market in reaction injection molding urethanes is declin-ing because thermoplastic polyolefins (TPO) are now the preferredmaterials over polyurethanes in bumpers.

The major driving forces, besides end-use growth, affecting urethanecatalysts will be the continued phase-out of CFC blowing agents andthe development of new blowing agent alternatives, along with therelated concern over VOC emissions, which also affects blowing agentand catalyst choice These forces will have more of an effect on cata-lyst mix than the overall volume of catalyst used

TABLE 4.25 Selected Suppliers of Polyurethane Catalysts

Type

Processing of Thermoplastics

Chapter

5

fabric (to produce vinyl upholstery), and using adhesives to join rials In contrast, both surfaces are molten during the heating sealing

mate-of polyethylene bags and ultrasonic welding mate-of plastics parts

Modifications include surface activation, mixing, and polymer ifications Surface activation improves adhesion or printability of plas-tics materials Typically, corona discharge and flame treatmentsoxidize the polymer surface to a depth of 1 nm; this oxidized surface ismore compatible with polar inks and adhesives Mixing reduces thenonuniformity of the polymer composition While polymer processinguses many types of mixers, there are two types of mixing The first,distributive or spatial mixing, causes randomization of a mixture but

mod-no physical changes It takes place in drum tumblers and ribbonblenders The second, dispersive mixing, involves heat and shearwhich reduce particle size and eliminate clumps or agglomerates Thismixing is observed in high-intensity mixers, Banbury mixers, two-rollmills, and extruders Polymer modifications, such as annealing moldedparts and radiation of plastics parts, change the amount of orientation,crystallinity, and/or cross-linking in the plastic

This chapter focuses on the primary processing of thermoplasticmaterials It begins with material concepts used in processing Thechapter continues with processing techniques, and each process is out-lined, equipment requirements are specified, and processing parame-ters are discussed

5.1 Material Concepts

Polymers are long-chain molecules with one or more repeat units called

mers The number of repeat units in a polymer, and thus the length of

the polymer chain, can be varied during manufacture of the resin Themolecular weight of a polymer is a way of indicating chain length The average molecular weight number is merely the molecular weight

of the repeat unit multiplied by the number of repeat units Since themolecular weight of the styrene repeat unit is 104 daltons, a poly-styrene with 2500 mers would have a molecular weight of 260,000 dal-tons However, not all polymer chains have the same length; somechains are short, while others are long The average chain length isindicated by the number average molecular weight, but the spread orrange of chains is given by the molecular weight distribution (MWD)

As discussed later in this section, both molecular weight and molecularweight distribution significantly affect flow during polymer processing

A homopolymer has one repeat unit while two or more mers merized together in a copolymer The properties and processingcharacteristics of copolymers are often very different from those ofthe corresponding homopolymers These characteristics also vary

poly-with the ratio of the components and their arrangement poly-within the

copolymer As shown in Fig 5.1a,2the repeat units of random mers are distributed randomly along the polymer chain Thus, eth-ylene propylene rubber (EPR) is an elastomer, whereas polyethyleneand polypropylene are plastics In poly(styrene-co-acrylonitrile)(SAN), the small amount of acrylonitrile improves the heat resis-tance and increases processing temperatures when compared topolystyrene Fluorinated ethylene propylene (FEP), unlike its “par-ent,” polytetrafluoroethylene, is melt processible Alternating

copoly-copolymers (Fig 5.1b2), in which every second repeat unit is thesame, have, until recently, been laboratory curiosities However,new catalysts may make these copolymers commercially viable

Block copolymers (Fig 5.1c2) contain alternating segments of eachrepeat unit, but the segments are often several repeat units long.Such materials include polyetheramides, hard segment–soft segmentpolyurethanes, and butadiene-styrene elastomers (SEBS) Graft

copolymers (Fig 5.1d2) consist of a main chain containing only onerepeat unit with side chains of the second mer These copolymerslink the two phases in high-impact polystyrene (HIPS) and acry-lonitrile butadiene styrene (ABS)

Blends are physical mixtures of polymers rather than monomers.Like copolymers, properties and processing characteristics are oftenvery different from those of the component polymers and also varywith the ratio of components Unlike copolymers, blend properties can

be sensitive to processing conditions Miscible blends mix on a ular level to produce a single phase and exhibit a single transitiontemperature that corresponds to the blend composition The mostimportant commercial miscible blend is polystyrene-polyphenylene

Types of copolymers (Adapted from Ref 2.)

oxide (modified polyphenylene oxide) Partially miscible blends canexist as a single- or two-phase system, depending on composition andprocessing conditions When partial miscible blends, such as polycar-bonate/acrylonitrile butadiene styrene (PC/ABS), polycarbonate/poly-ethylene terephthalate (PC/PET), and polycarbonate/polybutyleneterephthalate (PC/PBT), are modified so that the morphology is stable,

they are often called alloys Since immiscible blends cannot mix on a

molecular level, they exist as two phases These blends exhibit thetransition temperatures of the component polymers, and the morphol-ogy and properties are very sensitive to processing conditions.Immiscible blends are the basis of many impact-modified plastics.Plastics are usually not pure polymer, but contain the following sub-stances:

■ Fillers such as mica, talc, and calcium carbonate

■ Fibers such as glass fibers and carbon fibers

■ Plasticizers such as the dioctyl phthalate used in polyvinyl chloride(PVC)

5.1.1 Processing temperatures

Polymers are manufactured using two basic polymerization methods:

addition and condensation Addition polymerization generally produces

rapid chain growth, molecular weights greater than 100,000 daltons,

and no by-products In contrast, condensation polymerization provides

for lower chain growth, typical molecular weights of 10,000 to 50,000daltons, and by-products such as water As a result, addition polymersare less susceptible to water absorption, and seldom depolymerize dur-ing processing When these materials are dried prior to processing, it isusually to prevent foaming and surface defects such as splay However,

if poorly dried condensation polymers are melt processed, they tend todepolymerize Since this reduces the molecular weight, material prop-erties decrease Consequently, condensation polymers are always driedprior to processing (although with special screws and vented processingequipment condensation polymers can be dried during processing).Polyethylene, polypropylene, polystyrene, impact-modified polystyrene,acrylonitrile-butadiene-styrene terpolymer, polymethylmethacrylate,poly(vinyl chloride), and polytetrafluoroethylene are addition polymers,whereas polyacetal, polycarbonate, polyamides, poly(ethylene tereph-thalate), poly(butylene terephthalate), polysulfones, polyetherimide,and polyetheretherketones (PEEK) are condensation polymers Waterabsorption values, maximum water contents for molding, and suggesteddrying conditions are presented in Table 5.1.3,4

Processing temperatures (see Table 5.1) are associated with the

transition temperatures of a polymer The glass transition temperature (T g) is the temperature at which the amorphous (unordered) region of

a polymer goes from a glassy state to a rubbery state In amorphous

polymers, T gis related to processing temperatures As shown in Figure

5.2a, the modulus (stiffness) is relatively constant until the ture rises above the T g The modulus then decreases gradually When

tempera-the polymer reaches its melt processing temperature, tempera-the polymerflows easily and can be extruded, injection molded, and extrusion blowmolded For polycarbonate, the difference between the softening tem-perature and processing temperature is about 140°C Since this slowreduction in modulus over a wide temperature range facilitatesstretching of the rubbery material, amorphous materials, such as poly-carbonate, are easily thermoformed

Figure 5.2b presents the modulus-temperature curve of a

semicrys-talline polymer, polypropylene It exhibits a glass transition and a

melting transition (T m) The modulus of polypropylene, like otherpolymers with high levels of crystallinity, does not decrease substan-tially when the temperature is raised above the glass transition tem-perature Thus, polypropylene remains relatively rigid until it

reaches its T m At that point the crystallites (highly ordered regions)

in semicrystalline polymers break up and the polymer begins to flow.Since all polymers contain amorphous regions, they do not have well-defined melting temperatures Melt processing temperatures of semi-crystalline polymers are usually less than 100°C above their melttemperatures