Khairi Nagdi

Rubber as
an Engineering Material:
for Users

106 Vigyres nod 7t Titbles

Publishers, York
 CHAPTER 8
Typesof Crude Rubbers —Chemistry, Compounding,
VulcanizateProperties and Applications
8.1 Introduction
nomenclature and classification of elastomers according to different aspects
have been briefly reviewed in chapter 3. Furthermore, factors of their environment-
Jl aging and resistanCe to various contiguous materials have been described in
. and 6, respective'v.•
purpose of this chapter, is to give a brief, up-to-date summary of the
principal-types of crude (base) rubbers, starting with general-purpose (nonoil-
rcsistant) types and ending with special-purpose (oil-resistant) grades. ne topics
that arc considered for each rubber type include its chemistry and compounding as
as the •i.m
nortant pgoperties and applications of its vulcanizates. (Thermoplas-
elastomerswill be treated separately in chapter 9.)
figures and tables at the end of this chapter give a summary of the impor-
tant physical and chemical properties of the most common elastomer types. They
shouldbe regarded as güidclines for selecting elastomeric materials for different
applications.More details on chemical resistance to particular liquids are given in
chapter 15. However, the ftqal choice should be made after carrying out individual •
tc.sts.
typical trade names given below are examples only; the references are not
tntcndcd as a compiete list-of trade names.
4<.2Natural Rubbers (NR)
8.2.I Chemistry
chemical name for NR is polyisoprene, which is a homopolymer Ofisoprcne. It
has the cis-1,4configuration (Fig. 8.1), which means that carbon atoms I and 4 are
bornon the same side of the double bond. (In the trans-1,4 configuration, these
carcnjnatoms are on opposite sides of the double bond.) In addition, the
mec contains small amounts of nonrubber substances, notably fatty acids,
and resinous materials that function as accclcrators and activators-lor
ulcamzation.
NR is available in a variety of types and grades, including smoked sheets, air-
dried sheets and pale crepes.
8.2.2 Compounding
compoundsusually contain peptizers, carbon black or nonblack fillers or both,
t)(ides fatty acids, processing aids, plasticizers, antioxidants, antiozonants,
CHI
polymerization
-l
isoprene pot'fiscprene
-Hic —H2C
cis-1,L potyisoprene trans-I, L polyisoprene
(gutta-oerthcl
mg. 8.1: Possible Configurations of 1,4 Polyisoprene
protective waxes and vulcanizing ingredients (usually sulphur, low sulpnur or
nonelcmental sulphur vulcanizing systems; less frequently peroxides).
NR can be blended with other diene rubbers such as IR, SBR and BR-
8.213 Vulcanizate Properties
NR vulcanizates have high tensile strength over a wide hardness range. high
strength is due to crystallization of the polymer chains at high strains (section 1.7),
enabling NR to be used in unfilledcompounds. Furthermorc, NR
have the highest of all elastomers (except BR), which is responsible for
very low heat buildup (section 4.8), Further advantages inclucictow compression
set and stress relaxation, good electlical insulation and good resistance to abrasion,
tear and fatigue.
NR can be compounded for continuous use at 90 00 and for intermittent periods
up vulcanizates remain flexible at temperatures down to —55oc
without adding plasticizers. However they tend to crystallize readily when stored
for long periods at low temperatures (section 4.15).
Like other unsaturated elastomers. NR vulcanizates are susceptible to attack by
atmospheric ozone. Howeve{, Liteozone and weather resistance can be improved
by blending with a saturated rubber such as EPDM or by incorporating antiozon-
ants and protective waxes in the compound.
NR vuicanizates are not restståfi{ to petroieum-based ouis anci tuels but they can
be used with a wide range cf and inorganic chemicals,such as nonpe-
troleum-based automotive brake fluids, silicone oils and greases; glyco!s; alcohols:
water; and nonoxidizing aqueous solutions of acids, alkalis and salts.
8.2.4 Applications
NR elastomers remain the best choice for many applications that require low heat
buildup, such as large tires, carcasses of passenger-car tires. vibration mountsr
 - incluoehoses, conveyor
M} renc-dlttadlcne Rur ss•
rubberized fabric', elastic belts. gaskets, seals,
and pharmaceutical goods. 101
8.4 Styrene-Bu(adiene
Rubbers (SBR)
8.3 Synthetic Polyisoprene Rubbers (IR) Former Designations
Büna S
Trade Names GRS (Government Rubbcr
Styrene)
Satsyn (Goodyear Tire and Rubber Co.)
Shcll IsopreneRubber (Shell International Chemical Trade Names
Co.)
Buna Hüls (Chemische Werke
sHüls
8.3.1 Chemistry Plioflex, PI iolite (Goodyear Tire AG)
and Rubber Co.)
Cariflex S (Shell International
Chemical Co.)
no: conta:rathe nonrubber substances that . v.v. However, it
are present 8.4.i Chemistry
One can differentiate between two basic in NR.
types of synthetic polyisoprene. SBRs are copolymers of butadiene
depend upon the polymegization cqtalystsystern These and styrene (Fig. 8.2). The regulargrades
to as "high "'cis and •slow" cis t:.pcs.
used and are commonly referred tain 23% styrene. Increasing con-
styrene content leads to a Joss in resilience
in' the' freezing point of the vulcanizatcs. and a rise
high cis grades cont-ain approximately
causeof the high degree of stereoregularity, 96=-970/0 cis-1,4 polyisoprcng.
Be-
they are able to crystallize on polymerization
likc NR. Consequently, they can be stretch-
compounded without fillers, giving
«rcngth nearly as high as that Ofunfilled NR tensile
vulcanizates.
low cis grades contain about 92—93%
litnited use because the physical properties, cis-I,4 polyisoprenc. They have
those of high cis types.
of their vulcanizates are inferior
to
butadiene
O
styrene

ompounding
In general, synthctic IR can be compounded
using the same ingredients used for
NR. However, the addition of high levels of
fatty acids, activators and accelerators
svnthetic IR is necessary to achieve the same
Syntheuc IR
vulcanization rates of NR.
can -be blended with other diene rubbers such
o,
ftR. as NR, SBR and styrene-butadiene rubber (S8R)

fig. 8.2: Synthesisof SBR

8.3..3 Vulcanizate Properties
'he vuicanizatesOf' synthetic IR llave less tendency The oil-extended grades (with and without carbon black)
contain naphthenicor
to crystallize than do NR highly aromatic ons in the range of 25—50parts by weight per 100parts
tow-temperature applications. The aging by weight
of polymer.
roperies and resistance to chemicals are similar to
those of NR vulcanizates.
iinwever, the physical properties arc not as good as those of
NR elastomers. 8.4.2 Compounding
In general, SBR can'be compounded using the same ingredients for NR. However,
8.3.4 Applications SBR cures more.slowly than NR and hence more acceleratoror a more
in general, synt etic IR can be used alone or in blends active accelerator system is required than for NR.
with NR in.the manufacture SBR can be blended with other diene rubbers such as
of rnost products wh&reNR is the traditionai choicc. IR and BR, Poly-
mers containing a high proportion of styrene are widely used in blends with dienc

29163
620. 194

to itnproscd wear resistånceand high hardness in conjunction with
...«cific gravity
Properties
to NRC the tensile -strength of SBR gum vulcanizates (i.e., unfilled
nds) i?'very poor (about 10—15% or that of NR clastomcrs). This is bc-
the absencc of crystamzation on stretching the gum vulcanizatc (section
consequently, these Fybbers do not•develop high tensile strengths without the
reinforcingfillers. The resilience and low-temperature behavior of SBR
:rntcs are inferior .to those of NR, but heat aging characteristics are better)
vvkanirntc.shavc an operational!cinpcraturc rangc or —50to 4-100oc and
Ehow(notcndcncy to *t.40wl€mpcraturcs.
o-4—-..—.:-
h highly unsaturated elastomers, SBR vulcanizates show poor ozone
which can be impröved by biending with EPDM or by incorporating
antsand protective waxes;
vulcanizatesare not rcsisgnt to petroleum-basedoils and greases or
arbonfuels, they arc.rg$jscant to nonpetroleum-b_ascdautomotive brake
oils and greases; glycols; alcohols; water; and nonoxidizing aqueous
of acids, alkalis and salts.
Applications
producedduring the Seéond World War as a substitute for NR. Generally
SBR can be used iri many applications as a replacement for NR, except
dvnamic applications requiring low heat buildup on flexing (e.g., high-
tires for trucks).
.ft polybutadieneRubbers (BR)
r.nes
' GoodyearTire and Rubber Co.)
P (Bayer AG)
homooolymerof butadiene. The high cis grades contain approximately
CIS-I.4 butadiene units (Fig. 8.3). Oil-extended grades (yith and without
r, "lack) arc also available.
Compounding
'taJienerubbers are more difficult to process than NR or SBR. Therefore,
rormally used in blends with other rubbers such as NR, IR, SBR or NBR
vclym%izction
bJtodiene
trans-I, L pot'fbutcåene
cis-1,L potßutndiene
Fig. 8.3: Possiblc Configurations of I .4 Polybutadicne
to improve the abrasion resistance, resilience and iow-temperature flexibility.The
blends usually contain less than 50% of BR and often only 10—25%.
8.5.3 VulcanizateProperties
The vulcanizates of 100% BR have high abrasion resistance, the highest resilience
of all known elastomers and, with the exception of silicone vulcanizates, the lowest
glass transition temperature (Tg). However, the skid resistance on wet roads is
poor.
ne characteristics of environmental aging and chemical resistønce to fluids are
similar to those of SBR vulcanizatcs.
8.5.4 Applications
Polybutadienc rubbers are used mainly in blends with SBR in the.production of tire
treads and with NR for truck tires. They are also used in blends with other rubbers
such as NBR in manufacturing a great number of mechanical goods to increase
their resilience, to improve their low-temperature flexibility or to reduce their heat
buildup on flexing.
8.6 Polynorbornene Rubber
Trade Name
Norsorex (at the present time, CDF Chimie is the sole producer of polynorbor-
nene)
8.6.1 Chemistry
Norsorex is a homopolymer based on norbornene monomer. The polymerization
occurs through ring opening rather than through the reaction of a double bond or
 •rude Rubbers 1'olybutadiene Rubbers (BR)/8.6 Polynorbornenc Rut't•:•
S 'IYpcsOf(

sprir• reduced swelling or a shrinkage. The cxtcnt of swelling or shrinkagc depends on

polymerization
tH2
2 the plasticizer level in the vulcanizatc.
The resistance to mincral oils is comparable to that of somc oil-resistant clas-:
x
tomcrs. Table 8.1 shows thc volumc changesof a selcctcd norborncnc compound
(containing 200 phr naphthenicoil plus phr carbon black) in ASTM oil Nos. I.
polynorbornene rubber
mrbornene 2 and 3 at 700C. High shrinkage usuallyoccurs in oils with low swellingeffect, such
as ASTM oil No. l. On the other hand, liquidswith high swclling power (such as
Synthesisof Polynorbornene Rubber 100% aromatic and chlorinated hydrocarbons)cause rathcr high swelling to poly-
norbornene vulcanizates. However, the volume increase is still considerably lowcr
o»ndensation.The polymerization reaction is illustrated in Fig. 8.4. This type of than that of other hydrocarbon elastomers in the same liquid.
produces very high molecular weights. The molecular weight of
mttsorexexceeds Table 8.1* Resistance of a 'IYpicaI PolynorborneneVulcanizatc (Containing 200
unsaturationof the :nonomer is retained in the polymer, polynorborn- pi)! Naphthenic Oil and 200 phr-Carbon E'.iack')to .
bcjongsto thc group of highly unsaturated hydrocarbon rubbers. Polynorborn- at 70 0c
enc rubber is not yet identifie.d standard designation.
basicpolymer is a thermoplastic powder with a o!ass transition temperature Medium Approximate Volume Change ( % )
(Tg)of about 350C.By adding a wide variety of rnineral oils or ester plasticizers,
thc can bc lowered to about —60oc and the polymer acquires rubbery proper- ASTM GilNo. I -15
t:cs. In this respect, it resetnblcs polyvinyl chloride (PVC). ASTM oil No. 2
ASTM oil No. 3
Compounding
formulations usually contain plasticizers, fillers (carbon black or Table 8.2: Resistance of a 'IYpicalPolynorbornene Vulcanizate
„uncralfillers or both), antioxidants, antiozonants, protective waxes, zinc oxide, (Containing 200 phr Naphthenic Oil and 200 phr Carbon Black) to
aids and a curing svstem.
Orgnni
Piasticizersare necessary since they yvi!!depress the Tg below room tempera-
ture and thus determine the ultimate low-temperature flexibilityof the vulcanizate. Medium Approximate Volume Change ( % )
Atomaticoils are most compatible with polynorbornene, followed by naphthenic,
paraffinicand, finally, ester plasticizers. Polynorbornene is capable of accepting Acetone — 25
highlevels of both oil and filler. in many formulations 200 phr of a naphthenic Methylethyl ketone - 30
plus 200 phr fiiier are used. Ethyl acetate - 25
Vulcanizationis achieved with sulphur and conventional accelerators. Polynor- Ethanol 10
bornenccan be blended with EPDM to improve resistance to ozone and weather. ASTM fuel A 15
ASTM fuel B + 30
ASTM fuel C + 80
VuicanizaieProperties ASTM fuel D
Potynorbornenecan be compounded to give very soft -vulcanizateshaving a hard- Carbon 'tetrachloride + ! 70
ocssas low as 20 Shore A with tensiie strengths in excess of 10 N/mm 2. Trichioroethyiene
Resistånceto ozone ånd aging is poor. However, this resistance can be im-
proved bF1dding antioxidants, antiozonants and protective waxes or by blending
Table 8.2 shows the volume changesof the same norbornene compound as
ith EPDM. The normal operating temperature range is —30to +700C.
mentioned above but in different types of liquidsat room temperature.
Resistanceto liquids depends not only on the nature of the iiquid but also on
the type ahd level of plasticizer in the vulcanizates. Generally speaking,
polynor-
horncnevulcanizates swell,'in liquids considerably less than do the
other hydrocar-
bon elastomers. This is because of plasticizer extraction, which
results in either a
 .8.7 Butyl Rubbers (11R) 107
x. 'ISpcs or Crude Rubbers

-niere are three types of curc systems:

8.6.4 Applications 1) sulphur and sulphur donor systems in conjunction with
zinc oxide;
In general, polynorborncne vulcanizates can be advantageously used as a substitutc 2) p-quinone dioxime activated by lead oxide (PbQ2); and
halogen-containingrubbers
cellular elastomers in many applications. ney can be the first choicc for sealing 3) phenolic resins activated by tin chloride (SnC12) or
low between componentswith surface irregularity. Othqr applications such as CR.
since the peroxides
tncludc.printing roll coverings, vibration•and shock absorbers and electrical in- Butyl rubbers cannot be cross-linked with organic peroxides
sulators. degrade the polymer.
The p-guinone
Sulphur cures are widely used in general-purpose compounds.
insulation formulations to provide a max-
dioxime cure is largely used in electrical
8.7 Butyl Rubbers (IIR) mum of ozone and aging resistance to the vulcanizates. The resin cure provides
is utilized in formulations of
outstanding resistance to both wet and dry heat and
Trade Names
tire-curing bladders.
w...r
Exxon Butyl (Exxon Chemical Co.) Becauseof their lowunsaturation;butyl-rubbcrsaw
NBR. Even very small amounts
unsaturated rubbers such as NR, IR, SBR, BR and
the curatives, resulting in undercured
8.7.!' Chemistry of these rubbers will react preferentially with
been used for mixing or process-
Isobutene-isoprenerubbers (IIR), or butyl rubbers, are copolymers containing butyl rubber. Consequently, equipment that has
highly unsaturated rubbers must be thoroughly cleaned before it is used for
mostlyisobutene (isobutylene) units with just a small percentage of isoprene units contamination in highly unsatu-
(Fig.8.5). Unlike NR, IR, SBR, BR and NBR, butyl rubbers are highlysaturated butyl rubbers. Conversely, small amounts of IIR the vulcanizates will
because delamination of
hydrocarbonscontaining,onlY a small amount of double bonds. This small extent of rated rubbers must also be avoided
unsaturationis introduced to furnish the necessary sites for vulcanization. occur when the contaminant is present in the matrix.

CHI
polymerization
8,7.3 Ve!cgnizate Properties
c=CHz + distincgive properties of IIR vulcanizates are:
—very low gas and moisture permeability;
isobutene isoprene —high damping (ability to absorb mechanicalenergy);
(isobutylene) —excellent electrical insulation properties;
with decrease in unsat-
—good ozone and weathering resistance, which increases
uration of the polymer chain;
—good resistance to dry heat and steam; and
products such as
—good resistance to a great number of organic and inorganic greases. glycols,
phosphate ester hydraulic fluids (section 6.11), silicone oils and
isobutene-isoprenerubber (IIR) esters (e.g., ethyl
alcohols, ketones (e.g., acetone, MEK), low-molecular-weight
8.5: Synthesis of IIR acetate), aqueous solutions,of inorganic acids, alkalis and salts.
IIR vulcanizates to:
The various grades of IIR differ in their levels of unsaturation (determined by —mineral-oil-based fluids and greases;
the ratio of isoprene to isobutene). The grades with highest unsaturation have the — synthetic hydrocarbon lubricants (c.g., pc
curc ratc and somewhat lower ozone resistance than the more saturated —organic-ester-based lubricants; and
grades. For maximum ozone resistance, the butyl grades with low levels of un- — hydrocarbon fuels.
moderate; these sub-
saturation.should be used. Tneir resistance to animal and vegetable oils and fats is
stances can be tolerated in many static applications.
poorer than those of
8.7.2 Compounding The mechanical properties of iiR vulcanizates are gcnerally low resilience
However,
NR and SBR. The resilience is low at room temperature,
•IIR compoundsusually contain carbon black or mineral fillers or both, plasticizers can be of use in applications requiring high damping
characteristics. compres-
(mineraloils or esters). processingaids (e.g.. zinc stearate. waxes, coumarone- sion set is usually high but. when suitably compounded,
lowvalues can be achieved.
Indene resins), antioxida•nts. antiozonants and vulcanizing inoredients.
 and 109
8.8 Halobutyl
Crude Rubbcrs
S Typesof
bromine and
about —40to +1200C. Commercial bromobutyls contain typically 1.9—2.1wt%
operational temperature rangc of IIR elastomers is chlorobutyls 1.1—1.3 wt % chlorine.
exhibit elastic proper- the halogen
thc vulcanizatcsare not brittle, but they do not The halogenatedIIRs do not belong to polar rubbers because properties
At- and desirable
by chain scission, becoming soft and tacky.
• contents are very low. T%cyrctain most of the distinctive
Butyl elastomers degrade of unmodified IIR.

S.7.4 Applications 8.8.2 Compounding

elastomcrs is in gas retention applications such as tire inner TIR can be used
main use for
membranes. Other applications include tire nc same compoundingingredients and cure systems of regular
tubes.ball bladders, vacuum seals and systems can be
gaskets, wire and cable insulations, with the halogenated grades. In addition, several other vulcanizing
cunng bladders, steam hoses, shock absorbers, halogen atoms.
closures. used because of the presenceof both double bonds and reactive •outyis(i.e.,
The chlorobutyls are appreciably more cure-reactive than unmodified reactive
they are less
they cure much faster and reach a higher state.of cure), but
g.7.5 Cross-linkedButyl Rubbers than bromobutyls.
to activate the
The phenolic resin cure does not require the addition of halides
cross-linkedbutyl rubbers are obtained by polymerizing isobutene and isoprene resin, because halogen is already present in the rubber.
divinylbenzenc to form ,crpolymers. The extent of cross-linking vulcanized with
of divinylbenzcne. The terpolymer is used mostly in an Unlike regular butyls and chlorobutyls, bromobutyls can be
controlledby the Icvel zinc oxide or any
cured with any of the systems used to peroxides. Furthermore, they are capable of vulcanizingwithout importance for
cncurcdstate as a sealant, but it can also by other zinc salt using diamines as curatives. 'This is 'of particular
cure unmodified butyl rubbers. special applications requiring zinc-frec compounds (e.g., in
some special phar-
maceutical closures).
with highly
8.8 Halobutyl Rubbers (BIIR and CI!R) üniike regular IIR, the halobutyls can be blended and covulcanized there is
unsaturated rubbers such as NR, IR, SBR, BR and NBR. Consequently, and
with the mmng
8.8.i Chemistry no need for the stringent contamination precautions associated
processing of regular butyl rubbers (section 8.7.2).
Halobutyirubbers include brombutyl rubbers (BIIR) and' chlorobutyl rubbers
(CIIR) and are produced by reacting elemental bromine or chlorine, respectively,
viti'. IiR dissolved in a light aliphatic hydrocarbon such as hexanc. 8.83 Properties
halogenation is carried out under carefully controlled conditions to ensure characteristicpropertiesof regular ilR
BilR and CLR
that the original double bonds are largely retained. After halogenation, the unsat- such as low gas permeability, high hysteresis and high resistance
to
urationremains but the double bonds move from the backbone to adj2centpend-
ozone, weather and chemicals.
antpositions(fig. 8.6). Halobuty! vulcanizates usually contain small quantities of vulcanization
by-
products, mainly water-soluble salts. Consequvxw„j, are less moisture resistant
vulcanizates and are less suitable for use in electrical insulation.
C CHI— CH2
+

butyl rubber (ilR) 8.8.4 Appiications

and
The major applications of halobutyl rubbers include chemical-resistant O-rings
gaskets, vacuum seals—andmembranes, steam hoses, pharmaceutical closures,
cpq white tire sidewalls and tire inner tubeS.

hotobutylrubber or CNR)

Fig. 8.6: Synthesis of Haiobutyl Rubbers

F,

no 8 Typesof Crude Rubbers 8.9 Ethylene-Propylene Rubbers (EPM and EPDM) 11i

8.9 Ethylene-Propylene Rubbers (EPM and EPDM) ides, •radiation or sulphur, EPDM grades containirfg ENB as a component
(fig. 8.9) have greater reactivity toward sulphur vulcanization,and the reactivity
Tride Names increases with increasing the ENB level.
sordel (Du
Vtstalon(Exxon Chemicals Co.)
(DSM) (CH—CHJ
Buna AP (Chemische Werke Hüls AG)
ethylene propylene HCsx

8.9.1 Chemistry
rubbers are oftwo types:
!) F,PM: fully saturated copolymers of ethylene and 8.7); and dieae
vulcanization site

tH3

CH2 +
polymerization fig. 8.9: Structural Formula of an EPDM withENB
CH.

ethylene propylene ethylene-propylene rubber (EPH)

EPM and EPDM rubbers have varying ethylene/propyleneratios. Tie ethylene
content in the polymer can vary from aboui 75 tc 45%. Rubber grades of very high
fig. 8.7: •Synthesis of EPM molecular weight are extended with large amounts of mineral oil, typically 25 to 50
phr.
2) EPDM: and a small percentage of a noncon-
jvgated diene, which provides unsaturation in side chains pendent from the fully 8.942 Compounding
Såtüfated backbone. zraä and EFMM compouncis usuaiiy contain carbon biack or iight fiiiers or both,
rhere are three basic dienes (Fig. 8.8) used as the third monomer:
änc oxide, antioxidants, processing aids, petroleum-based plasticizersand curing
ingredients.
) dicyclopentadiene(DCPD); an Rubber grades with a higher ethylene content can be more easily processed and
3) 5-ethylidene norbornene (ENB). more highly loaded with fillers and oils, but the vulcanizates exhibit inferior
low-ternnerntltre and high compression set.
As has been mentioned, EPM rubbers can be cured only with peroxidesand
EPDMs with peroxides or conventionalsulphurcure systems. Peroxidesare used
for applications requiring good high-temperaturcperformance and low compres-
)ggdiene HO) 'i sion set.
it should be noted that many fiilers, antioxidants,plasticizersand processing
aids inhibit vulcanization by peroxides. Consequently, the compoundingingre-
\N CH?
Chi
i CH2i' EPDM grades containing a high level of ENB have the greatest tendency to be
blended with highly unsaturated rubbers such as NR, IR, SBR, BR and NBR.
CH

dicyttopentadiene (OCPD) 5-ethylidene norbornetie (ENB) 8.9.3 Vulcanizate Properties

F;g. 8.8: Basic Dienes Used for the Synthesis 0( EPDM The properties of vulcanizates producedtrom EPM and EPDM rubbersare bas-
ically the same. Both have fair tensile strength over a wide hardnessrange and
The EPM rubbers, being completely saturåted, require organic peroxides or excellent resistance toc ne, weathering and chemical attack. Furthermore, they
.acl
radiationfor vulcanization.The EPDM terpolymers can be vulcanizedwith perox- exhibit very good electri sulation properties.
 113
112 S Tyr-•soi Crude Rubbers 8.10 'ChemicallyCross-linkcdPolycthylcnc/S.Ii AcrvlonitriIe-ButadicneRubbcrs

Other properties. particularly compressionset, high-temperature performance Chemical cross-linking provides flow resistance above the melting point of the
andlow-temperature flexibility, are highly dependent on the formulation and poly- polymer. This allows applications of cross-linked PE at temperatures above 1250C.
mer composition:Peroxide-cured compounds exhibit excellent heat aging proper-
tics and resistance to compression set up to 1500C.As the ethylene content of the
NIymer increases, compression set resistance and low-temperature flexibility v,ill 8.10.2
deteriorate. Chemically cross-linked PE is used extensively without any fillers being com-
sulphür-curcd EPDM compounds have high compression set and are less resist- pounded, only with antioxidants and cross-linking agents. However, incorporation
ant high temperaturesz Peroxide-cured EPM and EPDM grades with low ethyl- of fillers can impart advantageous properties such as resistance to deformation,
content have a seryice temperature range from —40to +1500C•and'short flame and corona.
exposuresto even higher temperatures. Both peroxide and radiation cures require proper selection of the compounding
In contrast to IIR•, the double bonds in EPDM are located in the side groups. •ingredients,such as co-agents, antioxidants and fillers.
ranseauently, the EPDM vulcanizates (when peroxide cured) retain the
propertiesthat the EFM eiastomers possess.
EPMandEPDM to: 8.10.3 Properties
- nonpetroleum-based automotive brake fluids;
aryl and alkyl-aryi phosphate esters (section 6.11); Generally speaking, the environmcntal aging, electrical properties and fluid resist-
hot water and steam. up -to 2000C with peroxide-curedvulcanizates (in the ance are similar to those of EPM vulcanizates (section 8.9-3).
absenceof air);
- aqueoussolutions of.inörganic acids, alkalis and salts;
- polyalkylene-glycol-basedfluids; 8.10.4 Applicatiors
alcohols,glycols, ketones (e.g., acetone, MEK) and low-molecular-weight esters Chemicallycross-linked PE compounds are most extensively used in the wire and
(e.g., echyl acetate); and cable industry.
- siliconc oils and greases.
%eir resistanceto animal and vegetableoils and fats is moderate; these sub-
stancescar. be tolerated tn many static applications. 1-4.11 Acrylonitrile-Butadiene Rubbers (NBR)
EPM and EPDM vulcanizates are
- mineral-oil-basedfluids and greases; Former Designation
- •sinthetichydrocarboh lubricånts (e.g., polyalphaolefins);
organic-ester-based lubricants; and Buna N
hydrocarbon fuels.
Trade Names
Sa9.4Applications Chemigum (Goodyear Tire and Rubber Co.)
E:hylene-propylenerubbers are used for a w;de range of products, includingO- Perbunan (Bayer AG)
r:ngs,gaskets, window and door seals, wire and cable insulations, roller covers,
conveyorbelts, hoses and water-proofing sheets.
Chemistry

8.10 Chemically Cross-linked Polyethylene (PE) Acrylonitrile-butadiene rubbers (NBR), or, simply, nitrile rubbers, are copolymers
of butadiene and acrylonitrile (Fig. 8.10). They are available in five glades based on
H.JO.IChemistry the acrylonitrile (ACN) content:
1) very low nitriles: typically 18—20%ACN•,
Poiyethyiene(PE) is a thermoplastic homopoiymer(plastomer) produced by poly- 2) low nitriles: typically 28—29%ACN;
mcrizingethylene gas (see Fig.1.1). Like rubbers, PE can be converted to an 3) medium nitriles: typically 33—34%ACN;
elastomcricmaterial by cross-linking the polymer chain using a cros -linking agent, 4) high nitriles: typically 3S—39%ACN;
•tsuallyorganic pcroxidcs or clectron beams (radiation cure). 5) very high nitriles: typicaily 45—48%ACN.
 8 Typesof Crude Rubbers 8.11 Acrylonitrile-ButadicneRubber,

performance and low compression set. NBR has poor compatibility With natural
CHz= CH—CHFtH2
polymerization rubber, but it can be blended with SBR in all proportions. This reduces the overall
Oil resistanceof the vulcanizate, but it is sometimesused also as a technique to
butadiene acrylopitrile counteract shrinkage caused by oils with low s•.veflingpower such as polyalphaole-
fins.

-(CHz—tH-) m
x 8.11.3 VulcanizateProperties
acrylonitrile : butadiene-rubber As has been mentioned, many of the vulcanizateproperties will vary depending
upon the ACN content. However, it can be said tbat NBR vulcanizateshave, in
fig. 8.10: Synthesis of NBR general/ good physical properties overt wide hardnessrange. Tney are (Eke other
highly unsaturated elastomers) not inherently ozone resistant. However, this prop-
Manyof the vulcanizate properties are directly related to the proportion of erty can be improved through compounding_orthrough the use of NBPJPVC
.lcrylonitrilein the rubber. As the ACN content is increased, the following changes blends.
Inthe vulcanizate properties occur: ne *lectricai insuiation properties are poor although adequate for sheathing
resistanceto petroleum-based fluids and hydrocarbon fuels increases; when oil resistance is required. Instead, conductivecompounds can be obtained by
low-temperature flexibility decreases; using high nitriles with suitable compounding ingredients (section 4.17).
reboundresiliencedecreases; ' Gas permeaöiiity is gcnera%yioy! Vulcanizatesof high nitriles exhibit greater
- compression•set
deteriorates; resistance to permeation approaching that of IIR elastomers. The low-temperature
gaspermeability decreases; z. flexibilityof NBR vulcanizates can be improved by adding ester-based plasticizers
heat resistance improves; at some sacrifice in mechanical properties and heat resistance.
ozonc resls,aaavvimproves; Suitably formulated NBR compounds have low compression set, and continu-
abrasion resistance improves; ous ooerational temneratnre canoe from —40 to +100 0C and for intermittent
tensiie stren'gt:•,increases; periods (in the absence of air) up to 1200C.
hardness increases; and NBR vulcanizatesare resiStäntto a widerange of petroleum-based greases and
density increases. fluids, hydrocarbon fuels, vegetable and animal oils, siliceqg_greases and oils,
In general, the high and very high nitriles are used in applicationsrequiting organic-ester-based fluids, polyalkylene glycols, water and aqueous solutions of
resistanceto hydrocarbons of high aromatic contents (e.g., aromatic oils, noioxidizing chemicals. i-iowever,they are not resistant to phcsphate ester hy-
caselines). araunc fluids, nonpetroleum-hased automotive brake fluids, aromatic hydrocar-
The medium grades are used in cases where the Oilis of lower aromatic content bons (e.g. benzene, to:uene, xylene)b halogenated hydrocarbons (e.g., trichlo-
where higher•swellingof .the elastomer is toreraöle. 'Ihe low and very low nitriles roethylene, carbon tetrachloride), ketones (e.g., acetone, MEK), low-molecular-
used with liquids of low swelling effect [e.g., paraffinic oils and polyalphaole- weight esters (e.g., ethyl acetate), strong acids and oxidizing chemicals.
(section 6.8.I)] or in' cases where low-temperature flexibilityis Of greater
'trporlance than is oil resistance.
8.11.4 Applications
S.ii.2 Compounding NBR elastomers are the most widely used materials for oil- and fuel$esistant
with SBR, nitrile rubbers require reinforcingfillers to obtain high strength, components such as seals, gaskets, diaphragms, hoses and cable jacketing.
becausethe unfilled vulcanizates do not crystallize on stretching.
fte polymer selection is an important factor in obtaining the best balance of oil
and lowtemperature flexibility. 8.11.S Carboxylated Nitrile Rubbers (XNBR)
1 Basically,nitrile rubber compoundseontain nearly the same compoundingin- Carboxylated nitrile rubbers (XNBR) are terpolymers of butadiene, acrylonitrile
credientsused in NR and SBR. Ester-based plasticizers are generally used in NBR and an acidic monomer with a carboxylic group such as methacrylic or acrylic acid.
•o:npoundsto improve low-temperature properties. Sulphur donor and peroxide- The acrylonitrile and acidic monomers are distributed randomly through the poly-
systems are normally used for applications requiring good high-temperature mer chain.
 8.12 Acrylonitrilc-ButadicncRubbcrs(HNBR) 117
S Typcsof Crude Rubbers

carboxylatcdnitriles availableif grades that differ in ACN and acid con-

tcnt.The latter varies between about 2 and •10%. carboxylic groups provide
Eidnal cure sites for zinc oxide or zinc peroxide. (unscturctedi
XNBRvulcanizates retain the •distinctive properties of regulår NBR elasto-
but they show in addition Inuch higher modulus, tensile strength and abra- cctatrst
and resistancel Therefore, they arc used in applications that require oil
resistance,toughnessand high abrasion resistance.

8.11.6 NBRJPVCB1ends
and 'high nitriles give a homogene polymer phase with PVC. Söme Of
blendsare commercially avallaoie. Tney usuaiiy congain 30% PVC.
NBRJPVCvulcanizates have improved resistance to ozone; fire and swelling in
mineraloils and hydrocarbon solvents. However, their use is restricted because of
deficienciesin low-temperature flexibility and compression -set resistance.' Their
mainareas of•application include hose covers, hose tubes and wire and cable
covers.
must aiso be pointed out that there are blends in which PVC predominates.
In suchb!cnds, the rubber acts as a polymeric plasticizer for the PVC, which does
migrateand which improves properties such as cold flow and low-temperature
',lcxibility.
8.12 Hydrogenated Acryionitriie-Butadiene Rubbers (HNBR)
FormerDesignation
HSNlHighly Saturated Nitriles)
highly saturated nitrite rubber tHSH or HHBR)
Depending on the degree of hydrogenation,there are two types of commer-
cially available products. The first (almost saturated) contains just 1% oriess of the
original double bonds and can be cross-linked only v,ith peroxides. The other type
retains a larger percentage of•theoriginal double bonds (about 5—10%)and can be
vulcanizedwith either peroxide or sulphur. However, peroxide cure is generally
recommended for better compression set and heat resistance. Best results are
obtained with the almost completely hyrogenated polymers. They combine the oil
resistanceof NBR •withnearly the same amount of heat and ozone resistance of
EPDM. As would be expected, increasingthe nitrile content in HNBR results in
reduced sweüing in mineral oils, but with a surprisingly small amount of loss in low-
temperature flexibility,compared with the regular NBR. This suggeststhat HNBR
grades derived from a high acrylonitrile NBR should be used for the best balance oi
fluid resistance and low-temperature fiexibility.
ENBR is considerablymore expensivethan regular NBR because a low-cost,
specific hydrogenation catalyst has not yet been found.

EradeNaraes
8.12-2 Compounding
Ihccban (Bayer AG)
(tNipponZeon Co.)
In general, the compoundingprinciplesapplied to NBR are applicableto HNBR.
As has been mentioned, peroxides are used for the highlysaturated grades and
sulphur cure systems or peroxides are used for the less saturated t) pese
S. 12.1 Chemistry A postcure in an oven with circulatinghot air (typicallythree hours at 1600C)
improvesthe physical properties. particularlycompressionset (section2.10).
{ydrcgenated
acrylonitrile-butadiene
rubbers(HNBR) arc currentlyproducedby
selectiveand controlled hydrOgenationof NBR (section 8.11). The degree of hy-
drogenationcan be varied by' changing catalyst levels and reaction conditions. The 8.113 VulcanizateProperties
hydrogenatedpröduct consists 'essentiallyof polymethylene chains containing HNBR vulcanizates have very good mechanicalproperties and show good resist-
amounts.bftasmuration (double bonds) and carrying nitrile (—C=N) side ance to:
groups (Fig. 8.11). The highly saturated polymethylene
chains provide excellent
heat and ozone.resistancewhereas the nitrile groups give oil —ozone and weather;
Increasing and fuel resistance. —aging in hot air and hot industrial lubricants (including those containing sul-
th? degree of hydrogqnation results in improved heat
and ozone resist- phur);
hot water and steam up to 150cC;
 S of Crude Rubtxsn
t
- amine-based cotT0Sion inhibitors and sour gas; and
high-enérgy radiation:
•n-teswelling behavior of•HNBR vulcanizates in mineral oils and
dependson the nitrile content. It is importantto note that hydrogenationof
SBR results in an increase Of the volume changes of the vulcanizates in oils and
fuels.In other words, HNBR vulcanizates swell more than the vulcanizates of the
NBR. A vulcanizate of a hydrogenated NBR with 38% ÄCN, for example,
have nearly the same swelling behavior as regular NBR containing 34% ACN.
operational temperature range of peroxide-cured HNBR is —25to +150 0C
and for short periods up to +1700C.
8.12.4
HNBR elastomers fill a gap between NBR and FPM in many areas of application.
In general, •they arc rcplacing NBR elastomers in cases where resistance to exces-
siveheat or especially aggressiveenvironmentsis critical. In contrast to conven-
tional FPM compounds, HNBR, elastomers can withstand basic additives such as
-—;ne-basedcorrosion inhibitors. For this reason, HNBR components are finding
*ide applications, particularly in oil-field operations, where extreme hard condi-
tionsexist(section 6.29). They•seem to maintain their performanceunder these
conditions, whereas NBR and most conventional FPM elastomers show a degrada-
tion.
8.13 Chloroprene Rubbers (CR)
Trade Names
Neoprene.(Du Pont).
Baypren (Bayer AG)
8.13.1 Chemistry
C hloroprene. rubbers (CR) are essentially homopolymers of chloroprene•
(chlorobutadiene). Thé polymer chains have an almost entirely trans-I ,4 configura-
lion (Fig.8.12). Becayge of this high degreed stereoreguIaritHhey are able to
crystallize On stretching (section 1.7). Consequently, the gum vulcanizates have
high tensile strengih. in this respect'they resemble NR gum vulcanizates (section
The chlorine atoms in the polymer chains reduce the reactivityof the double
bonds toward,many •oxidizingagents, particularly oxygen and ozone (section
3.5.I). They also impart oil and flame resistance to the vulcanizates.
8.13 Chloroprene ($.22) 119
pc!ftneritction
chtoroprere pct'thtorovæne
— 82C
trans-IL polychtorcprpneICR),
fig. 8.12: Synthesis of CR
8.13.2 Compounding
Typical CR comncunds usually contain carbon black or mineralfillers or both,
processing aids (e.g., petroleirn oils, stearic acid, waxes and low-molecular-weignt
ester-based plasticizers, antioxidants, antiozonants and a vulcaniz-
ing agent.
In contrast to other highly unsaturated rubbers (e.g. NRt IR, SBR and NBR),
sulphur IS not an effective vulcanizingagent for CR. Instead, metal oxides in
combination with an organic accelerator are used. Tie metal oxides serve aisr•as
acid acceptors for trace amounts of hydrogen chloride (HCI) that may be released
from the polymer during processing, curing and vulcanizate aging. Usually a com-
bination of zinc oxide (ZnO) and magnesium_oxide(MgO) is used for general-
purpose applications.For improved resistance to water, lead oxide (Pb304) is
recommended in place of the MgOÆnO combination.
8.133 VulcanizateProperties
The distinctive properties cf CR vulcanizates include:
—good resistance to ozone cracking, heat aging and chemical attack;
low flammability(they burn when exposed to open flame and seiöextinguish
within a short time after removal from the flame); this property can be enhanced
by special compounding;
good resistance to siiicate ester iubricanls, silicone oils and greases;
-e moderate to good resistance to a wide range of refrigerants, aliphatic hydrocar-
bons, mineral oils and greases (Table 8.3 shows the average volume changes of
typical CR vulcanizates in ASTM oil Nos. 1, 2 and 3 at different temperatures):
and
—tendency to crystallize at low temperatures (section 4.15). This tendency can be
reduced by the correct choice of polymer type and by compounding.However.
crystallization is useful in the case of rubber-based adhesivesbecause crystalliza-
'tion develops high bond strength to the contiguous materials (metals. rubbers.
plastics, etc.).
 8.14 Chlorinatcd Polyethylcnc Rubbers (CM)
Crudc•RubbcrS
8 Typesof

to ASTM Oils after 70h at -

—CHI
8.3: Resistanceof IYpical CR Vulcanizatcs
DiffcrcntTemperatures polyethylene

CC)
Temperature Average Volume
ficdiurn Increase (% )

70
ASTM oil No. 1 100 5-10 chlorinated polyethylenerubber (CM)

120 5-10
Fig. 8.13: Synthesis of CM
70 20-25
ASTM oil No. 2 25-30 improved, but the low-
100 chlorine content increases, the oil and flame resistance are
120
70 45-50
ASTM oil No. 3
100 50-60
60-70 8.14.2 Compounding
120
stabilizers, ester-
The formulationsof CM compounds normally include fillers, hcat
bascd plasticizcrs, proccs.singaids, antioxidants and a cure system.
propcrlyformulated;compoundspermit servicc tcmperaturc bctwccn —40and ides are usually the prcfcrrcd cross-linking agents for CM rubbers.
Co-agents arc
1000C.Low compression set can be obtained by effecting a very tight cure. often added to improve-the rate and state of cure and to permit a lower peroxide
electricalproperties are poor, although adequate for sheathing. gas compounding ingredients should be
dosage. As with peroxide cures in general, the
pcrncability is fairly IOW. unsaturated materials can seriously impair cross-
selected with care since acidic and
CR vulcanizatcsarg not resistant to hydrocarbon fuels, phosphateesters and linking efficiency.%cre are also other disadvantagcs in using peroxides,
which
aromaticand chlorinated hydrocarbons. vulcanization systems (based on
have led to the development of "peroxide-less"
or a thiadiazole derivative), provide much greater flexi-
and
3-13.4 ADDIicfltiOus bilityto the compounder, but the vulcanizates show less satisfactory heat aging
compression set resistance.
some of the most important applications of CR elastomcrs include adhesives, Like all chlorinated polymers, CM rubbers require heat stabilizers (or acid
hoses,V belts, coated fabrics, wire and cable jackets, tire sidewalls and a variety of acceptors) to prevent the release ofhydrochloric acid (HCI) at high processing or
components(e.g. seals and gaskets) in contact with refrigerants, mild chemicals service temperatures. Magnesiumoxide is most commonly used for this purpose.
and atmospheric ozone.
Where low water absorption is required. lead compounds (e.g., lead silicate) are
used. Zinc oxidc and other zinc compounds must be avoided because they catalyt-
s. 14 Chlorinetcd Polyethylene Rubbers (CM) icallydecompose the polymer.
CM rubbers can be blended with peroxide vulcaaizable rubbers such as EPDM.
Jade Names
CPE Elastomers(Dow Chemical) 8.14.3 VulcanizateProperties
kclrinai (Hoechst AG)
'The maJor characteristiß of CM vulcanizates are:
high resistance to ozone, weather and a great number of corrosive and oxidizing
8.14.1 Chemistry chemicals;
chlorinatedpolyethylene rubbers (CM) are unusual among synthetic rubbers —very good color stability;
o
In that they are produced mndification of an existing polymer and not —good resistance to dry heat (continuouslyup to about 125 c and for limited
0
by pol m monomers. periods at temperatures as high as 150 C);
As the name imp les, chlorinated polyethylene rubbers are produced by react- —fair resistance to mineral oils and aliphatic solvents (resistance to swelling in-
algpolyethylenewith chlorine (Fig. 8.13). They are supplied in a wide varietyOf creases as the chlorine content increases);
gradeswithchlorinecontents ranging from about 25 to 42% by weight. As the low flammability, which can be enhanced by adding flame yetardants•,
 S Typesof Crude Rubbers 8.15 Chlorosutphonated PolyethyleneRubbers (CSWi) 123
122

_ lowcompression set at high temperatures (when peroxide cured); and Thc high reactivityof the sulphonyl chloride offers a wide choice of curing
poor lovetemperature flexibility (addition of ester plasticizers is frequently systems. However, the vulcanization is normally acØmplished by metal oxides in
needed for low,temperature applications). the presence of conventional sulphur donors and accelerators. Magnesium oxide is
usually used unless a vulcanizate of high water resistance is required. In this case
S.i4.4 Applications lead oxide (litharge) is recommended. The cross-linking reaction probably involves
interaction between the metal oxide and sulphonyl chloride groups of the polymer
CM clastomers find wide application in wire and cable sheathing where resistance chains to form metal sulphonate bridges.
to oils, chemicals, ozone and flame is required. Other applications include hoses metal oxides have another function in the compound. act as acid
and automotive parts. acceptors; that is, they absorb acid by-products of the curing reaction and maintain
sufficient alkalinity to allow effective curing. Zinc oxide and other zinc compounds
8 IS Chlorosulphonated Polyethylene Rubbers (CSM) are excluded because they cause polymer degradation on heat aging or natural
weathering.
Trade Names CSM rubbers can also be cured with peroxides, provided that care is excercised
in the selectionof fillers and othcr ingredients.Usually a co-agentis added to
I {ypa!on(Du Pont) improve the effectiveness of the peroxidc. An acid acceptor must also be added.
Soralon (Denki Kagaku Chemical Co.) The significant advantages of peroxide cure systems are the improvements in aeat
aging and compression set resistance.
8.15.1 Chemistry
Like CM (section 8.14), the chloioSulphonated polyethylene rubbers (CSM) are 8.15.3 VulcanizateProperties
also produced by modifiCation of an existing polymer. As the name implies, CSM
distinctive properties of CSM vulcanizates include:
rubbers are produced by reacting polyethylene with a mixture of chlorine (Cl) and
excellent resistance to ozone, weather and discolorationby sunlight and ut-
sulphur dioxide (S02) gas in appropriate ratio. The resulting polymer has the traviolet light;
chemicalstructure shown in Fig. 8.14. The chlorosulphonation changes the rather excellent resistance to a great number of corrosive or oxidizing chemicals;
polyethylene into a rubber with reactive cure sites which can be processed and —good resistanceto dry heat (continuousiyup to about 125oC and for iimiteü
vulcanizedlike any other rubber. periods at temperatures as high as ISOOC);
—low flammability (the best flame resistance is obtained with the high-chlorine
— —CH2
+ soz grades);
—moderate to good resistance to mineral oils, depending on the chlorine content
polyethylene
of the base rubber (Table 8.4 shows the averag-
purpose CSM in ASIM oil Nos. I, 2 and 3 at 1200C); Jower swell
—CHI — CH2 —CH —CH2 ¯ values are obtained with CSM grades having high chlorine contents at some
sacrifice in low-temperature flexibility;
good resistance to silicone oils and greases;
chlomsulphonatedpolyethylene rubber (CSM) —good hot water resistance (when cured tyith lead oxide); and
low gas permeability.
Fig. 8.j4: Synthesis of CSWi

The chlorine content of commercially available CSM grades ranges from about Table 8.4: Resistance of Typical CSM Vulcanizates to ASTM Oils after 70h at
1200C
24 to 43% by weight. ne range of sulphur contents is about 1.0—1.5%by weight,
:he majority having a sulphur content of about 1.0%.
Medium Average Volume Increase (%)
8.15.2 Compounding ASTM oil No. 1 8-12
ASTM oil No. 2 30-45
Typical CSM compoundsusually contain carbon black or mineral fillers or both, ASTM oil No. 3 70-90
piasticizers, processingaids, antioxidants and vulcanizing ingredients.
 S Of Crude Rubbers 8.16 Polyacryjdte Rubbers (ACM) •125

The IoW-temperatureresistance is generally limited depending on the chlorine CIF CH CHI = CH

contentof the •OSMgrade used. It can be improved by adding plasticizers. In
general,•thecomprcSsion set 'resistanceis not satisfactory.

[CH2h
8.15.4 Applications
GM elåstomersare widely used in electrical applications as protectivejacketing ethyl Ott 'tote butyl åctytote
whereresistance to heat, flame, Ozone, weather, corrosive chemicals and oils are
importantproperties.
Other applications include coating, weather-resistant membranes, hoses, roll
rovers. colored extrudates and acid-resistant tank linings.

8.15.5 Alkylated Chlorosulphonated Polyethylene Rubbers (ACSM)

tHz—OC2Hs
TradeName methoxyethyl ocryk,te ethoxyethyf acrytGtß
Ascium(Dü Pont)
Fig. 8.16: Typical Basic Monomers Used for the Synthesis of ACM
Alkylåted is a chemica!lymodifiedversion of Du Pont's CSM
(Hypalon) thathas •extraalkyl groups in the polymer-chains, as shown in fig. 8.15. ne more modern types of ACM rubbers contain minor amounts (less than 5%
Accordingto Du Pont, pelts made from ACSM have better aging resistance at by weight) of curc site monomers with functional groups whose presence Increases
140oc than ihöse based omHNBR. the cure ratc and improves the vulcanizate properties. The curc site monomers can
CH2=CH

302Ci
R : dkyl group CHä

Fig. 8.15: Structufal Formula of CSM (ACSM)

2-chloroethyl vinyl chloroccetate allylgtycidyl ether
•vinyl ether

8.16 Polyacrylate Rubbers (ACM) Fig. 8.17: Typical Used for the Synthesisof ACM

TradeNames he divided into two groups: one containing 'labile-chlorine atoms and the other
chlorine-free.The names and chemicalstructures of the most widely used cure site
('vanarrvl (Enichchl Elastomeri) monomersare given in fig. 8.17. The polymer chain of an ACM rubber with a
EuropreneAR (Enichem Elastomeri) chlorine-containing site monomeris shown in fig. 8.18.

8.16.1 Chemistry
Polyacry!aterubbers (.ACM) of today are saturated copolymers of monomeric
\icrylicesters and reactive cure.site monomers. The first commercial
products were
usedpredominantlyupon ethyl acrylate or butyl acrylate
ogetherwith acryiic monomers oühe aikoxyaikyvtype such as
methoxyethyl CHI CHI
rylåte and etho*yéthyl acrylate (Fig. 8.16)
Fig. 8.18: Structurai Formåia of a Chiorine•Containing ACM
 126 S Types of Crude Rubbers
8.17 Ethylene-Acrylic Rubbers(A EM) 127
Thc•fullysaturated backbooe.providcs thegqglLcnt heat and
OZQPf
of the vulcapizatcs, and the polar side groups give the oil resistance. resistance Table 8.5: Resistance of Various ACM Vulcanizatesto ASTM Oils after 70h at
latter 1500c
dependson the naturé ot the basic monomers (Fig. 8.16). ACM grades
based on
ethyl acrylatcs have excellent resistance but poor low-temperature.
properties, Medium
those-based on butyl acrylate show improved-law=tc-mperatuce-fkxibålity— Polymer Base Average Volume
but inferior oil resistance. For this reason, some ACM grades are Increase(%)
based on com-
promise lends o t ese monomers together with alkoxyalkyl
acrylatcs to achieve ASTM oil No. 1 Ethyl acry!ate
the best balance of fluid resistance and low-temperature flexibility.
Butyl acrylate 5-10
Ac late blends
8.16.2 Compounding ASTM oil No. 2 Ethyl acrylate
2-+_.sv; Butyl acrylate 15—25
reinforcing Ac fate blends 7-72
fillers,processing a:vs anu a curc system. Antioxidants are usually not
•obecause {he •vulcanizates necessary ASTMoil No. 3 Ethyl acrylate 12-15
have excellent heat aging properties. addition of
plasticizersto improve the low-teriperature propertiesis impractical Butyl acrylate 40-55
because
volatilizeduring postcure or when the finishedparts are exposed to high they Acrylate blends 20-30
service
temperatures. If plasticizersare, required, they must have iow volatility,but'
they
usually do not improve low-temperature flexibility. 8.16.4 Applications
Acidicfillers must be avoided, as they can seriously impair the cross-linking.
Pr&essing aids are essential to Prevent or reduce mill and mold sticking. ACM elastomers are used primarily in applications requiring combined resistance
ACM rubbers cannot be cured with sulphur, becauSe the backbone.is fully to heat, oils and oil additives (e.g. , O-rings, lip seals and gaskets).
saturated. Many curing systems have been proposed over the years, such as
poly-
amines,.ammoniumbenzoate and ammoniumadipate. The most commonlyused 8.17 Ethylene-Acrylic Rubbers (AEM)
for modern sutpnur-soap .curc systemcon-
sisting of a combination of sodium stearate, potassium stearate and small amounts Trade Name
of sulphur (about 0.3 phr). In this Case, sulphur functions as an accelerator. ms
system Okers improved processibility but results in vulcanizates with relatively high Vamac(at the present time Du Pont is the sole producer of ethyicne-acrylic rubbers)
compressionset at 1500C.
ACM vulcanizates require postcure in an oven with circulating air (typically 6 h 5 8.17.1 Qeinistry
0
a: 1.7-f C) to complete the cross-linkingprocess and to develop optimum physical Vamacis a terpolymer of ethylene and methyl acrylate with a cure site monomer
properties, especially compression set. that contains a carboxylic acid group (Fig. presence of carboxylic acid
+ CH=CH2 +
8.io.3 Properties
The useful properties that ACM elastomers offer can be summarized as follows:
—excellentheat resistance (thev can be used continuously at temperatures up to
O
ISOC and can withstand limited exposure to temperatures as high as 1750C); ethylene methyl cure site
high resistance to ozone and oxygen; and ocrylate monomer
good resistance to hot industrial oils, includingthose containing gulphur,sul-
phur-bearingchemicals and other additives. The extent of swelling depends on
the aromatic content of the oil and the composition of the base
8.5 shows the average volume changes of ACM vulcanizates with different poly-
mer bases in ASTM oil Nos. 1, 2 and 3 at 1500C. otH3 OH
Resistance to water is usually poor. Other properties, such as compression set ethylene-acrylic
rubber(ÅEM
}
and low-temperature ficxibility, depend on compounding and polymer
choice. Fig. 8.19: Synthesisof AEM
 8.18 Ethylcnc-VinylAcctatc Rubbers ( EAM) 129
ofCqudc•Rubbers
12S- 8 Types
The
rubbers have yjg.yugflaiß contcnts ranging usually from 40 to 70% by weight.
the polymer'chain peqrnitscross-linkingby reaction with certain bifunc- fully saturated backbonc provides exccllcnt heal and ozone rcsistance, whereas the
reagentssuch asdianiinesv-Thc fully saturated backboneprovides excellent vinyl acetate groups provide oil resistance. As thc vinyl acetate content increases.
heatand ozone methyl acrylate groups provide oil resistance.
the oil resistance improves, but the electrical insulation propcrtics are impaired.
does not contain halogens.
fic polymer
tH=CHi
Compounding
g.17.2 0
polymerization
VatnaCis compounded in the sqrne way as ACM rubbers. most common curing
is a combinationof a uanidine and a blocked prima diamine (Diak
So. Peroxide systems may e used, particularly orca e applications.
vulcanizatcsrequire postcurc (usually 6h at 1750C) to completc the
éthytene vinyt oc;tot
u,lcmizationprocess and to' produce optimum rxopcrtics, particuiarly compres-
sion set.

8.17.3 Vulcanizate Properties

AEM vulcanizåtcs offer an interesting combination of properties:
highheat resistanceintermediate Vetwccnthat of CSM and that of VMQ clas-
tomcrs(they can be use4 continuously at æw.peratnrcs up to 1500C and for short
0
periods up 175 C);
ethylene-yinyt
acetaterubber (EÅM)
excellent ozone and'.weather rcsistance;
moderateresistance to mineral oils; Fig. 8.20: Synthesis of EAM
- good low-tcmpcratufc flexibility (down to —300C);
to hot water (in contrast to ACM); and
- hightensilestrength. 8.18.2 Compounding
EAM rubbers cannot be vulcanized with sulphur because they have a saturated
8.17.4Applications backbone. Vulcanizationis achieved either by exposure to high-energy radiation or
applicationsof ACM and AEM elastomersare similar. Vamacis specified by reacting with peroxides, usualiy in conjunction with a co-agent for increased
whenlow-temperatureile»aoincyis required. ne main applications include seals, state of cure. Carbon black is the preferred filler. Mineral fillers, plasticizers and
boots, hoses,ignition-wire jackets and cable jackets. processing aids should be selected carefully because acidic fillers and unsaturated
compounds can seriously impair the peroxide cure.
6.18 Ethylene-Viny! Acetate Rubbers (EAM) The addition of antioxidants is usually not necessary- However, they may be
added for optimum heat resistance. If a plasticizer is required, low-volatile paraf-
FormerDesignation finic oils or esters may be used

Vukanizate Properties
TradcNames main characteristicproperties of EAM vulcanizates include:
!ßvapren (Bayer AG) — high resistance to ozone and weather;
Fivax (Du Pont). good dry-heat resistance (continuously up to about 125oc and for limited periods
at temperatures as highas ISOOC);
S.18.1Chemistry — low compression set at high temperatures;
—fair oil resistance, depending on the vinyl acetate content;
ErhyJcnc-vinyl acetate rubbc.-s (EAM) are copolymers of ethylene and vinyl ace- I
—moderate electrical insulationproperties witfrlow vinyl acetate grades; and
tate with fully saturated backbones (Fig. 8.20). The
commercially available EAM — poor low-temperature flexibility.
 Applications
c 18.4
EAMelastomersfind wide application in wire and cable sheathing where resist-
.r,cc to ozone. weather, dry heat and oils are important properties.
copolymers

8.19 FluorocarbonRubbers (FPM)

Tadc Names terpotymers

Viton(Du Pont)
(3M) —CFI),— -
'Daikin Industries) •
Tccnoflon(Monteflups)
peroxide-curable tetropolymers

8-19.1Chemistry
quorocarbon rubbers are highly fluorinated hydrocarbon polymers. In general, all
highlyfluorinatedpolymers are very stable and possess exceptional resistance to 0—CF3
oxidation,weather, flame, chemical attack 2nd swelling in a wide range of liquids. peroxide-curable tetropotymers (low-temperature (IT) types)
nis stability is mainly dug to the high strength of the C-F bond as compared with
thcC-H bond. The names and chefiical structures of the monomers that are used
• CS = cure site monomer (e.g., trifluoro-monobromo-ethylene(—Ch—CF8r —l)
for the production of these rubbers are given in Fig. 8.21.

CF=CF2 Fig. 8.22: 'IYpes of FPM Polymers

CF3

Yinytidenefluoride hexafluoropropylene
FPM.rubbers are available in various grades, which differ mainly in the polymer
(HFP) composition and fluorine content. Tie different polymer types and their chemical
structures are shown in Fig. 8.22. The fluorine and hydrogen contents of the differ-
ent FPM rubbers are liSted in Table 8.6.
cc—rc
CF2Ä The terpolymer vulcanizates exhibit, in general, better fluid and chemical re-
sistance than do copolymers. The resistance to swellingimproves with increasing
the fluorine content of the polymer, but at a sacrifice in low-temperatureproper-
tetrafluoroethytene perfluoromethyl vinyl
(TFE) ether (PMVE) ties. FPM grades with perfluoromethyl vinyi ether (PMVE) instead of hexafluoro-
propylene (HFP) offer improved low-temperature performance over conventional
FF. S.21: Basic Monomers Used for the Synthesis of FPM FPM elastomers, with no associated sacrifice in the fundamental properties (sec-
tion 6.21.1). However, these low-temperature grades are much more expensive
tnan the conventional types.
Table8.6: Fluorine and Hydrogen Contents of Different FPM Rubbers

Polymer Type Monomers Used Fluorine Content Hydrogen Content 8.19.2 Compounding
(% ) (approx.) (% ) (approx.)
FPM comoounds contain rather few ingredients as compared with other rubber
i C opolymer VF-HFP 1.9
65, compounds. In addition to the curing system, a typical FPM compound usually
T&polymer VF-HFP-TFE 1.4
68 contains a filler (carbon black or mineral filler or both), a metal oxide and a small
Tetrapolymer VF-HFP-TFE-CS 70 1.1
amount of a processing aid (typicallycarnauba wax or low-molecular-weightpoly
LT tetraoolvmer VF-PMVE-TFE-CS 67 1.1
ethylene).
 8.19 Fluorocarbon Rubbers (FPM) 133
S OfCrude Rubbers

at
FPMrubbérs accept limited amounts of fillers (typically 30—50phr), The addi- tomcricpropertiesin hot air alrnost indefinitelyup to 200oc and can be used
excel-
of plasticizerssuch as mineral oils or organic esters is impractical because Of temperatures as high as 3000Cfor short-term applications. Coupled with this
tent heat aging resistance. FPM elastomcrs exhibit exccllcnt resistance to swelling
theirlimitedcompatibility with the rubber and volatilization during the postcure at
,Q If a plasticizer is required, a low-molecular-weightFPM liquid rubber in a wide variety of oils, fuels, solvents and chemicals. For example, they are
rccomrnendcd for:
maybe used.
addition Of metal oxides (or acid acceptors) is essential since they serve to petroleum oils and hydrocarbon fuels;
neutralizehydrogen fluoride generated during the •ure or when the vulcanizatcs organic-ester:based lubricants;
exposed to high service temperatures. Magnesium oxide is probably the most silicate-ester-based lubricants;
used oxide. However, It is not recommended when optimum water, Steam -o silicone fluids and greases;
or acidresistance is required. In such cases, lead oxides as litharge should be aryl phosphate ester fluids (e.g., selected Pydraul types);
-- aromatic hydrocarbons (e.g., benzene, toluene, xylCnc); and
There are three types of Cure systems: halognatcd hydrocarbons (e.g.. carbon tetrachloride).
-diantiues;-- 8.7 shows thc average volume changes of typical FPM vulcanizates in
L.) ASTM test fluids.

preferred amines are blocked diamines such as hexamethylene diaminc Tnble 8.7: Resistance of Typical FPM Vulcanizates to ASTM Test Fluids after 70 h
earbamate(Diak No. t). Immersion Test
bisphenol cure Åystecnsare supplied cither already tnixed in the base poly-
or separately as masger batches. 1lie preferred accelerator is a phosphonium Medium •tumperature CC) Average Volutnc
In addition, calcium hydroxide is added to act as a vulcanization promotor. Increase (% )
bisphenol cure systems provide vulcanizates with outstanding resistancc to
compressionset. ASTM oil No. 1 150
peroxide cure systems are applicable only to FPM grades containing cure ASTM oil No. 2 150
nurnomers.A co-agent such as triallyJisocvanurateis usually added. nese ASTM oil No. 3 150
curesyste»s provide vulcanizates with improved resistance to steam and amine- ASTM fuel A
hased lubricant additives. ASTM fuel B
vulcanizatesusuallyrequire an oven pöstcure up to 24h at temperatures in ASTM fuel C RT
the range of 230—260•C to develop optimum physical properties, particulariy com- ASTM fuel D 8—12
prcssionset. During the postcure, dissolved or trapped air as well as volatile
ulleaaization by-products, mainly water, wili be expanded and driven from the
article, In order to avoid fissufing or cracking of thick parts, postcure is Despitc this ey-ceiien:resistance to a wide variety of fluids, there arc certain
donegradually, starting at 100oc and increasing in increments of 25oc until the chemicals that severely attack FPM vuicanizates. For example, they are not recom-
(i&red oven cure temperature is reached. ms gradual postcure permits the slow mended for:
gases. —polar solvents such as ketones (e.g., acetone, MEK) and esters (e.g., ethyl
For applications where extreme temperatures will not be encountered, such as acetate);
coated fabrics or hose linings, elimination or reduction of the postcure may be —low-molecular-weight organic acids such as formic acid and acetic acid;
—hot water and steam/ unless compounded Withiead oxide;
—methanol, unless based on highly fluorinated polymers (with low hydrogen con-
S.!9.3 -tent (s.ction 6.21.3)];
Properties • —alkyl-aryl phosphate ester hydraulic fluids (Skydrol fluids)-(however, they are
Certain vulcanizate properties (e.g., resistance to compression set, methanol, resistant to aryl phosphate esters (section 6, 11)];
amine-basedadditives. hot water and steam) depend upon the base polymer com- —glycol-based-automotivc brake fluids;
position,curing system and metal oxide used. However, it can be said that FPM —anhydrous ammonia and amines (the highly fluorinated peroxide-curable FPM
vulcaåizates, in general, have outstanding resistance to heat, oxygen, ozone, grades result in vulcanizates with improved resistance to amine-based additives
aQd oxidative chemicals. They maintain, for example, their elas- such as those found in engine and gear oils (section 6.7)):
 (00
by

the,y

than (town (o
itutny effective nboot D'i0"C beon
with based upon eottveniionnl copolytnot•tg.
that involved, conventionnl lobot•ntory IOWA
tests be POO"iltdieat0iS
As has been 'inerttioned. the FPM base polymets containing I'MVI', provide
(flexibility, but theic in their vet)' site monomer

gas Of FPM is very low. Fig. 8.23: of FFKM

Il R eiastotnet•s. The highly fluorinated FPM clostontevs have the lowest permea-
tton to fuels (section 6.21.5). Owing to complex manufacturing tcchniquer., Karrcz pcrfluorociastorner parts
electiical insulation properties are not outstanding but ore adequate for ore availabic only from Du Pont, ncse include O-rings. tubing, rods, shccting ano
sheathingwhere exceptibnatty high resistance to elevated temperatures, ozone, custom-dcsigncdpart', that are offered in different hardncwes, ranging between
chemicalsand flame is rcquit•d. about 70 and 95 Shore A.
Generally speaking, thcsc products combine the resilience and scaling force of
clostomcr with •thc thcrmal stability and chemical resistance Of polytetra-
Applicntioms fluorocthylcnc (ITEE) rc%in. retain eiastic pgopcflics :ocwtcrm ;ctV•
0
elastomcrs are widely used in eritical applications requiring high resistance to ice at temperatures as high as 260 C and can be 'used at tcmpcraturcs u!" 'to 315T.'
for short-term applications. Furthermorc, they resist the majority of chcmicalg that
fuels. flame and Chemicals at elevated temperatures. main uses arc ns O-
shaft sc.'!ls, gaskets, fuel hoses, diaphragms and cable sheathing for extreme attack other elastomers, including FPM (e.g., amines, oil-field sour gas, hot
sodium hydroxide, fuming nitric acid. kctoncs, tetrahydrofuran, acrylonitrile. sty-
vonditions.
rcne, vinyl chloride and low-molecular-weightesters and ethers), However, they
are not recommended for use perfluorinatcd hydrocarbons section 6.3, 1) and
S.2()Perfluorocnrbon Rubbers (FFKM) molten alkali metals.

'rode Names Table 8.8 compares the resistance OfKalrez and FPM clastomcrs to selected
fluids.
Kalrez elastomers have poor resistance to extrusion and therefore musi be
(Daikin Industries) backed up by harder materials syhcn subjected to relatively high oressurc. fic low-
temperature flexibility is very poor.
8.20.i Kalrez Pernuoroclnstomer Parts
8.20.2 Dai-el Perfluor
Kalrezpatts are made from a perfluorocarbon rubber (FFKM) that is chemically a
of tetrafluoroethylene (TFE) and pertluoromethyl vinyl ether (PMVE) In contrast to Kalrez, Dai-el Pcrfluor is offered irr the form of uncured stocks that
a small amount of a perfluorinated cure site monomer (Fig. 8.23). result- can be manufactured and marketed directly by the producers of elastomeric parts.
an: cured polymer does not contain hydrogen atoms in the molecule. absence As compared with Kalrez,•the vulcanizates of Dai-el Perfluor have a similar
hydrogen dramatically increases the heat and chemical resistance as compared chemical resistance profile, better compression set and low-temperature flexibility
FPM elastomcrs. but at a considerable sacrifice in the heat resistance.
 (TFEt7) i 37
S. 21

i (Frg-
vet-ses FPS! be considered as an improved ethylene-propylene bond
are replaced by fluorine- Toc
in the hydrogen atoms of ethylene resistance
and heat
and the saturated polyner chain provide the excellent chemical
i •cease of the su}unizztes-
Val•æaiates
8-21.2Compounding
filter, snail
Lüe FPM, TFE? compounds contain few ingredients, namely a most com-
anoints cf a processing aid and 2 cure system- urSoa blacks are the
(typically
s moa fillets used. The addition of small amounts of a præessing aid mold
or polyethylene) to re:dzce
is effectedby oreanic peroxides in conjunctioa Fith a
>200 co-agent, usually trianyiiso.anurate (TAIC).
'Postcureis necessary to develop optimum properties, particularly compression
>200 set resistance. A typicai postcure is 16h at 200 thick pans
postcure to avoid fissuring or cracking (similar to F?M compounds)-
s
8-213 Vulaninte Properties
As comparedvith elastomers,TEE? vulæniætes have about the same
'-27-3 thermal stability but better electriæl insulation properties and a differe:atchemical
extremely eæeagve, are iz ±emiæl resi.stanceprofile. They resist a vide variety of chemicals, including:
—amines, amine inhibitors and additive packages;
— steam and hot water;
— souroiland gasCHS);
Rubbers (TTL'?)
—all typs of hydraulic fluids (including alkyl-aryl phosphate esters);
—all types ofbrake fluids (glycol base, mineral oil, silicone oil);
Neme —petoieum Oilsand greases (better than NBR, AQvf, ECO and AU, but not as
is by sold under the
3M ejmpzzy has become the west-em European and — alcohols and various industrial soivents;
Japznzsz-made
ofthe AE". —ad&, alkalis and oxidizing chemiæls•,
— ozone and weather; and
Chemise-y —high-energy radiation.
TFEIP "ruiünizates are not resrstant to:
this Afias tctranuoroethylene-propylene rubbers will be refer-
—aromatic hydrocarbons (e.g., benzene, to!uene,
TFEj?-is 7 copolymer of tetrafiuoroethvlene
— chlonnated åyärccaröon (e-g-,äichlozæthy!ene and carbon tetrachloride);
'.CF-FCF2) and propylerse with a fluorine content of only 53.5%
écrnpzred with in FPM copolymers). tetrafiuoroethy!enc and propylené —ketones (e.g., NIEK, acetone);
arranged alternately in an orderly manner, as shown in fig. 8.24. —ethers (e.g., diethyl ether);
—acetic acid and organic acetates; and
— most organic refrigerants (section 6.22).
Table 8.9 shows the resistance oɕatypical compound to selected fluids.
The compression set resistance is not as good as that of FPM elastomers, Tie
low temperature flexibility is poor. However, it has been found that IFEIP seals
frequently perform at lower temperatures than laboratory tests would indicate.
3.2-4; Structural Formula of Tctrafiuorocthyicnc.Propyiene Rubbcr (TFFJP) This is because some fluids plasticizethe elastomer 'to some extent, making it more
 •S of Rubb:rs 8.22 SZi.cooc

at temperatures whea they arc in contact with these fluids. Therefore,

recommended to erry out functional tests under the working conditions.

S.9-. äuid Resistanæ of a Typical TFE•? Vulcanizate with 70 IRED

Temperaturc Time Volume

CC) (h)

IOO 168 8
32k: fluid (glycol base) IOO 163 4 FVY,Z Sce
6.5)
EFC (secticaSS} 672 62.825: Tvr•• of Silicone Rubbers
ET-A 6S) 60 672 6
100 672 9 canization rate and comoressionset resistance.Tae phenyl groups in PMQ -and
fuel
c so 70 76 improverlow-temprature fieribfiity and resistance to
so 168 tion. The addition of trifiuoropropyi groups to the polymer chain results in a
tetrachloride SO 168 spedal type of silicone rubbers commonly knova
70 63 and FVMQ). vulcanizates oi these rc%cz exhibit eiceEzkt resistance to oiE,
fuels and Z2ny solvents vhiie retaining the basic -propertiescf silicone e'.2$-omez-
(Fluorosilicone rubbers are decribed in section 8-22.5.)
8.27.4 Applications
Silicone rubbers can be divided into three groups:
eias.tcmers are-finding wide application mainly in oil-field operations and 1) heat-vulcanizablesolid rubbers;v/
heat-vulcanizableliquid designed the
roll uvm-ing, hose liners, wire and cable insulation and jacketing. None of of molded parts; and
applications should ran for low-temperature requirements. 3) room-temperature rubbers (RTM), usually _flowabieliquidssupplied
in a "ready to use" form for such applications building sealants, encapsula-
tion,coating and flexiblemol&.
8.22 Silicone Rubbers (Q)
Trade Names
8.22 Compounding
Säastic(Dow Corning Corporation) Heat-vulcanizable solid silicone rubbers usually supplied already reinforced in
a base form requiring only addition of pigments, curing agent or other ingredients
(BayerAG) on a two-roll mili- Some of these iæ»eedients are available as pastes or master
8.22.! Chemistry batches. However, many manufacturers prefer to purchasesiliconc compounds in a
•sready to use" form rather than mixing
the;rovn formulations-
are ur,usuz! among synthetic rubbers that the; are partly inor- •stall? number. s2icozz con-
and partly organic in nature. They have a backbone that consists of alternate pounds contain reinforcing or extending fillers or both. pigments and organic
silicon and oxygen atoms (—Si—O—Si—)
in place of the more usual carbon- peroxides as curing agent. Special additives may be added Ito achieve specific
czrbon (—C—C—) linkage- silicon-oxygen linkage in silicone rubbers is similar processing or performance properties- Tmere is no necessity for antioxidants-
linkage in quartz-and glass, Very fine fumed silica is the main reinforcing filler used to develop bigh tensile
Chemicaiiy, siiicone rubbers are substituted poiysiioxanes (fig. are and tear strength. Extending fillers ineude caucÜumcarbonate,
e.eno:edgenerical!yby the letter Q. Tae the basic silicone diatomaceousearth n•tesefillers impart only fair strength,
.%öbersthat have only methyl substituents in the polysiloxane chain. By replacing but they offer other advantages.such as irqproved processing and performance
snail amountsof these methyl groups with other groups, significant variations in characteristics or cost reductions. Acetylene carbon blacks and metals. such as
graperies can be achieved. Tie presenceof vinyl groups in VMQ improves vul- silver, are used to develop electrically conductive or antistatic compounds-
 C,'
g40

COjO/
toot/ o! oij iron
both i' pigment iit%it
OVOti,
of (up typicøj, be
"t "Void Ot
Vito
"Cing
iiqnid cilicone (jBR) fire products iti
formOf two and mixed in : j rotiO Pigments O' tend fO to
additive can be added during the mixing ntoce. tire for ninnofncfur. jitter contact in the
"boot
by additioo eutc end proce.% completod o — good to up to (crjmpeøtrv$s Ott
',cconds, not no by-prod(jctg formed doting JEVM() radiation
Hovcvcr, postcuring is required where low compre«ion sct cle- very high porrneabiji'•y of OJI
temperatutcq if,ncedcd or to modify hardncc•gand modulug, poor to fair pliygicol (in to organic
room•tempcroture.vulcaoizing (RTV) liquid silicone compounds ore gop- phygicolproperties of silicone ate maintained a/ the
plied in both one and two-component gygtcms. Jn the one-component gyn!cms, the operational tcmpcr;jturc range); and
cross-finkingagent iocorpOrated io the base compound at the time or poor rmi%tanceto chcmicaJdegradation by acid4, and steam above
tvrc, vulcanization taker, place upon exposure to atmospheric tnoi%ture.Jt will
stmt first at the surface and then progrc%t,inward with thc diffusion Ofmoifiturc into
rubber compound, Jn the twou»mponent systems, tbc cross-linking ngcnt 8.22/1 Applicttijong
added to the basc compound junt bcfotc
major applications Ofsilicorie inciudc ignition
gagketsj O-ring,g,static scalo (dynamic arc recommended), oxyzcn
812,3 VuJcgnf%itc
Properties masks, food and medical grade tubing and roll
distinctive properties Of clastoqncrs Ctin bC listed as follows:
outstanding rcsistcnce to ozone and corona, outdoor wcathcr and sunlight; nuorosflicone Rubbcrg (EMO
—excellent high-temperaturestability (if dry heat is the only criterion, special
oompOundswill offer ac.ccptabJcservice life, vp to 300"C; howcvcr, in the Fluorosilicone rubbers arc fluorine-modified silicone rubbers containing trifluoro-
gr.iiCCOf air, fiificxjncclastomers can revert to a pestc, even at lower terna propyl sidc groups (tog. 8.25), ency are designated according to ISO 1629as FMC)
pcratures, probably because of hydrolysispf0tnotcd by trappcd moisture; OBI/ tind FVMQ, %roughout this book. all fluorosilicone rubbers Oncluding thc vinyl.
slig!it ventilation is required to preventtcversion; the usual Ijigh-tcmpcratutc containing types) are denoted by the letters T•MQe
limit rccommcndcd continuous scrvicc in dry air is about In gencrai, FMC)rubbers are compounded and processed i" the same fashion as
exccl!entlow-temperaturc (MO and M VO vulcanizates maintain flexi' conventional silicone rubbers. Their vulcamzates have the most useful properties
bilitv at ternncra'ture%
as IOWas PMG)and PVMO rubbér%can yield Ofregular silicone elastorncrs plus improved fluid resistance, but they have a more
compounds flexible at --90 to —10000; restricted high temperature jtmite iong•tcrm heat resistance of E•MQelasto-
—excellcnt electrical insulation properties, which are maintained fairly constant ct mcrs is not as good as that of conventional silicones or FPM vulcanizates. Consc-
the service temperature range (electrically conductivc compounds arc also avail' quently, the recommended high-temperature limit for continuous service is about
able); 175'C,
low level,of combustiblc components, (even when exposed to flame, tho FMQ elastomcrs, which are considerably more expcnsivc than regular silicones.
tomct will burn (o a nonconducting silica ash); arc used where 'best low-temperature flexibility and low swell in fluids are required.
- excellentcompression set over the entire service temperature range; With few exceptions, such as ketoncs and Some esters. the fluid resistance of FMQ
high physiological inertness (when properly postcurcd, thc vulcanizatcs arc ciastomers is generally good. Tables 8.10 and 8.11 show the fluid resistance of typical
Odorlcssj tastc[css atiO completely nontoxic); FMC) compared with that Of VNfQ and PMG)vulcanizates,
 813 æyurcthar
S, 01 Crude Rut'b:ts

S.to: Resistance 'of TypicalFMQ. VMQ and PMQ Vulcanizatesto ASTM

after at 12-S•C

E!astooer Base Average Volume increase (%) in

ASI-MO-aNo. ASTMOil No-2 ASTMOi1No.3

12 25—40
6—12 15—25

Resistance of and VMO Vulcanizates to ASTM Fuels

after ISS h at Room Temperature

F-hstoae.t Base Average Volume Increase (%) in

ASTM
FuelC FuelD fig. 8.26: Formation of Urethane Groups
< 25 < 25 < 25
>102 >lco >tco >100

o' FMQ elastomers indude O-rings, seals, diaphragms and

S-23 Polyurethane Rubbers (AUÆU)

(Bayer AG)
Fig. 8.27: Synthesis of Polyvethanes
(DO* Chania!)
(Uniroyal)
diiqxyanates have reia:iveiy small molecules. Examples oi the üiscx-y•
anates most commonly used for the production oi are s.öowain
S-Z3.i Fig.
cSeak21 polyurethanes is the group (—N=C=O) and
as zbi%tyto rect *ith hydroxyl (—OH) groups to form the urethane linkage
( shows the reaction of a monotsocyanate *Ith a mono-
hydroxy compound as ethanoi-
formation of polyurethanz requires difunctional reactants to enable the
d.large chains, as shown in Fig. 8M. The basic compnents used to
prepare polyurethanes are:
— diisoe•anate
oo o
a long-chainmacroglycol or (HO —R—OH);
z short-chain glycol (HO—R' —OH) or amine (H2N—R'—NH2) as chain extender
andcycss-iinker. fig. 8-28: Most Common Diisocyanates Used for the Synthesis of Polyurethanes

8 •Typesoi Crude Rubbers
have a large influence on the properties of the final
The
Both polyester ari.d•polyether macroglycolSare used. The polymers dc-
ö.ed,from these two classes are known as polyester urethanes (AU) ånd polyether
urethane (E U), respectively.
chain extende•rshåve relatively small molecules, about tbe same size as the
diisocyanates.One of the most frequently used chain extender for the production
butane-diol
ofpolyurethanesis 1,4
unsaturation (dbuble bonds) can be introduced into both AU and EU by using
enable•sulphur cure.
JD unsaturateddiol such as glycerol monoallyl ether to
The great variety Of'startirig materials results in a wide range of polyurethanc
gradesthat differ in processing, •curingsystems and also in properties Of the final
8.23.2 Compounding
polyurethanerubbcrs can bc classificd according to the way in which they ate
processed-in three main groups: .
1) millablerubbers that are processed and subsequently cured using the conven-
(ional mixing anu processin o methods of the rubber industry;
2) liquid reactantsthat are processed by casting and reaction injection molding
(RIM) techniques; and
3) thermdplastic elastomers that •are processcd by techniques used for thermoplas-
tics.
polyurethanemillable 'rubbers are available in various grades that differ
mainlyin the polymer composition, Thc compounding principles Of these rubbers
arc similar-to those applied to other rubbers. Reinforcing •fillers are usually re-
quired to develop optimum physical properties. Small amounts Of lubricants are
normaiiyadded to improve mold release. Ester-based piasticizers are sometimes
added to improvethe processibility and lower the hardness of the vulcanizates
scnously affecting other properties unless used in excessive amounts. Anti-
oxidants are usually not required, but the addition of a hydrolysis protective agent
'polycarbodiimide)is important for the hydrolysis-proneAU types. On the other
"and, the EU types require the addition of ari ultraviolet protective agent.
ne main vuicanizing agents used are organic peroxides and diisocyanates.
Grades that have double bonds in the rubber molecule can be
sulphurand accelerators. Each vulcanizing system offers a distinct set of vulcani-
properties. For exampic; compounds cured with peroxides have the best heat
stabliityand compressica sc, rcs;stancc. Isocyanate-cured compounds may be use-
ii:l where low heat buildup is required. Ihe sulphur-cured compounds may be used
in general-purvose applications.
Liquid reactants. processing methods such as casting and
a-actioninjection molding (RIM). Most of the components are room-temperature
liquidsor low-meltingSolids. Chain extensionand cross-linking are part of the
polymerizationprocess in the liquid systems. If high fluidity is required, solid
.pddi:ivelevels must be restricted to a few parts of inert materials.
145
8.23 Poiyuæthane Rubbcrs (AU/EU)
mixture is
The procedure of casting is relatively simple: the preheated reaction into
and then promptly poured
briefly dcgascd under reduced pressurc with stirring
strength
preheated lubricated molds. *Ihc parts are demoldcd as soon as their green
allows and subsequently postcurcd in an oven at about 110•C for 24 h.
RIM is a præess of growing importance in the polvurethanc elastomer produc-
tion. It differs from casting in that the reaction components are rapidly impingement-
mixed under pressureand instantly injected into a lubricatcd m014,all in very short
cyclcs. After dcmolding, the parts are postcurcd to develop optimum properties.
%crmoplastic polyurcthane clastomers are block copolymers that do not
require vulcanization (section 9.5). Ihcy are usually supplied in dice form or
granulate, which can bc directly processed on conventional plastics equipment.
Additives, if required, are rcstrictcd to a fC%"parts of pigments, light
stabilizers, hydrolysis protective agents, and so on.
yutcanizateProperties
In view of the several types and compositions of poiyurethane elastomers,-it is
preferable to discuss the polymer properties in very general terms.
The distinctive properties of polyurethane elastomers can be summarized as
follOws:
—outstanding tensile strength, tear and •abrasionresistance, better than all other
elastomers;
—excellent resistance to degradation by oxygen and ozone because of chemical
saturation of the polymer chains (in practice, however, polyurcthancs do dc-
tcriorate outdoors, particularly in hot and topical climates; the main reasons for
outdoor deterioration are susceptibility to hydrolytic and microbiological attack
in the case of AU elastomer types and susceptibility to attack by ultraviolet light
in the case of EU elastomer types);
—upper temperature limit for continuous use in dry conditions is about 80—1000C;
—fair to good iow-temperature flexibility, typically between —25and —35oc (the
EU elastomer types have better low temperature properties than thc AU types);
—excellent resistance to high-energy radiation (usually little deterioration is ex-
perienced after exposure to 107 rad);
—low gas permeability, comparable to that cf HR e\astomers;
— poor compression set resistance above 70 0C, unless based on peroxide-curable
millable rubbers;
—good resistance to mineral oils and greases [the EU types arc less resistant and
show higher swelling; as mentioned earlier (section 6.7), many industrial oils and
greases contain additives that can cause deterioration of AU and EU elasto-
mersj;
—fair to good •resistance-to swelling in aliphatic hydrocarbon Solvents (section
6.24); and
—good resistance to cold water (about 20—250C) (however, hydrolytic deteriora-
tion is catalyzed by any acidic or alkaline environment; concentrated solutions of
acids or alkalis will corrode polyurethanes rapidly. even at room temperature).
 S El'pc.sof Crude'Rubbers. 8.24 Epichtorohydrin Rubbers (CO, ECO and GECO) 147
146

As a general rule, the rate.of hydrolysis increases •rapidlywith.increasing tern:

polymerization
perature.,In applicåtions invölving contact with neutral waters the servicc.tcmpera-•
ture should not exceed 60?C if long-term service is required. CH2Cl
la the'Caseof AU elastomers, hydro!ysis will occur at the ester linkage and the
urethane linkage. EU elastomers are more resistant to hydrolvsis because ether lorohydrin
epich homopotymer
epichtorthydrin {CO)
linkagesare more hydrplytically stable than ester linkages and hydrolysis•canoccur
only at the urethane linkage. However, specially formulated AU elas,tomers fig. 8.29: Synthesis of CO
(stabilizedwith polycarbodiimide) will also provide adequate hydfolysis resistance.
carbodiimide group reacts with the carboxylic groups generated by the hydro-
Ivsisof ester groups that otherwise would catalyze further hydrolysis. + H2C polymerization
-=-CH2
polyurethane Clastomers; as a group, are not recommended for use in:
•bes•ed fluids:
phosphate ester hydraulic fluids: epichlorohydrin ethyleneoxide
polyalkylene-glycol-basedfluids;
aromatic hydrocarbons such as benzene, toluene and xylene;
chiorinated hydrocarbons such as trichloroethylene and carbon tetrachloride;
and tH2tt
kctones such as acetone, MEK and cyclohexanone. copolymer(EC
epichtorohydrin

fig. 8.30: Synthesis of ECO

8.23.4 Applications
polyurethane elastomers are used mainly in applications requiring high abrasion
rcsistance or,oil and solvent reSistance or both. Typical applications include hy-
séds, gaskeis, diaphragms, hoses, cabic sheathing, conveyor beits, wheeis
for roller skates and skateboards,-soling for high-quality shoes, and coated fabriß.
In ali applications„the danger of hydrolysis and the limited heat resistance should
be considered.
2
3) terpolymers of epichlorohydrin, ethylene oxide and an unsaturated monomer
(allyl giycidyl ether) (fig. 8.31) designated according to ASTM D 1418as GECO
(the unsaturated monomer provides double bonds in side chains pendant from
the fully saturated backbone to enable sulphur cure).
-5
—tH—tH2—O—CHI—thro

O —tH.=CH2
8.24 Eppch!orohydrinRubbers (CO, ECO and GECO)
Fig. 8.31: Structural Formula of GECO TerpolY1ner
TradeNames
The saturation of the backbone imparts high resistance to oxygen and ozonct
: (.NipponZeon Co.) while the oxygen and chlorine atoms provide polarity to the polymer chains and
Fpichlomer(Osaka Soga Co.) hence resistance to nonpolar or hydrocarbon fluids.

8.24.1Chemistry 8.24.2 Compounding

Epichlorohydrin-rubbers are saturated polymers of aiiphatic polyethers with
caloromethylside chains. Three types of epichlorohydrin rubbers are currently
twaiiable:
I) homopolymcrsof epichlorohydrin (Fig. 8.29) designated as CO;
2) copolymers.of epichlorohydrin and ethylene oxide (Fig. 8.30) designated as
ECO; and
Epichlorohydrin compounds usually contain carbon black or mineral fillers or
both, processing aids, ester-type plasticizers, antioxidants, acid acceptors and a
cure system. Satisfactory acid acceptors include red lead oxide, dibasic lead phos-
phite, basic lead silicate and magnesium oxide. Their presence is essential to
i stabilize the vulcanizate by reacting with the small amounts of hydrogen chloride,
which may be released when the elastomer is exposed to high temperatures.
 CO 'and ECO rubbersé being fully saturated, cannot be cured with sulphur. Table 8.12: Rcsistanceof Typical ECO 'Vulcanizatcsto ASTM Oils after 168h at
cured with diamine«nr ethylene thiourra. which react with the 1250C
groups. terpolyner (GECO) can be cured with conventional
peroxide systems or ethylene.thiourea. Mcdium AÜerage Volume Increase (% )
Blendsof CO, ECO and GECO offer vulcanizates with intermediate properties ASTM oil No. 1
that are dependent on, the amount of each polymer. The terpolymer GECO can be ASTM oil No. 2
SGthconventional rubbers such as SBR and NBR using sulphur or perox- ASTM oil No. 3 8—12
tdeas a wrnmon curing agent.
Most ECO vulcariiiates need a postcure in an oven with circulating air to
do clop optimum physical properties, particularly compression set. A period of 6 h Table 8.13: Resistance of Typical ECO Vulcanizates to Various Liquids after 168h
17SOCis typical. at Room Temperature

Medium Average Volume Increase (% )

8-24.3 Vulcanizate Properties
of the vulcanizatc properties willA'ary depending on the polymer type. ASTM fuel A
mei B 15-20
However,åtcan generally be said that the vulcanizatcs of the three epichlorohydrin 40—45
ASTM fuel C
typesare resistant to high temperatures, oils, ozone and flame. ASTM fuel D >100
vulcanizatesof. the homopolymer (CO) are outstanding in their low air
Water 5-10
v€rmeabi!ity,
being less than half,that of IIR elastomers. In addition, their flame,
and heat resistance are superior to those of the copolymer (ECO). On the
Ethanol 20-25
Methanol 20-25
other hand, thc copolymer vulcanizatcs arc much more resilient and flexible at low
Trichloroethylene
temperatures,but the air permeabilityis- higher, being comparable to that of Acetone > i(FJ
NBR elastomers.•
•e: and CA—A.' good swe%ing-iii Ethvl acetate > 100
ruccral oils and aliphatic hydrocarbons:Æheir electrical insulation properties and
radiationresistance are generally poor. The temperature range for continuous use 8.24.4 Applications
IS OCto +130 oc with CO and —400C to +120 oc with ECO elastomers.
Typical applications of epichiorohydrin eiastomers include seals, gaskets, dia-
properties of the terpolymer (GECO)-vulcanizates are comparable to those phragms, hoses, belting, wire and cable jackets, coated fabrics and printing roils. In ali
of the copolymer. However. the heat resistance-and compression set are poorer these applications the corrosion resistance of contiguous metals must 'be considered.
-•tnhur-cured. These disadvantages will be eliminated when peroxäde cure is

Epichlorohydrin elastomers, as a group, are not recommended for use in: 8.25 Propylene Oxide Rubbers (GPO)
•romaticand chlorinated hydrocarbons;
%ade Name
ketones and esters; .
Parel (Nippon Zeon Co.)
civco!-hascdbraketfluids;
phosphateester hydraulic fluids; 8.25.1 Chemistry
gasoholsand sour gasolines (section 6.21); and
• hot water and steam. Propylene oxide rubbers (GPO) are copolymers of propylene oxide and allyl gly-
Tables8.12 and 8.13 show the resistance of typical ECO compounds to different cidyl ether, which provides double bonds in side chains pendant from the fully
:lasses. saturated backbone (Fig. S.32).
widespread use of epichlorohydrin clastomers has been inhibited because The double bonds in the side chains enable vulcanization with sulphur and
otbcr drawbacks; mainly their corrosive effects on metals and their tendency to conventional accelerators, saturated backbone imparts resistance to oxygen.
(soften) after long-term exposure to high temperatures, However, these ozone and elevated temperatures.
i': mtckscan be Overcome to some extent by compounding,
 150 S, IYpcs of Crudc Rubbers 8.26 PolysulphidcRubbers(T)

Table 8. 14: Fluid Resistarweof Typical GPO Vulcanizatesafter 168h Immersion

polymerization Test
CH2
Medium Temperature
CC) Average Volume
02 Increase (% )
propylene oxi4e •
ASTM oil No. 1 100 10-15
ASTM oil No. 2 40—45
ASTM oil No. 3 100 95-105
Brake fluid (glycol base) 100 >100
ASTM fuel A Room 50-60
ASTM fuel B Room > 150
pmpytene, oxide- cooolymer ASTM fuei C Room >2Cn3
ASTM fuel D Room >250
fig. 8.32: Synthesis of GPO Water Room
Water 100 10-20
8.25.2 Compounding Ethanol Room >150
Methanol Room >lff)
A typical GPO compound usually contains carbon black, zinc oxide, an antioxid- Trichloroethylene Room
ant, a processing aid and a vulcanizing agent consisting of sulphur and conventional Acetone Room >150
accelerators. Ethyl acetate Room >200

8-25.3 Vulcanizate Properties 8.26 Polysulphide Rubbers (T)

GPO eiastomers show high resilience, excellent flex-crack resistance and excellent
low-temperatureflexibility. In several respects they are similar to NR elastomers,
hut have in addition the following advantages: FA and ST Polysulphide Rubbers
good resistance to heat agipg and ozone; arid LP Liquid PolysulphidQolymers (Marton Thiokol is the major manufacturer of
moderateresistance to mineral oils and aliphatic hydrocarbons. polysulphide rubbers worldwide. Other manufacturers include Toray Tliokol, a
The „ range is about —500Cto +120öc. Marton joint venture in Japan. It is also lieved that both the former Soviet Union
However, GPO elastomers are not, recommendea for use in aromatic and ard China produce polysulphide rub )
:hiorinated hydrocarbons, alcohols, ketones and esters. Table 8.14 shows the fluid
resistance of typical GPO Vulcanizates. 8.26.I Chemistry
Polysu!phide rubbers (T) are produced by reacting a suitable z.liphaticdichloride
K.25.4Applications with aqueous solution of sodium polysulphide, as shown in fig. 8.33. They are
3C; ciastomcrs toe expected to perform similarly to NR vulcanizates in dy- available in two forms: solids and liquids.
narnicapplications. They may be us'ed wherc hiph temperature and weather resist-
ancearc required in addidion to good dynamic properties. + cc—R
ctiphalic dichloride sodium polysulphide

I-R-s -R-ln
polysvlphide rubber sodium chloride 2-1

Fig. 8.33: General Method for Synthesis of Polysulphide Rubbers

 8.26 Polysulphidc Rubbcrs (T) 153
19 8 Typesof Crude Rubbgrs

solid rubbers can be processed on conventional rubbeö equipment and

subsequentlycured at high temperatures. The liquid polymers are obtained by
•curedin
controlledchain-scission of high-molecular-weight polymers and can be ethylene dichloride sodium tetrasulphide
temperature to solid polymers without shrinkage. They are discussed
placeat room
separately below because théyaredifferent materials from the
processing point of
view.
-CH2—CH2-S-S-tHz-CHz—
Rubbers
826.2 Solid Polysulphide s s
The SQIidrubbers to.be cpnsidered arc the polysulphide typcs: A, FA•and ST of
Mar-tonftiokol. The raw materials for production of these rubbers, the total Thiokol A
...-3„,.- t. e -ermina!'groups of the polymer chains and the specific gravity
Oiven in Table 8.15. fig. 8.34: Synthesisof Thiokoi A
oi the
Production qype FA has eliminated many of the disadvantages of type A. Its vulcanizates
Tab!e8.15: Pölysuiphide Rubbers and Raw Materials for
have jess odor, better physicai properties and a wider service temperature range.
Polysul-• Base Monomer Sulphur Sulphur Termi- Specific However, the solvent resistance is not as good as that of type A vulcanizates.The
phide Rank* Content nalss Gravity compression set is also poor.
Type ST polysulphiderubber was developed later. The chlorides used for its synth-
84 -OH 1.60 csis are dichloroethyl format and about 2% 1,2,3 trichloropropane (CH2Cl—
Eth lene dichloride CHCl—CH2Cl).The latter is included to introduce some branches in the polymer
Dichloroethyl formal 2 -OH 1.34 chains.
After polymerization, the water dispersion of the obtained high-molecular-
I Ethylbné dichloride weight polymer is given an additional treatment prior to coagulation and drying.
ST Dichiorocthyl iormai 37 This process is carried out to cleave some of the disulphide iinks in the polymer and
thus lower its molecular weight. The terminals of the polymer chains and thc
2%' I ,2,3 trichloropiopanc branches are mcrcaptan or thiol (—SH)groups, being generated in the "splitting
(to provide branching and operation."
cross-linkihg) 'Ihe vulcanizationof polysulphide rubbers proceeds terminal groups.
With type FA, the process is a chain extension rather than cross-linking.fte
Sulphur rank is, thc amount of suiphur in the Specific sodium sulphide used rubber, even when vulcanized, has no compression sct because it is a linear poly-
(N2Sx).It represents an average va;ue. mer without cross-linking.
In the case of type ST (being a branched polymer), chain extension could
filiokoi wqs.t.fiefirst commercial polysulphidc rubber. It was made from proceed in three directions to give few chemical cross-links. After prolonged press
cthv\enedichioride •andsodium tetrasuiphide, as shown in rgg. 8.34. Aner vulca%- cure foiiowed by oven postcuring, the eiastomer exhibits fair compression sci up {o
ization,it showed the .highest solvent resistance, which is due to its high sulphur 700C. Other advantages include the absence of much odor and the excellent Iow-
contentj at-rout c disadvahtaae of this tvne was thc difficult orocessi- w;th However. these, improved
bility.It had an unpleasant odor and gave off irritating fumes during processing. Jn properties are obtained at some sacrifice in the solvent resistance. because of its
addition,thecompression set, heat resistance and low-temperature flexibilityof its low sulphur content of 37%.
vulcanizates were very poor. FA polysulphide rubber is normally cured with zinc oxide. The actual mecha-
Subsequently,the improved type, FA, was developed to replace type A. It is a nism is not clear. Presumably. zinc oxide reacts with the hydroxyl terminal groups
iinear poiysuiphide Polymer, synthesized by rcactiag mixture of ethylene' dichlor- in the following manner:
ide•and dichloéoethyl formal (Cl-CH2-CH2-O-CH2-O-CH2-CH2-C1) with
R-OH + zno + HO-R R-O-R +
sodium polysulphide. The terminals of the po!ymcr chains are presumably hy-
droxyl groups (—:OH) formed by hydrolysis of the organic chlorides during the Since type FA has a very high viscosityahe rubber must be plasticized chemi-
polymerization process: cauy by adding a peptizer (section 2.6) prior to further compounding. After plas-
 8.26 Polysulphide Rubbcrs (T) 155
•
8 I'pes of Crtrde•.Ru11bers

tkizing. reinforcement fillers, normally various grades of carbon black, are added. 8.26.4 Vulcanizate Properties
stearic acid is usually included as a mill and mold release agent. 'The properties of polysulphide elastomers are determined by the type of chain
i ST polysulphide rubber is vulcanized via oxidation of the mercaptan end groups structure (linear or branched) and the sulphur content of the base rubber.'Äs the
The
to sulphidc bondsu The most frequently used oxidizing agent is iinc peroxide. sulphur content is increased, the solvent resistance is improved) High sulphur
sulcanization mechanism may be illustrated as follows: content also reduces the permeability to vapors and gases. However, the basic
R—SH+ znP2+ HS-R-* R-S-S-R + znQ H20 characteristics of polysulphide elastomers, as a group, can be summarized as follows:
—(excellcnt resistance to mineral oils and they tend to shrink
pcptization is not necessary because, as has been mentioned, the molecular 0
excessively at temperatures above 70 0 as shoWn in Table 8.16;
g eight (i.e., viscosisty) of the S.Ttype can be adjusted to the desired range during
manufacture. As with type FA, reinforcement is obtained by incorporating carbon Table 8.16: Resistance of Typical FA and ST Polysulphide Vulcanizatesto ASTYf
black. Stearic acid is also included as a mill and mold release agent. Oils at 70 and 1000C after 168h
BOtn anu o a
primarilyNBR and CR, to overcome some of drawbacks in processing and Medium Temperature AverageVolumeChange (%)
physicalproperties. At the same time, advantage is taken of polysulphide'shigh CC) FA VulcanizatesI ST Vulcanizates
resistance to solvents, ozone and weather. —2
ASTM oil No. 1 70
100
8.26.3 Liquid Polysulphide Polymers ASTM oil No. 2 70 —1
—10 —3
Liquid poiysuiphide (LP). •polymers are available in various viscosities. The 100
+3
chloridesused for their synthesis are dichloroethyl formalandsmall amounts of ASTM oil No. 3 70
100 +4
12,3 trichloropropane to introduce some branching. They are manufactured using
a procedure similar to that described for the solid type ST, except that the molecu-
lar weight of the polymer is reduced to a considerably greater degree. Tiey have a {good resistance to swelling in various solvents, depending upon the sulphur
cc,-taltipropo: r CitaiüS curcd content Of the base poiymeÅTabie 8.17 shows the solvent resistance of typical
temperature to solid rubbers with very little cross-linking. The cured compounds FA vulcanizates versus ST vulcanizates; tile solvent resistance of cured LP poly-
exhibit more or less the general properies of solid ST vulcahizates, but the physical mers is comparable to that of ST elastomers) ;
properties are poorer.
LP polysulphides can be compounded with a variety of fillers to give the re- TBble8.17: Fluid Resistance of Typical FA Polysulphidc Vulcanizatesversus ST
quired Viscosityand to improve the vulcanizate properties. Curing is accomplished Vulcanizates after 168h at Room Temperature
by oxidizing the mercaptan tcrminals to sulphide bonds, as with the solid type ST Average Volume Increase (% )
Medium
(see above).
most commonly used curing agents are lead dioxide, certain grades of FA Vulcanizates ST Vulcanizates
ma dioxide , ca!ciumPeroxide, zinc peroxide and p-quinone dioxime. The rate Benzene 95 115
of curing may be accelerated or retarded by using small amounts of specific additives. TOIuene 55 75
AdheSion•of LP Compoundsto various substrates is achieved by adding adnc- Xylene 30 40
nromoters, Ttcan be improved by treating the substrate with suitable orimers Carbon tetrachloride 35 45
suchas epoxy resins. Acetone 20 35
LP compo'undsare commonlyformulated as one- or twozcomponentsystems. Methylethyl ketone 30 so
The one-componeni mix contains all ingredients (including the curing agent) in a Ethyl acetate 20 35
dry condition. It is package-stable and will cure when exposed to atmospheric Water 1
moisture. two-component systems include a base component (containing the
I.,Ppolymer with all ingredients exccpt curing agent) and a curing agent component
In paste form. The two components are blended on site just before use. —excellent resistance to oxidation, ozone, sunlight and weather in general;
I-morxåpounds are applied by pouring or by pressure gun, spatula or brush, —low permeability to gases and vapors, depending upon the sulphur content of the
depending upon the viscosity. base polymer: and