New Functional Polymers for Specialty ApplicationsBy Dr. Satyasankar Jana, Dr. Alexander Jackson and Prof. Alexander van Herk

In recent years, there has been tremendous interest to use controlled or living radical polymerisation (CRP/LRP) techniques for the synthesis of well-defined and functional polymers. Reversible Addition Fragmentation chain Transfer (RAFT) mediated polymerisation is believed to be one of the most versatile CRP techniques available to date to obtain well defined polymer architectures and functionality. The Polymer Engineering and Characterisation (PEC) division of Institute of Chemical and Engineering Sciences (ICES) has long been active in this area and has developed deep and scientific expertise aligned to the needs of industry. However, although this polymerisation technique is hugely explored in academia worldwide, industrial applications are rather limited to date. Targeting the application of RAFT generated polymers for specialty applications the team consisting of Dr. Satyasankar Jana, Dr. Alexander Jackson and Prof. Alexander van Herk from PEC division in ICES recently entered into its first collaboration agreement with a team (Hideki Toya and Yuhei Ishigaki) the Japanese chemical company, Denka.

Poly(chloroprene) (PCR) – with an annual global consumption of around 300KMkt – is a well-known specialty elastomer because of its good oil, ozone and flame resistance properties combined with other mechanical and physical properties. PCR is used in many technical areas including rubber industries, as adhesives, molded foam, improvement of bitumen and latexes for dipped articles (gloves). Denka is a major producer of PCR with ~30% of total annual global production. The present collaboration will focus on the development of special functional properties of PCR to broaden its application.

The key focus in this collaborative work is the marriage of RAFT polymerisation to the industrially utilised traditional emulsion polymerisation system to achieve better physical and mechanical properties and desired functionality of the resultant polymer product and to achieve rapid industrial adoption. Dr. Keith Carpenter, Executive Director of ICES, observed: “Denka is a well-known and innovative materials company, with a strong background in polymers. By working with them we benefit from their strong practical experience and commercial knowledge. We believe that our expertise in RAFT polymerisation can help them to develop a new approach to make specialty polymers.” ICES is looking forward to a fruitful long-term collaboration with Denka.

June 2016 | Vol. 35MCI (P) L006/09/2015

01 New Functional Polymers for Specialty Applications

02 Research and Development of

Acrylic Acid Production

03 Care Chemicals, Products and Processes: A New Industry Programme in ICES

04 Keep Global Warming Below 2°C: Zero CO2 Emissions or Negative

CO2 Emissions?

05 ICES Partner’s Appreciation Evening 2016

06 Building the Futuristic Glimpse of Singapore!

Reaching Out to SMEs

07 Advancing in Encapsulation & Formulation

Reaching the One-Year Milestone

with Our Valued Members

08 We Go GREEN!

Practical Assessment Methodology for Converting Fine Chemicals Processes from Batch to Continuous

Upcoming Events

CONTENTS

Figure B: Application of PCR in different commercial products

Di-block copolymer

Tri-block copolymerStar copolymer

Figure A: Different polymer architectures can be synthesised by RAFT

mediated polymerisation

Wet and dry suits Oil resistant gloves Adhesive

Cable and hose Belt, seal, o-ring for automotive

Research and Development of Acrylic Acid ProductionBy Dr. Wang Chuan

Reference: Patent: WO 2015/147752 A1, Method for preparing a sodium faujasite catalyst and its use in producing acrylic acid

Recently, biomass has attracted increasing attention as a renewable chemical feedstock. The value chain in biomass-to-chemicals offers a new economic opportunity for the chemical industry. To strengthen our capabilities in this emerging area, A*STAR launched the Biomass-to-Chemicals (B2C) programme in 2012, with the Institute of Chemical and Engineering Sciences (ICES) as the leading research institute. One target product is the acrylic acid. Acrylic acid is widely used in the manufacture of paint additives, adhesives, textiles and super-absorbent materials. The global market for acrylic acid was valued at USD$15.50 billion in 2014 and is expected to grow to USD$22.50 billion by 2020. The current technology for acrylic acid production is by the oxidation of propylene. One concern of this technology is it is fully dependent on the non-renewable fossil resources. Therefore, finding an alternative and sustainable route to produce acrylic acid is desirable.

Scientists from ICES have proposed a pathway for acrylic acid production from biomass through lactic acid (Figure 1). The first step is to produce lactic acid from biomass by pretreatment, saccharification and fermentation. The lactic acid is converted to acrylic acid by catalytic dehydration. The main challenge for this process is the catalytic dehydration, which has been studied for decades, but still remains challenging today due to the low yield of acrylic acid. There are many side reactions that happen under the same reaction condition. So, the key for this process is the development of an efficient catalyst. The Heterogeneous Catalysis group in ICES has developed a very promising catalyst, which has the highest yield of acrylic acid ever reported. From screening a wide range of materials, Si-A based zeolite was found to be the best catalyst candidate. The activity of the catalyst is improved by surface modification

with appropriate functional groups. Various characterisation techniques, such as N2 physisorption, XRD, XPS, FTIR, ICP, TGA, TPD and XAS have been used to understand the catalyst. Such high activity is attributed to its acid-base sites, suitable pore size and large surface area. The ICES catalyst also shows relatively good stability in a preliminary long term test. Figure 2 shows the yield of acrylic acid over 60 hours testing. The highest yield (83%) was obtained at the 6th hour. Subsequently, the catalyst started to deactivate slowly. The yield of acrylic acid remains above 50% after 60 hours run and the average yield is around 70%. Such a high yield of acrylic acid makes the production of acrylic acid from lactic acid economically viable. This work has attracted industry interests and is leading to potential industry collaborations.

02 Research Highlights

Figure 2: Stability test of modified NaY catalyst on the dehydration of lactic acid to acrylic acid

0 10 20 30 40 50 600

20

40

60

80

100

A

cryl

ic A

cid

Yiel

d (%

)

Time on Stream (h)

Figure 1: ICES route of acrylic acid production from biomass

Biomass

OH

OH

O

Lactic Acid (LA)

OH

O

Acrylic Acid (AA)

Fermentation Catalyst

-H2O

Research Highlights 03

Care Chemicals, Products and Processes: A New Industry Programme in ICESBy Dr. Brendan Burkett

In January 2016, the Prime Minister of Singapore, Mr. Lee Hsien Loong, announced the Research Innovation and Enterprise Council’s plan for funding for the next five years – RIE2020. This plan sees an increase in R&D funding available across Singapore’s research ecosystem with an emphasis on value creation through national level collaboration in four domains of relevance to Singapore’s future economy; Advanced Manufacturing and Engineering (AME); Health and Biomedical Sciences (HBMS); Services and Digital Economy (SDE) and Urban Solutions and Sustainability (USS). The chemicals sector falls under AME, and this domain is therefore the most significant to the Institute of Chemical and Engineering Sciences (ICES) as we aim to enable expansion of the value-added chemicals industry in Singapore. To build momentum in this area, we have elevated some of our activities from our specialty chemicals programme (ICEScope Vol. 28, pp 2) to form a new industry programme named ‘Care Chemicals, Products and Processes’.

The Care Chemicals, Products and Processes programme covers additives and formulated systems for the personal care, home care and health care sectors. With a focus on enabling the generation of smart formulated products and additives through

advanced formulation and understanding the fundamental nature of complex fluids, we also aim to use chemistry to offer new paradigms for the next generation care chemical additives, where stimulus responsive and multifunctional ingredients will offer new opportunities for distinctive and targeted performance (Figure 1). These broad thematic areas are well supported by ICES’ skill divisions and draw on our long history of excellence in the areas advanced chemometrics, encapsulation sciences, polymer sciences, organic synthesis and formulation sciences. However, we cannot achieve this alone.

In the spirit of the new RIE framework, the new programme aims to bring the combined expertise from within ICES to a national level where we will work with our sister research institutes in the A*STAR family, as well as other research performers in the landscape. We seek to interact with both Fast Moving Consumer Goods (FMCG) companies and their suppliers in a safe and efficient multidisciplinary research ecosystem geared towards innovation for the emerging middle class in South East Asia. In doing so, we will provide a stimulating and innovation-focussed environment for companies to ideate their next-generation technologies for the region and beyond.

Figure 1: Key strategic thrusts of Care Chemicals, Products and Processes

CARE CHEMICALS AND PRODUCTS

Liquid and Solid

Forms

“Living” Formulated

ProductsDeposition

AnalysisMulti-scale Analytics

Programmable Systems for Care

Chemicals

Multifunctional Ingredients

and Stimulus Responsive Molecules

Encapsulated Systems

Advanced Formulation of Care Chemicals

Physical Chemistry

of Complex Fluids

Next Generation Additives

Keep Global Warming Below 2°C:Zero CO2 Emissions or Negative CO2 Emissions? By Dr. Bu Jie and Mr. Yeo Tze Yuen

Anthropogenic greenhouse gas emissions have resulted in a rapid and unprecedented increase in atmospheric CO2 levels. Pledged actions to reduce these emissions, such as those recently submitted for the Paris Agreement, can only slow the rate of climate change but they are not enough to totally prevent it. To truly avoid catastrophic climate change, experts have suggested that negative CO2 emissions are needed1,2,3. This means that CO2 must be removed from the atmosphere and regulated to pre-industrial levels. There are many methods to achieve this; some of them are outlined in Figure 13. These technologies are in various stages of development, and some are more practical than others depending on individual and local circumstances.

Although Singapore only emits a small fraction (around 0.1%) of the world’s total CO2 emissions, it has done a lot to reduce its CO2emissions. In fact, Singapore is currently one of the least carbon intensive countries in terms of CO2 emissions per dollar of GDP. The nation’s mitigation strategies (for example fuel-switching

to natural gas and implementation of energy efficiency initiatives) have been very effective. Even so, being a small and land-scarce island nation, Singapore remains at risk of being affected by rising sea levels due to climate change. Thus, it should further adopt adaptation strategies to cope with climate change. To this end, researchers at the Institute of Chemical and Engineering Sciences have been developing mineral carbonation technology, which is one of the negative emission technologies (NET) that are suitable to the unique circumstances of Singapore. Mineral carbonation can capture and convert CO2 into solid carbonates. These carbonates are chemically stable, and can sequester the captured CO2 for long periods without risk of re-release into the atmosphere. In addition, these solid products can also be used to strengthen the shoreline of Singapore, helping it to adapt against the threat of rising sea levels. Other economic benefits can also be gained, especially through the production of valuable metals from the raw minerals used for mineral carbonation.

04 Research Highlights

Figure 1: Negative emissions technologies to remove CO2 the atmosphere3

Reference: 1. Mathesius, Sabine, et al. “Long-term response of oceans to CO2 removal from the atmosphere.” Nature Climate Change (2015).2. Gasser, T., et al. “Negative emissions physically needed to keep global warming below 2 °C.” Nature Communications 6 (2015).3. Caldeira, Ken, Govindasamy Bala, and Long Cao. “The science of geoengineering.” Annual Review of Earth and Planetary Sciences 41 (2013).

As the sun set over the western shores of Singapore on the Friday evening of 11 March 2016, excitement of the Partners’ Appreciation evening, organised by Institute of Chemical and Engineering Sciences (ICES), began to heat up at Portico, a hippy restaurant-bar tucked away at the former Institute of Technical Education (ITE) building located at Pasir Panjang. “Wow, I didn’t know such a place existed”, one guest exclaimed with delight, echoing the sentiments of many others. An evening of dégustation treats awaited as the cheery service crew served up delectable canapés like Crisp Fish and Mashed Potato Croquettes, Truffle Soba Noodles with Buckwheat, Deconstructed Blackforest in a Cup. To top it off, free-flow fruit juices, wine and beer kept 107 guests and ICES hosts in high spirits through the night.

ICES Partners’ Appreciation Evening is an annual event which brings our collaborators together for a casual chill-out evening. We thank our friends for their support and trust, and we look forward to more successful collaborations.

Event Highlights 05

FEEDBACKS FROM OUR PARTNERS:

“Thanks for the invitation. It was very well organised!”

Dr. Lena TangClariant Inernational Ltd

“It was pleasure meetingyour team in a relaxed atmosphere, looking

forward to continue oursuccessful collaboration.”

Mr. Alex BockBluConnection Pte Ltd “Thank you for another

lovely evening.”Dr. Sanjay Kuttan

DNV GL

ICES Partner’s Appreciation Evening 2016

Toasts Up!To StrategicPartnerships!By Ms. Chia Siao-Wei

06 Event Highlights

Singapore Future Exhibition 2016

Building the Futuristic Glimpse of Singapore!By Dr. Teo Peili

A*STAR SME Day 2016 was held on 5 April this year at Sands Expo & Convention Centre. A*STAR SME Day, which was inaugurated in 2014, provides a key platform to promote technology and collaboration opportunities to help the growth and productivity of Small and Medium-sized Enterprises (SMEs). At this year’s event, Institute of Chemical and Engineering Sciences (ICES), together with other A*STAR Research Institutes, exhibited expertise and showcased technologies relevant to SMEs.

A*STAR has rolled out a number of programmes to help SMEs over the years. An example of A*STAR’s initiatives is the Growing Enterprises with Technology Upgrade (GET-Up) Programme which was highlighted by the Guest of Honour, Mr. S. Iswaran, Minister for Trade and Industry (Industry) during the event. Under this programme, one particular assistance scheme that ICES actively supports is the Technology for Enterprise Capability Upgrading (T-Up) scheme. Through this scheme, A*STAR researchers are seconded to SMEs for up to two years, providing businesses with Research & Developmemt (R&D) technology expertise to help improve or provide solutions to their existing production processes, or to assist in product development. To date, ICES has secured 24 T-Ups with SMEs since the launch of the T-Up scheme in 2003.

A*STAR SME Day 2016

Reaching out to SMEsBy Ms. Natalie Soh

Minister of Trade and Industry (Industry), Mr. S. Iswaran, visiting A*STAR exhibition

booths at the event

Research by the Institute of Chemical and Engineering Sciences (ICES) in converting oil palm waste to acrylic acid was displayed at the Singapore Future Exhibition on 31 January 2016. The display described ICES’ method of integrating both biological and chemical processes to obtain an important commodity chemical, acrylic acid. Acrylic acid is a key ingredient used in super-absorbent materials for diapers, hygiene products, paints, textiles and paper. The biological process utilises a bacteria isolated from fungi found in Singapore and the novel catalyst for the chemical process was developed in-house by ICES researchers.

The exhibition attracted many members of the public to understand more about the process as well as understanding how small quantities of super absorbent acrylic acid polymers could absorb large quantities of water through hands-on experience. We demonstrated how sustainable production of important chemical raw materials, currently produced from crude oil, can be achieved from agricultural waste products through our integrated process.

(From left to right) Mr. Wang Peiyi, Dr. Teo Peili, Dr. Ng Wai Kiong at the exhibition booth

Institute of Chemical and Engineering Sciences (ICES) held its second round of training session ‘Encapsulation & Formulation Technologies’ from 18 to 20 January 2016. Its advanced content is tailored to the industry and is built upon the basic module ‘General Science behind Encapsulation’ conducted previously in July 2015. The training included interactive case studies and application examples

in the current installment in response to feedback obtained.

We are pleased to have industry participants from eight companies joining the three-day training to share a cosy learning experience together with the trainers. In addition to trainers from ICES, we are also delighted to have A/Prof. Giorgia Pastorin from National University

of Singapore (NUS) to share with us her expertise on ‘Micelles, Vesicles, and Liposomes’, and Dr. Maria Antipina from Institute of Materials Research and Engineering (IMRE) on ‘Layer-by-Layer Encapsulation’. This reflects the ongoing effort by ICES to engage external experts to share their expertise with our industry partners, enhancing the content offered by ICES.

Dr. Ng Wai Kiong, Programme Manager & Team Leader of Crystallisation & Particle Science from Institute of Chemical and Engineering Sciences (ICES), conducting his session on the topic ‘Formulation Sciences (Capsules)’

CoRE-Net held its second Roundtable Discussion for our industry members at Fusionopolis Two on 15 April 2016 – approximately a year’s anniversary from its launch on 17 April 2015. The network counts seven members, with Nipo International being the latest addition. Our Executive Director, Dr. Keith Carpenter, gave the opening address and interacted with the member representatives.

The members were updated on various items such as the launch of CoRE-Net website and upcoming events. Dr. Alexander Jackson presented on ‘Commercial Examples of Encapsulation Technologies’, while we are also pleased to have invited Ms. Geraldine Goh and Ms. Tan Yi Xin from Singapore Economic Development Board (EDB) to present EDB’s inputs on the megatrends of specialty chemicals worldwide and the relevance to Singapore.

The session was concluded with insightful discussions on topics such as CoRE-Net and SMEs, trends in encapsulation, biodegradable capsules, micron to submicron capsules, and the USA ban of microbeads in cosmetics. For more information on CoRE-Net, please visit www.a-star.edu.sg/core-net.

Event Highlights 07

ICES Training: Encapsulation & Formulation Technologies

Advancing in Encapsulation & FormulationBy Mr. Eugene Chia

CoRE-Net: Roundtable Discussion #2

Reaching the One-Year Milestone with Our Valued MembersBy Mr. Eugene Chia

Dr. Keith Carpenter, Executive Director of Institute of Chemical and Engineering

Sciences (ICES), giving the opening address at the start of the event

We Go GREEN!By Dr. Valerio Isoni

ICEScope is published by the Institute of Chemical and Engineering Sciences (ICES). Reproduction of material in this publication without written permission from ICES is prohibited. For enquiries, please contact: enquiry@ices.a-star.edu.sg

Editorial TeamDr. Keith CarpenterProf. Paul SharrattDr. Abdul Majeed SeayadMr. V. Ravi

Ms. Chia Siao-WeiMs. Kess ChuaMs. Yvonne Xie

20 – 21 June 2016ICES Training: Basic Encapsulation Technologies

22 June 2016 Yoga Stretch-Out Hour

4 – 5 July 2016 ICES Training: Coatings Technology NoSOC (Continuation)

15 & 22 July 2016Inter-Division Friendly Games - Badminton

August 2016Inter-Division Friendly Games - Photography

2 August 2016MRCA Signing with Mitsui Chemicals

12 August 2016ICES Safety Day 2016

September 2016 Energy Efficiency in Chemical Industry Workshop

19 September 2016 iPSP Day

30 September 2016 ICES Annual Dinner 2016

October 2016 Major Hazard Installation (MHI) Symposium

On 30 March 2016, a group of enthusiastic students from National University of Singapore (NUS) Department of Chemistry visited the Institute of Chemical Engineering Sciences (ICES) in Jurong Island. In its second year, this ICES-NUS interaction between undergraduate students and researchers aims to show different applications of green chemistry and green engineering. This yearly appointment is in conjunction with the CM4269 Sustainable & Green Chemistry module conducted by Assoc. Prof. Simon Watts in NUS. As the group embarked on the journey to Jurong Island and into process science, they had the chance to attend a guest lecture by Dr. Valerio Isoni and interact with our staff to discuss career possibilities in Research

& Development (R&D) outside academia. It was also a golden opportunity for them to visit the well-known pilot-plant in ICES, where the students appeared to be fascinated by the unique laboratory setup. We are very happy to continuously achieve the objective of connecting the industry and academia. The event was successful and we are looking forward to host a new batch of students for our third edition next year!

08 Outreach Programmes | Publication

Students from National University of Singapore (NUS) Department of Chemistry attending a guest lecture on process science presented by Dr. Valerio Isoni

Our methodology helps the user to consider quickly and systematically whether a batch process should be converted to a continuous process. Simple guidelines facilitate decision making at different stages of the evaluation, and in particular they support a swift first-pass decision to proceed or to kill the idea, thereby minimising wasted effort. The ordered approach also provides a ‘whole process’ assessment and enables decision making for the appropriate choice of continuous or hybrid processing

mode. Where continuous processing has promise the method helps in systematically identifying the nature and extent of the work required to refine the design. The methodology consists of three stages: initial screening, extended evaluation and process execution. We have used the methods ourselves on three multistep processes that have been operated at kilogram scale; these are presented in some detail in the paper to demonstrate the application of this methodology.

Reference: Teoh, S. K.; Rathi, C.; Sharratt, P., Practical assessment methodology for converting fine chemicals processes from batch to continuous. Organic Process Research & Development 2016, 20 (2), 414-431.

Practical Assessment Methodology for Converting Fine Chemicals Processes from Batch to ContinuousBy Dr. Teoh Soo Khean, Dr. Chetankumar Rathi, Prof. Paul Sharratt Practical Assesment Methodology for Converting Fine

Chemicals Processes from Batch to Continuous

   

Extended Evaluation

Process Execution

Initial Screening

UPCOMING EVENTS