1. Enabling the cost-effective and environmentally friendly production of Perspex
Submitting InstitutionCardiff University
Unit of AssessmentChemistry
Summary Impact TypeTechnological
Research Subject Area(s)
Chemical Sciences: Inorganic Chemistry, Organic Chemistry, Other Chemical Sciences
Summary of the impact
Cardiff University, through developing and patenting a commercially
viable synthetic route to a catalyst, has enabled the application of a new
process, the Alpha Process, for the production of methyl methacrylate
(MMA), a key commodity precursor to Perspex. The Alpha Process has had
economic and environmental impacts.
Lucite International, the world's leading MMA producer, has invested in
major Alpha Process production facilities in Singapore and Saudi Arabia,
benefitting from a production route which is more efficient, more reliable
and cheaper than conventional routes.
The Alpha Process also brings environmental benefits, as it does not rely
on the use of corrosive and toxic feedstocks, such as hydrogen cyanide,
which are associated with conventional MMA processes.
In 1996 Lucite International (then Ineos Acrylics Ltd., and since
incorporated into the Mitsubishi Group) provided a research grant to
Professor Peter G. Edwards (Professor of Inorganic Chemistry, Cardiff
University) to investigate novel synthetic routes to phosphine ligands for
palladium of relevance to the catalysis of the addition of carbon monoxide
to ethylene, for the production of MMA and derivative plastics (i.e.,
PMMA, Perspex or Lucite) [3.1]. This research was carried out in
conjunction with Dr Paul Newman (post-doctoral researcher, 1996-99).
Fundamental studies into the reaction and mechanistic chemistry that
contributed to the understanding of ligand behaviour and key catalyst
design concepts were performed under this grant leading to high-quality
outputs in a leading journal [3.2, 3.3]. This work resulted in a much
improved synthetic route to the key catalyst ligand component, 1,2-bis(di-t-
butylphosphinomethyl)benzene. Palladium complexes of this ligand are
remarkably active and selective and also show excellent stability
(longevity) under reaction conditions; it provides 99.99% efficiency for
the addition of carbon monoxide to ethylene in methanol to give the
intermediate methyl propanoate.
The new technology this catalyst supports leads to several major
a) it utilises the efficient conversion of cheap readily available
feedstocks (ethylene and methanol),
b) it avoids the requirement for the highly toxic liquid hydrogen cyanide
used in the conventional (competitor) process,
c) it is intrinsically more environmentally benign with no toxic waste
d) it produces a purer higher quality acrylic resin product for higher
value end applications, and
e) it is economically cheaper to operate under milder conditions saving
up to 40% on operating costs over the main competitor technologies [3.4].
This methodology was the basis for a patent application, with a priority
date of 16th March 1998, naming the Cardiff researchers as inventors
[3.5]. Patents have been granted world- wide and are maintained to the
In view of its impact, the Alpha process has been recognised by several
The Biennial Kirkpatrick Chemical Engineering Award 2009 - Winner
Chemical Industry Association 2009 Innovation Award - Winner
ICIS Innovations Awards 2009 - Short-listed for Best Product Innovation
The Royal Academy of Engineering MacRobert Award 2010 - Finalist
References to the research
[3.1] Research grant: Catalytic reactions of carbon monoxide with
alkenes and alkynes, ICI Acrylics (name change to Ineos Acrylics),
£125,000, 9/12/1996-30/10/1999, PI: Prof. P. G. Edwards.
[3.2] Comments on the Catalytic Alkoxycarbonylation of Alkynes, A.
Dervisi, P. G. Edwards, P. D. Newman, R. P. Tooze, S. J.
Coles and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1999,
1113-1120. Publication date: 01/01/1999.
[3.3] Synthesis and chemistry of diphenyl-2-pyridylphosphine complexes of
palladium(0). X-Ray characterisation of Pd(Ph2Ppy)2-(03b72-DMAD)
A. Dervisi, P.G. Edwards, P.D. Newman and R.P.
Tooze, J. Chem. Soc., Dalton Trans., 2000, 523-528. Publication
[3.5] Patent: Process for the preparation of bisphosphines, Paul
D. Newman, Richard A. Campbell, Robert P. Tooze, Graham R. Eastham,
Jamie M. Thorpe, Peter G. Edwards. GB/9805348; PCT/GB/99/00797;
WO99/47528; US/6376715. Patent assigned to Ineos then transferred to
Lucite and maintained to present.
Details of the impact
Advances in bisphosphine ligand synthesis carried out at Cardiff
University have enabled industrial scale application of a cost-effective
new process, the Alpha Process, for the production of methyl methacrylate
monomer for acrylic resins and Perspex production.
The economic impact is demonstrated by investment of US$230 million by
Lucite International, part of the Mitsubishi Group, in a new plant in
Singapore which has been producing 120 kilotonnes of MMA per annum since
This process brings major environmental benefits, as it produces only
environmentally benign waste products and does not rely on the use of
toxic feedstocks, such as hydrogen cyanide and sulphuric acid, commonly
used in alternative processes.
Enabling increased end-user applications and industrial production
The success of the Alpha Process was enabled by a patented process
developed by Cardiff University [3.5] to scale-up Lucite International's
production of the bisphosphine ligand for production of Perspex. Dr.
Graham Eastham (Senior Research Scientist for ALPHA Technology, Lucite
International) recognised the significance of the Cardiff contribution in
developing "a commercially viable synthetic route to produce the phosphine
ligand...without this early innovation the Alpha process may well not have
become the unqualified success that it is" [5.1].
The key to the process is the remarkable efficiency of the catalyst for
the addition of carbon monoxide to ethylene, which is fast (producing 13
kg of methyl propanoate for 1 g of palladium metal per hour of operation)
and cost efficient with regard to the amount of expensive and rare
palladium metal consumed (10 tonnes of product produced for 1 g of metal
consumed). The remarkable selectivity and efficiency of the catalyst
allows reliable production under milder reaction conditions, which has a
significant beneficial impact on operating costs, safety and energy
efficiency. Lucite International estimates that the Alpha process reduces
costs by 30-40% compared to the established acetone-cyanohydrin (ACH)
process, the mainstay of US and European MMA production, which has
remained largely unchanged since the 1930s.
The Alpha process has removed constraints on plant size allowing
significantly improved operating economies. As a result of the industrial
viability of the process, Lucite invested US$230 Million in 2008 in a
manufacturing plant in Singapore to produce 120 kilotonnes of MMA per
annum [5.2]. The plant has been running at 100% capacity to date, and
accounts for around 3% of global MMA production. Based on the success of
the Singapore plant, Mitsubishi Group signed a Letter of Intent with Saudi
Basic Industries Corporation, with the tender to issue in 2013, to build
the largest MMA plant in the world, costing US$500 million and producing
250 kilotonnes annually (around 6% of global production) [5.3].
The Alpha Process also produces purer MMA, which increases end-user
applications. Lucite Perspex is in demand for high margin applications
such as screens for mobile phones, televisions and computer monitors,
since Alpha process Perspex offers maximum light transmission without
disturbing surface hot spots. Growing demand in this area complements
conventional uses, including glazing, signage and lighting, moulding and
extrusion compounds for automotive, medical and optical industries,
surface coatings, emulsion polymers, adhesives, and enamels. Lucite
International is the world leader in MMA and PMMA production, with around
25-30% of the global market share, which is valued in excess of US$7
Billion annually and projected to show annual growth of 6.5% up to 2017
The Alpha process brings environmental benefits compared to conventional
manufacturing technologies, such as the ACH process, which rely on the use
of feedstocks that are highly toxic (hydrogen cyanide) and highly
corrosive (sulfuric acid). For example, Alpha Process production at the
Lucite Singapore plant produces annual savings of 19 kilotonnes of
hydrogen cyanide and annual savings of 360 kilotonnes of spent acid,
including sulfuric acid and ammonium sulphate, compared to the
conventional ACH route.
A further supply chain benefit of the Alpha Process is that it uses
cheap, relatively non- hazardous and readily available feedstocks (carbon
monoxide, ethylene, formaldehyde and methanol). The atom-efficiency of the
process also brings waste management benefits, as it means that there are
no toxic wastes or by-products [5.2].
These environmental benefits also have an impact on manufacturing
efficiencies through, for example, the reduced use of solvents and reduced
storage and waste management facilities required at the Singapore and
Saudi facilities. A purer MMA product also has knock-on benefits for
downstream users and applications industries in minimising requirements
for further purification as well as providing assurance of a dependable
supply of higher quality plastics from readily available feedstocks.
Sources to corroborate the impact
[5.1] Personal Confirmation of Cardiff's contribution, including through
developing patented technology, to the commercial viability of the Alpha
process from the Senior Research Scientist for ALPHA Technology, Lucite
International. (Letter on file at UoA)
[5.2] Confirmation of Lucite investment in Alpha process, together with
environmental and other benefits, as part of a feature on the Alpha
process as a finalist in the Royal Academy of Engineering MacRobert Award
Acrylics for the future, B. Harris, Ingenia, issue 45,
December 2010, Royal Academy of Engineering,
[5.3] Confirmation of agreement between Sabic and Mitsubishi Rayon to
build the largest MMA plant in the world in Saudi Arabia (capital
expenditure of $500 million), using the Alpha process.
[5.4] Confirmation of global value of MMA production