Polychloroprene (CR), chloroprene rubber

Applications

Among the speciality elastomers polychloroprene [poly(2-chloro-1,3-

butadiene)] is one of the most important with an annual consumption of nearly
300 000 tons worldwide. First production was in 1932 by DuPont (“Duprene”, later
“Neoprene”) and since then CR has an outstanding position due to its favourable
combination of technical properties.
CR is used in different technical areas, mainly in the rubber industry (ca.61%),
but is also important as a raw material for adhesives (both solvent based and water
based, ca.33%) and has different latex applications (ca.6%) such as dipped articles
(e.g. gloves), moulded foam and improvement of bitumen.
The typical delivery form of CR is “chips” (picture 1), a consequence of the
special production process (see below).

Picture 1: Picture 2 :
Typical polychloroprene “chips” Rubber applications
(belts, hoses)

Application areas in the elastomer field are widely spread, such as moulded goods,
cables, transmission belts, conveyor belts, profiles etc. (See picture 2) .

Rubber Properties

CR is not characterised by one outstanding property, but its balance of

properties is unique among the synthetic elastomers. It has:

Good mechanical strength

High ozone and weather resistance
Good aging resistance
Low flammability
Good resistance toward chemicals
Moderate oil and fuel resistance
Adhesion to many substrates

Polychloroprene can be vulcanized by using various accelerator systems over a wide

temperature range.
Chemistry and Manufacture

From the beginning until the 1960s, chloroprene was produced by the older
“acetylene process”. This process has the disadvantages of being very energy-
intensive and having high investment costs. The modern chloroprene process, which
is now used by nearly all producers, is based on butadiene, which is readily available.
Butadiene is converted into the monomer 2-chlorobutadiene-1,3 (chloroprene) via
3,4-dichlorobutene-1.

In principle it is possible to polymerize chloroprene by anionic, cationic and Ziegler-

Natta catalysis techniques. However, because of product properties and economic
considerations, free radical emulsion polymerization is used exclusively today. It is
carried out in a commercial scale using both batch and continuous processes.

A production flow diagram is shown in Picture 3 :

Schematic of the production of polychloroprene

Sulfur
Acid

Emulsifier
C F

Modifier
unreacted D
monomer G M
Chloroprene

Water

B
M M
L

A E I
K
H
J

A) Polymerization reactor; B) Stripper; C) Purification; D) Neutralization; E) Peptization; F) Rotating cooling drum; G) Coagulation by freezing
H) Latex concentration; I) Chopping machine; J) Dusting machine; K) Roping machine; L) Dryer; M) Washing

Picture 3 :
Production scheme

With the aid of radical initiators, chloroprene in the form of an aqueous emulsion is
converted into homopolymers or, in the presence of comonomers into copolymers.
The polymerization is stopped at the desired conversion by the addition of a short
stopping agent. The latex is freeze-coagulated on large, refrigerated revolving drums,
from which it is drawn as a thin sheet. After washing and drying, the sheet is formed
into a rope and then chopped to form the familiar chips (Picture 1) or granules.
 Cl
R . Cl H2
C CH 2 C C
n H 2C C C C
H H2 H n

H2 H2 H2
C 2 3 H C 2 3 C
1 1 4
C C C C
4
Cl C Cl H
H2
1,4 -trans 1,4 -cis

H H H 2 Cl
2
C C2
3C C 4 1

C Cl 3CH
2
CH 2
1CH 2 4

3,4 1,2

Structure and structural units

The basic polymerization scheme leads to incorporation of the monomer into a

polymer consisting of different structural units (Picture 4) :

Picture 4 :
Basic polymerization scheme and structural units

The physical, chemical and rheological properties of the different grades of

commercial polychloroprene are dependent on the ability to change the molecular
structure by changing polymerization conditions, e.g. polymerization temperature or
monomer conversion, polymerization aids (comonomers, type and amount of
molecular weight modifier and emulsifier) and conditions during finishing.

The high amount of trans-1,4-units in the polymer (about 90 % at standard

polymerization conditions) leads to synthetic rubber, which has cristallization as an
inherent property.

Types of Polychloroprene: Structure and properties of elastomers

Normal linear grades (general-purpose grades):

General-purpose grades are mostly produced with n-dodecyl mercaptan as the chain
transfer agent and occasionally with xanthogen disulfides. If xanthogen disulfides are
used, the elastomers are more readily processible and give vulcanizates with
improved mechanical properties.

Precrosslinked grades:

Precrosslinked grades consist of a blend of soluble polychloroprene and crosslinked

polychloroprene. They show less swelling after extrusion (die swell) and better
calenderability. Precrosslinked grades are particularly suitable for the extrusion of
profiled parts.

Sulfur-modified grades:

Sulfur-modified grades are copolymers of chloroprene and elemental sulfur. The

viscosity is adjusted – in contrast to general-purpose grades - mostly after
polymerization by “peptization” of the polysulfide bonds by e.g. thiuramdisulfides as
peptization agents. Sulfur modification improves the breakdown of the rubber during
mastication (lowering of viscosity). Sulfur-modified grades are used in particular for
parts exposed to dynamic stress, such as driving belts, timing belts or conveyor belts
because of their excellent mechanical properties. But the polymers are less stable
during storage and the vulcanizates less resistant to aging.

Slow cristallizing grades:

Slow cristallizing grades are polymerized with 2,3-dichloro-1,3-butadiene as a

comonomer. This comonomer reduces the degree of cristallization by introducing
irregularities into the polymer chain. High polymerization temperatures also make
structural irregularities, if this comonomer is not available. Crystallization resistant
grades are used to produce rubber articles, which have to retain their rubbery
properties at very low temperatures.

Producers and capacities:

According to the IISRP in 2000 the following production facilities and producers are
shipping polychloroprene into the market place:

Company name Country capacity (Metric Tons)

DuPont Dow Elastomers USA 100 000

Bayer AG Germany 65 000

EniChem France 40 000

Denki Kagaku Kogyo Japan 48 000

TOSOH Japan 30 000

Showa DDE Japan 20 000

Additional capacities are located in Peoples Republic of China and Armenia.

Conclusion:

Polychloroprene will continue to be one of the most important synthetic speciality

elastomers because its balance of properties is unique.