3.3.
4 Poly-2Chlorobutadiene, Chloroprene Rubber (CR)
[Link] General Bckground about CR
The polymerizability of 2-chlorobutadiene, or chloroprene, was discovered in
1930 by [Link] and coworkers. In 1931/1932, large scale production
began in the USA using a bulk polymerization process (1932 production was 250
tons), and the material was initially marketed in the USA under the name of
Duprene as an oil resistant rubber. The first general purpose CR became known in
1939 as Neoprene GN. With a global production capcity in 1985 of 0,556 million
tons, which is 4,6% of the SR capacity. CR is besides IIR and NBR the most
widely used specially rubber.
Depending on how it was produced, a distinction is made between sulphur
modified and mercaptan modiefied CRs. In addition, one distinguishes grades of
low medium and high crystallizability. The latter are especially useful for the
production of adhesives.
[Link] Production of CR
Today, CR is exclusively produced in emulsion and using free radical initiators.
Preferred emulsifiers are sodium soaps of rosin acids and sodium naphthalin
sulfonate is frequently added as an additional stabilizer. Redox systems are
suitable initiators as for instance, sulfinic acid in the presence of oxygen or
persulfate. In order to prevent the formation of peroxides, small amounts of
inhibitors are added, such as tert-butyl pyrocatechol but these reduce the rate of
monomer conversion. With the so called sulphur modified CR grades ( or thiuram
grades ), the molecular weight is controlled by adding sulphur, which
copolymerizes and form S, segments in the polymer chain. These CR grades are
stabillzed with thiurams, such as TETD. With the so-called mercaptan CR grades,
the molecular weight is controlled with n-dodecyl mercaptan. After reaching the
desired degree of monomer conversion of about 70%, the polymerization reaction
is terminated by adding phenothiazine or [Link] pyrocatechol. After removing
unreacted monomer and adding the stabillizer, the polymer is coagulated on a
freezing drum, washed and dried.
1
In the production of CR a similar number of parameters have to be considered as
in the case of SBR. Which results in a wide range of commercially available
grades. The important parameters are Sulphur modification (thiuram grades,
ability to masticate the rubber), Mercaptan modification ( mercaptan grades ),
Polymerization temperature ( tendency to crystallize ), Modifier ( different
Mooney viscosities, processibility ), Stabillizer ( colour and storage stabillity ),
Copolymerization with other monomers ( tendency to crystallize ),
Precrosslinking ( Processing behaviour ), Reactive groups ( ability to crosslink
without sulphur and accelerator. Only important for latices )
[Link] Structure of CR and its Influence on Properties
Viscosity. The molecular weight distribution, the degree of long chain branching
and the average molecular weight have the same effect on CR as on NBR. The
Mooney viscosity has an influence on the ability of the rubber to band on mills,
the heat build up during mixing, the acceptance of filler,the extrudabillity die
swell and calenderabillity to name a few.
Microstructure. The microstructure of CR influences the processing behaviour
and elastic properties of the rubber, and it depends very much on the
polymerization temperature. With increasing proportions of 1.2 and 3.4 moieties
and different isomers in the monomer sequences. This formation of more irregular
chain structures reduces the rate of crystallization of the polymers. On the other
hand, those CR grades, which have been polymerized at low temperatures, have a
strong tendency to crystallize at high rates, which is an important requirement for
adhesives with good immediate tack. These CR grades are, however, less suited
for the production of rubber products, because they harden very rapidly with an
attending loss of elasticity. Therefore, CR grades which, on account of their low
tendency to crystallize, are useful for the production of rubber goods, are usually
polymerized at higher temperatures. The copolymerization of chloroprene with
small amounts of 2.3-di-chloro butadiene, acrylonitrile or styrene, also result in
the desirable structural irregularity of the polymer chains and this. Therefore
reduces the tendency to crystallize. Since the rate of vulcanization of CR depends
2
to agreat extent on the amount of allylic chlorine in the polymer chains, the higher
polymerization temperatures have also beneficial effect in this respect.
[Link] Compounding of CR
Blends. The typical property spectrum of CRs can be modified through blend with
other rubbers. NR improves for instance, the elaticity and low temperature
flexiblility. BR reduces the brittleness temperature considerably. Blends with NBR
improve the swelling resistance in industrial oils. With all these blends, it is a
problem to adjust the cure system in such a manner, to make it adequate for the
individual blend [Link], frequently used cure systems in these
blends are sulphur and thiourea derivates with the addition of thiuram and
guanidine accelerators.
Vulcanizing Agents. Contrary to other diene rubbers, the vulcanization of CR
compounds is not carried out using sulphur, but metal oxides. In general, the best
proven cure systems are combinations of, for instance, 4phr MgO with 5phr ZnO,
or if very low water absorption is required, lead oxides. With mercaptan CR
grades, sulphur can be added to enhance degree of vulcanization but this also
reduces the heat resistance of the vulcanizate. The choice of accelerators for CR is
also governed by different rules than for other deine rubbers. In general, cure
systems that provide faster cure rates tend to be more [Link] those, that give
a higher degree of vulcanization, i.e higher tensile strength, lower elongation at
break, higher rebound elasticity and less compression set, tend to have less scorch
safety.
As already mentioned, in most instances the thiuram CR grades do not require
additional accelerator. The presence of metal oxides is by itself already sufficient
in most caes to achieve rate of vulcanization. However, by adding accelerators,
the cure rate of these compunds can be even further increashed with an attendant
reduction in storage stability and time to completion of the vulcanization reaction.
By contrast, the mercaptan Cr grades require accelerators besides MgO and ZnO
of lead oxides. Most conventionally used accelerators are not very effective in
CR, and instead, the most important one is thiourea (ETU). However, in spite of
being a good and most effective vulcanizing agent for CR, it s, because of its
3
toxicity being progressively replaced by detu, or other recent developments in
thiokeones and thiadiazines, such as thiadiazole. A newly developed thioketone
derivative as well as 3-methyl-thiazolidin-thione-2 appear to surpass even ETU
with respect to scorch safety and cure rate and the obtainable degree of
vulcanization.
Protective Agents. In spite of the inherently excellent oxidative stabillity of CR,
additional agents are aded to protect CR vulcanizates against oxygen and ozone
degradation. To meet particularly stringent requiments for some applications.
Such agents are especially aromatic amines, such as IPPD and diphenyl amine
derivatives, like ODPA or SDPA, as well as sterically hindered phenols for light
coloured compunds. With the use of MBI, one has consider its accelerating
influence on the cure of CR compunds. Therefore, it is seldomly used to improve
thw ozone resistance of black vulcanizates.
Fillers. For gum vulcanizates or those formulated with non-reinforcing fillers.
Thhe tensile and tear strengths are higher fro CR than for corresponding ones
based on SBR or NBR. Yet, vulcanizates from CR do not reach the property level
of those from NR, unless reinfrocing or semi reinforcing blacks or reinforcing
white fillers are used with CR. Particularly notewhorthy is the high tear resistance
which is obtainable with reinforcing silica in compounds of CR, to reach a level
which can not obtained with other rubbers.
Sofreners. To reduce compound cost and to improve processibility, CRs are
compunded with softeners, mainly minerals oils. Naphthenic oils or relatively low
molecular weight are primarily used, because they are easily incorporated in the
rubber compound and give a good level of properties. However, these oils are
relatively volatile during heat aging, cause bloom at high loadings, and are
expensive. Less costly aromatic oils can also be used even in high concentrations
but they give less fovourable, vulcanizate properties at low loadings, give poorer
low temperature flexibility ate high loadings, and hes discolour llight compounds.
On the other hand, aromatic oils reduces the tendency of compounds and
vulcanizates to crystallize. Depending on the avarage molecular weight, paraffinic
oils are only comptible with CRs in low concentrations and they serve generally
4
only are processing aids that is,to reduce sticking of compounds to mill rolls. For
special formulations of CR, synthetic platicizers must be used instead of oils. This
is especially important if improved flame resistance, low temperature flexibility
and elasticity are required of the vulcanizate. Of particular importance are the
flame resistant esters of phosphoric acid to repalace oils which burn readily. A
further improvement in the flame resistance of CR compounds in achieved
through the addition of chlorinated hydrocarbons together with hyrated alumina.
Elasticity and low temperature flexibility of CR vulcanizates can be improvd by
using ester and ether based plasticizers same as for SBR. Various resins, such as
xylene formaldehyde resins. Koresin, rosin and coumarone resins can be used in
CR compunds to improve the fller dispersion and the building tack.
Factice. Since CR vulcanizates have a relatively good strenght for gum
compounds and at low filler loadings, it is possible to formulate very sofr
vulcanizates with aquate mechanical properties by using factice to plasticizers.
Such vulcanizates are required forf printing roll covers, seals and hoses. In
addition, as with other rubbers, factices impreve the processibillity of CR
compounds and the compatibility of CRs with oils. Particularly successful are the
facties, that were especially developed for CR, to give a high resistance to solvent
swell.
Process Aids. Those particularly suitable for CR compounds are estes of fatty
alcohols, to improve flow behaviour. Due to the interaction with zine ions, zine
soaps strengthen the CR compounds, but reduce their processibility and Ca soaps
tend to bloom. Other process aid recommended in the litelature, such as emulsion
plasticizers, have only little effect. Therefore esters of fatty alcohols are of great
importance. Stearic acid and paraffinic oils are also important for reducing the
stickiness of CR compounds and to aid in the filler dispersion.
[Link] Processing of CR
The mixing and processing of CR compounds is done using conventional rubber
machinery and processes. Because of their tendency to scorch, the heat history of
CR compounds has to be kept as short as possible during processing.
5
[Link] Properties of CR Vulcanizates
Mechanical Properties. Gum compounds or those with non-reinforcing fillers
have a higher mechanical strenght than those from most types of SRs because due
to ther ability to strain crystallize, CRs have a certain self-reinforcing ability. The
greatest influence on the mechanical properties has, of course, the activity of the
filler in the compound, same as with other SRs. With highly reinforcing blacks
and silicas, one obtains tensile properties which are only slightly below those
comparable NR vulcanizates. The resistance of CR vulcanizates to teat initiantion
and propagation is excellent, if low structure blacks and in particular active silicas
are used. Semi-reinfrocing blacks together with ester- and ester-based plasticizers
give a high elasticily for CR vulcanizates. To obatain a good resisitance to
compression set at high temperatures, mercaptan modified CRs are used
compounded with semi-reinforcing blacks, but with as little plasticizer as possible
and with a higher degree of crosslinking. Crystallization can aggrevate the
compression set at low temperatures. Therefore, the same compounding measures
are to be implemented for good low temperature compression set, as for
depresssing the freezing point and the tendency towards crystallization.
Heat and Aging Resistance. To obtain a good resistance, mercaptan grades should
be used instead of the thiurams grades, and a sulphur free vulcanization. Light
coloured fillers, especially talc and the use of protective agents based on diphenyl
amine, such a ODPA or SDPA, give an optimum in heat resistance, namely of the
same order as NBR vulcanizates with EV cures. In addition to very good
oxidative stabillity, unprotected CR vulcanizates have already a significantly
better weather and ozone resistance than other diene rubbers. Of fillers, carcon
blacks have a possitive influence and of plasticizers, aromatic oils and unsaturated
fatty acid esters have a negative one on the ozone resistance of vulcanizates. Since
the ozone resistance improves as the vulcanizates become less stressed, any
measure which reduces the stress in vulcanizates has a positive effect regarding
ozone resistance. The presence of appropriate protective agents gives, however, a
high level of ozone resistance, which suffices for amny applications. Depending
on the specific compound, light coloured vulcanizates tend to discolour under
sustained influence of light.
6
Flammability. Because of the chlorine content, CRs have a favourable flame
resistance, and in this respect they are superior the other rubber. Although CR
vulcanizates burn when exposed to high temperatures and open flames, ther
selfextinguish within a short time after removal the flame. The requires, however,
that the vulcanizate has not been compounded with large can be or quantities for
combustible ingredients, such as oils. Vulcanizates with high degree of flame
resistance obtained by using non burning plasticizers, like esters of phosphoric
acid, and it can be improved even further by using chorinated hyrocarbons in
combination with antimony trioxide or hydrated alumina. When chlorinated
polymers, including CR, burn, they develop great quantities of toxic and corrosive
fumes, which are extremely dangerous and cannot be tolerated in areas where
there is a high demand for safety. Therefore, halogen free vulvanizates have been
recently specified for these applications, and examples are oxygen containing
polymers, like EVM or EAM, which are compounded with hydrated alumina.
Optimized EVM vulcanizates, which are halogen free and develop little smoke,
have oxygen indices of 50% and thus approach those 55% for the optimum
compositions based on CR and chlorinated paraffias. Since, in the event of fire,
the EVM vulcanizates create less danger regarding toxicity and corrosion, they
will be increasingly used inthe future, and they will replace CR in one of its major
applications cable jackets.
Tendency Towards Crystallization. This underirable property of CR has already
been dicussed on several occasions. Crystallization is determinal in the production
of certain technical rubber good, since it reduces the building tack. Also with cold
feed extruders, which are almost exclusively used in moern production processes
a strong crystallization can have a negative effect because of an excenssive
hardness of compounds. The reversible hardening due to crytallization is most
pronounced in the raw rubber, less so in the compounds, and least, of course, in
the finished product. And yet, products from CR harden in a reversible manner
after extended exposure to low temperature. This tendency to crystallize depends
primarily on the CR type. Fillers have little influence on this phenomenon, and it
can be reduced ny high degrees of crosslinking of the ruber, and by adding high
molecular weight aromatic oils for some of the ester or ether-based plasticizers.
7
The crytallizability of CRs results also in high degree of adhesive strength
between CR and other rubbers, such as SBR. Comtraty to the requiments for
rubber goods, the crystallizabillity of CRs is of great benefit in the production of
ahesives. In solution, no crystallization occurs but after evaporation of the solvent,
the adhesive film hardens rapidly due to crystallizarion, giving food adhesion to
substates and good bonding of two surfaces by simply pressing them together.
Therefore, these adhesives are referred to as contact adhesives.
Resistance to Solvent Swell and Chemicals. As already mentioned, CR
vulcanizates sre, on account of their polarity, sufficiently oil resistance for many
applications. Their solvent swell compares with that of an NBR with about 18%
acrylonitrile, or with MQ.
Permeation. Regarding gas permeability, CR is distinctly superior to NR or SBR
but it does not reach the low permeabilities of CO, ECO, IIR or NBR.
Electical Conductivity. Due to its polarity, CR is a better conductor of electricity
than the non-polar NR and SBR, but a poorer conductro than NBR. In order to
obtain technically acceptable insulations based on CR, the proper choice of fillers
plasticizers and resins assumes particullar importance. At normal concentrations,
protective agents have partically no influence on the conductivity of CR
compounds. Regarding fillers, special grades of talc and hard and calcined kaolin,
reduce the electrical conductivity.
[Link] Uses of CR
CR grades with little or a moderate tendency towards crystallization are used in
many different technical rubber goods, which are flamce resistant and resistant to
oils and fats, weathering and ozone, these rubber goods include moukdings,
extrusions, seals, hoses, profiles, rolls, belts, V-belts, bearings, linlings, ruberized
fabrics, shoe solings, and many applications in the contruction industry, such as
window and contruction profiles, roofing membranes and also cable jackets. For
the latter application, the CR grades with a moderate crystallizabillity are often
preferred. In several automotive applications, the use of CR has shrunk for
similiar reasons as with NBR. In weather stripping, the use of CR has suffered due
8
to the strong competition of EPDM, SBR/ETER and NBR/EPDM blends have
also made inroads on CR usage, because of their more favourable price. Strongly
crystallizable CR grades are preferably used for the production of contract
adhesives.