Dicyclopentadiene, abbreviated DCPD, is a
chemical compound
A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with formula C
10H
12. At room temperature, it is a white brittle wax, although lower purity samples can be straw coloured liquids. The pure material smells somewhat of soy wax or
camphor
Camphor () is a waxy, colorless solid with a strong aroma. It is classified as a terpenoid and a cyclic ketone. It is found in the wood of the camphor laurel ('' Cinnamomum camphora''), a large evergreen tree found in East Asia; and in the k ...
, with less pure samples possessing a stronger acrid odor. Its
energy density
In physics, energy density is the amount of energy stored in a given system or region of space per unit volume. It is sometimes confused with energy per unit mass which is properly called specific energy or .
Often only the ''useful'' or extract ...
is 10,975
Wh/l.
Dicyclopentadiene is a co-produced in large quantities in the steam cracking of
naphtha
Naphtha ( or ) is a flammable liquid hydrocarbon mixture.
Mixtures labelled ''naphtha'' have been produced from natural gas condensates, petroleum distillates, and the distillation of coal tar and peat. In different industries and regions ''n ...
and
gas oil
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
s to
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
. The major use is in
resin
In polymer chemistry and materials science, resin is a solid or highly viscous substance of plant or synthetic origin that is typically convertible into polymers. Resins are usually mixtures of organic compounds. This article focuses on natu ...
s, particularly, unsaturated polyester resins. It is also used in inks, adhesives, and paints.
The top seven suppliers worldwide together had an annual capacity in 2001 of 179 kilotonnes (395 million pounds).
Synthesis and structure
The spontaneous dimerization of cyclopentadiene at room temperature to form dicyclopentadiene proceeds to around 50% conversion over 24 hours and yields the ''endo'' isomer in better than 99:1 ratio as the kinetically favored product (about 150:1 ''endo'':''exo'' at 80 °C). However, prolonged heating results in
isomerization
In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomeriz ...
to the ''exo'' isomer. The pure ''exo'' isomer was first prepared by base-mediated elimination of hydroiodo-''exo''-dicyclopentadiene. Thermodynamically, the ''exo'' isomer is about 0.7 kcal/mol more stable than the ''endo'' isomer. The ''exo'' isomer also has a lower reported melting point of 19°C.
Reactions
Above 150 °C, dicyclopentadiene undergoes a retro-
Diels–Alder reaction
In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a peric ...
at an appreciable rate to yield
cyclopentadiene
Cyclopentadiene is an organic compound with the chemical formula, formula C5H6.LeRoy H. Scharpen and Victor W. Laurie (1965): "Structure of cyclopentadiene". ''The Journal of Chemical Physics'', volume 43, issue 8, pages 2765-2766. It is often ab ...
. The reaction is reversible and at room temperature cyclopentadiene dimerizes over the course of hours to re-form dicyclopentadiene.
Cyclopentadiene
Cyclopentadiene is an organic compound with the chemical formula, formula C5H6.LeRoy H. Scharpen and Victor W. Laurie (1965): "Structure of cyclopentadiene". ''The Journal of Chemical Physics'', volume 43, issue 8, pages 2765-2766. It is often ab ...
is a useful diene in Diels–Alder reactions as well as a precursor to
metallocene
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metallic element, metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are ...
s in
organometallic chemistry
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...
. It is not available commercially as the monomer, due to the rapid formation of dicyclopentadiene; hence, it must be prepared by "cracking" the dicyclopentadiene (heating the dimer and isolating the monomer by distillation) shortly before it is needed.
The thermodynamic parameters of this process have been measured. At temperatures above about 125 °C in the vapor phase, dissociation to cyclopentadiene monomer starts to become thermodynamically favored (the dissociation constant ''K''
d = ). For instance, the values of ''K''
d at 149 °C and 195 °C were found to be 277 and 2200, respectively. By extrapolation, ''K''
d is on the order of 10
–4 at 25 °C, and dissociation is disfavored. In accord with the negative values of Δ''H''° and Δ''S''° for the Diels–Alder reaction, dissociation of dicyclopentadiene is more thermodynamically favorable at high temperatures. Equilibrium constant measurements imply that Δ''H''° = –18 kcal/mol and Δ''S''° = –40 eu for cyclopentadiene dimerization.
Dicyclopentadiene
polymerizes
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many for ...
.
Copolymer
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are some ...
s are formed with
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
or
styrene
Styrene () is an organic compound with the chemical formula C6H5CH=CH2. This derivative of benzene is a colorless oily liquid, although aged samples can appear yellowish. The compound evaporates easily and has a sweet smell, although high concen ...
. The "
norbornene
Norbornene or norbornylene or norcamphene is a highly strained bridged cyclic hydrocarbon. It is a white solid with a pungent sour odor. The molecule consists of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The molecule carr ...
double bond" participates. Using
ring-opening metathesis polymerization
Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins (e.g. norbornene or cyclopentene). A variety of heterogeneous ...
a homopolymer
polydicyclopentadiene
Polydicyclopentadiene (PDCPD) is a polymer material which is formed through ring-opening metathesis polymerization(ROMP) of dicyclopentadiene (DCPD). PDCPD exhibits high crosslinking, which grants its properties, such as high impact resistance, g ...
is formed.
Hydroformylation of DCP gives the dialdehyde called TCD dialdehyde (TCD =
tricyclodecane). This dialdehyde can be oxidized to the
dicarboxylic acid
In organic chemistry, a dicarboxylic acid is an organic compound containing two carboxyl groups (). The general molecular formula for dicarboxylic acids can be written as , where R can be aliphatic or aromatic. In general, dicarboxylic acids show ...
and to a
diol
A diol is a chemical compound containing two hydroxyl groups ( groups). An aliphatic diol is also called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified.
The most common industrial diol is e ...
. All of these derivatives have some use in polymer science.
Hydrogenation
Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a Catalysis, catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or S ...
of dicyclopentadiene gives tetrahydrodicyclopentadiene, , which is a component of
jet fuel
Jet fuel or aviation turbine fuel (ATF, also abbreviated avtur) is a type of aviation fuel designed for use in aircraft powered by gas-turbine engines. It is colorless to straw-colored in appearance. The most commonly used fuels for commercial a ...
JP-10,
and rearranges to
adamantane
Adamantane is an organic compound with a formula C10H16 or, more descriptively, (CH)4(CH2)6. Adamantane molecules can be described as the fusion of three cyclohexane rings. The molecule is both rigid and virtually stress-free. Adamantane is the m ...
with
aluminium chloride
Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula . It forms hexahydrate with the formula , containing six water molecules of hydration. Both are colourless crystals, but samples are often contam ...
or acid at elevated temperature.
References
External links
MSDS for dicyclopentadiene
{{Commonscat
Cyclopentadienes
Monomers
Dimers (chemistry)
Cyclopentenes