Escolar Documentos
Profissional Documentos
Cultura Documentos
Polypropylene
T. GEOFFREY HEGGS, current address: The Mill, Great Ayrton, TS9 6PX,
United Kingdom
NATTA, Professor and Director of the Milan Table 1. Global PP capacity (103 t/a) and its distribution
Institute of Industrial Chemistry, was a consul- Country/region End 1990 End 1994 Growth* 1990 –
tant to Montecatini, to whom NATTA assigned his 1994, %
patents. The close collaboration between ZIEGLER
Western Europe 4530 5705 26
and NATTA was acknowledged in 1963 by the North America 4400 5440 24
joint award of a Nobel prize in Chemistry for Japan 1870 2656 42
their outstanding contributions to polymer sci- Other Far East/ 2734 4090 50
ence. A fascinating account of ZIEGLER and Australia
Middle East/Africa 280 655 34
NATTA’s personal approach to these discoveries South America 450 1035 30
is provided by MCMILLAN [1]. Eastern Europe 790 930 18
In the the United States, patents on crystalline Total/average 15 054 20 511 36
polypropylene were awarded originally to NATTA *
7 % per annum growth for four years is 31 % total growth.
et al. (on behalf of Montecatini), but were over-
turned later in favor of Phillips Petroleum Com- various fibers, large and small moldings from
pany. The immense legal procedings to establish boat hulls to instrument parts. In addition, new
inventor rights to crystalline polypropylene in the manufacturing technologies based on MgCl2
United States are outlined by HOGAN and BANKS supported catalyst systems yielded both cost
[2], with more recent comments by PINO and savings and improved products by eliminating
MORETTI on this costly litigation [3]. Phillip’s atactic PP removal steps and then the deashing
polymerization catalyst, consisting of chromi- stage. Some 40 years on there are expectations
um-ion promoted silica – alumina, has not been that the new metallocene catalyts will extend
used in any commercial plant to manufacture these uses, even to the extent of challenging
crystalline polypropylene. products such as polyamide, ABS, and flexible
Notwithstanding the complexities and hazard- PVC for part of their market [6].
ous nature of these new coordinated catalysts,
industrialists and academe alike were stimulated
by ZIEGLER and NATTA’s prompt and prolific 2. Polymer Structure
disclosures concerning this new, high-melting
polymer. Industrial-scale production of PP 2.1. Molecular and Chain Structure
started at Ferrara, Italy, in 1957 with a 6103
t/a plant. By the end of 1994 global capacity had Polypropylene is a synthetic, high molecular
risen to 20.5103 t/a (Table 1), spread over 35 mass linear addition polymer of propene. In
countries [4]; today, new plants are expected to 1954/5, NATTA et al. prepared sufficiently large
be capable of producing 200103 t/a to achieve amounts of PP to isolate and characterize various
reasonable economies of scale. stereoisomers. This led to a new descriptive
There are several reasons for this phenomenal nomenclature still used today. Commercial in-
growth, which exceeds that of other bulk plastics terest lies primarily in highly crystalline PP,
[5] (Table 2). At first propene was readily avail- together with its further modifications through
able, almost at byproduct prices, from petro- copolymerization.
chemical cracker plants making ethylene. The In perfectly isotactic PP, each monomer unit
polymer itself was suitable for a wide range of in the chain is arranged in a regular head-to-tail
existing and new applications such as films, assembly without any branching or 1,3 additions
(Fig. 1 A). This is the result of template-type Until recently, syndiotactic PP (Fig. 1 C) was
constraints by the heterogeneous stereospecific not commercially important because of unac-
catalyst. In practice such perfection is hard to ceptable polymerization difficulties at low tem-
achieve. An occasional error (Fig. 1 B), averag- peratures. Some metallocene catalysts overcome
ing about 0.3 – 1.5 per hundred chain links, this problem to produce a regular sequence of
occurs in some, but not equally in all chains. racemic (r) propene placements yielding a crys-
The multisite nature of solid catalysts is thought talline polymer melting at 130 C. Mitsui Toatsu
to be responsible for this behavior. and Fina have entered into a joint venture to
Solvay and MgCl2 supported systems reduce assess costs and customer reaction to syndiotac-
the extent of these errors, and with them the tic PP.
amount of noncrystalline (atactic) polymer. Still Complete loss of steric regulation generates
at the development stage, metallocene-based atactic polymer chains (Fig. 1 D), incapable of
single-site catalysts (SSCs) also produce stereo- crystallizing. Hitherto this low molecular mass
regularity errors, but these seem to be distributed byproduct had only a few commercial outlets for
more uniformly along the chains, regardless of adhesives. The position could change with the
their length (Fig. 1 E). This contrasts with mul- emergence of high molecular mass versions de-
tisite catalysts (MSCs), for which misplacements liberately made with a metallocene-based cata-
vary in frequency and in number. The tendency lyst, [(Me2SiFlu2)ZrCl2] (Flu ¼ fluorenyl)[7].
here is for the high molecular mass fraction to All Ziegler – Natta commercial polymers
contain fewer faults, while the short chains suffer have broad molecular mass distributions within
from excessive dispruptions, which lead to re- the range Mw/Mn ¼ 5 – 10 for ex-reactor mate-
duced crystallinity. rial. Any reduction is achieved by peroxide-
384 Polypropylene Vol. 29
Sensitive Ziegler – Natta catalysts require pure Ethylene and 1-butene copolymerize with
propene to ensure high polymerization rates and propene to marginally reduce the polymer soft-
good yields of isotactic polymer, without waste- ening point. Hydrogen is a powerful chain-trans-
ful byproducts. Harmful impurities can be fer agent whose concentration must be accurately
grouped into two main categories which have controlled in the reactor.
different effects on the process. The most de- Propene is normally manufactured outside the
structive contaminants are polar and highly un- PP plant. An important source of both ethylene
saturated compounds which react directly with and propene, in the approximate weight ratio of
the catalyst systems, retarding polymerization 2: 1, is from steam cracking naphtha or gas oil at
and impairing stereospecificity. Examples in- 700 – 950 C, followed by fractionation. Refin-
clude acetylenes, dienes, carbon monoxide and ery catalytic cracking of petroleum products
dioxide, carbonyl sulfide, water, alcohols, and yields 2 – 5 % of propene, which is isolated as
ammonia. The second group contains materials a chemical grade containing 90 – 95 % of the
which adversely influence the process, but not the monomer with much propane. This can be puri-
chemistry, by raising the pressure during reaction fied further to polymer-grade specification, but
due to an accumulation of inert substances. These some PP plants which are able to handle the extra
further complicate the monomer recovery sec- propane may bypass further refining or add a
tion and recycle streams. This group contains simplified hydrogenation unit to reduce dienes
materials such as methane, ethane, propane, bu- [15]. These possibilities arise at the milder end of
tane, and nitrogen. the cracking range of 400 – 500 C, which then
Most manufacturers use polymer-grade pro- generates lower amounts of harmful highly un-
pene as feedstock, which can be further refined saturated products. Currently there is some inter-
by passing it through local guard columns con- est in building propane dehydrogenation plants
taining alkali, molecular sieve, alumina, sup- as a third source of pure propene [15, 16].
ported copper, etc. to guarantee consistently high Some properties of propene relevant to poly-
purity [12, 13]. Typically, monomer conforming propylene production are as follows:
to the following specification, is adequate for
most plants, but certain sensitive supported cat-
alysts require the lower levels listed for carbonyl Heat of polymerization 2514 kJ/kg
sulfide, carbon monoxide, and oxygen (this qual- bp 47.7 C
ity is said to be suitable for metallocene catalysts) Critical temperature 92 C
Critical pressure 4.6 MPa
[14]: Vapor pressure at 20 C 0.98 MPa
1st Generation
1957 – 1970 0.8 – 1.2 88 – 93 deash and remove
TiCl3 AlEt2Cl atactic
2nd Generation
1970 – 1980 3–5 92 – 97 deash/deactivate,
TiCl3 AlEt2Cl þ atactic usually remains
Lewis base (Solvay)
3rd Generation
1980 – 1990 5 – 20 98 no deash and
MgCl2-supported TiCl4 AlEt3 no atactic removal
4th Generation
1995 ca. 20 ? no deash and
Metallocene/MAO systems no atactic removal
MMD ca. 2 – 4
*
Isotactic index ( % insoluble in boiling heptane).
Vol. 29 Polypropylene 387
critical to achieve good stereoregulation and high 2. The brown b-TiCl3 solid is treated with dii-
activity with these catalyst components. soamyl ether to dissolve out most of the
Early work by the NATTA school used pure aluminum compounds
TiCl3 made by hydrogen reduction of TiCl4, 3. The extracted solid is reacted with neat tita-
followed by ball milling to give a high surface nium tetrachloride at 65 C to transform the b
area. crystallites to the violet d-form
TiCl4 þ1=2 H2 !TiCl3 þHCl
The novelty lies in removing much of the
aluminum residues at the b stage, without col-
A more active form is made by reduction with lapsing the particle, and then transforming to the
aluminum powder, followed by ball milling. stereoregulating d-form while retaining a spon-
gelike structure with a surface area of 150 m2/g
3 TiCl4 þAl!3 TiCl3 AlCl3
[18]. Analogous commercial products are avail-
able in Japan and the United States.
Much of the aluminum chloride is present as a
true solid solution in crystalline d-TiCl3. This
catalyst has a larger surface area of 10 – 40 m2/g 3.3.2. Supported Catalysts
and is commercially available from several com-
panies. Nowadays, a Lewis base, such as an ester The third-generation, supported titanium cata-
or ketone, may be introduced at the milling stage lysts, are based on research by Montedison (now
to increase stereospecificity. Montell) in Italy and Mitsui Petrochemical In-
Another important route dispenses with ball dustries (now Mitsui Sekka) in Japan. Collabo-
milling by reducing a hydrocarbon solution of ration and cross-licensing between these two
TiCl4 with an organoaluminum compound below companies avoided incipient interference claims.
room temperature. Di- and trialkylaluminum Starting around 1968 with finely milled magne-
compounds are suitable. In this process the tita- sium chloride, which has a similar layer structure
nium trichloride precipitates in the brown, b to violet TiCl3, ways were discovered of deposit-
form. Heating to 80 – 120 C completes the ing stereoregulating titanium compounds on the
reduction and transforms this solid to the re- surface.
quired purple variety. Several hydrocarbon A particle-form supported catalyst may be
washes remove some of the aluminum com- prepared as follows [21]:
pounds to leave an active, stereospecific catalyst.
A useful aspect of this technique is that condi- 1. A spheroidal support is prepared by making a
tions can be selected to precipitate spherical fine dispersion of molten (125 C) magne-
catalyst particles. Subsequent propene polymer- sium chloride ethanolate complex in hot ker-
ization then yields spherical polymer particles osene containing sorbitan distearate as surfac-
that exhibit good flow characteristics. This abili- tant. The dispersion is quenched by pumping
ty to replicate the shape of catalyst particles is into kerosene at 15 C to give particles
quite general in Ziegler – Natta polymerization. with a diameter of 5 – 30 mm.
Polymer forms throughout the agglomerate of 2. A slurry of the particles is added to neat TiCl4
small catalyst clusters, expanding the particle at 20 C.
uniformly in all dimensions as polymerization 3. Diisobutyl phthalate (17 % v/w) is added and
continues. the mixture heated to 120 C.
Major refinements in alkyl-reduced TiCl3 sys- 4. Decant, and heat with further TiCl4 to 130 C.
tems were made by Solvay [18–20] in their three- Isolate by hot filtration and washing. The
stage process, which gives a 4 – 5-fold increase product contains 2.3 wt % Ti, 63 wt % Cl,
in activity: 20 wt % Mg, and 9.9 wt % diisobutyl
phthalate.
1. Titanium tetrachloride solution is reduced
with diethylaluminum chloride at 0 C For the polymerization of propene, triethyla-
TiCl4 þ AlEt2Cl ! TiCl3 x AlCl3 z AlEtCl2 luminum is used as a cocatalyst, and phenyl-
where x ¼ 0.15, z ¼ 0.20 triethoxysilane as an additional external Lewis
388 Polypropylene Vol. 29
3.4. Hydrogen
stream capacities increased sizes up to 100 m3 part of the reaction train. Propene in solution is
have been installed. Another common practice gradually converted into polymer as the poly-
involves linking reactors together in series or in merization rate falls exponentionally in the first-
parallel configurations. The maximum output order reaction. This simple scheme entirely elim-
rate of a reactor is determined by the heat remov- inates the recovery stage, but it does call for
al system, which no longer relies simply on additional reactors working at low rates.
water- cooled polymerizer jackets. Internal and
external cooling circuits provide the necessary Catalyst Removal (Deashing). Catalyst re-
extra cooling at these high rates (> 0.3 t h1 moval, steps c and d in Figure 5, involves the
m3). extraction of highly polar particulate TiCl3 from
It is only necessary to meter catalyst into the a hydrophobic polymer particle. Procedures dif-
first reactor of a cascade system, both because the fer appreciably, but the first step always converts
activity decay is fairly small, and because it is not titanium and aluminum residues into complexes
desirable on quality grounds to generate a second or alkoxides that are soluble in the diluent,
family of particles downstream. Propylene and usually by heating to 60 C with 2 – 20 % of an
hydrogen feeds to each reactor maintain the alcohol, though acetylacetone has also been used.
required pressure and gas compositions to secure The choice of ethanol, propanol, or butanol is
the correct polymerization rate and molecular influenced by the diluent boiling point and sub-
mass. Most of the reaction diluent is metered into sequent recovery schemes.
the first vessel in the train, but some can be added Step d, Figure 5, shows a widely practised
further downstream to minimize fouling as the arrangement whereby water washing is used to
polymer concentration increases. Slurry viscosi- transfer all these catalyst complexes into an
ty increases rapidly during the latter stages of aqueous phase, leaving behind a purified polymer
polymerization as the swollen polymer particles slurry.
approach close packing. This point is strongly
dependent on the size and shape of the catalyst
particles. Seldom will the slurry concentration be
allowed to exceed 42 wt % unless a very low
density diluent is used.
As a rule, polymerization temperatures lie It is vital to work with either a strongly acidic
between 50 and 75 C; the desirability of using or strongly alkaline complexing medium to re-
a higher temperature being countered by de- press hydrolysis and polycondensation, which
creased catalyst stereospecificity causing in- impair the extraction efficiency. This technique
creased solubles and poorer properties. While normally yields polymer containing 10 –
reactor pressures of 0.5 – 1.0 MPa typified ear- 30 ppm of Ti, 10 – 40 ppm of Al, and 20 –
lier plants, intensified processes expand this to 40 ppm of Cl residues. Very pure polymer can
2 MPa. be made in an alternative form of step d. Here,
the polymer is isolated by filtration, and is re-
Propene Flashing and Recovery. Two peatedly washed by reslurrying in diluent/alco-
ways of removing and recovering unreacted pro- hol mixtures to remove all solubilized catalyst
pene, stages b and k in Figure 5, are practiced without introducing water. This process adds to
commercially. Most commonly, slurry from the the load on diluent and alcohol recovery, but PP
last reactor discharges into a heated vessel at quality improves.
lower pressure to flash off propene vapor and
other volatiles. After cooling and condensation, Centrifuging. Centrifuging the deashed
fractional distillation recovers pure propene as an slurry (step e, Figure 5) removes most of the
overhead stream with a bottom discharge of free diluent, but the wet cake can still hold up to
propane and some diluent. In certain cases it is 50 wt % (dry basis) of diluent containing dis-
more economical to return the flashed propene to solved atactic polymer. Depending on the grade
an adjacent plant for use there. The alternative of polymer being produced, it is sometimes
scheme simply allows polymerization to contin- beneficial to introduce a washing stage with
ue without feeding any fresh propene to the latter diluent while centrifuging to reduce the amount
392 Polypropylene Vol. 29
of soluble polymer in the final product. Centri- 5.2. Bulk Polymerization in Liquid
fuges can be of the filtering (basket) or decant- Propene
ing type according to the powder characteri-
stics. A special case of the slurry is to use liquid
propene, with its poorer solvent power, instead
Drying. Drying the wet cake sometimes of an inert diluent. Polymerization rates increase
requires more than one stage, particularly in considerably with pressures around 3 – 4 MPa.
processes using high-boiling solvents. Steam Stirred autoclaves incorporating evaporative
distillation removes most of the diluent to leave cooling, and loop reactors provide good heat-
an aqueous slurry from which the polymer is transfer rates. The chemistry parallels that de-
readily isolated by filtration. A conventional scribed in Section 5.1, but the engineering de-
drier removes the small amount of water still mands are greater [32]. After polymerization, the
adhering to the hydrophobic particles. More catalyst is solubilized with polar complexing
elaborate driers, operating under a nitrogen at- agents to permit extraction from the polymer by
mosphere, remove diluent directly in flash dry- countercurrent washing with liquid propene. Hy-
ing, fluidized beds, or hot surface contact type brid plants are known which use liquid propene
systems. Before the advent of high-technology for polymerization, followed by flashing and
systems (Section 5.4), some manufacturers had resuspension in heptane for polymer deashing.
already improved catalyst stereospecifity such
that the low level of atactic polymer in the diluent
could be left in the product. In this case, the total 5.3. Solution Polymerization
slurry can be dried without previous centrifuga-
tion. This avoids all atactic polymer handling In contradistinction to polyethylene manufac-
problems. All these drying stages must use nitro- ture, solution polymerization at high temperature
gen blankets throughout to minimize hazards is rarely practiced for isotactic PP. Special cat-
with flammable hydrocarbons, as well as to alysts are necessary to minimize the customary
protect the polymer. reduction in stereospecificity above 100 C, but
the activity and stereoregularity still remains too
Extrusion and Pelletizing. Powder leaving low to dispense with catalyst extraction and
the driers at about 100 – 120 C can be fed removal of atactic PP. The original Eastman –
directly to a pelletizing extruder, in which it is Kodak process makes grades for some special
stabilized and converted into dense granules. As markets, but there are no plans for further new
intermediate powder storage is often necessary, plants along these lines. While polymerization at
common practice introduces a cooling stage to ca. 150 – 200 C should permit some useful
70 – 80 C to prevent adventitious oxidation recovery of polymerization heat, overall costs
when antioxidants are absent. are high for isotactic PP. It is reported [33] that
the solution process is being used to make atactic
Diluent and Alcohol Recovery. An essen- PP, for which it seems more suited. Commercial
tial part of the schematic plant shown in Figure 5 plants dedicated to make only atactic PP have
is solvent and alcohol recovery, and atactic poly- been announced by Himont (Canada), El Paso
mer separation (stages h – j). Diluent from the (Texas), and Huls (Germany).
centrifuge contains soluble polymer and traces of
alcohol. This mixture, together with liquid from
the driers, is separated by multistage distillation. 5.4. Spheripol Process [34]
Pure diluent is then recycled to the polymerizers,
while viscous atactic polymer separates out as a Figure 6 depicts a modern state-of-the-art plant
heavy end. Wiped film evaporators can be used to based on Himont technology [34] for making
strip the last traces of diluent from highly viscous homopolymer and impact copolymers (Sec-
solutions. tion 5.7.2) with supported catalysts. The latter
Most of the alcohol is recovered from the first are sufficiently active not to require any catalyst
few water washes by fractional distillation (step extraction, nor removal of atactic polymer be-
h) followed by azeotrope splitting. cause of the high stereospecificity. Homopoly-
Vol. 29 Polypropylene 393
merization takes place at ca. 70 C and 4 MPa in (Section 5.7.2). Unreacted propene flashes off
liquid propene circulating round one or more from the first cyclone and is condensed with
loop reactors. A single axial flow agitator in each cooling water and recycled to the reactor. A
loop maintains high flow rates to ensure good compressor is required for gas from cyclone
heat transfer to the water-cooled jackets, whilst (d). Polymer powder from the cyclone is fed into
also preventing any polymer particles settling vessel (e) for deactivation with small amounts of
from the slurry [35]. Typically the PP concentra- steam and undisclosed additives. Residual mois-
tion is ca. 40 wt %. ture and volatiles are removed by a hot nitrogen
Continuously metered catalyst, triethylalumi- purge in vessel (f) before conveying polymer to
num, and a Lewis base stereoregulator such as a storage silos for conventional finishing as stabi-
dialkyldimethoxysilane are fed into the reactor to lized powder or extruded pellets.
maintain polymerization and stereocontrol. The Provided the expensive extrusion stage can be
initial few seconds of polymerization with a new dispensed with by selling powder, then it is
high-activity catalyst particle are quite critical to claimed that the capital cost of Himonts Spher-
secure good performance. For this reason, some ipol process is only 50 % of the suspension
processes have a prepolymerization stage in process described in Section 5.1 [34].
which the catalyst components react at lower
temperature and monomer concentration. This
can be either a batch or continuous pretreatment 5.5. Hypol Process
which produces only small amounts of polymer
(< 100 g/g) in the catalyst. This prepolymerized Mitsui Petrochemical, co-inventor with Himont
catalyst is then fed into the loop reactor as usual. of the supported catalyst system, has developed an
Mean residence time in a single polymerizer is analogous cheap process using bulk polymeriza-
1 – 2 h. Two loop reactors can be operated in tion with their own supported catalysts. It differs
series to narrow residence time distributions, from the Spheripol system in that batch prepoly-
modify the polymer, and increase output. merization is used with washing. Two conven-
A continuous stream of polymer slurry dis- tional stirred polymerizers are used in series, with
charges through a heated zone for the first stage heat removal by evaporative cooling of liquid
of pressure let down in cyclone (b). For homo- propene in the reactors. Slurry is then discharged
polymers, this connects directly to the secondary into a stirred, heated flash vessel, where propene is
cyclone (d), bypassing the copolymerization unit recovered from polymer, as in the Himont system.
394 Polypropylene Vol. 29
5.6. Gas-Phase Processes and 3 – 4 MPa ensure that the monomer phase is
gaseous in the reactor. Low concentrations of
In gas-phase processes, gaseous propene is con- hydrogen are used to control molecular mass
tacted with solid catalyst intimately dispersed in over wide ranges. The temperature is controlled
dry polymer powder. Industry uses two different by removing gaseous propene from the reactor
methods of carrying out this reaction depending head space, condensing it with cooling water, and
on the chosen method of heat removal. The then recirculating it back into the reactor, where
Union Carbide/Shell process uses an adaptation its evaporation provides the required cooling, as
of the Unipol polyethylene fluidized-bed system. well as further aeration of the stirred powder bed.
BASF and Amoco use mechanically agitated dry Each tonne of polymer made requires ca. 6 t of
powder beds with evaporative cooling in vertical liquid propene to be evaporated as coolant.
and horizontal autoclaves, respectively. Powder and associated gas discharge contin-
uously from the primary reactor dip tube directly
BASF Novolen Process [36]. Figure 7 into a low-pressure cyclone (g). Propene carrier
shows the BASF continuous process for making gas from this cyclone is recycled to the reactor
homopolymers, impact copolymers, and random after compression, liquifaction, and, sometimes,
propylene – ethylene copolymers using high-ac- distillation. The powder then passes to a purge
tivity, highly stereospecific catalysts. The reactor vessel where a deactivator quenches all residual
vessels, of 25, 50, or 75 m3 capacity, are catalyst activity, and nitrogen strips out traces of
equipped with proprietary helical agitators, propene from the hot powder. From here powder
which give excellent agitation. Homopolymer- is conveyed into silos for stabilization and extru-
ization needs only the primary reactor, into which sion into granules. BASF also offers a post-
the catalyst components are fed. These must be granulation steam-stripping package to remove
very well dispersed in the powder bed to avoid any oligomers and oxidized residues from the
build-up. The reaction conditions of 70 – 80 C granules for demanding applications.
BASF pioneered their gas-phase process with degree of plug flow, roughly equivalent to that of
commercial production in 1969. The products 2 – 3 fully back mixed reactors in series [37].
made, Novolen 1300 series, were based on high
molecular mass total work up polymers (i.e., Unipol – Shell Fluidized-Bed Process
containing atactic PP and catalyst residues) hav- [38]. The Unipol – Shell plants, commissioned
ing reduced stereoregularity. Today, such grades in 1986, combine technologies from Union Car-
still find niche markets, although they are vul- bide and Shell. Most conspicuous in this process,
nerable to competition from random copolymers. Figure 9, is the tall fluidized-bed reactor with its
Production is to be phased out shortly. expanded upper section to reduce gas velocity
BASF also uses their process with a cheaper and powder entrainment. Continuous feeds of
second-generation catalyst TiCl3/AlEt2Cl, which catalyst components, comonomer, if any, hydro-
then requires an additional dry-powder dechlori- gen, and propene are thoroughly mixed in the
nation stage. dense-phase fluidized bed of powder. A large
cooler in the gas recirculation loop removes all
Amoco – Chisso Stirred-Bed Process. the reaction heat from the considerable gas flow.
Collaboration between Amoco and Chisso re- In this system the fluidized bed is said to behave
sulted in joint licensing arrangements from 1985. as a fully back mixed reactor, without undue
This process uses a horizontally stirred reactor, separation of coarse particles. No mechanical
Figure 8, instead of the vertical helical agitator of agitation is needed. Reaction conditions are re-
the BASF process. Condensed recycled mono- ported as < 88 C and < 4 MPa.
mer sprayed into the top of the reactor provides Product powder and associated gas are dis-
cooling, while uncondensed monomer and hy- charged from just above the distributor plate by
drogen injected into the base maintain the gas timed valves into a cyclone separator (e) and then
composition. Figure 8 also includes a fluidized- directly to a purge vessel (g) to remove residual
bed deactivation system for use with second- monomer. Neither catalyst removal nor atactic
generation, chlorine-rich catalysts. Amoco – polymer extraction is necessary with the modern
Chisso claim that their reactor achieves some Shell catalysts used in the Unipol process.
5.7.2. Impact (Block) Copolymerization discharge directly into the copolymerizer, oper-
[42, 43] ated at 1 – 2 MPa lower pressure and lower
temperature. Normally, the propene/ethylene/
Impact copolymerization is regarded as the low- hydrogen ratio is adjusted such that the rubbery
est cost process for making toughened PP. It can copolymer made in this reactor contains 40 –
be visualized as a method for producing an 60 wt % ethylene, depending on the particular
intimate blend of PP homopolymer with a tough- grade. This gas composition is not readily con-
ening ethylene – propene elastomer. Approxi- densed with cooling water alone, so a compres-
mately 10 – 20 wt % of this elastomer suffices sion stage is added to liquify some of the recycled
for most applications, though the recent avail- gas returned to the reactor base. Copolymer
ability of products containing 30 – 40 wt % will powder, with its associated carrier gas, dis-
expand their use. charges into the low-pressure cyclone separator
The minimum requirement for block copoly- (g), which passes this carrier gas to recompres-
merization is a two-stage process. In one stage sion for return to the copolymerizer. Residual
homopolymer is prepared by any of the methods monomer in the copolymer is removed in a
described in Sections 5.2, 5.3, 5.4, 5.5, 5.6. The combined purging and deactivation vessel (h)
other stage uses a mixed monomer feed of ethyl- before conveying powder into silos for extrusion.
ene and propene to produce a largely amorphous, Analogous gas-phase techniques are used by
elastomeric phase within the polymer particles. other manufacturers. Amoco – Chisso (see
Many other more complex configurations have Fig. 8) add a second horizontal stirred reactor
claimed to be advantageous for certain products, when making impact copolymers, and El Paso
but two stages are generally adequate [42, 43]. also add a similar polymerizer after their bulk
Homopolymer, or a very low ethylene copol- first stage. Unipol – Shell introduce a second,
ymer, is always made in the first reactor because but smaller, fluidized bed (Fig. 9), operating at
the elastomer fragments catalyst particles in ca. 1.5 MPa, for their impact copolymers, thus
diluent systems and produces sticky products in taking advantage of enhanced copolymerization
gas-phase reactors. This first stage of reaction, activity. Sumitomo’s new process also uses two
using propene and hydrogen as molecular mass fluidized beds. Himont (Fig. 6) and Mitsui Pet-
controller, is indistinguishable from conventional rochemical retain their normal bulk polymeriza-
homopolymerization. In batch slurry systems, tion for the first, homopolymerization step, but
propene is metered into a reactor until the amount use gas-phase copolymerization in a fluidized bed
of polymer formed is 80 – 90 % of the intended for producing impact copolymers. Such dry pow-
final make. The remaining 10 – 20 % is made in der reactions overcome the problems arising from
the second stage as follows. Normally the propene extraction of soluble copolymer species in liquid-
concentration is allowed to fall, by continued based processes. At the same time, copolymer
polymerization, to a predetermined value before diffusion to the surface should be reduced by the
introducing ethylene, propene, and possibly hy- lower degree of swelling in dry powder systems.
drogen. No further catalyst is needed for the While copolymers containing 40 %, or more,
second stage, and the reaction temperature might of elastomer can be handled satisfactorily in plant
be lowered to reduce the amount of soluble poly- processes, their cohesiveness calls for more care
mer diffusing out of the particles. The high reac- than with homopolymers. Himont patents sug-
tivity of ethylene promotes rapid copolymeriza- gest that their fluidized-bed technology recog-
tion in a more exothermic reaction. Venting and nizes this aspect. Overall, there is complete
polymer isolation follow the procedure already unanimity that a gas-phase copolymerization
described in Section 5.1, but filtration and atactic stage is preferred for this class of copolymer in
polymer separation are more difficult because of modern plant.
additional amounts of viscous soluble copolymer.
Gas-phase systems using modern catalysts
avoid much of this difficulty. Figure 7 shows a 5.8. Product Finishing
typical BASF continuous process using two stir-
red reactors for making impact copolymers [36]. Considerable capital is involved in the finishing
Active polymer and gas from the first reactor areas of all plants after the dry powder stage. The
398 Polypropylene Vol. 29
great majority of this powder is extruded with a stabilization systems are established with me-
variety of additives, pelletized, tested, and then chanically robust coarse particles. This will en-
stored in various packages for sale. Direct sale of tail some additional manufacturing costs, and
suitably stabilized reactor powder circumvents perhaps more product constraints, but this expen-
some, but not all, of these costs. diture should be less than that for capital and
energy intensive extrusion and pelletization op-
Extrusion and Pelletization. Proprietary erations. Himont is constructing a PP plant in
equipment from specialist manufacturers will Brazil, due for completion in 1991, which is
always be used for high-throughput plants oper- claimed to have no extrusion facilities. However,
ating at 5 – 20 t/h and 250 C. In selecting ex- these have subsequently been installed.
truders the following factors are relevant (in
addition to costs): powder morphology, product Additive Incorporation. Extrusion pro-
MFI range, melt filtration needs, devolataliza- vides an efficient and convenient way of incor-
tion, turn down ability (i.e., efficient operation at porating antioxidants and other modifiers into
low rates), temperature control, mixing needs, polymers. Metered amounts are mixed with the
and additive feeds. The types of extruder avail- main powder feed to the extruder and homoge-
able include long, single-screw machines and nized in the molten polymer. Good mixing is
two-stage systems in which powder is melted in essential to prevent extrusion of unstabilized
a continuous high-speed mixer which discharges product at high temperature. Nitrogen blanketing
the melt into a short, pressure-generating extrud- is common practice. Highly specialized and low-
er. Twin-screw machines with corotating and tonnage formulations are either made on a sepa-
segmented screws are increasingly used for ad- rate plant having appropriately sized equipment,
ditional flexibility. Versatility and output can or the customer himself adds concentrates in the
also be increased by installing a gear pump form of stabilizer master batches.
between the die plate and the discharge end of Liquid additives, such as some antistats, can
the screw in any of these systems. be metered directly into the melt, given good
Pelletization takes two forms. Extruded laces subsequent homogenization in the extruder.
from the die plate are quenched in water to give
rigid strands. High-speed cutters then chop the
continuous strands into 2 – 5 mm lengths to 5.9. Additives
produce so-called lace-cut pellets. In the other
system, high-speed knives rotate against the Stabilizers [44]. Like most hydrocarbons,
extruder die plate to cut off short lengths of the PP must be protected against oxidation, particu-
molten extrudate. Either the insulated die plate is larly above 100 C. The dominant reaction is
immersed in water, or the molten pellets are chain scission by free-radical attack at the tertiary
instantly solidified by being flung into a water carbon atoms of the backbone. This generates
ring quench zone to prevent cohesion. These die hydroxyl and carbonyl groups, accompanied by
face cut granules are increasingly common in yellow discoloration and brittleness. Incorporat-
large plants. ing radical scavengers considerably delays the
onset of embrittlement and increase of the MFI.
Salable Powder. Densification is avoided Antioxidants are always incorporated into PP
entirely for those outlets willing to use suitably before or during extrusion at manufacturing
stabilized powder. Spherical particles, up to ca. plants. Usually a peroxide decomposer, such as
0.3 mm diameter, have been available for many a phosphite, is introduced to improve melt sta-
years, but in most applications pellets are pre- bility, together with hindered phenols to confer
ferred because of their better housekeeping (spil- long-term aging resistance. Typically, the
lages, dust, etc.), easier handling in standard amount of each of these additives is 0.05 –
systems, and absence of concern about possible 0.2 wt %, but in more aggressive environments
dust explosions due to powder attrition. Emer- the levels might rise to 0.5 %, with thiodipropio-
gence of coarse Spheripol powders from Himont, nate esters as peroxide decomposers. The choice
1 – 5 mm diameter, should dispel some of these of stabilizer is influenced by the application,
concerns provided adequate and nonseparating for example, interaction with spin finishes
Vol. 29 Polypropylene 399
[45], resistance to extraction by hot water, and and sodium stearates have also been used, and
regulatory constraints. more recently synthetic hydrotalcite (a hydrated
Traces of copper or cobalt powerfully accel- magnesium aluminum hydroxycarbonate). Low-
erate thermal oxidation, especially at sustained er levels of such additives are still widely used.
temperatures above 60 C. In these cases a che-
lating agent such as a bishydrazone is added [46]. Slip and Antiblock Agents are mainly used
Continuous outdoor exposure also requires in film production where high-speed handling
protection from the damaging effects of UV requires a controlled reduction in frictional
radiation. The severity of embrittlement in- forces. 0.1 – 0.5 wt % of oleamide, erucamide,
creases at high temperature and with rainfall in glyceryl monostearate, etc., usually suffices. Fi-
some polypropylenes. Atmospheric pollution ne, spherical particles of silica incorporated at the
can deposit protective layers on the surface. pelletization stage prevent layers of film adhering
Ultraviolet-absorbing compounds, such as al- to each other during storage.
koxybenzophenones and hydroxybenzotriazoles
for thick sections, and hindered amine light Crystallization Nucleants. Although pure
stabilizers (HALS) for films, provide protection PP has a final melting point of 176 C, the melt
at contents of 0.1 – 1.0 wt % [47]. Screening supercools by 50 – 60 C before crystallization
with some fine pigments or carbon black is sets in at ca. 115 C. Small amounts of certain
effective, but restrictive on appearance. additives [48] nucleate the melt, raising the
Gamma radiation, used for packaged food and crystallization temperature by 10 – 15 C.
sterilization of medical equipment, degrades PP, Smaller spherulites result, sometimes having
causing embrittlement. The effects can be miti- different structures. Advantages of nucleated
gated by the careful choice of stabilizer. grades include shorter injection molding cycles,
higher moduli, greater transparency, and higher
Antistats. The familiar static charges and heat distortion temperatures. Suitable additives
resulting dust deposits on many plastics can be include dibenzylidene sorbitol and substituted
overcome in PP by incorporating 0.2 – 1.0 wt % variants, di-tert-butylbenzoate salts, sodium ben-
of polar additives. Suitable materials, such as zoate, finely divided talc, sodium diaryl phos-
polyether fatty amide and fatty amine conden- phates, and some pthalocyanine pigments. These
sates and glyceryl monostearate reduce the sur- materials are somewhat selective in their effects,
face resistivity from > 1013 to ca. 107 W. The i.e., some are particularly good for transparency
mechanism involves slow diffusion of the addi- improvement, but less effective for modulus
tive to the surface where it picks up atmospheric enhancement. Careful balancing of the overall
moisture. Hence, time and humidity are impor- additives recipe is also essential because both
tant. At 50 % RH most of the recommended adverse and beneficial interactions occur be-
additives are satisfactory, but at 30 % RH the tween some of the components [49].
fatty amine derivatives are advantageous. A few
days storage at room temperature is sufficient to
develop the conducting surface layer. 6. Compounding
Compositions containing moderate amounts
of conductive carbon black are also effective, as Compounding includes incorporating mineral
are small amounts of polyacetylenes. The latter, fillers, glass fibers, elastomers, flame retardants,
and the incorporation of small amounts of fine pigments, and carbon black. It is a specialized
metallic wire, are too expensive for PP operation dealing with relatively short run
applications. lengths in specified compounding extruders or
mixers. For this reason, and for concern about
Antacids. Most of the earlier PP formula- cross contaminating unmodified PP grades, com-
tions contained 0.05 – 0.2 wt % of calcium stea- pounding plants usually operate separately from
rate to prevent traces of acidic catalyst residues main PP production plants.
from corroding customers’ equipment. It be- Substantial property enhancements enable
haves as a mild slip agent and suppresses attack polypropylene-based products to compete in
of HCl on certain antioxidants. Zinc, magnesium, quite demanding areas where unmodified PP
400 Polypropylene Vol. 29
would be inadequate (see Table 6). Examples of very long chains. Hence MFI is often mea-
include tough front and rear bumpers for cars, sured at two different shear rates to give some
rigid coupled glass compositions for washing idea of MMD. Increasing importance is being
machine tubs, dense grades for outdoor garden attached to a more comprehensive rheological
furniture, and temperature-resistant composi- characterization [51, 52].
tions for car under hood applications. Long- A typical, medium-flow polymer has an MFI
fiber-reinforced PP secures further increases in (230 C/2.16 kg) value of 3 dg/min, correspond-
toughness and stiffness over short-glass-fiber ing to a Mw of 460 000 and Mn of 54 000. The
compounds [50]. Fibers with a minimum length practical grade range of 0.3 – 50 MFI covers
of between 0.8 and 3 mm, depending on the applications from sheet and pipe extrusion to
coupling between matrix and fiber, are likely to high-speed fiber spinning.
be satisfactory. These form an interlocking skel- Heterogeneous Ziegler – Natta catalysts
etal structure which dissipates the impact energy yield broad MMD polymers having Mw/Mn of
over a large area of the molding. 5 – 10, the lower values being associated with
The combination of lower production rates, the more recent Solvay and supported catalysts.
specialized equipment, and dense additives mean Very narrow MMDs are still made by preferen-
that PP compounds are always more expensive tially cleaving long chains in an extruder, usually
than natural grades. with the assistance of organic peroxides. Such
grades, commonly referred to as controlled rhe-
ology (CR) polymers, reduce extrusion and
7. Properties molding orientation caused by high molecular
mass species with their long relaxation times
7.1. Homopolymer [53]. Note that reworked polymer is likely to
have a higher MFI and a correspondingly nar-
Basic mechanical properties are largely influ- rower MMD than the starting material.
enced by molecular mass and molecular mass
distribution (MMD), chain stereoregularity, and Stereoregularity. Very high stereoregular-
processing conditions, which introduce orienta- ity is now achievable with modern catalysts, even
tion, strain, etc. Various additive packages must without removing any soluble byproduct. In
be tailored to the application to achieve good and some applications processing is helped by a small
durable performance. lowering (detuning) of the isotactic index. This is
readily achieved by minor changes to the poly-
Molecular Mass. At low shear rates melt merization recipe, and by introducing small
viscosities are proportional to the 3.4 power of amounts of copolymerized ethylene.
the weight-average molecular mass. At the high-
er shear rates found with most processing equip- Metallocene-Based PP. An expanded
ment, the dependence is still greater than a power range of products is iminent following the en-
of 2 because much chain entanglement still ex- couraging metallocene developments. Further
ists. As a result of this sensitivity, and the direct pilot trials and customer assessment of proces-
relevance to processing, the melt flow index sing, product, and economics is needed before
(MFI) is always used to describe the viscosity precise definition is possible. The advantages
characteristics of each polymer grade. The de- already seen include higher extrusion rates for
pendence of melt viscosity on shear rate is also films and fibers, enhanced clarity, absence of
related to MMD as a result of the strong influence oligomers, superior property balances, and the
Vol. 29 Polypropylene 401
Table 7. Mechanical and thermal properties of PP Origin ‘‘Propathene’’ (with permission of ICI Chemicals & Polymers)
Melt flow index (230 C/2.16 kg), ISO 1133 1.00 4.00 12.00 33.00 6.00 2.00 7.50
g/10 min (dg/min)
Tensile yield stress, MPa ISO 527 33.50 34.50 34.50 34.00 27.00 23.50 25.00
Flex. modulus, GPa ISO 178 (10 mm/min) 1.45 1.50 1.50 1.55 1.15 1.00 0.85
Izod impact strength, kJ/m2 ISO 180 (0.25 mm 23 C 4.50 4.50 4.00 3.00 9.50 no break 5.00
notch radius)
0 C 3.00 3.00 2.50 2.00 5.50 10.00 2.50
20 C 2.00 2.00 2.00 3.50 7.50
40 C 5.00
Instrumented drop weight ICI method 23 C 7.00 10.00 10.00
impact strength, J
0 C 6.00 11.00 2.00
20 C 6.00 11.00
40 C 9.50
Embrittlement temperature, C ICI method > 23 > 23 > 23 > 23 20.00 45.00
Rockwell hardness ISO 2039/2, ASTM D785 R scale 93.00 95.00 95.00 95.00 90.00 75.00
Vicat softening temperature ISO 306A, BS 2782: 120A 154.00 154.00 154.00 154.00 147.00 143.00 135.00
(10N force), C
Heat distortion temperature, C ISO 75/A & /B
A – 1.8 MPa 65.00 65.00 65.00 68.00 60.00 50.00 46.00
B – 0.45 MPa 100.00 100.00 100.00 102.00 95.00 90.00 71.00
Vol. 29
Vol. 29 Polypropylene 403
the overall crystallinity, gives a broader soft- often referred to as block copolymers, toughened
ening range with reduced melting points polypropylene, or more pedantically heteropha-
(Figs. 10 A, 10 B), increases the fraction of sic copolymers [34].
soluble polymer, and improves transparency Essentially, these products are best viewed
and surface gloss. These changes are dependent as an intimate dispersion of elastomer in a PP
on the amount of comonomer and its distribu- matrix. The particulate rubber phase confers
tion along the chain. Table 7 shows how the good toughness, while the homopolymer matrix
modulus decreases for a random copolymer is responsible for retaining good high-tempera-
containing ca. 3 wt % of combined ethylene. ture performance and adequate stiffness. In this
Several applications take advantage of the respect they are far superior to random copo-
lower melting point to make thermoweldable lymers, and become the first choice when im-
film. Ideally, it would be useful to have a low pact strength and rigidity are called for. In
melting range without undue increases in the extruded pellets or molded articles the rubbery
proportion of xylene-soluble residues. This is copolymer phase is well distributed in the form
claimed to be possible with butene copolymers, of droplets 1 – 5 mm in diameter. Such a struc-
perhaps because the solubles are produced at ture (Fig. 11) is produced during melting and
semi-exposed catalyst sites more easily accesible recrystallization. Powder direct from the reac-
to ethylene [40]. Some advantages are also tor has elastomer permeating throughout the
claimed for propene – ethylene – butene terpo- particle in a more continuous form. Many of
lymers [34, 39]. Butene helps the development of the complex interactions which control the
low-melting g-triclinic crystallites. Random co- stability of this phase structure and the resulting
polymers are somewhat tougher than homopo- toughness, await further study, but current
lymers, and do not exhibit the familiar stress- views are very well discussed by VAN DER VEN
whitening behavior of the tougher copolymer [43].
impact grades. Toughness, stiffness, and softening points are
given in Table 7 for two impact copolymers
Impact Copolymers. Section 5.7.2 de- containing ca. 10 and 20 % of elastomer. Gas-
scribes block copolymerization systems for mak- phase polymerization systems are able to
ing high impact strength grades of PP. These are increase the rubber content to 40 %, but the
404 Polypropylene Vol. 29
products are not available in large commercial sulation of PE makes it behave more like rubber
quantities at present. These impact copolymers towards the matrix, thereby increasing tough-
naturally contain more soluble polymer than ness at the expense of modulus in such ternary
homopolymer, and this second phase reduces the blends.
translucency. Severe deformation causes some
whitening or blushing [54] in the stressed re-
gions, particularly in very high impact grades. In 8. Uses
other respects the rules relating processing and
properties to MFI, nucleation, controlled rheolo- Polypropylene is readily processed in conven-
gy, stabilization, etc., are the same as for homo- tional equipment used for other thermoplastics.
polymer. Injection molding, commonly using screw-type
reciprocating machines, accounts for 40 – 50 %
of all applications. Extrusion processes account
for the remainder with domination by fiber and
7.3. Elastomer Blends with film.
Polypropylene A more detailed picture is obtained by ana-
lysing the North American 1996 sales data (in
Originally, PP was toughened by blending with 103 t/a) listed in the following [56] :
ca. 10 wt % of polyisobutylene (PIB) elastomer.
In some situations the same technique is used
today, with ethylene – propene rubber (EPR) or Blow molding
ethylene – propene – diene rubber (EPDM) re- Containers 74
Others 5
placing PIB. Total blow molding 79
As rubbers are incompatible with PP, consid- Extrusion
erable mechanical work is necessary to secure the Coatings 5
vital fine dispersion of elastomer. Good blending Fibers and filaments 1463
Film (up to 0.25 mm)
also requires a reasonable viscosity match be- Oriented 503
tween the two components. Common practice is Unoriented 111
to use a two-stage process in which the elastomer Pipe and conduit
is first compounded with PP to give a 50 – Sheet (over 0.25 mm) 110
Wire and cable 5
70 wt % masterbatch of the rubber as free flow- Others 43
ing granules. Such masterbatches can be pur- Total extrusion 2240
chased at extra cost. Good mixing devices are Injection molding
essential for the final compounding step with PP. Appliances 139
Consumer products 565
Twin-screw extruders or high-speed mixing de- Rigid packaging 523
vices perform satisfactorily. Transportation 186
Well-prepared blends have physical proper- Others 131
ty combinations only just short of those of Total injection molding 1544
Export 503
directly polymerized impact copolymers. How- All others 1177
ever, the latter are generally preferred on ac- Total 5543
count of consistency and grade versatility. Elas-
tomer blending is also part of the broad spec-
trum of compounds referred to in Section 14.
Here they are used to uprate the toughness of 8.1. Injection Molding
homopolymer and impact copolymers in these
complex formulations. Some manufacturers al- An exceptionally wide range of injection-molded
so introduce HD polyethylene, in addition to products stems from the rigidity, toughness, and
rubber, to secure further toughness improve- chemical and temperature resistance of PP. Ex-
ments. In these cases, electron microscopy re- amples include automotive trim and ventilation
veals that in well-dispersed systems the poly- components, bottle crates, industrial containers,
ethylene is always located inside and towards washing machine tops and tubs, kitchenware,
the center of these rubber droplets. This encap- tool handles, domestic waste systems, and small
Vol. 29 Polypropylene 405
using two separate injection barrels. As the produce wide mouth containers having improved
skin is unfoamed, high-quality surfaces result. dimensional accuracy and appearance.
2. In the Varitherm Process (BASF, Krauss Injection stretch blow molding is a further
Maffei), improved surface finish is achieved refinement which introduces a plunger stretching
by using a hot mold (100 – 120 C) followed stage to elongate a conditioned parison or pre-
by rapid cooling after a short shot of the melt form just before the final blow (see ! Plastics,
(i.e., an injection of polymer insufficient to fill Processing, 1. Processing of Thermoplastics).
the mold). Better mechanical properties and enhanced
3. In the counterpressure method the mold is transparency stem from partial orientation. This
pressurized prior to filling to prevent degas- technique is sometimes referred to as the melt
sing at the melt front. phase process.
4. In hollow section molding (e.g., CINPRES) In stretch blow molding, the extruded or
nitrogen is injected in a continuous stream molded preform is carefully conditioned to just
into the mold at the same time as the polymer below the polymer melting point before stretch-
melt. Under appropriate conditions, hollow or ing. Axial stretching of the preform with simul-
ribbed moldings are produced when gas flows taneous or almost immediate blowing in the mold
preferentially down thick, hot sections of the produces a very high quality container. Correctly
molding. This technique is of increasing carried out, this process secures increased rigidi-
interest. ty and toughness, high transparancies, and re-
duced permeabilities as a direct result of signifi-
cant amounts of orientation. The more complex
8.2. Blow Molding technique increases capital and operating costs,
but it is of growing interest [60] and is already
The extrusion blow molding process for PP being applied extensively to biaxially oriented
copies that already well established for low- and PETP bottles.
high-density polyethylene. However, application Coextruded parisons can be used as precursers
to PP has been slow while suitably viscous and for blow molding when special barrier properties
tough polymers were developed at attractive are required [61]. In particular, a central layer of
prices. At present, the important areas are smaller ethylene vinyl alcohol copolymer (EVOH) to
packaging containers which take advantage of reduce oxygen diffusion, combined with mois-
good transparency, good form stability up to ture protective outer layers of propene – ethyl-
140 C for hot filling or sterilization, and greater ene random copolymer, give containers suitable
freedom from environmental stress cracking with for storing oxygen-sensitive food products.
aggressive products. Brake fluid reservoirs ex-
emplify this. Very large containers are dominat-
ed by high-density polyethylene. 8.3. Fibers and Flat Yarns
Extrusion blow molding employs two linked
processes [59] in which an extruded molten Very large amounts of polypropylene homopo-
parison is transferred to a mold for inflation with lymers are used for fiber manufacture in Europe
low-pressure air at 0.4 – 1.0 MPa. High molec- and the United States. These applications exploit
ular mass polymer, MFI(230 C/2.16 kg) 0.4 – the wide range of physical forms, including
2.0 dg/min, combined with low melt tempera- increasing amounts of versatile nonwoven fab-
tures at the die of 200 – 210 C, provide a suit- rics [62–64]. Monoaxial orientation can be ap-
ably stiff melt. If the melt stress in a heavy PP plied to conventional spinneret yarns, as with
parison exceeds ca. 20 kPa, then the resulting polyamides and polyesters, and to flat tapes made
tension thinning will be troublesome as regards from extruded film. These differ in the following
parison stability and uniform wall thickness. respects (Table 8).
Injection blow molding replaces the extruded
parison with an injection-molded preform. Blow- Spinneret Type Yarns. Here melt is extrud-
ing takes place in a second mold which maintains ed through a die plate perforated by many small
the high-definition neck of the preform. This holes to generate individual thread lines. In the
process eliminates scrap and makes it easier to long spin process [65] (see ! Fibers, 7. Poly-
Vol. 29 Polypropylene 407
Long spin 0.2 – 3.0 high-tenacity monofilament; drawing integral or separate; high output
BCF yarn 0.2 – 2.0 special case of long spin making only bulked continuous fiber
Spunbonded 0.2 – 2.0 venturi haul off; no 2nd stage draw. bonded mat output
Shortspin 0.2 – 40 compact unit; tow stretched and cut in line for staple
Melt blown 0.002 – 0.02 low orientation, very fine fiber; only bonded mat output
Fibrillated yarn 110 – 500 oriented slit film; fibrillated for baler twine, rope, etc.
Weaving tape ca. 110 nonfibrillated slit film for carpet backing, sacks, etc.
Strapping tape 500 – 1000 thick, oriented tape as a steel alternative
pffiffiffiffiffiffi
*
tex ¼ weight in grams of 1000 m of yarn; equivalent cylindrical fiber diameter in mm ¼ 37 tex.
olefin Fibers, Section 1.2.2), which has integral filaments become finer. These find use in geo-
spinning and finishing stages as well as out of line textiles, carpet face fiber, and diaper cover stock
drawing options, there may be 50 – 250 holes per applications. A useful feature of PP fabrics made
spinneret. An air cooling gap of 2 – 5 m is needed from fine fibers is the ability of underwear gar-
between the die plate and the wind-up roll. Line ments to reduce claminess by transferring mois-
speeds up to 1000 m/min at the spinning stage, ture away from the skin to an outer absorbent
increasing to 3000 m/min during solid drawing layer. Polypropylene based fabrics are also used
over hot rolls, call for complex and expensive for sports clothing and socks, but the low melting
haul off, drawing, and wind-up sections. Product point of PP calls for special attention to the heat
may be packed off as continuous yarn, tow, or setting of the average domestic iron.
staple. Suitable polymers have MFI(230 C/ In the third, and most recent production pro-
2.16 kg) in the range 12 – 25 dg/min, with nar- cess (Fig. 14), air is blown through a very fluid
rower molecular mass distribution grades offering polymer melt maintained at high temperature to
some advantage with such high rates of melt assist chain scission in the spinning process itself
draw. These are high-throughput plants, best [66, 67]. Polymer MFI(230 C/2.16 kg) at the
suited to long runs of a single grade of product. nozzle can range from 35 to 300 dg/min or high-
In a variation of this technique [66], the er. The specially designed die, having a row of
integrated spunbonded process (see ! Fibers, nozzles along its width, sprays a stream of short,
3. General Production Technology, Chap. 6),
yields a continuous bonded mat of partially
oriented yarn as a consequence of some draw in
the venturi type haul off operating at up to
5000 m/min. There is no further drawing as the
fiber is collected as a mat on the take-off belt for
conversion into nonwoven fabrics. These are
used, for example, in geotextiles, furnishings,
carpet backing, etc. The balance of drawdown
rate and orientation in this process is influenced
by the polymer molecular mass distribution.
Figure 13 depicts a compact shortspin pro-
cess for staple production using a die containing
ca. 40 000 holes. Cooling air jets freeze the melt
within about 20 mm so that Godet haul off rolls
can be placed only 1 m away from the die.
Orientation is achieved by the in-line stretching
of this tow in an air oven, followed by chopping
in line to produce staple [61]. Broad molecular
mass distribution polymers give the necessary Figure 13. Shortspin process
a) Spinneret; b) Quenched fibers; c) Air-jet cooling
melt strength, while MFI(230 C/2.16 kg) re- Courtesy of the ‘‘Propathene’’ Business, ICI Chemicals &
quirements increase from 7 to 20 dg/min as the Polymers
408 Polypropylene Vol. 29
8.4. Film
aggressive media and its better performance at plasticizers or chlorine-rich species. Re-extruding
elevated temperatures are advantageous. PP usually lowers its molecular mass and narrows
Extrusion at ca. 225 C is straightforward; a the molecular mass distribution, particularly in
central torpedo is used to make the hollow pipe aged feedstock. This can be helpful in some
[72]. Homogeneous melts require an extruder applications that require enhanced flow. Adverse
having a length-to-diameter ratio of 25 : 1 and factors which must be assessed include some loss
a compression ratio of 4 : 1 to reduce the risk of of strength from reprocessing/ageing, oxidation
trapping air in the extrudate. Pipe up to 300 mm stability, discoloration, and contamination.
outside diameter is generally vacuum sized in a
water bath: semi-molten pipe passes through a PP Manufacturers. Manufacturers usually
finely perforated steel tube having vacuum ap- produce small proportions of PP which do not
plied to its external surface. Larger pipes are meet their full quality requirements. Examples
made by pressure sizing where nitrogen or air is include deviations in MFI/MMD, antioxidant
injected via a small capillary into the torpedo to levels, copolymer characteristics, and gels. Pro-
expand the pipe to the sizing die form. Both vided these faults are within predetermined limits
homopolymers and impact copolymers are used in the quality protocol, the material may be
in the MFI(230 C/2.16 kg) range 0.3 to 2.0 dg/ recycled in small proportions, sometimes with
min, increasing to 4.0 for drinking straws and further corrective adjustments to the composi-
ballpoint pen tubing. tion. This operation calls for additional work, and
Copolymers, providing superior impact can reduce plant output by having to process the
strength with some flexibility, find use in domes- polymer twice. For this reason, and in those cases
tic waste systems. Homopolymers have higher where recycle is not permitted or the deviations
resistance to stress. It is essential to have a heavy are too large, manufacturers either reclassify the
duty stabilization system which will withstand product to a lower grade, or sell to an outside
extraction for applications involving aggressive compounder for further reprocessing. This mini-
and hot environments, such as chemical plants mizes disturbances to continuous manufacturing
and effluent pipes. Manufacturers offer guidance processes.
[72] on polymer selection and pipe design con- A second source of much lower grade materi-
forming to the various pressure classes in al, arises when manufacturing conditions are
BS 4991, and to BS 52 254 and BS 5255 for severely disturbed. This can be due to instrumen-
domestic waste pipes and fittings. Creep data are tal and human error, blockages, equipment fail-
available [72] for pressure pipes predicting per- ure, or extrusion disturbances. In these cases
formance for up to 50 years. scrap can vary from substandard reactor powder
Pipe jointing uses all the common techniques, to blocks of polymer from extruder dumps. Ex-
with the exception of solvent welding. Ring seals ternal reprocessors convert such products into
with rubber inserts allow some movement in surprisingly useful materials by blending and
domestic waste pipes. Also used are flanged recompounding. To them, the availability of
joints, hot plate butt welding, and socket fusion essentially pure PP is the prime requirement.
welding, the latter being optionally supplemen-
ted with hot-gas bead welding. Compression Plastics Converters. Turning PP into mold-
joints involving copper alloys should not be used ings, pipe, film, etc., invariably involves some
at temperatures exceeding 60 C because of scrap production. Apart from substandard arti-
reduced life expectancy. cles, there are sprues from moldings, edge trim
from film and sheet, parison waste, and stamped
sheet from thermoforming. These are recovered
9. Environmental Aspects for recycling by the converter himself if the
application allows, or more often by an outside
9.1. Recycling compounder. In favorable situations involving
long runs of a standard product, the converter
The structure and properties of PP make it well segregates waste, grinds it, and then recycles it by
suited to recycling operations. There is no fear blending small amounts with virgin feedstock
about cross-linking, nor of complications with when specifications permit. Occasionally there is
412 Polypropylene Vol. 29
an undemanding application which can accept In the case of PP, notable success rests with
large proportions of such regrind without diffi- recycling old plastic bottle crates and battery
culty. Storage and segregation problems are re- boxes in Western Europe and the United States.
duced when the converter simply collects his This is mainly attributable to the ease with which
scrap together in the form of regrind for sale to large amounts of a clean single polymer can be
a compounder. collected without cross contamination from other
The British Plastics Federation (BPF) estimates plastics. Cooksons Plastics [80] and others [81,
[73] that there are about 60 reprocessing compa- 82] have expanded on lead recovery to retrieve
nies in the United Kingdom handling at least PP battery cases themselves. A mechanised sort-
150 000 t/a of polymer. Forty three of these pro- ing system has to separate stones, metal, wood,
cess an estimated 25 000 t/a of PP [74]. Only a few string, ebonite paper, and residual acid. The
of these also process recovered scrap into molded Cookson process involves crushing, several
products such as horticultural, highway, safety, stages of washing, flotation, and screening fol-
and street furniture, which do not make excessive lowed by drying and extrusion. The final pro-
demands on polymer behavior. Included in the ducts include good-quality PP capable of being
estimated figure are 15 000 t of recovered used used in automotive products and for certain types
battery cases and crates which can be converted of battery cases. Success here rests in quality
into quite respectable compounds. Most reproces- upgrading by adding elastomer to enhance tough-
sors only handle single polymers, not mixtures. ness, stabilizers, and antacid incorporation to
Their main supply sources are plastics converters recoup oxidative stability, and molecular mass
and industrial or commercial establishments as tailoring with peroxides for specific applications.
suppliers of fairly well defined PP scrap [75]. Hoechst [83] plan to collect plastic waste from
scrap cars, household appliance industries, and
Recycling PP After a Full Service Life. presorted packaging waste. The 5000 t/a plant
Nearly half the thermoplastics used in Europe are near Cologne should be in operation by mid-
converted into packaging [76]. In the United 1992. ICI studies on scrap recycling from used PP
Kingdom 13 % of this is based on PP, involving crates stress the need to incorporate additional
an estimated 142 000 t of polymer in 1988. stabilizer in weathered products, and to allow for
Polymers used in United Kingdom for pack- some reduction in impact strength for seven-
aging in 1988 (in 103 t) broke down as follows year-old crates.
[76]: Recovery and reuse of mixed plastics is more
difficult. The real need is to develop applications
and fabrication processes for such comingled
Low-density polyethylene (LLDPE and LDPE) 510 polymers, which are essentially incompatible
High-density polyethylene 255
Polypropylene 142
and contaminated. Generally, they will be chan-
Polystyrene 78 neled into some massive products, such as posts,
Poly(vinyl chloride) 68 construction boards, and other bulky structures
Poly(ethylene terepthalate) 53 where resistance to water and decay is more
Expanded Polystyrene 21
Total 1127
important than high inherent strength. Some 20
different European schemes aim to make re-
cycled plastic components as wood and concrete
Inevitably, much of this has only a short life replacements for agricultural applications [77,
before it ends up as waste in some form. Domes- 84]. Comingled scrap can be upgraded by blend-
tic waste contains 5 – 7 wt % (up to 20 % by ing with other recycled polymers to assist
volume) of such products [74], very little of processing.
which is currently recovered. Public concern
about the environment naturally includes highly
visible plastic litter, which is made unduly prom- 9.2. Pyrolysis
inent by its low density and durability. This is an
additional factor accelerating legislation for re- PP can be cracked to liquid hydrocarbons by
covery of all types of packaging, including glass, thermal pyrolysis at 400 – 550 C. In a recent
metal, paper, as well as plastic [77–79]. process developed in Japan [85], zeolite catalysts
Vol. 29 Polypropylene 413
enable this temperature to be reduced to 200 – Table 9. U.K. energy requirements for the manufacture of natural and
420 C by using a two-stage heating process. synthetic materials [86]
remaining complexed residues will require dis- 2 J. P. Hogan, R. L. Banks in R. B. Seymour, Tai Cheng
posal. Often, this involves hydrolysis with water (eds.): History of Polyolefins, Reidel Publ. Co., Dordrecht
to generate corrosive HCl and titanium dioxide 1986, p. 103.
3 P. Pino, G. Moretti: ‘‘The Impact of the Discovery of the
suspensions. After neutralization with alkali,
Polymerization of a-Olefins on the Development of Ste-
these slurries are either discharged as aqueous reospecific Polymerization of Vinyl-monomers, ’’ Poly-
effluent or settled out and used in landfill. Some mer 28 (1987) 683.
incineration is planned. Disposal facilities also 4 D. J. B. Potter, The Manor, Goose Lane, Ilminster, Som-
need to be capable of receiving occasional faulty erset TA19 9RU: Consultant for Polypropylene Produ-
catalyst batches. Older plants still using catalyst cers and Their Technologies, page preceding p. 55, con-
extraction processes simply use aqueous slurry sultant’s Fig. 4.16.
discharges, or dump concentrated residues from 5 D. J. B. Potter, The Manor, Goose Lane, Ilminster, Som-
erset TA19 9RU: Consultant for Polypropylene Produ-
the base of stills.
cers and Their Technologies, page following p. 30, con-
Lower aluminum alkyls are pyrophoric, react sultant’s Fig. 4.1.
violently with water, and are intensely aggressive 6 E. Seiler, Kunststoffe Plast. Eur. 1995, no. 8, 31.
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for full protective clothing. Disposal can be by 1st Int. Congr. Mettalocene Polym., Brussels, April 26 –
burning to generate alumina, or quite often, by 27, 1995, p. 209.
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9 J. Brandrupp, E. H. Immergut: Polymer Handbook, 3rd
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11 S. van der Ven: Polypropylene and other Polyolefins,
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22 Chem. Eng. (1985) July 8, 22.
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78 C. H. Kline, Chem. Ind. (London) 1989, July, 440. Encyclopedia of Chemical Technology, 5th edition, John
79 C. H. Kline, Chem. Ind. (London) 1989, Aug., 483. Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
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82 British Plastics & Rubber: Case Study by DTI (London) of Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
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p. 15. N. Maraschin: ‘‘Polyethylene, Low Density’’, Kirk Othmer
83 Plast. Rubber Wkly, Dec. 8, 1990, no. 1365, 2. Encyclopedia of Chemical Technology, 5th edition, John
84 J. Maczko, Plast. Eng. 44 (1988) no. 6, 39. Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
85 Chem. Eng. (N.Y.) 97 (1990) no. 6, 15. 0471238961.12152316050219.a01.pub2.
86 ICI, The Competiveness of LDPE, PP, PVC after the 1973 D. Nwabunma: Polyolefin Blends, Wiley, Hoboken, NJ 2008.
Oil Crisis, the ICI View, Welwyn Garden City, 1974. D. Nwabunma, T. Kyu: Polyolefin Composites, Wiley, Ho-
boken, NJ 2008.
M. Tolinski: Additives for Polyolefins, William Andrew,
Oxford 2009.
Further Reading S. C. O. Ugbolue: Polyolefin Fibres, Woodhead Publ., Cam-
bridge 2009.
E. Benham, M. McDaniel: ‘‘Polyethylene, High Density’’,
Kirk Othmer Encyclopedia of Chemical Technology, 5th