Durham E-Theses Ring opening metathesis polymerisation of

Durham E-Theses

Ring opening metathesis polymerisation of

phenylnorbornene dicarboxyimide derivatives

Mzanywa, Neeba Lucky

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Ring Opening Metathesis Polymerisation of

phenylnorbornene dicarboxyimide

derivatives

A thesis submitted for the degree of Master of Science

at the University of Durham

By

N ceba Lucky, Mzanywa

First degree in Chemistry (Fort Hare, South Africa)

A copyright of this thesis rests with the author. No quotation from it should be published without his prior written consent and information derived from it should be acknowledged.

September 2003

2 3 JUN 2004

Nceba lLuncky M.ZANYW A

JRiDll.g Opening Metathesis Polymerisation of lPhenylnorbornene Dicarboxyimide Derivatives

M§c 2003

ABSTRACT

The work described in this thesis illustrates that a series of exo-phenyl

norbomene dicarboxyimide derivatives are synthesised and characterised using several

spectroscopic methods. It also demonstrates that polymeric material can be prepared

from phenylnorbomene dicarboxyimide derivatives using ROMP. Three well-defined

initiators, ruthenium t-butoxy molybdenum

Mo[CHC(CH3)3][CIOH17N][OC(CH3)3h, Mo (1), and hexafluoro-t-butoxy molybdenum

Mo[CHC(CH3)2C6Hs][CwH!7N][OC(CF3)2CH3h, Mo (2), were used. The polymers

prepared were fully characterised using 1H NMR, 13CNMR, elemental analysis, GPC

and DSC.

The cis I trans contents of the polymers are readily determined from the 1 H

NMR spectrum from the integration of the resonance attributable to cis and trans

olefinic hydrogen. Generally the trans vinylene content for polymers prepared by

ruthenium initiator is about 83%, for the polymers prepared by t-butoxy molybdenum

initiator is about 97% and for the polymers prepared by hexafluoro-t-butoxy

molybdenum initiator is about 31%. The t-butoxy molybdenum initiator produced

polymers with narrow PDI compared to hexafluoro-t-butoxy molybdenum and

ruthenium initiators. This is an indication of a well-controlled living polymerisation

reaction. The hexafluoro-t-butoxy molybdenum initiator produced polymers with

broader PDI. This can be attributed to the secondary metathesis reactions or to the rate

of propagation being faster than the rate of initiation. Polymers obtained by ruthenium

initiator also gave polymers with broader PDI due to secondary metathesis reaction.

The Tg for the polymers prepared by t-butoxy molybdenum initiator were about

l5°C higher than the polymers produced using hexafluoro-t-butoxy molybdenum and

the ruthenium initiators, suggesting that the higher the trans content of the polymer, the

higher the Tg. It was also found that the longer the alkyl chain in the polymer, the lower

the glass transition temperatures. The Tg for the polymers prepared from of exo-phenyl

norbomene dicarboxyimides are generally higher than the polymers obtained from exo

alkyl norbomene dicarboxyimides.

11

ACKNOWLEDGEMENTS

First, I would like to thank my supervisor, Dr Ezat Khosravi for his support and

guidance throughout my work in the department. I would like to thank the NMR staff:

Dr Alan Kenwright, Mr Ian McKeag and Mrs Catherine Heffeman, GPC staff, mass

spectroscopy staff: Miss Lara Turner and Dr M. Jones, Leeds University for DSC: Peter

Hine, and elementary analysis staff: Mrs Joroslava Dostal. I would like also to thank my

colleagues in Dr Ezat's group and all the IRC colleagues. I would also like to thank

Ruth First scholarship friends, African & Caribbean society friends, Durham Amigos

friends, and Dr Luthando Adams for their support throughout my stay in Durham and,

finally my family for their prayers.

MEMORANDUM

The work of this thesis was carried out in the IRC Chemistry laboratories of the

University of Durham between October 2002 and September 2003. This work has not

been submitted for any other degree and is the original work of the author, except where

acknowledged by reference.

FINANCIAL SUPPORl!

I gratefully acknowledge the funding provided by Ruth First Scholarship and Durham

University.

lV

Contents Page

Abstract .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ii

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. iv

Memorandum .. .. . . .. . .. . .. . .. . .. . .. . .. .. .. .. . .. . .. . .. .. .. . .. .. .. .. . .. .. . .. .. .. .. . .. .. .. .. . .. .. iv

Financial support .. . .. . .. . .. . .. . .. . .. . . .. .. . .. . .. . .. .. .. . .. .. . .. .. . . .. . .. .. .. .. . . . .. .. .. .. .. .. . iv

Chapter 1: General introduction and background

1.1 Aims and objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

1.2 Ring opening Metathesis polymerisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.1 Definition and historical background of olefin

metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.2 ROMP mechanism . . .. .. .. . . . . . .. .. . .. . .. . .. . . .. .. .. .. . . . .. . . .. .. . .. ..... 7

1.2.3 ROMP initiators . .. . . . .. . .. . .. . . .. .. . .. . .. . . . . .. . .. . . . . . . . . .. .. .... .. .... .. .. 8

1.2.3.1 Ill-defined initiators .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ....... 8

1.2.3.2 Well-defined initiators .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ........ 9

1.2.4 Microstructure and polymer chains ................................... 15

Chapter 2: Synthesis and characterisation o~ monomers

2.1 Introduction .... 0 0 .... 0 0 0 0 ..... 0 0 00. 00 •••• 0 ... 00 •••••••••••••••••••••• 0 .. 0 .... 00 0 .... 19

2.2 Diels-Alder reaction 0 ................ 00 ............................................ 19

2.2.1 Synthesis and characterisation of

exo-norbomene-5,6 dicarboxyanhydride. 0. 00 ......................... 21

2.3 Synthesis and characterisation of exo-phenylrtorbomene

dicarboxyimide derivatives oooooooooooooo•••••••oo• 24

2.4 Experimental .. 0 ............................................. 0 ....... 0 0 0 ....... 0..... 27


exo-norbomene-5,6 dicarboxyanhydride .. 0 .......... 0 0 ........ 0 0 0 0 ... 27

2.402 Synthesis and characterisation of

exo-N-phenylnorbomene-5,6-dicarboxyimide . 0 ...... 0. 0 ............ 0 28


exo-N-benzylnorbomene-5,6-dicarboxyimide .... 0 0. 0 ... . . .......... 29


exo-N-phenylethylnorbomene-5,6-dicarboxyimide 0 0 0 0 0 0 0 0 0 .. 0. 0 0 30

2.405 Synthesis and characterisation of

V

exo-N-phenylpropylnorbomene-5,6-dicarboxyimide . . . . . ... . . .... 31


exo-N-phenylbutylnorbomene-5,6-dicarboxyimide .. . . . .... . .. .. . 31


exo-N-tert-butylphenylnorbomene-5,6-dicarboxyimide . . . . . . . ... 32


exo-N -pentylphenylnorbomene-5, 6-dicarboxyimide . . . . . . . . . . . . . . 3 3


exo-N-hexylphenylnorbomene-5,6-dicarboxyimide ................ 34

2.4.1 0 Synthesis and characterisation of

exo-N-hexylnorbomene-5,6-dicarboxyimide ........................ 35

Chapter 3: Polymer synthesis and characterisation

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . 3 7

3.2 NMR scale solution polymerisation of

exo-phenylnorbomene dicarboxyimide monomers . . . . . . . . . . . .............. 37

3 .2.1.Polymerisation using ruthenium initiator. .................... 3 7

3.2.2 Polymerisation using t-butoxy molybdenum initiator ...... 39

3.2.3 Polymerisation using hexafluoro-t-butoxy

molybdenum initiator......................................... 40

3.2.4 Copolymerisation of exo-ethylphenylnorbomene

dicarboxyimide and exo-hexylnorbomene dicarboxyimide ..... .41

3 .2.5 Block copolymerisation of exo-ethylphenylnorbomene

dicarboxyimide and exo,endo-norbomene

dimethylcarboxylate ......................................... .44

3.3 Scale up polymerisation reaction .................................................. 47

3.3.1 Polymer characterisation by 1H and 13C

spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 49

3. 3.2 Polymer characterisation by elemental analysis . . . . . . . . . 61

3.3.3 Polymer characterisation by GPC .. .. . .. .. . .. .. .... 62

3.3.4 Polymer characterisation by DSC . . . . . . . . . . . . . . .... .. . . ... 63

Chapter 4: Overall conclusion and proposal for future work

4.1 Overall conclusion................................................................. 66

4.2 Proposal for future work. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 67

VI

Appendix 1: Instrumentation and procedure for measl!lrements ..................... 68

Appendix 2: Analytical data for chapter 2 ................................................. 71

Appendix 3: Analytical data for chapter 3. .. .. .. .. ..... .. . .. .. .. .. ...... .. .. .. .. .. . ...... . 84

Appendix 4: Conferences and seminars attended ....................................... 100

REFERENCE§ .............................................................................. 102

VII

Chapter 1

General introduction and background

Chapter I

1.1 Aims and objectives

Dicyclopentadiene (DCPD) has been widely used as a monomer for polymer processing

methods like Ring Opening Metathesis Polymerisation (ROMP)-Reaction Injection

Moulding (RIM) and ROMP-Resin Transfer Moulding (RTM) for producing material

with good mechanical properties, figure 1.1. 1, 2 Although this has resulted in important

commercial applications, there are some drawbacks like strong monomer odours,

strongly exothermic reaction and problems surrounding the cross-linked material.3

ROMP

Dicyclopentadiene

Poly(dicyclopentadiene)

f-·0~

Cross-linked polymer

Figure 1.1: Cross linking in dicyclopentadiene

In the earlier work4, a series of mono functional n-alkyl norbornene dicarboxyimides

and difunction n-alkylene dinorbornene dicarboxyimides was successfully synthesised,

figure 1.2. The monomers were subjected to ROMP using classical initiators and also

well-detlned molybdenum initiators; the t-butoxy molybdenum initiator

Chapter I 2

Mo[CHC(CH3h][C 10H17N][OC(CH3)3]2, and hexafluoro-t-butoxy molybdenum initiator

Mo[CHC(CH3)2C6Hs][CJOH17N][OC(CF3)2CH3]2. This work served as a benchmark

towards the synthesis and characterisation of polymeric material using RIM-ROMP and

RTM-ROMP.

Figure 1.2: Structure of the (a) monofuntional monomer and (b) the difuntional monomer

The work5 that followed explored further the physical and thermal properties and

provided guidelines and basic parameters for ROMP-RTM processing of norbomene

dicarboxyimides. The initiator used for ROMP reactions was well defined ruthenium

initiator Ch[(C6H 11 )3P]2Ru=CHC6Hs. The Copolymerisation of monofunctional and

difunctional monomers produced well-defined crosslinked materials, figure 1.3.

Chapter I 3

+

RTM-ROMP

Figure 1.3: Cross linking in substituted norbomene

The physical and mechanical properties of the cross linked materials were comparable or

better than some engineering polymers such as polycarbonates and Telene 1100, table

1.1.

I

Polymer Tg Density Modulus Yield/Fracture

kg/m3 Strength

(oC) GP a (Mpa) C4M/2%C12D ~120 1136 2.7+- 0.2 61 +- 15 (F)

C5M/2%Cl2D 106 1120 2.2+- 0.2 72 +- 2 (Y)

C6M/2%C12D 87 1092 1.9 +- 0.1 59+- 3 (Y)

Poly carbonate 150 1200 2.3 62 (Y)

Poly(DCPD) 145 1030 1.9 45 Telene1100

Table 1.1: Shows the comparison of' the new polymeric material with poly(dicyclopentadiene)

However, the Tg of the crosslinked materials were lower than the commercial materials

based on Poly(DCPD).

Chapter I 4

The aim of this work was to improve the glass transition temperature of the material

produced by ROMP-RTM. According to the literature the presence of the phenyl ring

on the side chain of the polymer would raise the glass transition temperature.6

Therefore the objective of the work presented in this thesis was to synthesise and fully

characterise a series of exo-phenyl norbornene dicarboxyimide derivatives, figure 1.4,

subject them to ROMP using well-defined Grubbs ruthenium initiator, and evaluate

their Tgs of the resulting polymers.

Figure 1.4: Structures of phenyl norbornene dicarboxyimide

This work is divided into 4 chapters. The first chapter deals with the historical

background to ROMP and the latest developments on the initiators used in this process.

The second chapter deals with the synthesis and characterisation of monomer, the third

chapter deals with the polymer synthesis and characterisation and the last chapter deals

with conclusion and proposal for future work.

1.2 Ring Opening Metathesis polymerisation (ROMP)

1.2.1 Definition and! historican background of olefin metathesis

Olefin metathesis was discovered in 1920s. It was only 50 years later that it found

usefulness in polymer chemistry and only recently that a lot of useful materials are

produced through this method. Olefin metathesis can be described as the catalytically

induced bond reorganisation reaction that lead to the breaking and making of carbon

carbon double bonds without losing the total and type of chemical bond in the process.

For acyclic olefins the process lead to the exchange of alkylidene units (a) and, for

Chapter I 5

cyclic olefins the process lead to ring scission and the formation of linear polymer (b),

figure 1.5.

(a) +

Figure 1.5: Schematic presentation of olefin metathesis

(a) Schematic representation for acyclic olefins

(b) Schematic representation for cyclic olefins

The reaction for acyclic olefins was first reported by Banks and Barley in 1964 and was

termed 'olefin disproportionation' .7 Three years later, in 1967, Calderon et a/

acknowledged that acylic disproportionation of olefins and ring scission of cyclic

olefins to form linear polymers were example of the same process and hence they

commonly name these reactions 'olefin metathesis' .8 Anderson and Merkling, in 1955,

discovered evidence of olefin metathesis although it was only reported in the 1960s.9 In

the experiment they successfully polymerised bicyclo[2.2.1 ]hept-2-ene using a mixture /

of titanium tetrachloride and ethylmagnesium bromide to initiate the polymerisation,

figure 1.6.

nab TiC14 / EtMgBr

Bicyclo[2.2.1]hept-2-ene Poly(norbornene)

Figure 1.6: Romp of norbornene

Chapter l 6

Several mechanisms were proposed for the olefin metathesis reaction. I0-!2 The widely

accepted mechanism was proposed by Chauvin. The mechanism involved cycloaddition

reaction between metal alkylidene complex and the olefin. The addition proceeds via an

intermediate metallacyclobutane that breaks up to give new alkylidene and a new olefin,

figure 1. 7. This mechanism was a break through to catalyst development as it provided

the basis for the understanding of the way the catalyst system work. This resulted in the

development of single component and well-defined homogeneous catalyst in 1970s and

1980s.14 These new catalysts will be discussed under ROMP initiators

R

[M]~

~~~ --........

Figure 1.7: Chauvin's mechanism for olefin metathesis

1.2.2 ROMP mechanism

Ring opening metathesis polymerisation (ROMP) is a variant of olefin metathesis in

which cyclic olefins are used and new olefin remains attached to the catalyst as part of

the growing chain, figure 1.8. Although ROMP has the same mechanism as the one

Chauvin proposed, the difference is with the second step of ROMP, which is in most

cases is irreversible. With advancement in catalyst development, ROMP system are

considered as living system as there is no termination step, which means that the

polymer chain ends remain active and on addition of the same monomer, the chain

continue to grow until tem1ination is induced. The sequential addition ofthe monomers

results in the synthesis of block polymers.6

Chapter 1 7

0 + -----il>

0 I I

[M]-CHR

-----il>

[M]=CHR

j n 0

Figure 1.8: Mechanistic pathway for ROMP

1.2.3 ROMP initiators

The initiator systems used for ROMP are based on group IV to group IX transition

elements such as Ti, V, Nb, Ta, Mo, W, Re, Ru, Os, and Ir.4'15 The history of initiators

started as early as in 1960's with development of catalyst that were ill-defined but

useful at the time to the present catalyst that are well-defined. The initiators are

therefore categorised into two systems, namely classical (ill-defined systems) and single

component initiators (well-defined systems).

1.2.3.1 Ill-defined initiators

Classical initiators are multiple component systems and are derived from chlorides,

oxides, and oxychlorides of Mo, W, and Re. Cocatalyst for these systems are usually

EtAlCh and ~Sn were R= Ph, Bu or Me and promoters being 0 2, EtOH and PhOH.

These systems can be homogeneous, e.g. WCl6/EtAlCh/EtOH and heterogeneous, e.g.

Mo03/Al03. These initiators suffer from a lot of drawbacks such as:

Chapter 1 8

e The precise nature of the active site at the metal centre is unknown, thus the system

is ill-defined

• The metal carbene must be generated before initiation and subsequent propagation

can commence and this process usually proceeds in a very low yield

• The activity of a given initiation system is dependent upon its chemical, thermal and

mechanical history, and upon the order and rate of mixing ofthe catalyst, eo-catalyst

and monomer

• They have limited tolerance towards functional groups in the monomer or solvent,

• There is a lack of control of molecular weight and molecular weight distribution due

to intra and intermolecular reactions with the double bond

• They display an element of irreproducibility

1.2.3.2 Well-defined initiators

Although classical initiators are still having their place in commercial applications, the

development of single component initiators has promoted a lot of research in ROMP

and resulted in synthesis of polymers with complex architectures that would not have

been possible with ill-defined initiators. Most of this success is due to the fact that the

development of single component initiators has set a benchmark for more improved

initiators with greater functional group tolerance.

The Fischer carbene, which was heteroatom stabilised complex, was the first isolated

metal cm·bene species to be reported in 1964, figure 1.9. 16 The discovery of Casey

carbene, a diphenyl complex followed this in 1973, figure 1.9. 17 Although Casey

carbene was not heteroatom stabilised complex, it was proved to be more reactive

capable of polymerising less strained olefins.

Fischer carbene Casey carbene

Figure1.9: Structural representation of Fischer and Casey car bene Chapter I 9

Table 1.2 show the advancement of functional group tolerance of the initiators from

Titanium initiator, which was only reactive to olefins but could not survive other

functional groups to ruthenium, which is tolerant to wide range of functional groups.

Due to this tolerance, ruthenium has gained a lot of attention in ROMP and this has lead

to more research done to improve the initiation capability of this initiator. Researchers

have noticed that the development of more reactive initiators has a cost on the stability

of the initiator. There is a growing interest to develop initiators that would be more

reactive but maintain the stability.

;, ftt'lhlillm , ; f ifimgst~n iii\16IY.tia~~~rtl : "l,tlltlieniUn,t, '

,>

Alcohol, water Alcohol, water Alcohol, water OLEFINS

Acids Acids Acids ALCOHOL, WATER

Aldehydes Aldehydes Aldehydes ACIDS

Ketones Ketones OLEFINS ALDEHYDES

Esters, amides OLEFINS KETONES KETONES

OLEFINS ESTERS, AMIDES ESTERS, AMIDES ESTERS, AMIDES

Figure 1.2: Outline of different initiators and their respective tolerance to a range

offunctional groups. The tolerance is increased from left to right. The

reactivity of the functional groups is increased from bottom to top.

Tebbe et al prepared a bimetallic methyledene18•19 (Tebbe reagent), which can be

classified as a well defined Ti carbene that is stabilised by coordination of Me2A1Cl and

this carbene set as the benchmark for the discovery of living polymerisation.

Titanacyclobutane complexes shown in figure 1.10 produced the first living

polymerisation of cycloolefin?0-23 These Ti complexes were prepared from Tebbe

reagent. Although these complexes were capable of forming polynorbornene with

narrow molecular weight distribution, the disadvantages were that the polymerisation

required a temperature of 50°C and the functional group tolerance was limited to

olefins.

Chapter 1 10

Tebbe reagent

Cp';,- ~ l c~ II_JJ0

Cp". )r crflj

Tit~nacyclobutane complexes

Figure 1.10: Structural representation ofTebbe reagent and Titanacyclobutane

complexes

Tungsten alkylidene complexes were the next to be isolated. Kress and Osborn prepared

the first well-defined tungsten alkylidene complex24, which required a strong Lewis acid

eo-catalyst such as GaBr3 for increased activity, figure 1.11 The functional group

tolerance was extended esters and amides. Schrock and eo-workers reported well

defined tungsten and molybdenum complexes with bulky alkoxide and arylimido

ligands, figure 1.12.25 The bulky alkoxide groups and imido ligand of both complexes

served as a shield towards intermolecular reactions. Moreover, molybdenum complexes

showed better tolerance, compared to tungsten, which extended functional group

tolerance to ketones.

Figure 1.11: Structural representation ofKress and Osborn complex

m--N M= Wor Mo

11 R = CM8:J or CMe2Ph

R'O-M =CHR R' =CM~ or CM~CF3 or CMe(CF3)2

I R'O

Figure 1.12: Structural representation ofSchrock's initiators

Chapter I 11

The most widely studied are t-butoxy substituted molybdenum initiator (complex 1) and

hexafluoro-t-butoxy substituted molybdenum initiator (complex 2), figure 1.13. 4'25

-29

Molybdenum complex 2 was found to be the most reactive of all the molybdenum

derivatives.

1 2

Figure 1.13: Structural representation of two molybdenum complexes and ruthenium

complex.

The discovery of ruthenium alkyledene complexes extended the scope to a wide range

of functional group tolerance and hence they have been widely studied in recent years.

The history of ruthenium based initiators started with the simple salts to well-defined

ruthenium alkyledene complexes. Ruthenium salts did not get much exposure in ROMP

because of low reactivity and limited functional group tolerance. Other attempts resulted

in ROMP but with longer reaction time and the complexes were only limited to highly

strained substrates14. The isolation of ruthenium alkyledene complex 3 was a

breakthrough in ruthenium catalyst development, figure 1.14. 30 Although the discovery

of this complex was a step forward, the drawback was that the complex was limited to

only highly strained monomers. The research work that followed, led to the discovery of

the second series of these ruthenium alkylidene complexes, complex 431 and 532,

figure 1.14. The work focused on modification of the ligand environment so as to extend

the activity to low strained monomers. Complex 4, was found to have a broader

metathesis activity that incorporated metathesis of acyclic olefins and an increased33

tolerance to most functionalities. However, complex 5 was found to be the most active

complex of the series.

Chapter I 12

PPh3 PCy3 PC~ Cl" I Cl" I Cl" I I: /Ru~Ph CI/R~Ph CI/Ru

Cl I - Ph I Ph I H PPh3 PCy3

PCy3

3 4 5

Figure 1.14: Series of ruthenium complexes

Further work led to the discovery of a family of mesityl-substituted N-heterocyclic

carbeme, figure 1.15. It was reported that complexes 634 and 735 were more reactive

than complex 5 and complex 735 was the most reactive. These complexes expanded the

scope ofthe monomers to sterically hindered olefins?4,3

6

6 7

Figure 1.15: Mesityl-substituted N-heterocyclic carbenes

The drawback to complex 5 or its most active derivative 7 was broad polydispersity

indices (between 1.3 and 1.5), which are attributed to unfavourable rate of initiation (k;)

as compared to propagation (kp) and secondary metathesis. This has resulted in

synthesis of a new family of Ru-based initiators by substituting one of PCy3 ligand with

different phosphines. Gibson and eo-worker established that the initiation efficiency of

5 can be enhanced by replacing one of the PCy3 ligand with Cy2PCH2Si(CH)3 to form a

new initiation complex 8, figure 1.16?7 The enhanced initiation was attributed to lower

basicity and smaller size of Cy2PCH2Si(CH3)3.

Chapter 1 13

Figure 1.16: TMS ligand exchange in ruthenium initiator

Work by Grubbs et al showed that the olefin metathesis reaction catalysed by ruthenium

complexes 5 or 7 proceed via a dissociative mechanism which can either bind to free

PCy3 to form the initial alkyledene complex or bind to the substrate and undergo

metathesis, figure 1.17.38

L

Cl" I (J Cl/ Ru-====<:::

H

k2 +olefin

-olefin

k_2

Figure 1.17: Dissociative mechanism of olefin metathesis

L

Cl" I 11) Cl/ Ru-====<::: / I H

R

Recent research by Bielawski and Grubbs has shown that addition of phosphine in the

polymerisation reaction can enhance the initiation efficiency, without having to

synthesize a new complex. The PDis in a particular experiment improved from 1.25

without the added phosphine to 1.04, depending on the type and number of equivalents

of phosphine added and also to the number of equivalents of monomer. This was due to

the fact that the rate of phosphine exchange is faster, as the result the formation of a new

complex with labile phosphine can occur before initiation. They concluded that

polymers with narrow polydispersity could be achieved this way, figure 1.18.39

Chapter 1 14

PR3 (fast)

Figure 1.18: Schematic representation of phosphine exchange mechanism

1.2.4 Microstructure of polymer chains and stereo regularity

For ROMP systems there are three main factors that define the microstructure of the

polymers:

o Cis/trans vinylene ratios and distribution

o Tacticity effect

o Head to head, head to tail and tail-to-tail arrangements

(i) Cis/trans vinylene ratios and distribution.

The repeating units in the backbone of the polymer chain are distributed in a cis and

trans configuration, figure 1.19. The distribution depends on the type of solvent,

monomer and catalyst system and concentration. For example for molybdenum catalyst

systems, the molybdenum (1) catalyst gives high trans distribution whereas

molybdenum (2) gives high cis configuration.4

Cis

Trans

Figure 1.19: Cis I trans double bonds in polynorbomene

Chapter 1 15

(ii) Tacticity effect

The repeating units of polymers like polynorbornene have chiral centres and each

configurational unit of a polymer chain is the dyad, figure 1.20. A meso dyad is

observed when the chiralities of the two chiral carbons adjacent to the double bond are

opposite and a series of meso dyads gives isotactic polymers. A racemic dyad on the

other hand is observed when the chiralities of the two chiral carbons adjacent to double

bond are the same and a series of racemic dyads gives syndiotatic polymers.

Cis - isotactic

Cis - syndiotactic

Trans - isotactic

Trans - syndiotactic

Figure 1.20: Tacticity effect in polynorbornene

(iii) Head to head, head to tail and tail-to-tail arrangements.

Unsymmetrically substituted monomers give rise to head to head, head to tail or tail-to

tail form. Figure 1.21 shows the different fonns. The polymers prepared from this thesis

are synthesized from symmetrically substituted monomer and therefore, the polymers

will not experience the tail I head effects.

Chapter 1 16

R TTTT HH HH TH HT

Figure 1.21: Head I Tail effects in the polymer ofunsymmetrical

substituted monomer

Chapter 1 17

Chapter 2

Synthesis and characterisation of the monomers

18

2.1 Introduction

The focus of this chapter is on the synthesis of monofunctional phenylnorbornene

dicarboxyimide derivatives. These are synthesised in two steps. The first step is the

Diels-Alder cycloaddition reaction of maleic anhydride and dicyclopentadiene to give a

mixture of exo I endo -norbornene-5,6-dicarboxyanhydride. This is followed by

rec1ystallisation in acetone for several times (at least five times) to give pure exo

norbornene dicarboxyanhydride (exo-AN). The second step is the reaction of the pure

exo-AN with phenylamines to produce phenylnorbornene dicarboxyimide derivatives.

Only exo-monomers are synthesized in this work, as they have proved in previous work

to be very reactive for ROMP reactions.5•40

2.2 Diels-Alder reaction

The reaction involves conjugate addition of a conjugated diene to an alkene, dienophile,

to produce a cyclohexene. It is one of the few methods available for forming cyclic

molecules and hence it is also called cycloaddition as the reaction produce cyclic

products.41 The simplest example is the reaction of 1,3-butadiene with alkene to form

cyclohexene. The reaction proceeds through a cyclic transition state in a single step

process.42

+ 11

heat 0 1 ,3-butadiene ethene cyclohexene

Figure 2.1: The Diels-Alder reaction between a conjugated diene and dienophile.

It is a widely used and studied method in organic synthesis ever since it was first

reported in 1928.43 It has gained synthetic applicability in the synthesis of compounds

such as drugs, dyes and polymers chemistry. The experimental procedures for this

reaction are usually simple and it produces good yields. For Diels-Alder cycloaddition

19

to occur under normal conditions the dienophile must contain electron withdrawing

group and the diene must contain electron-donating group.

Diels-Alder reaction is stereospecific with respect to both the diene and dienophile as

the result the stereochemistry of the dienophile determines the stereochemistry of the

resulting product.41 Most importantly the diene must be in the cis conformation in order

to react.44 This relationship is illustrated in figure 2.2.

( +

R'

( R

- CCR R

cis-dienophile cis-substituted product

R'

f R --trans-dienophile trans-substituted product

Figure 2.2: A schematic representation showing the dependence of the stereochemistry of the

product on the stereochemistry of the dienophile in a Diels-Alder reaction.

The stereoisomeric product of cyclic dienes depends on the orientation of dienophile to

the diene in the transition state and that results in two possible additions that is endo and

exo.45 If the dienophile lies under the diene an endo product is formed and if the

dienophile lies away form the diene the exo is formed. Endo product is usually the

major product due to kinetic control and due to the best overlap when the two reactant

lies on top of each other.46'47

20

~0 0

exo addition

Orientation of dienophile in the transition state

Hesunder I

0

~saway

~ 0~ 0

--- ~0 0

Endo addition

Figure 2.3: The schematic representation showing the dependence of type of addition on the orientation of the

dienophile from the diene in the transition state of a Diels-Alder reaction.

2.2.1 Synthesis and characterisation

dicarboxyanhydride

~: 0

Maleic anhydride

+ Dichlorobenzene

180°C

Dicyclopentadiene

of exo-norbornerne-5,6-

~0 0

Mixture of exo and endo-AN

Recrystallisation (in acetone)

~0 0

Pure exo-AN

Figure 2.4: Outline ofthe synthetic route for exo-AN

The synthesis of exo-norbomene-5,6-dicarboxyanhydride (exo-AN) was the result of a

Diels-Alder reaction between maleic anhydride and dicyclopentadiene.4·5•48 The

21

reaction was carried out at 180°e in dichlorobenzene as the solvent for 16 hours. At this

temperature, which is the boiling point of dichlorobenzene, dicyclopentadiene was

cracked into two cyclopentadiene, which then react with the maleic anhydride .. The

product formed by the reaction was the mixture of exo and endo-norbornene-5,6-

dicarboxyanhydride. In order to get a pure exo-adduct, the mixture was recrystallised

several times from acetone (at least five times). The product was clear, crystalline solid.

Analytical methods like 1 H and 13e NMR, elemental analysis, and mass spectroscopy

were used to confinn the product. The mass spectrum showed a parent peak (M) at

164, which corresponded with the molecular weight of exo-AN and the peak at 66

correspond to cyclopentadiene. The mass spectrum is shown in figure 2.5. The peaks in

the 1H and 13e NMR are similar to the peaks for exo-AN in the previous work5 and the

spectrum is shown in figure 2.6. The results are found in the experimental section ofthis

chapter.

1001 66 4.0E6

95 M+-C,H,01 3.8E6

90 91 3.6E6

85 3.4E6

80 '3 .2E6

75 3.0E6

70 2.8E6

65 2 .6E6

60 2.4E6

55 2.2E6

50 2.0E6

45 1.8E6

40 1.6E6

35 _1.4E6

30 1.2E6

25 l.OE6

20 8.0E5 51 120

6.0E5 15

10

,J 11

M·-co, 164 4.0ES

5 J~ ~~~~ y -f. M•, C,H801 2.0ES

0 I O.OEO

40 50_ 60 70 80 90 160 iio 1 0 l:lo 140 lSO 160 i?o 1ao i9o 260 2 0 m/z

Figure 2.5: Mass spectrum of exo-norbornene-5,6-dicarboxyanhydride

22

(a)

2,3

7 6 5 4

2,3

8,9

5,6

1,4

3 2

1,4 5,6

7

*

I I

pp m

I) 11 iljfil ijlli I ji ill Jllii jlliijii I 1]1 illjlllljillljlllfjll I I) ill 1 jlliijll iljllllji 11 ijlllljililj

180 160 140 120 100 80 60 40

Figure 2.6: (a) 1HNMR spectrum of exo-AN in acetone

(b) 13CNMR spectrum ofexo-AN in acetone

* Residual hydrogen in acetone

o Water in acetone

pp m

23

2.3 Synthesis and characterisation of exo-phenylnorbornene dicarboxyimides

~0 118-120°C AcOH

~N-R 0 0

Pure Exo-AN Exo-monomer

Figure 2.7: Outline of the synthetic route for exo-monomers where R-NH2 is phenyl amines

Synthesis of exo-monofuntional and exo-difuntional monomers using aliphatic amines

has been done successfully in the previous work using Diels-Alder reaction giving

product in high yields. In this work the focus was on the use of a series of phenyl

amines. The synthesis of the monomers was the result of a reaction between the pure

exo-AN and a series of phenyl amines. The reaction was carried out at l20°C using the

solvent glacial acetic acid. At this temperature, amines were added drop wise for a

certain period of time to react with exo-AN. After the addition was complete, the

reaction mixture was left for a further two. hours to reflux. All monomers were

recovered as solids except exo-C6M, which was recovered as the clear liquid. A single

recrystallisation was necessary to purify the. solid monomers, while exo-C6M was

purified by distillation. All monomers were soluble in chlorinated solvents. Analytical

methods like 1H and 13C NMR, elemental analysis, and mass spectroscopy were used to

confirm the product. Figure 2.8 shows an example of one of the monomers.

~0 AcOH

~N-o 0 0

Pure Exo-AN Exo-PhM

Figure 2.8: Outline ofthe synthetic route for exo-N-phenylnorbornene-5,6-dicarboxyimide

24

The NMR analysis of these monomers was similar to that of the previous work, with the

phenyl protons found in the region from 7.26 to 7.47ppm and the phenyl carbons in the

region from 126.03-151.89ppm. The result for mass spectroscopy showed that the

parent peak (M+) of each spectrum corresponded with the molecular weight of the

corresponding monomer and in addition there were two peaks, (66) and ~-66), which

are characteristic peak of reverse Diels-Alder reaction. The result found for elemental

analysis was close and in some cases the same as the calculated values. The results of

these monomers are found in the experimental section of this chapter. To illustrate the

characterisation of the monomers, figure 2. 9 shows the mass spectrum of the exo-PhM

monomer and figure 2.10 shows the 1H NMR and 13C NMR. The expanded part in

figure 2.10 (a) and (b) shows the proton and carbon signal in the phenyl ring

respectively.

'10 eo ~0 T?O J 0 T10 J~O r~o :SQO :s~o 3 0 3~o - :s~o. JQO 3~0 3f0 3~0 W\~

0 11'" 11'111' 11 :sfo· O'OEO

2 .l'JE<J

TO J"2E2

12 3':SE2 103

:so ~ f'-C QH,No,na 3'31!2

:i2 2'1 .l 3".lE2

30 J:Sil M·-c,H,; <f"<fE2

32 2"JE2

'10 2"8E2

'12 e·eE2

20 M·-c.H.o, .l"3E2

22 M', C15H13NO, 8"0E2

eo 8"81!2

e2 333 il"2E2

.lO T"OEe

.l2 ilJ r·rEe

eo r:sEe

82 r:SEe

ilO J"JEe

32 T.l3 r<rEe

JOOi ee r·2Ee

Figure 2.9: Mass spectrum of exo-N-phenlynorbomene-5,6-dicarboxyimide

25

0

(a)

(b)

11 12

N~13 15 14

12,14 11,15

13

I I I I' I I I I I I I I I I I I I I' I I I I' I I I I' I I I I' I I I I' I I •

7

7.:/J

I I

I

10

I

I I

I I

I I

I 2,3

7.40 7.30 ppm

1,4

6 5 4

12,14 11,15

13

5,6

3

I I I I I I I I I 11 J I I I I I I 1 I I I I I I 1 I I I I I I I ) I I I I I I I I I I I I I I I I

• 134 131 128 pp m

2,3

* 8,9

1 I

7 7'

' I '

2 pp m

1,4 5,6

7

_l_ -'----4---l-'l: I _.e____;.-.---__}L_ _ _A.J._J___

jtlllj I I 11j I iltji it I j I 11 f[llltjll I I (1 I !1 j If I lj I 11 I if I I ljlltljtlltjl ri ij I 1 I tjt I I! j 11 ttjlf I I

180 160 140 120 100 80 60

Figure 2.10: (a) 1HNMR spectrum of exo-PhM in CDCh

(b) 13CNMR spectrum ofexo-PhM in CDCh

* Residual hydrogen in CDCh

40 pp m

26

2.4 Experimental

Reagents

Maleic anhydride, dicyclopentadiene, 1.2-diclorobenzene, n-alkylamine and n

phenylamines were purchased from A ldrich Company Ltd, acetic acid, acetone were

purchased from BDH Chemical Company Ltd. All reagents and solvents were used

without further purification.

2.4.1 Synthesis and characterisation of exo-norbornerne-5,6-dicarboxyanhydride

Maleic anhydride (490.2g, 5.0mol) and 1,2-dichlorobenzene (500ml) were placed in a,

3-necked round bottom flask (lOOOml). The flask was fitted with a stopper, a condenser

and a dropping funnel. The mixture was heated to 180°C and dicyclopentadiene (335ml,

2.5mol) was added via a dropping funnel. The mixture was left overnight to reflux and

brown solution was formed. The product was recovered from the solution by filtration

and dried in the vacuum oven. The product was yellow crystals, which was a mixture of

exo and endo-norbomene dicarboxyanhydride. The product was recrystallised five times

in hot acetone to give 100% pure exo-norbomene-5,6-dicarboxyanhydride.

(a) Elemental analysis of C9Hs03: calculated (found)

C = 65.85% (65.75%), H = 4.91% (4.89%), 0 = 29.24% (29.36%)

(b) 1H NMR (see appendix x), CDCh, 500 MHz, o (ppm)

6.37 (s, 2H, Hz,3 ), 3.34 (s, 2H, H1,4), 3.13 (s, 2H, Hs,6), 1.59 (d, 1H, H7),

1.39 (d, 1H, HT)

(c) 13C NMR (see appendix y), CDCh, 500 l.VIHz, o (ppm)

177.37 (Cs,9), 138.05 (Cz,3), 49.13 (Cs,6), 46.73 (CI,4), 43.95 (C7).

(d) Mass spectrum (see appendix z), (Ell:

164 (M+, C9Hs03), 120 (M+- COz), 66 (M+- C4H203)

27

Assignment of C and H atoms of exo-AN

2.4.2 Synthesis and characterisation of exo-N-phenylnorbornene-5,6-

dicarboxyimide: (exo-PhM)

Exo-norbornene-5,6-dicarboxyanhydride (5.003g, 0.03mol) and glacial acetic acid

(35ml) were placed in a 3-necked round-bottomed flask (lOOml). The flask was fitted

with a suba-seal, condenser and a thermometer. The top of the condenser was fitted with

drying tube. The mixture was heated to 120°C and aniline (2.84g, 0.03mol) was added

drop wise for 25min using a disposable syringe via a suba seal. The resulting yellow

solution was left to reflux for 2 hours. The solution was then poured into cold distilled

water (50ml) and a white precipitate was formed. Dichloromethane (50ml) was added

twice to extract the monomer. The monomer was then washed twice with distilled water

(50ml). The monomer was then dried over anhydrous magnesium sulphate.

Dichloromethane was removed under reduce pressure to give pale yellow crystals. The

monomer was recrystallised from toluene and was dried using a vacuum oven (5.6g,

0.023mol, 77%, mpt: 201 °C).

(a) Elemental Analysis of C15H13N02: calculated (found)

C = 75.30% (75.40%), H = 5.48% (5.47%), N = 5.85% (5.89%), 0 = 13.37% (13.24%)


7.47 (t, 2H, H12,14), 7.39 (t, 1H, H 13), 7.26 (d, 2H, Hll,Is), 6.35 (s, 2H, H2,3 ),

3.41 (s, 2H, HI,4), 2.86 (s, 2H, Hs,6), 1.62 (d, lH, H7), 1.49 (d, 1H, HT)

(c) 13C NMR (see appendix y), CDCh, 500 MHz, o (ppm)

177.32 (Cs,9), 138.23 (C2,3), 132.05 (C 10), 129.42 (Cl2,I4), 128.91 (C13), 126.60 (CII,I5 ),

48.10 (Cs,6), 46.06 (CI,4), 43.20 (C7).

28

(d) Mass spectrum (see appendix z), (E:r).

239 ~' CisH13N02), 173 (~- CsH6), 91 ~- C9Hs02), 66 (~- CwH1N02)

7

11 12 ~ 11 12

3~---'013

Hh.!7 Hr 3 N~13

2 0 15 14 2 0 15 14

Assignments for C and H atoms of exo-PhM

2.4.3 Synthesis and characterisation of exo-N-benzylnorbornene-5,6-

dicarboxyimide: ( exo-PhCM)

The same procedure as in section 2.4.2 was followed using exo-AN (5.004g, 0.03mol)

and benzylamine (3.26g, 0.030mol). The monomer was recovered as white crystals,

which was recrystallised in hexane to give white solid (4.93g, 0.020mol, 64% yield,

mpt: 103°C).

(a) Elemental Analysis of C16H1sN02: calculated (found)

C = 75.87% (75.92%), H =5.97% (5.96%), N = 5.53% (5.53%), 0 =12.63% (12.59%)


7.38 (d, 2H, H 12,t6), 7.30 (t, 2H, Hl3,I5), 7.28 (t, 1H, H14), 6.27 (s, 2H, H2,3), 4.61 (s, 2H,

H 10), 3.24 (s, 2H, H 1,4), 2.67 (s, 2H, H5,6), 1.40 (d, 1H, H1), 1.06 (d, 1H, HT)

(c) 13C NMR (see appendix y), CDCb, 500 MHz, o (ppm)

177.93 (C8,9), 138.16 (C2,3), 136.13 (C 11), 129.11 (CI2,I6), 128.88 (CI3,I5), 128.15 (C14),

48.02 (Cs,6), 45.52 (Ct,4), 42.87 (C1), 42.58 (Cw)

(d) Mass spectrum (see appendix z), (El+).

253 (~, C16HtsN02), 187 (~- CsH6), 91 (~- C9HsN02), 66 (M+- C1IH9N02)

29

H

12 13

8 10 -u11j \\ N-cH \ 14

9 2 ---

16 15 0

Assignment of C and H atoms for exo-PhCM

2.4.4 Synthesis and characterisation of exo-N-phenyletlllylnorbornene-5,6-

dicarboxyimide: ( exo-PhC2M).

The same procedure as in section 2.4.2 was followed using exo-AN (5.002g, 0.03mol)

and phenylethylamine (3.69g, 0.030mol). The monomer was recovered as yellow liquid,

which then solidified at room temperature. The monomer was recrystallised in ether to

give white solid (5.29g, 0.020mol, 65% yield, mpt: 94°C).

(a) Elementary Analysis of C17H17N02: calculated (found)

C = 76.38% (76.41 %), H = 6.41% (6.41 %), N = 5.24% (5.03%), 0 = 11.97% (12.15%)

(b) 1H NMR (see appendix x), CDCh, 500 MHz, c) (ppm)

7.28 (t, 2H, Ht4,t6), 7.23 (d, 2H, H13,t7), 7.22 (t, 1H, Hts), 6.26 (s, 2H, H2,J ),

3.72 (t, 2H, Hw), 3.22 (s, 2H, Ht,4), 2.88 (t, 2H, H 11 ), 2.63 (s, 2H, H5,6), 1.41 (d, IH,

H1), 1.02 (d, 1H, HT)

(c) 13C NMR (see appendix y), CDCh, 500 MHz, c) (ppm)

178.10 (Cs,9), 138.04 (C2,3), 137.93 (C12), 129.06 (Cn,!7), 128.76 (Ct4,t6), 126.92 (Cts),

48.00 (Cs,6), 45.33 (Ct,4), 42.86 (C7), 39.91 (Cw), 33.70 (Ctt).

(d) Mass spectrum (see appendix z), (Ell.

267 (~, Ct7H17N02), 104* (~- C9H9N02), 91 (M+- CwHwN02), 66 (~- C12HttN02)

13 14

8 N~Hb~~15 9 2 2~---

17 16 0

Assignment of C and H atoms of exo-PhC2M

30

2.4.5 Synthesis and characterisation of exo-N-phenylpropylnorbornene-5,6-

dicarboxyimide: ( exo-PhC3M)

The same procedure as in section 2.4.2 was followed using exo-AN (5.00lg, 0.03mol)

and phenylpropylamine ( 4.12g, 0.030mol). The monomer was recovered as white

crystals, which was recrystallised in ether to give pale yellow solid (6.49g, 0.023mol,

76% yield, mpt: 64°C)

(a) Elementary Analysis of C18H 19N02: calculated (found)

C = 76.84% (76.86%), H = 6.81% (6.82%), N = 4.98% (4.88%), 0 = 11.37% (11.44%)

(b) 1H NMR (see appendix x), CDCh, 500 Mllz, o (ppm)

7.26 (t, 2H, His,J7), 7.23 (d, 2H, H14,Is), 7.22 (t, 1H, HI6), 6.26 (s, 2H, H2,3 ), 3.52 (t, 2H,

H10), 3.25 (s, 2H, H1,4), 2.63 (t, 2H, H12), 2.61 (s, 2H, Hs,6), 1.89 (p; 2H, HII), 1.48 (d,

1H, H1), 1.20 (d, 1H, H7')

(c) 13C NMR (see appendix y), CDCh, 500 Mllz, o (ppm)

178.28 (Cs,9), 141.17 (Cn), 138.04 (C2,3), 128.66 (Cis,!7), 128.52 (CI4,I8), 126.30 (C16 ),

48.02 (Cs,6), 45.37 (CI,4), 42.98 (C1), 38.75 (Cw), 33.55 (C12), 29.33 (C11).


281 (M\ C1sHI9N02), 177 (MH+-CsH9), 117* ~- C9H10N02), 91 (M+- C11H12N02),

66 (M+- C13H13N02)

H 7 7 Hr

0


2.4.6 Synthesis and characterisation of exo-N-phenylbutylnorbornene-5,6-

dicarboxyimide: (exo-PhC4M)

The same procedure as in 2.4.2 was followed using exo-AN (5.002g, 0.03mol) and

phenylbutylamine (4.553g, 0.030mol). The monomer was recovered as white crystals,

which was recrystallised in toluene to give white solid (4.93g, 0.02lmol, 68% yield,

mpt: 115°C).

31

(a) Elementary Analysis of e 19H21N02: calculated (found)

C = 77.26% (77.32%), H = 7.17% (7.19%), N = 4.74% (4.73%), 0 = 10.83% (10.76%)

(b) 1H NMR (see appendix x), eDCh, 500 MHz, o (ppm)

7.26 (t, 2H, HI6,Is), 7.16 (t, 1H, H17), 7.15 (d, 2H, His,I9),6.27 (s, 2H, H2,3), 3.48 (t, 2H,

Hw), 3.25 (s, 2H, H1,4), 2.65 (s, 2H, Hs,6), 2.62 (t, 2H, H13), 1.60 (t, 4H, H 11 ,12), 1.49 (d,

1H, H1), 1.20 (d, 1H, HT)

(c) ne NMR (see appendix y), eDCh, 500 MHz, o (ppm)

178.33 (Cs,9), 142.17 (CI4), 138.06 (C2,3), 128.64 (CI5,I9), 128.59 (CI6,I8), 126.08 (C!7 ),

48.04 (Cs,6), 45.39 (CI,4), 42.98 (C7), 38.67 (Cw), 35.58 (CII), 29.05 (C12), 27.64 (C13).


295 (M\ C19H21N02), 230 (M.l-t-CsH6), 91 (M+- C12H14N02), 66 (M+- C14HisN02)


2.4. 7 Synthesis and characterisation of exo-N-tert-butylphenylnorbornene-5,6-

dicarboxyimide: ( exo-e4PhM)

The same procedure as in figure 2.4.2 was followed using exo-AN (5.008g, 0.03mol)

and 4-tert-butylaniline (3.26g, 0.030mol). The monomer was recovered as white

crystals, which was recrystallised in toluene to give white solid (4.556g, 0.020mol, 68%

yield, mpt: 165°C).


C = 77.26% (77.39%), H = 7.17% (7.19%), N = 4.74% (4.73%), 0 = 10.83% (10.69%)

(b) 1H NMR (see appendix x), CDC13, 500 MHz, o (ppm)

7.47 (d, 2H, H 11 ,1 5), 7.18 (d, 2H, H12,14), 6.33 (s, 2H, H2,J ), 3.39 (s, 2H, H1,4), 2.84 (s,

2H, H5,6), 1.60 (d, 1H, H1), 1.48 (d, 1H, HT), 1.32 (s,9H, H17).

(c) ne NMR (see appendix y), eDCh, 500 MHz, o (ppm)

32

177.51 (Cs,9), 151.89 (C JO), 138.23 (Cz,J), 129.33 (C13), 126.46 (CII,Is), 126.03 (CI2,I4),

48.08 (Cs,6), 46.05 (CI,4), 43.19 (C7), 34.98 (CI6), 31.51 (C17).

(d) Mass spectrum (see appendix z), (E:r).

295 (~, C19HziNOz), 280 ~-CH3), 229 ~- CI4HisNOz), 214 ~-CH3-CsH6), 66

(M+- C14H1sNOz)

Analysis data for exo-C4PhM

2.4.8 Synthesis and characterisation of exo-N-pentylphenylnorbornene-5,6-

dicarboxyimide: ( exo-C5PhM).

The same procedure as in figure 2.4.2 was followed using exo-AN (5.006g, 0.03mol)

and benzylamine (4.978g, 0.03mol). The monomer was recovered as pink crystals,

which was recrystallised in hexane to give pinkish solid (8.lg, 0.026mol, 86% yield,

mpt: 108°C)

(a) Elemental Analysis of C20H23NOz: calculated (found)

C = 77.64% (77.90%), H = 7.49% (7.53%), N = 4.53% (4.55%), 0 = 10.34% (10.02%)

(b) 1H NMR (see appendix x), CDCb, 500 MHz, () (ppm)

7.27 (d, 2H, Hll,Is), 7.15 (d, 2H, H12,14), 6.34 (s, 2H, H2,3 ), 3.39 (s, 2H, H1,4), 2.84 (s,

2H, H5,6), 2.62 (HI6), 1.61 (m, 3H, H17 and H7), 1.48 (d, 1H, Hr), 1.32 (m, 4H, His,I9),

0.89 (t, 3H, Hzo).

(c) 13C NMR (see appendix y), CDCb, 500 MHz, () (ppm)

177.50 (Cs,9), 143,91 (C 10), 138.22 (Cz,J), 129.52 (C13), 129.42 (CII,Is), 126.32 (Cn,I4),

48.07 (Cs,6), 46.03 (CI,4), 43.18 (C7), 35.86 (CI6), 31.67 (C17), 31.21 (Cis), 22.75 (C19),

14.26 (Czo).

(d) Mass spectrum (see appendix z)

309 (~, CzoH23NOz), 243 (~-CsH6), 186 (M+-C6Hs-C4H9), 66 (~- C1sH17NOz)

33

0 11 12

HM7 H7' 16 17 18 19 20

3 ~of ~ CHCHCHCHCH 2 2 2 2 3 -

2 15 14 0

Assignment of C and H atoms for exo-C5PhM

2.4.9 Synthesis and characterisation of exo-N-hexylphenylnorbornene-5,6-

dicarboxyimide: ( exo-C6PhM).

The same procedure as in 2.4.2 was followed using exo-AN (4.631g, 0.028mol) and

benzylamine (5.000g, 0.028mol). The monomer was recovered as white crystals, which

was recrystallised in hexane to give white solid (7.7g, 0.024mol, 84% yield, mpt: 96°C)


C = 77.99% (77.93%), H = 7.79% (7.73%), N = 4.33% (4.23%), 0 = 9.89% (10.11%)


7.26 (d, 2H, Hll,Js), 7.15 (d, 2H, H12,I4), 6.34 (s, 2H, H2.3 ), 3.39 (s, 2H, H1,4); 2.84 (s,

2H, Hs,6), 2.62 (H16), 1.61 (m, 3H, H17 and H7), 1.48 (d, lH, HT), 1.30 (m, 6H, H18_20),

0.88 (t, 3H, H21).

(c) 13C NMR (see appendix y), CDCb, 500 MHz, o (ppm)

177.49 (Cs,9), 143.92 (C JO), 138.22 (C2,3), 129.51 (C13), 129.41 (CII,Is), 126.31 (CI2,I4),

48.07 (Cs,6), 46.03 (CI,4), 43.18 (C7), 35.90 (CI6), 31.93(CI7), 31.50 (Cis), 29.20 (C19),

22.83 (C20), 14.35 (C21).


323 (~, c21H2sN02), 257 (M+-CsH6), 186 (M+- C6Hs- CsHJI), 66 (~- CI6HI9N02)

Assignment of C and H atoms for exo-C6PhM

34

2.4.10 Synthesis and characterisation of exo-N-hexylnorbornene-5,6-

dicarboxyimide: ( exo-C6M).

The same procedure as in 2.4.2 was followed using exo-AN (1 0.09g, 0.060mol) and

hexylamine (6.16g, 0.060mol). The monomer was recovered as pale yellow liquid,

which was distilled to give colourless liquid (87% yield, bpt: 130@ 4mmbar).

(a) Elemental Analysis of C1sH21N02: calculated (found)

C = 72.84% (72.49%), H = 8.56% (8.52%), N = 5.66% (6.80%), 0 = 12.94% (12.19%)

(b) 1H NMR (see appendix x), CDCh, 500 MHz, () (ppm)

6.28 (s, 2H, H2,3 ), 3.45 (t, 2H, H10), 3.27 (s, 2H, H1,4), 2.67 (s, 2H, Hs,6), 1.52 (m, 3H,

H11 and H7), 1.28 (m, 6H, H 12_14), 1.23 (d, 1H, HT), 0.87 (t, 3H, His).

(c) 13C NMR (see appendix y), CDCh, 500 MHz, <> (ppm)

178.33 (Cs,9), 138.04 (C2,3), 48.00 (Cs,6), 45.36 (CI,4), 42.91 (C7), 38.96 (CIO), 31.52

(CII), 27.93 (C12), 26.82 (C13), 22.68 (CI4), 14.20 (Cis).


247 (M+, CisH21N02), 182 (M+-CsH6), 186 ~- CsH6- CsHII), 66 (~- C10HisN02)

7

10 11 12 13 14 15 3 N-CH2CH2CH2CH 2CH2CH3

2 0

Assignment of C and H atoms for exo-C6M

35

Chapter 3

Polymer synthesis and characterisation

Chapter 3 36

3.1 Introduction

The focus of this chapter is on the synthesis of linear polymers via ROMP of exo

phenyl norbomene dicarboxyimide monomers using well-defined initiators. The

initiators used for polymerisation reaction were well defined ruthenium carbene initiator

{Ch[(C6HII)3PhRu=CHC6Hs}, the t-butoxy substituted molybdenum initiator

{Mo[CHC(CH3)3][CIOH17N][OC(CH3)3]2}, Mo (1), and hexafluoro-t-butoxy substituted

molybdenum initiator {Mo[CHC(CH3)2C6Hs][CwHl7N][OC(CF3)2CH3]2}, Mo (2).

NMR scale ROMP reactions were carried out to provide information on the reactivity of

a series of exo- phenyl norbomene dicarboxyimides. The ROMP reactions were scaled

up to provide polymer samples for 1 H NMR, 13C NMR, and elemental analysis, the

molecular weight measurement by GPC and thermal properties evaluation by DSC

(differential Scanning Calorimetry) and DMTA (dynamic mechanical thermal analysis).

The cis and trans content of the polymers were estimated from 1HNMR and 13CNMR

spectra.

3.2 NMR scale solution polymerisation of exo-phenylnorbornene dicarboxyimide

monomers

3.2.1 Polymerisation using ruthenium initiator

Polyn1erisation reactions were performed in the glove box (Braun) at room temperature.

The initiator (10 mg) and monomer (10 equivalents) were dissolved in CDCh; in two

separate vials and were stirred for few minutes to allow them to dissolve. The initiator

solution was transferred into the monomer vial and the mixture was stirred for few

minutes. The reaction mixture was then transferred to the screw capped NMR tube. The

NRM tube was removed from the glove box and the spectrum was recorded. The

polymerisation reaction is illustrated in figure3 .1. · In all cases, the monomer was

consumed within ten minutes of the reaction. This was shown by the disappearance of

the monomer signal at 6.30ppm in the 1H NMR spectra of the reaction mixture.

The alkylidene region in the 1H NMR spectra showed signals due to initiator alkylidene

hydrogens at 19.98 pp m and signals due to the propagating alkylidene hydrogens was at

19.52 ppm and 18.67 ppm. A typical example is shown in figure 3.2. On addition of20

equivalents of the monomer, the polymerisation was continued; the initiator signal was

reduced with subsequent growth in the propagation signal. This suggested that the

polymerisation was living. The initiator signal was still observable after the addition of

Chapter 3 37

70 equivalents of the monomer. This indicates that the rate of propagation is faster than

the rate of initiation i.e. kp >> ki.

(a) Initiation

PC::p PCy3 I""

cr......__ I I.& ~N-o Cl" I .& Ru + - Ru

Cl/ I H Cl/ I H

PCy3 0 Cy3P 0

N Ru-initiator Exo-monomer 0

Exo-propagating species

(b) Propagation

PCy3 "" ~N-o

PCy3

Cl" I h Cl" I Ru + - Ru

cr .. ..-- I H Cl/ I Gyp 0 Gyp

N Exo-monomer N

0 0 Exo-propagating species Poly(exo)

Figure 3.1: (a) Outline of the initiation reaction by well defined Ru-initiator.

(b) Outline of the propagation step.

Alkylidene hydrogen of Ru initiator

Exo-propagating alkylidene hydrogen

r

19.4 ppm

: :

'TiTfiTiTfiTi"'l'[illljllll[lllllllll[lllllllll[lllllllllflllllllll[lllllllll[lllllllll[lllllllll[lllllll

20 18 16 14 12 8 6 4 pp m

Figure 3.2: 1H NMR spectra from polymerisation of exo-monomer by well-defined ruthenium initiator.

Chapter 3 38

3.2.2 Polymerisation using t-butoxy substituted molybdenum initiator

The same procedure as in section 3.2.1 was followed using t-butoxy substituted

molybdenum initiator. The polymerisation reaction is illustrated in figure 3.3. The

alkylidene region in the 1H NMR spectra showed signals due to initiator alkylidene

hydrogens at 11.21 ppm and signals due to the propagating alkylidene hydrogens was at

11.59 ppm. A typical example is shown in figure 3.4.

(a) Initiation

+ ~N-o 0

Me-initiator Exo-monomer


(b) Propagation

Exo-monomer

Exo-propagating species Poly(exo)

Figure 3.3: (a) Outline of the initiation reaction by well defined Mo (1) initiator.


Chapter 3 39

Alkylidene hydrogen ofMo (I) initiator ?

(b) Exo-propagating alkylidene hydrogen ~

11f1111f1111f1111f1111f1111f1111f1111f1111f1111f1111f111

+ 11.8 11.4 ppm

11 10 9 8 6 5 4 pp m

Figure 3.4: 1H NMR spectra from polymerisation of exo-monomer by well-defined Mo (1) initiator.

3.2.3 Polymerisation using hexafluoro-t-butoxy substituted molybdenum initiator

The same procedure as in section 3.2.1 was followed using t-butoxy substituted

molybdenum initiator. The polymerisation reaction is illustrated in figure 3.5. The

alkylidene region in the 1H NMR spectra showed signals due to initiator alkylidene

hydrogens at 12.40 ppm and signals due to the propagating alkylidene hydrogens was at

12.77 ppm. A typical example is shown in figure 3.6.

(a) Initiation

~N-o 0


(b) Propagation Exo-propagating species

Exo-monomer

Exo-propagating species Poly(exo)

Figure 3.5: (a) Outline of the initiation reaction by well defined Mo (2)-initiator.


Chapter 3 40

Alkylidene hydrogen ofMo (2) initiator

Exo-propagating alkylidene hydrogen

Q

iijiilljillijitltjlllljili:Jilitjtttijtlltjlllijli

12.5 t

: :

r I l:·rr--r .. ,. .. , .. ,..TT ,. .. 1: I I I I I I l. I I \ I I I I I I r I 1 I ) I I I I I I I I I I I 1 I I I I I I I I I 1 r I I I I I I I I I

13 12 11 10 9 8 7 6 5 4 3 2 ppm

Figure 3.6: 1H NMR spectra from polymerisation of exo-monomer by well-defined Mo (1) initiator.

3.2.4 Copolymerisation of exo-ethylphenyl norbornene dicarboxyimide and exo

hexyl norbornene dicarboxyimide

The alkyl norbomene dicarboxyimides prepared in the previous work were liquid and

therefore it possible to carry out ROMP using well-defined ruthenium initiator in both

solution and bulk. However, all the phenyl norbomene dicarboxyimide monomers in i

this work were solids. The exo-ethylphenyl norbomene dicarboxyimide (exo-PhC2M)

monomer was found to be soluble in exo-hexyl norbornene dicarboxyimide (exo-C6M)

monomer. The aim of this section was to test the possibility of carrying out ROMP on a

mixture of monomers and obtain some information on the reactivity ratios of the

monomers in the mixture. Three experiments were performed using the ruthenium

initiator (lOmg): the first polymerisation reaction contain 20 equivalents of exo-C6M,

the second polymerisation reaction contain 20 equivalents of exo-PhC2Mand the third

polymerisation reaction contained a mixture of 20 equivalents of exo-C6M and exo

PhC2M. All the experiments were analysed by 1H NMR within the first ten minutes. All

the monomers were consumed within the first ten minutes and no resonances due to the

monomer could be found. It appears that in the case of the experiment using a mixture

of two monomers both monomers are polymerising at a same rate. The alkylidene

region in the NMR spectra of the homopolymerisation of the two monomers showed

expected signals for initiator alkylidene and propagating alkylidene hydrogens. The

polymerisation of the mixture is a random copolymerisation and we expect to see two

Chapter 3 41

propagating alkylidene signals, see figure 3.7. The alkylidene region in the NMR

spectrum showed a multiplet signal for the propagating alkylidene, which appears to be

the results of overlapping of the two propagating signals characteristic of the two

monomers. The 1H NMR spectra for the three ROMP reactions are shown in figure 3.8.

PC::p3

"" Cl......._ I I .0

Ru Cl/ I H +

PCy3

Ru-initiator

exo-C1;M c

0

~~CH2CH2--o 0

mix

exo-Phc;M propagating species

or

exo-C6M propagating species

Figure 3.7: Expected propagation reaction in a mixture of exo-C6M and exo-PhC2M

Chapter 3 42


.......

(a) .····

!..20 ............... 18 .....•


~-.

(b)

"' ~

~ 20 18


(c)

20 18

Propagating alkylidene hydrogen

.··"

16 I

14 12


:tf

1S.O

16

16

""'

14 12


14 12

10 B 6 4 pp m

I'

10 B 6 4 2 ppm

10 8 6 4 2 ppm

Figure 3.8: 1H NMR spectra of the polymerisation of a mixture of exo-C6M and exoPhC2M. (a) Exo-C6M spectra. (b) Exo-PhC2M (c) Mixture of exo-C6M and exo-PhC,M

Chapter 3 43

3.2.5 Block copolymerisation of exo-phenyl norbornene dicarboxyimides and exo,

endo-norbornene dimethylcarboxylate

To establish the living nature of the ROMP of exo-phenyl norbomene dicarboxyimides

block copolymers were synthesised via sequential addition of monomers using exo,

endo-norbomene dimethylcarboxylate as the co-monomer, see figure 3.9.

In a typical block copolymerisation reaction, ruthenium initiator (lOmg) was dissolved

in CDCh and was added to exo-ethyl phenyl norbomene dicarboxyimide (1 00

equivalents) dissolved in CDCh. The reaction was stirred for 1 hr to allow all the

monomer to be consumed m the reaction. Then exo, endo-norbomene

dimethylcarboxylate ( 100 equivalents) dissolved in C DCh was added to the reaction

mixture. The reaction was allowed to stir for 1 hr and the reaction mixture was

analysed by 1H NMR. Figure 3.10 shows the 1HNMR spectra ofthe living ROMP

reaction for exo-ethyl phenyl norbomene dicarboxyimide (a), exo, endo-norbomene

dimethylcarboxylate (b) and block copolymer (c). The alkylidene region in figure

3 .1 0( c) shows that the resonances due the propagating alkylidene for exo-ethyl phenyl

norbomene dicarboxyimide have disappeared and new set of resonances are appeared.

Two sets of signals are observed in the alkylidene region for the homopolymerisation of

exo, endo-norbomene dimethylcarboxylate figure 3.1 O(b ), one at 19.3 5ppm and

19.12ppm and the other at 18.65ppm and 18.45ppm probably due to cis and trans

vinylene contents although not absolute certain. The alkylidene region for the block

copolymer shows only one set of signals at 18.64ppm and 18.43ppm, figure 3.10(c).

This suggests that a block copolymer have been formed. It appears that the propagating

ends in poly( exo-ethyl phenyl norbomene dicarboxyimide) polymerise exo, endo

norbomene dimethylcarboxylate in a different fashion to that of the initiator.

Chapter 3 44

PC::p3

""" Cl'-.. I I ~

Ru Cl/ I H

PCy3

Ru-initiator

0

+ n ~N-cH,cH,--Q 0

0

n H



+ m ~COOMe ~COO Me

Exo,endo-diester

block copolymer

Figure 3.9: Outline of the polymerisation reaction between exo, endo-diester and exo-PhC2M

Chapter 3 45


(a)

19.!

20 18


(b)

1"'111 "1"' .ff .... ··

··2o ·· ·······Ti(

(c)


\9.0

16 14 12 10


16 14 12


10

'·············zo ..... · ·······18 I

16 14 12

8 6 4 2 pp m

8 6 4 pp m

10 8 6 4 2 pp m

Figure 3.10: 1H NMR spectra of the polymerisation of copolymer of exo-PhC2M and a diester. (a) Exo-PhC2M (b) Diester (c) Diblock copolymer.

Chapter 3 46

3.3 Scale up polymerisation reaction

The ROMP reactions of exo-phenyl norbornene dicarboxyimides using well-defined

initiators were scaled up to provide polymer samples for 1H NMR, 13C NMR, and

elemental analysis, the molecular weight measurement by GPC and thermal properties

evaluation by DSC (differential Scanning Calorimetry) and DMTA (dynamic

mechanical thermal analysis).

The polymerisation reaction schemes and the termination reaction for exo-phenyl

norbornene dicarboxyimide using ruthenium initiator is shown in figure 3.11 and for

using molybdenum initiator (Mo (1) or (2)) in figure 3.12. The terminating reagents for

ROMP using ruthenium and molybdenum initiators are ethyl vinyl ether and

benzaldehyde respectively.

+ ~N-o 0

Ru-initiator Exo-monomer

Poly(exo)

PCX<?3

..., Cl" I I A

---- Ru- -Cl/ I H Cy3P 0 0

N

0 Exo-propagating species

H2C =cHOC2H5

Ethyl vinyl ether

Poly(exo)

Figure 3.11: Outline of the synthesis and termination route for ROMP using ruthenium initiator

Chapter 3 47

+ ~N-o 0


R


Poly(exo)

0 11

e-H

6 R

+ [Mo}=o

Figure 3.12: Outline of the polymerisation and termination route for ROMP using Mo (I) or Mo (2)

initiator

For ruthenium initiator, 0.75 g and for both molybdenum initiators, 0.5g of each

monomer was used. The ratio of monomer to initiator was 150:1. The polymerisation

reactions were carried out in the glove box (Braun) at room temperature. Both initiator

and monomer were dissolved in separate vials in dichloromethane and stirred for few

minutes. The monomer solution was added to the initiator solution and the reaction

mixture was stirred overnight. The polymerisation reaction was terminated by the

addition of the tenninating reagent. The polymers were recovered by precipitation

twice in methanol and dried under vacuum resulting in white solids. All the polymers

were film forming. The polymers formed from ruthenium initiator were soluble in THF,

chloroform, dichloromethane and DMF.

Chapter 3 48

3.3.1 Polymer characterisation using 1H and 13C NMR spectroscopy

The cis I trans contents of the polymers are readily determined from the 1H NMR

spectrum from the integration of the resonance attributable to cis and trans olefinic

hydrogen (H2,3). The resonances due to trans and cis vinylenes for the polymers

obtained by the well defined initiators are similar and for the trans vinylenes appears at

5.74ppm and for the cis vinylenes at 5.51ppm., see figures 3.13-3. Table 3.1 shows the

cis and trans vinylene content of polymers prepared by each initiator. Generally the

trans vinylene content for polymers prepared by ruthenium initiator is about 83%, for

the polymers prepared by t-butoxy molybdenum initiator is about 97% and for the

polymers prepared by hexafluoro-t-butoxy molybdenum initiator is about 31%. These

results are consistent with the previous result49 that ruthenium initiator give polymers

with 80% trans content and that t-butoxy molybdenum initiator give polymers with high

trans content while hexafluoro-t-butoxy molybdenum initiator give polymers with high

cis content.

Chapter 3 49

HNMR

Polymer M]/[I] Initiator % Trans %Cis

Poly(exo-PhM) 150 Ru 83 17

150 Mo (1) 99 1

Poly(exo-PhCM) 150 Ru 83 17

150 Mo (1) 97 3

150 Mo (2) 30 70

Poly(exo-PhC2M) 150 Ru 83 17

150 Mo (1) 94 6


150 Mo (1) 94 6


Poly( exo-C4PhM) 150 Ru 83 17

150 Mo (1) 97 3

150 Mo (2) 32 68


150 Mo (I) 92 8

150 Mo (2) 30 70


150 Mo (I) 96 4

Table 3.1: cis I trans distribution of the polymers produced by the three initiators

The 1H and 13C NMR spectra ofthe polymers obtained from ROMP of alkyl norbomene

dicarboxyimides have been assigned in details in previous studies. The 1H and 13C

NMR spectra of the polymers prepared from ROMP of .phenyl norbomene

dicarboxyimides were assigned in a similar manner. A typical 1H and 13C NMR spectra

for the polymers obtained by ruthenium initiator, t-butoxy molybdenum, and hexofluoro

t-butoxy molybdenum initiators are shown in figures 3.13-3.15, respectively. The

assignment of the 1H and 13C NMR spectra for the polymers obtained by ruthenium

initiator, t-butoxy molybdenum, and hexofluoro t-butoxy molybdenum initiators are

very similar and are tabulated in tables 3.2-3.4, respectively.

Chapter 3 50

N I

10CH I '

11yH2

()

12CH2

18 14

17 15 16

(a)

5

r---------: a=Hl,4cis : b=Hs,6cis 1---------

H,,,...,

e 14,18

0 B 9 0 e,,,,

18

17

IN 10CH

I 11 CH

I

2

2

2

14

15 en 612CH

16

(b) e,. en

8,9 r---------., I I I a=C1,4cis I

e I ----------' e"

e,,.,,., Cl,41ru1S e,,,~

e,.",J je, je,

Cs,6<Js 1r

I' If I I' I If I' I If I' If I I'' I I I'' ''I'' If I''' 'I' I I I I' I If I',, I I''' 'I' '''I'''' I' I If I'' 160 140 120 100 90 80 70 60 50

Figure 3.13: (a) 1H NMR spectrum of poly (exo-PhC3M) using Ru initiator in CDCI3

(b) 13C NMR spectrum of poly (exo-PhC3M) using Ru initiator in CDCI3

* Residual hydrogen in CDCh

• Solvent CH2Ciz

Chapter 3

40 ppm

51

1Hnmr 13 Cnmr Polymer

Ru Hydrogen Chemical shift (ppm) Carbon Chemical shift (ppm)

sr Hl2,t4 7.44 Cs,9 177.45

Hn I H11.ts 7.36 I 7.26 c2.3 134.12 (cis), 132.05 (trans)

H2,J 5.78 (trans), 5.56(cis) c,2,141 c10 129.33 I 128.73

H,,4 3.51 (cis), 3.13 (trans) c,JI c,,,,s 126.93 I 126.63

'6" Hs,6 2.86 (trans) Cs,6 52.98 (cis), 51.17 (trans) 14 12

13 H1IH7' 2.19 I 1.68 c,,4 46.37 (trans), 41.14 (cis)

c1 41.87

Poly (exo-PhM)

};[ H12-t6 7.30 (m, 7.2-7.4) Cs,9 178.14

H2,J 5.73 (trans), 5.50 (cis) c,, 136.16

Hw 4.58 C2,J 133.70(cis), 131.98 (trans) N I Ht,4 3.21 (cis), 2.99 (trans) C12,t6 128.93

1~1 H2

161 '"-': 12 Hs,6 2.72 (cis), 2.64 (trans) CIJ,tsl Ct4 128.87 I 128.16

15 ~13 H1IH7' 2.1011.61 Cs,6 52.81 (cis), 51.09 (trans) 14

Poly (exo-PhCM) Ct,4 45.89 (trans), 41.12 (cis)

C71 CIO 42.41

};[ Ht4,t6 7.30 Cs,9 178.31

H 13,171 Cts 7.22 (m, 7.18-7.26) cl2 137.83

Hz,J 5.66 (trans), 5.50 (cis) C2.J 133.64 (cis), 131.89 (trans) N I Hw 3.73 CIJ,t7 129.33 10CH I 2

"6" Ht,4 3.10 (cis), 2.91 (trans) Ct4,t61 Cts 128.73 I 126.99

H11 2.91 Cs,6 52.63 (cis), 50.94 (trans)

16 14 Hs,6 2.60 (cis), 2.42 (trans) Ct,4 45.92 (trans), 41.19 (cis) 15

Poly (exo-PhC2M) H1IH1' 2.03 I 1.55 c1 42.29

CIOICII 39.37 I 33.44

Table 3.2: Summary of 1H NMR assignment exo-monomers catalysed by well-defined

ruthenium cat·bene initiator

Chapter 3 52

1Hnmr 13Cnmr

Polymer


=rr H1s,11 7.27 Cs,9 178.50

H14,1s I C16 7.18 I 7.17 Cn 141.21

Hz,3 5.74 (trans), 5.51 (cis) c2,3 133.79 (cis), 132.00 (trans) N I Hto 3.51 C1s,n 128.68

10CH I 2

Hl,4 3.22 (cis), 2.92 (trans) cl4,ls/ C16 128.52 I 126.30 11 CH

I 2

12CH Hs,6 2.71 (cis), 2.62 (trans) Cs,6 52.78 (cis), 51.03 (trans)

"6" H12 2.62 cl,4 45.94 (trans), 41.04 (cis)

17 15 H7/ HT 2.11 I 1.61 c7 42.37

16 H11 1.91 C1o/C12 38.68 I 33.43

Poly (exo-PhC3M) C11 29.13

_2 - H16,1s 7.26 Cs,9 178.54

1 7 4 Hn/ C1s,19 7.16 C14 142.21

6 5

0 6 9 0 H2,3 5.75 (trans), 5.52 (cis) Cz,3 133.82 (cis), 132.01 (trans) N I Hto 3.46 C1s.19 128.68

10CH I 2

Hl,4 3.24 (cis), 2.97 (trans) C161s I Cn 128.62 I 126.11 11 CH

2 I 12CH Hs,6 2.75 (cis), 2.62 (trans) Cs,6 52.83 (cis), 51.08 (trans)

I 2

0 Hn 2.62 cl,4 46.10 (trans), 41.13 (cis)

19 15 H 7 I H1· 2.13 I 1.65 c7 42.44

16 16 H11,12 1.59 Ctol Cn 38.51 I 35.57

17 c11/ c12 28.87 I 27.53 Poly (exo-PhC4M)

13: H11,1s 7.45 Cs,9 177.62

Hl2,14 7.18 C1o 151.69

Hz,3 5.81 (trans), 5.56 (cis) c2,3 134.27 (cis), 132.45 (trans)

'i)" Hl,4 3.55 (cis), 3.15 (trans) Cn 129.33

14 12 Hs,6 2.86 (trans) C11,1S I C1z.14 126.35 I 126.05

C~CH3 ) 3 H1/HT 2.19 I 1.70 Cs,6 53.04 (cis), 51.16 (trans) 16 7

Poly (exo-C4PhM) Hn 1.31 cl,4 46.42 (trans), 41.12 (cis)

c7 42.23

c16/C17 34.97 I 31.53

Table 3.2: Summary continued ....

Chapter 3 53

1Hnmr 13 Cnmr

Polymer


:;[ H11,15 7.24 Cs,9 177.65

H12.16 7.15 Cw 143.64

Hz,J 5.81 (trans), 5.56 (cis) c2.1 134.26 (cis), 132.32 (trans)

'Q" HI,4 3.53 (cis), 3.12 (trans) Cn 129.52

14 12 Hs,6 2.86 (trans) cll,Is 1 cl2,14 129.30 I 126.34

169H2 H16 2.60 Cs,6 53.02 (cis), 51.13 (trans)

179H2 H1/HT 2.1911.68 cl,4 46.40 (trans), 41.12 (cis) 1BCH

I 2 Hl1 1.60 c1 41.91 19CH2 20tH 3

HlS-19' 1.31 c161c11 35.84 I 31.67

Hzo 0.88 C1s I C19 31.221 22.76

Poly (exo-C5PhM) Czo 14.28

}[[ HILlS 7.24 Cs,9 177.57

H12.14 7.15 Cw 143.64

H2,J 5.81 (trans), 5.56 (cis) c2,3 134,22 (cis), 132.31 (trans)

HI,4 3.53 (cis), 3.12 (trans) Cn 129.51

'Q" Hs,6 2.85 (trans) cll,Isl cl2,14 129.29 I 126.34 14 12

H16 2.61 Cs,6 53.02 (cis), 51.13 (trans) 16CH

I 2 H1IHT 2.19 I 1.69 cl,4 46.40 (trans), 41.11 (cis)

17CH I 2

Hl1 1.59 c1 41.91 1BCH I 2

19CH HlS-20 1.29 c16/ c11 35.88 I 31.94 I 2

20CH2 H21 0.88 C1s I C19 31.51129.20 21 CH

3 Czo I C21 22.85 I 14.37 Poly (exo-C~hM)


Chapter 3 54

18

17

I 10CH

I 2 c"'' 11 CH

2 I c,,,,,

B 14

15 16

(b) c,, c,o

ell Cs,9

Cz,Jtraru: c,, Cs,o u.ru Cl,4trans

cl jc!O

''I' I I I I'' ''I' I I I I' I I I I'' I 'I' I I 'I',, I )I 11 'I' I I I I' 11 I I' 11 I I' I I 'I''' 'I' '''I' I 11 I' I

180 160 140 120 100 80 60

Figure 3.14: (a) 1H NMR spectrum of poly (exo-PhC3M) using Mo (I) initiator in CDC13

(b) 13C NMR spectrum of poly (exo-PhC3M) using Mo (I) initiator in CDCh

• Residual hydrogen in CDCh

Chapter 3

pp m

55

Polymer 1Hnmr 13Cnmr

Mo (1) Hydrogen Chemical shift (ppm) Carbon Chemical shift (ppm)

13: H,z,I4 7.44 Cs,9 177.53

Hn I Hll,IS 7.36 I 7.26 Cz,3 132.37 (trans)

H2.3 5.80 (trans), 5.57(cis) c101 c,2,14 132.11 I 129.30

H,,4 3.51 (cis), 3.16 (tra11s) Cn I cii,IS 128.71 I 126.63 1611 Hs,6 2.87 (trans) Cs,6 51.19 (trans)

14 12 H1IH7' 2.1911.70 c,,4 46.42 (trans), 41.21(cis) 13

Poly (exo-PhM) c1 42.08

~s:i-H12-16 7.30 (m, 7.24-7.34) Cs,9 178.13

H2.3 5.74 (trans), 5.50 (cis) c" 136.19

.ko HIO 4.58 Cz.3 132.03 (trans) N I H,,4 3.20 (cis), 2.99 (trans) c,2,16 128.92

10 H2 11 Hs,6 2.65 (trans) Cn,IS I c,4 128.84 I 128.14

161 ~12

15 ~13 H1IH7' 2.11 I 1.62 Cs,6 51.13 (trans) 14

c,,4 45.90 (trans) Poly (exo-PhCM)

C71 CIO 42.30

1f{: H,4,16 7.30 Cs,9 178.34

Hn,I7 I C,s 7.23 (m, 7.18-7.26) cl2 137.83

H2.3 5.65 (trans), 5.50 (cis) Cz,3 131.92 (trans)

I HIO 3.73 Cn,I7 129.33 10CH I 2

17~5, H,,4 3.11 (cis), 2.92 (trans) C,4,161 C,s 128.73 I 126.98

H11 2.92 Cs,6 52.62 (cis), 50.94 (trans)

16 14 Hs,6 2.60 (cis), 2.42 (trans) c,,4 45.93 (trans), 41.15 (cis) 15

Poly (exo-PhCzM) H71H7' 2.04 I 1.57 c7 42.16

c101 c" 39.38 I 33.44

Table 3.3: Summary of 1H NMR assignment exo-monomers catalysed by t-butoxy

substituted molybdenum initiator

Chapter 3 56


Chapter 3 57

1Hnrnr 13Cnmr

Polymer


![ Hn.Is 7.24 Cs,9 177.61

H12,16 7.15 CIO 143.61

Hz,J 5.81 (trans), 5.57 (cis) Cz,3 132.31 (trans)

·Q" HI.4 3.53 (cis), 3.12 (trans) Cn 129.59

14 12 Hs,6 2.86 (trans) c11.1s 1 c12,14 129.25 I 126.33

16CH H16 2.60 Cs,6 51.17 (trans) I 2

11yH2 H7 1 H?' 2.1911.70 c1.4 46.43 (trans) 18CH

I 2 H11 1.60 c? 42.08 19CH2

2ocH, HJs.J9 1.32 c161c11 35.82 I 31.66

Poly (exo-C5PhM) H2o 0.88 C1s 1 C19 31.15 I 22.72

Czo 14.22

~-r:r: Hn.Is 7.24 Cs,9 177.65

H1214 7.15 CIO 143.65

Hz,J 5.81 (trans), 5.56 (cis) Cz,3 132.27 (trans)

HI,4 3.53 (cis), 3.16 (trans) Cn 129.50 ·Q" 14 ~ 12 Hs,6 2.85(trans) c,,,1sl cl2.14 129.28 I 126.33

H,6 2.61 Cs,6 51.13 (trans) 16CH

I 2 H7 1 H?' 2.19 I 1.69 c,,4 46.40 (trans)

17yH2

18CH H11 1.59 c? 41.94 I 2

19yH2 H,s.2o 1.29 c16IC11 35.88 I 31.94

20CH2 H21 0.88 C,s I C,9 31.51129.20 z1cH,

C2o I C21 22.84 I 14.37 Poly (exo-C6PhM)


Chapter 3 58

0 8 9 0

15 11

14 12

16CH I 2

17CH I 2

18CH I 2

19CH I 2

20CH3

0 8 9 0

15~11 14~12

16yH2

11yH2

18yH2

19CH2 20CH

3

180

*

160

H,,,,s & 12,14

7 6

r-----------, : a=C2.Jcis : I a' = c2 3 tnns I

b=Cil. I

c=CII,I5 d=CI2,14

140

,---t--, I I I I C I d

b

120

5 4

100

Hl,4 & Hs,6

l ___ t __ , I I

*

80

c 8

60 40

Figure 3.14: (a) 'HNMRspectrumofpoly (exo-CsPhM) using Mo (2) initiator in CDCb (b) 13CNMRspectrum of poly (exo-CsPhM) using Mo (2) initiator in CDCb

* Residual hydrogen in CDCb

Chapter 3

pp m

pp m

59

1Hnmr 13Cnmr

Polymer


}([ H12-16 7.23 (m, 7.12-7.33) Cs,9 178.13

Hz,J 5.71 (trans), 5.48 (cis) ell 136.41

Hw 4.51 c2,3 133.80 (cis), 131.99 (trans)

I Ht,41 Hs,6 3.06 (m) C12,16 128.92 10 H2 11

H?l HT 161 ~12

2.04 I 1.48 Cn,ts 1 C14 128.75 I 127.93

15 ~13 Cs,6 53.22 (cis), 51.22 (trans) 14

Poly (exo-PhCM) Ct,4 45.89 (trans), 41.28 (cis)

C1l Cw 43.15 I 42.64

- 3- Hn,tsl Ct2,14 7.28 (m, 7.11-7.47) Cs,9 177.56

1 7 4 H2,J 5.76 (trans), 5.52 (cis) CIO 151.31 6 5

0 8 9 0 Ht,41 Hs,6 3.13 (m) c2,3 134.14 (cis), 132.39 (trans)

H?l HT 2.17 I 1.69 Cn 129.68

'Q" H!7 1.29 Ctt,ts1Cl2t4 126.12 (m) 14 12

C ~CH 3 ) 3

Cs,6 53.31 (cis), 51.33 (trans)

16 7 Ct,4 46.48(trans), 42.09 (cis) Poly (exo-C4PhM)

c1 43.59

Ct61C17 34.93 I 31.54

)[ Hn,ts I C12,t6 7.09 (m, 7.04-7.16) Cs,9 177.55

H2,J 5.78 (trans), 5.52 (cis) CIO 143.06

Ht,4/Hs,6 3.14 (m) c2,3 134.06 (cis), 132.24 (trans)

'i~t Ht6 2.59 Cn 129.86

14 12 H?l HT 2.16 I 1.60 Ctt,ts I Ct2,t4 128.89 I 126.38

16CH H!7 1.60 Cs,6 53.28 (cis), 51.31 (trans) I 2

11yH2 Hts-19 1.33 Ct,4 46.41 (trans), 41.97 (cis) 1BCH

I 2 Hzo 0.89 C1 43.12 19CH2 20tH

3 Ct6IC11 35.83 I 31.75

Poly (exo-C5PhM) Cts I Ct9 31.24 I 22.77

Czo 14.26

Table 3.4: Summary of 1H NMR assignment exo-monomers catalysed by hexafluoro-t-butoxy substituted molybdenum initiator

Chapter 3 60

3.3.2 Polymer characterisation by elemental analysis

The polymers obtained from ROMP . of exo-phenyl norbornene dicarboxyimide derivatives using the well-defined initiators were characterised by elemental analysis. The results are tabulated in table 3.5. Generally a good agreement between the calculated and found values has been obtained for all the polymer samples.

Polymer Initiator Calculated(found) in%

Poly(exo-PhM) Ru c = 75.30(73.84) H = 5.48(5.54) N = 5.85(5.82)

Mo (1) c = (72.86) H = (5.30) N = (5.58)

Poly( exo-PhCM) Ru c = 75.87(74.30) H =5.97 (5.86) N =5.53 (6.15)

Mo (1) c = (74.76) H = (5.84) N = (5.52)

Mo (2) c = (74.46) H = (5.79) N = (5.20)

Poly( exo-PhC2M) Ru c =76.38(75.33) H =6.41(6.32) N = 5.24(5.22)

Mo (1) c = (75.91) H = (6.54) N = (6.25)

Poly( exo-PhC3M) Ru c = 76.84(75.59) H = 6.81(6.71) N = 4.98( 4.94)

Mo (1) c = (76.33) H = (6.87) N = (6.13)

Poly( exo-PhC4M) Ru c = 77.26(76.56) H =_7.17(7.14) N = 4. 74(5.86)

Poly( exo-C4PhM) Ru c = 77.26(77.07) H = 7.17(7.25) N = 4.74(4.57)

Mo (1) c = (75.89) H = (6.99) N = (4.60)

Mo (2) c = (75.89) H = (7.05) N = (4.50)

Poly( exo-C5PhM) Ru c = 77.64(76.45) H = 7.49(7.43) N = 4.53(5.41)

Mo (1) c = (76.45) H = (7.38) N = (4.36)

Mo (2) c = (76.52) H = (7.34) N = (4.13)

Poly( exo-C6PhM) Ru c = 77.99(78.81) H = 7.79(7.96) N = 4.33( 4.96)

Mo (1) c = (77.06) H = (7.74) N = (5.49)

Table 3.5: Elemental analysis results of the polymers

Chapter 3 61

3.3.3 Polymer characterisation by GPC

The polymers obtained from ROMP of phenyl norbomene dicarboxyimide derivatives

using the well-defined initiators were subjected to Gel Permeation Chromatography

(GPC) to determine their molecular weights and Polydispersity Indices (PDI). The

results are tabulated in table 3.6. It can be seen that the t-butoxy molybdenum initiator

produced polymers with narrow PDI compared to hexafluoro-t-butoxy molybdenum and

ruthenium initiators. This is an indication of a well-controlled living polymerisation

reaction. The hexafluoro-t-butoxy molybdenum initiator produced polymers with

broader PDI. This can be attributed to due to the secondary metathesis reactions50 or to

the rate of propagation being faster than the rate of initiation. Polymers obtained by

ruthenium initiator also gave polymers with broader PDI due to secondary metathesis

reaction. Similar trend have bee previous been observed.4

GPC

Polymer Initiator [M]/[I] Mn Mw PDI

Poly(exo-PhM) Ru 150 62,400 83,200 1.3'

Mo (1) 150 11,400 11,700 1.03

Poly( exo-PhCM) Ru 150 46,500 61,600 1.3

Mo (1) 150 39,400 45,500 1.1

Mo (2) 150 18,600 31,000 1.7

Poly(exo-PhC2M) Ru 150 44,300 56,900 1.3

Mo (1) 150 35,800 47,200 1.1

Poly( exo-PhC3M) Ru 150 48,800 59,000 1.2

Mo (1) 150 42,400 53,000 1.2

Poly( exo-PhC4M) Ru 150 53,000 54,600 1.03

Poly( exo-C4PhM) Ru 150 51,000 64,600 1.3

Mo (1) 150 59,700 66,500 1.1

Mo (2) 150 45,000 94,500 2.1

Poly( exo-C5PhM) Ru 150 47,800 59,000 1.2

Mo (1) 150 35,800 41,000 1.1

Mo (2) 150 19,400 47,600 1.7

Poly( exo-C6PhM) Ru 150 45,700 55,300 1.2

Mo (1) 150 45,100 54,000 1.2

Table 3.6: GPC results of the polymers

Chapter 3 62

3.3.4 Polymer characterisation using DSC

The glass transition temperatures, Tgs, for all the polymers have been obtained by DSC

analysis and the results are shown in table 3.7. It can be seen that the Tgs for the

polymers prepared by t-butoxy molybdenum initiator were about l5°C higher than the

polymers produced using hexafluoro-t-butoxy molybdenum and the ruthenium

initiators. The results suggest that for the systems studied the higher the trans content of

the polymer, the higher the glass transition temperature. It was also found that the

longer the alkyl chain in the polymer, entry l-5 and 6-8, the lower the glass transition

temperatures. This is consistent with the previous result by Feast52 et a/ and earlier

work by Hoffthat followed the same trend. 53

DSC

Entry Polymer Initiator [M]/[I] Mn Tg (°C)

1 Poly( exo-PhM) Ru 150 62,400 223

Mo (1) 150 11,400 241

2 Poly(exo-PhCM) Ru 150 46,500 143

Mo (1) 150 39,400 161

Mo (2) 150 18,600 148

3 Poly( exo-PhC2M) Ru 150 44,300 103

Mo (1) 150 35,800 121

4 Poly( exo-PhC3M) Ru 150 48,800 88

Mo (1) 150 42,400 98

5 Poly( exo-PhC4M) Ru 150 53,000 69

6 Poly( exo-C4PhM) Ru 150 51,000 245

Mo (1) 150 59,700 260

Mo (2) 150 45,000 242

7 Poly( exo-C5PhM) Ru 150 47,800 162

Mo (1) 150 35,800 175

Mo (2) 150 19,400 173

8 Poly( exo-C6PhM) Ru 150 45,700 142

Mo (1) 150 45,100 148

Table 3. 7: DSC results showing Tg of the polymers

Chapter 3 63

The results also show that the Tg for the polymers prepared from ROMP of exo-phenyl

norbomene dicarboxyimides are generally a lot higher than the polymers obtained from

exo-alkyl norbomene dicarboxyimides studied previously.

Chapter 3 64

Chapter 4

Overall conclusion and proposal for future work

Chapter 4 65

4.1 Overall conclusion

The work described in this thesis illustrates that a series of exo-phenyl norbornene

dicarboxyimide derivatives are synthesised and characterised usmg several

spectroscopic methods. It also demonstrates that polymeric material can be prepared

from phenylnorbornene d icarboxyimide derivatives using ROMP. Three well-defined

initiators, ruthenium Ch[(C6H11 ) 3P]zRu=CHC6H5, t-butoxy molybdenum

Mo[CHC(CHJ)J](CtoH17N][OC(CH3hh, Mo (1), and hexafluoro-t-butoxy molybdenum

Mo[CHC(CH3)zC6Hs][CwH17N][OC(CF3)2CH3h, Mo (2), were used.

The polymers prepared were fully characterised using lH NMR, 13CNMR, elemental

analysis, GPC and DSC.

The cis I trans contents of the polymers are readily determined from the 1H NMR

spectrum from the integration of the resonance attributable to cis and trans olefinic

hydrogen. Generally the trans vinylene content for polymers prepared by ruthenium

initiator is about 83%, for the polymers prepared by t-butoxy molybdenum initiator is

about 97% and for the polymers prepared by hexafluoro-t-butoxy molybdenum initiator

is about 31%.

The t-butoxy molybdenum initiator produced polymers with narrow PDI compared to

hexafluoro-t-butoxy molybdenum and ruthenium initiators. This is an indication of a

well-controlled living polymerisation reaction. The hexafluoro-t-butoxy molybdenum

initiator produced polymers with broader PDI. This can be attributed to due to the

secondary metathesis reactions or to the rate of propagation being faster than the rate of

initiation. Polymers obtained by ruthenium initiator also gave polymers with broader

PDI due to secondary metathesis reaction. Similar trend have bee previous been

observed.

The elemental analysis of polymers showed a good agreement between the calculated

and found values has been obtained for all the polymer samples.

The Tgs for the polymers prepared by t-butoxy molybdenum initiator were about l5°C

higher than the polymers produced using hexafluoro-t-butoxy molybdenum and the

ruthenium initiators, suggesting that the higher the trans content of the polymer, the

higher the glass transition temperature. It was also found that the longer the alkyl chain

in the polymer, the lower the glass transition temperatures. The results also showed that

the Tg for the polymers prepared from ROMP of exo-phenyl norbornene

Chapter 4 66

dicarboxyimides are generally a lot higher than the polymers obtained from exo-alkyl

norbomene dicarboxyimides studied previously.

4.2 Proposal for future work

The prevwus work showed that exo-alkyl norbomene dicarbcixyimides could

successfully be subjected to ROMP using well-defined ruthenium initiator resulting in

well-defined linear polymers in both solution and bulk. It was also demonstrated that

the copolymerisation of exo-alkyl norbomene dicarboxyimides with exo-alkyl

dinorbomene dicarboxyimides difunctional monomers results in a well-defined

crosslinked materials, using resin transfer moulding process (RTM). However, the Tg

of the crosslinked materials were lower than the commercial materials based on

Poly(DCPD). The linear polymeric materials produced here from the ROMP of exo

phenyl norbomene dicarboxyimides exhibited higher Tgs than Poly(DCPD). The

monomers were all solid but soluble in exo-alkyl norbomene dicarboxyimides. It will

therefore be possible to carry out ROMP-RTM processing of the monomers to obtain

linear materials and also well-defined crosslinked materials using exo-alkyl

dinorbomene dicarboxyimides difunctional monomers with higher Tgs.

Chapter 4 67

Appendix 1

Instrumentation and procedures for measurements

Appendix 1 68

i. NMR spectroscopy: 1H, 13C, COSY, DEPT

The samples were analysed either on a V ARIAN INOV A 500 NMR spectrometer at

499.78 eH) I 125.67 (13C) MHz, or V ARIAN MERCURY 400 NMR spectrometer at

399.96 eH) I 100.57 (13C) MHz, or BRUKER AV ANCE 400 NMR spectrometer at . I .

400.13 (H). The solvents used were deuterated chloroform and deuterated acetone.

ii. GEL PERMEATION CHROMATOGRAPHY (GPC)

o The samples were dissolved in one of the solvents; chloroform (CHCh),

dimethylformamide (DMF), and tetrahydrofuran (THF). The choice of solvent

depends on the solubility of the polymer. Each solvent was run at a different

instrument.

• THF: Viscotek 200 with refractive index, viscosity and light scattering detectors,

and 2 x 300mm PLgel 5flm mixed C columns; THF was used as the eluent with a

flow rate of 1.0mllmin and a constant temperature of 30°C. Molecular weights were

obtained using a conventional calibration curve generated from narrow molecular

weight distribution PEG/PEO standards.

• DMF: Viscotek TDA 302 with refractive index detector, and 2 x 300mm PLgel

5flm mixed C colunms; DMF was used as the eluent with a flow rate of l.Omllmin

and a constant temperature of 80°C. Molecular weight were obtained using triple

detection, the detectors were calibrated with a single narrow molecular weight

distribution polystyrene standard.

• CHCI3 : Viscotek TDA 301 with refractive index, viscosity and light scattering

detectors, and 1 x 300mm PLgel 5!lm mixed C columns; CDCh was used as the

eluent with a flow rate of 1.0mllmin and a constant temperature of 30°C. Molecular

weight were obtained using triple detection, the detectors were calibrated with a

single narrow molecular weight distribution polystyrene standard.

iii. MASS SPECROSCOPY

The samples were analysed on an EXETER ANALYTICAL, Inc CE-440 elemental

analyser.

Appendix 1 69

iv. DIFFERENTIAL SCANNING CALORIMETER (DSC)

The samples were analysed on a Perkin Elmer DSC 7 or a Pyris 1 differential

scanning calorimeter at a ramp rate of 1 0°C/min.

Appendix 1 70

Appendix 2

Analytical data for chapter 2

Appendix 2 71

_j I ~ ~

I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

7 6 5 4 3 2 ~~m

Appendix 2.1: 1H NMR spectrum of exo-PhCM

I lljllllllllljlllllll I ljlll lllllljllllllllljllllllllljlllllll 11 jllll llllljlllllll

180 160 140 120 100 80 60 ppm

Appendix 2.2: 13C NMR spectrum of exo-PhCM

Appendix 2 72

1001 66 8.285

95 7.885

90 7.4E5

as· 7.0ES

80 6.6E5

7s 187 6.185

70 5.7ES

65 91 253 S.JBS

60 4.9ES

55 4.SES

50 4.1ES

45 J.?ES

40 3.3ES

35 2.985

30- 2.585

2s 2.085

20 106 1.6ES

15 1.285

10

r, ~ ~I TT 8.2E4

159 5 sh .. -1 1f9 4.1E4

0 . [, O.OEO 40 6o 80 160 1Jo i!o 160 iao 260 220 240 2/;o 2so 300 3:\o 3!o J6o m/z

Appendix 2.3: Mass spectrum of exo-PhCM

I I I I

8 7 6 5 4 3 2 pp m

Appendix 2.4: 1H NMR spectrum of exo-PhC2M

Appendix 2 73

I111111111Ji 111111 IIJIIII 1 illlJIIiljll r 11''' r 11 ltijlillj 1 t 111 t t 1 t 1''''1'1 1 ijlllll 1 t 11

180 160 140 120 100 80 60 40 pp m

Appendix 2.5: 13 C NMR spectrum of exo-PhC2M

1001 1 4 7.1'1!6

95 7.4E6

90 7.0E6

85 6.6E6

80 6,2E6

75 5.8E6

70 5.4E6

65 5.0E6

60 4.6E6

55 4.3E6

50 3.9E6

45 3.5E6

40 91 267 3.1E6

35 :i.7E6

30 66 2.3E6

J5 1.9E6

20 110 l.SE6

15 1.2E6

10 7.7E5

:bl J,

77 5 Jil, 2r 3.9ES

0 1r 176 O.OEO 40 ·6o 80 160 120 140 160 u\o 260 220 240 260 280 360 3:20 340 360 m/z

Appendix 2.6: Mass spectrum of exo-PhC2M

Appendix 2 74

__ __) L__ __ __l\._ _________ _JL_JL. .--' \._ _ __!lJL__ll__ __ I I I

8 7 6 5 4 3 2 pp m


I lllljllllllllljllllllllljllllllllljllllllllljllllllllljllll llllljllllllllljllllllllljll

180 160 140 120 100 80 60 40 pp m


Appendix 2 75

1001

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 40

l 1 .9.3E5

8.BE5

8.4E5

7.9E5

1.4E5

7.0ES

91 6.5E5

6.0E5

5.685

5.1E5

111 4.6E5

4.2E5 66 3. 7E5

3.3ES 281

177 2.8E5

2.3E5

216 1.9E5

l.4ES 82

.·~ 164

9.3E4

~~( .1, 9~8J~ I I~ :i4

1t8 ·r 4.6E4 1~0 O.OEO

60 80 160 1 0 14o 1/;0 180 260 22o 240 26o 2 0 360 32o · J4o Jlo m/z


'--------'L_ _____ _J~ L__)'---,_1...____, ll1L__)L__ I

7 I

6

I I I I I

5 4

I I I

3

I I


Appendix 2

2 ppm

76

I I lllllllljl 11111111111111111111111111111111111111111 I I I' I Ill I 1111111 I 111111111111111

180 160 140 120 100 80 60 40 pp m


100l 91 5.2E6

95 4.9E6

90 4.7E6 66 4.4E6 85

80 295 4.2E6

75 3.9E6

70 3.6E6

65 3.4E6

60 3.1E6

55 2.9E6

50 2.6E6

45 230 2.3E6

40 I 2.1E6 110 131

35 204 1.8Efi

30 194 138 1.6E6

25 1.3E6 164

20 1.0E6

15 82 7.8E5

10

lilt I~ 98 177 5.2E5

~5 II I 5 d 1fl6 2.6E5

0 '~. . I ll 2f7 O.OEO

40 60 80 100 120 1 0 1~0 1~0 2bo 2Io 2!o 2~o 280 360 32o 3!o 36o m/•


Appendix 2 77

----~L~L----~~--------------------~'--~·~-~----~Illu_ __ __

8 I

7 6 5 4 3

Appendix 2.13: 1H NMR spectrum of exo-C4PhM

2 pp m

lllllllllllllllllllllllllllllllllllllllllll!tlllllllllllllllllijilllllllllillllllllltillllillll

180 160 140 120 100 80 60 40 pp m

Appendix 2.14: 13C NMR spectrum of exo-C4PhM

Appendix 2 78

10 2 4 3.8E6

95 3.6E6

90 3.4E6

85 3.2E6

80 3.0E6

75 2.8E6

70 2.7E6

65 2.5E6

60 2.3E6

55 2.1E6

50 1.9E6

45 280 i.7E6 295

40 1.5E6

35 1.3E6

30 91 66

1.1E6

25

20 132

229 9.5E5

7.6E5 186

15 5.7E5 115

10 3.8E5

5 l.9E5

m/z

Appendix 2.15: Mass spectrum of exo-C4PhM

•u \.___j

7 6 5 4 3 2 pp m


Appendix 2 79

I I I I I It '1''''1'' I 'I I llljlll I 1''''1''''1''''1''' I l I I 11 I I I ''I'' I 'I''') jll I 'I'' I I I I llljl I I 'I I

180 160 140 120 100 80 60 40 pp m

Appendix 2.17: 13C NMR spectrum of exo-C5PhM

liMll 1 6 );SE6

95 3.4E6

90 3.2E6

85 3.0E6

80 2.8E6

75 2.7E6

70 243 2.5E6·

65 2.3E6

60 2.1E6

55 2.0E6

309 1.BE6 so 45

1.6E6

40 1.4E6

66 91 ·J5 1. 2E~

30 132 ! 1.1E6

·25 158 8.9E5

20 7.1ES

15 77 5.3E5

10

]f~ t T256

3.5E5 51 . T 5 l! Lu, T

l.8E5

145 214 O.'OEO 0 40 '6o so i6o i:lo 1!o ao iso :ioo 2~o :i4o 2/;o 28o .:i6o :iio :i{o 3/;o :ieo 46o 4~o 44o .. m/z


Appendix 2 80

7 6 5 4 3 1 ppm


llli[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJIIII[IIIIJII

180 160 140 120 100 80 60 40 ppm

Appendix 2.20: 13 C NMR spectrum of exo-C6PhM

Appendix 2 81

1001 1 6 6.886

95 6.5E6

90 6.2E6

85 5.8E6

80 5.5E6

75 257

5.1E6

70 323 4.8E6

65 4.4E6

60 4.1E6

55 3.BE6

50 3.4E6

45 3.1E6

40 2.7E6

35 66 91 2.4E6

30 132 2.1E6

25 158 1. 7E6

20 1.4E6

15 l.OE6

10

l l 6.8E5

5 l 1

irlk ~ ~r T 3',4E5

0 214 O.OEO

40 '6o 80 ioo Ho iAo 1 o iao .2oo :i2o 24o 2 a :iao :ioo 3 o :i4o _:i~o :iao 4oo 42o 44o m/z


I I u 'L- I I I I I I I I I I I I I I I I I

8 7 6 5 4 3 2 1 .Q pp m

Appendix 2.22: 1H NMR spectrum of exo-C6M

Appendix 2 82

IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIIIIII[IIIIJIIII[II

180 160 140 120 100 80 60 40 pp m

Appendix 2.23: 13C NMR spectrum of exo-C6M

100! 66 3. SE6

95 3.6E6

90 3.4E6

85 3. 2E6

u 3.0~

7S 2. 8E6

70 2.7E6

65 182 2.5E6

60 2.3E6

ss· 2.1E6

50 1.9E6

45 1.7E6

40 1.5E6

3S 91 1.3E6

30 110 247 1.1E6

25. 98 9.5ES

20 ss 164 7. 6E5

15 82 120 5.7ES

1

: l .~: 1!1~ ,;. lk ~13

f8

l]s2

::::: 19o 2 ?4 2~8 01~~~! ~~~~~~~~~~l~l~~~~~~~~~~~~~~~O.OEO 40 6o 80 160 1 o Ho i~o 1 o :ibo 2:2o :i~o ito i~o 36o 3:lo 3~o :lto )~o 46o m/z

Appendix 2.24: Mass spectrum of exo-C6M

Appendix 2 83

Appendix 3

Analytical data for chapter 3

Appendix 3 84

L_ 7 6 5 4 3 2 pp m

Appendix 3.1: 1H NMR spectrum poly(exo-PhM)- Ru

lllllll(lllijlilijlilljllli[iilllllii[illljlrll]llil[iili[iilfjllll]litiflifi[iiiljilli[liiiliiii[iilijilii[iiiljllll[lilllll

220 200 180 160 140 120 100 80 60 40 20 pp m

Appendix 3.2: 13C NMR spectrum poly(exo-PhM)- Ru

Appendix 3 85

I

7 6 5 4 3 2

Appendix 3.3: 1H NMR spectrum poly(exo-PhCM)- Ru

ppm

'''I''' I 1''''1''''1''''1''''1''''1''''1''''1''''1''''1''''1'' 11 1''''1''''1''''1''''1 11

180 160 140 120 100 80 60 pp m

Appendix 3.4: 13C NMR spectrum poly(exo-PhCM)- Ru

Appendix 3 86

7 6 5 4 3 2 pp m

Appendix 3.5: 1H NMR spectrum poly(exo-PhC2M)- Ru

J JJJ.J I 11, 'I,, ,, 1, ,, , I',, IJI r, 1 1,,,, 1,, 11l''t, 1,, ''I, 11, 1,, ''l'l, , 11 '''!'l''l 1,, 1 I', ''l''''l' 1,

180 160 140 120 100 80 60 40 pp m

Appendix 3.6: 13C NMR spectrum poly(exo-PhC2M)- Ru

Appendix 3 87

7 6 5 4 3 2 ppm

Appendix 3.7: 1H NMR spectrum poly(exo-PhC4M)- Ru

I I I I [ I ( I I I 11 11 I' 11 I I I I I I I' I I I I I I I I I I I I I I I I I I I' I I I I I I I I I ( I I l I l ( [ I I' I I I I I I I I I' I I ( I I I I I I I I I I I

180 160 140 120 100 80 60 40 pp m

Appendix 3.8: IJC NMR spectrum poly(exo-PhC4M)- Ru

Appendix 3 88

8 7 6 5 4 3 2 ppm

Appendix 3.9: 1H NMR spectrum poly(exo-C4PhM)- Ru

llllliij I I If JIIIIJIIIIJIIIIJIIIIJII I IJII I 'I I lll[lllijili f Jllll I IIIIJ t I IIJI I I ljlllljiliijl I

180 160 140 120 100 80 60 40 pp m

Appendix 3.10: llC NMR spectrum poly(exo-C4PhM)- Ru

Appendix 3 89

7 6 5 4 3 2 pp m

Appendix 3.11: 1H NMR spectrum poly(exo-C5PhM)- Ru

I J IIJ!Illjillljlliijlllljl!iijllllllllljlllfJIIIIjllii)lilljll!l]iilljllliJIIIIjllllllllijliiiJIIIIjllif)lllljliiiJIIIIjllll)il

220 200 180 160 140 120 100 80 60 40 20 pp m

Appendix 3.12: 13C NMR spectrum poly(exo-C5PhM)- Ru

Appendix 3 90

Appendix 3.13: 1H NMR spectrum poly(exo-CJ'hM)- Ru

J I J tJ!ll 1 1]11 t tlliltJlillji 111 ]I I 1 ljllii]li 1 ljll!l]lllijllll]iitl] 111 IJII 1 'I' 1 11]111 t 1 t 1111 r 1

160 140 120 100 80 60 40 pp m

Appendix 3.14: 13C NMR spectrum poly(exo-C6PhM)- Ru

Appendix 3 91

8 I

7 6 5 4 3 2

Appendix 3.15: 1H NMR spectrum poly(exo-PhM)- Mo (I)

pp m

I I I I I I I i I I I I I I I I I' I 1 I I I I I I 1 I I I I I I I 11 I I I I I I 1 1 If I I I I I l I I I I ,. I I I I I I I I I' I I I I I I I I I I J I I I I I l I jl

180 160 140 120 100 80 60 40 pp m

Appendix 3.16: 13C NMR spectrum poly(exo-PhM)- Mo (1)

Appendix 3 92

8 7 6 5 4 3 2 ppm

Appendix 3.17: 1H NMR spectrum poly(exo-PhCM)- Mo (1)

I I I I I l I l I I I I 1 I 1 I I I I I I I I f I I I I I I I ~ I I I I I ,·I I I I I I I I I I I I I I I 1 I 1 I 1 I I 1 I I I I I I I I I I I 1 I I 1 l I I I I I I I I

160 140 120 100 80 60 40 pp m

Appendix 3.18: 13C NMR spectrum poly(exo-PhM)- Mo (1)

Appendix 3 93

8 7 6 5 4 3 2 pp m

Appendix 3.19: 1H NMR spectrum poly(exo-PhC2M)- Mo (I)

I I I I I 11 I jlllijlllljl I I ljll I I) I I I 1!1_1 I 1) I I .I I Ill I I 11 I I 1 I 11 I I) I I I I Ill I ill I I I I I llljllillll

180 160 140 120 100 80 60 40 pp m

Appendix 3.20: 13C NMR spectrum poly(exo-PhC2M)- Mo (1)

Appendix 3 94

I I

8 7 6 5 pp m

Appendix 3.21: 1H NMR spectrum poly(exo-C4PhM)- Mo (I)

I 11 I

lljlllljlllljtflljllllllllljlllljllfijlllllfllljiilf(lllljlllljlilijlll!fll!ljlillllltljlilljlllijliiiJiiiljllll!lllljllll!ll

220 200 180 160 140 120 100 80 60 40 20 pp m

Appendix 3 95

Appendix 3.22: ne NMR spectrum poly(exo-C4PhM)- Mo (1)

7 6 5 4 3 2 pp m

Appendix 3.23: 1H NMR spectrum poly(exo-C5PhM)- Mo (1)

I I L 1 1 t 1 1 I' t 1 1 1 1 1 1 1 I' 1 1 1 1 t 1 1 1 I' t 1 1 11 1 1 1 1 t 1 1 1 1 1 1 1 1 I' 1 1 1 1 1 t 1 1 1 1 1 1 1 ! 1 1 1 1 11 1 1 1 1 1 1 1 1 I' r 1 1 1 1 1 1t 1 t 1 1 1 1 1 t 1 1 jll 1

180 160 140 120 100 80 60 40 20 pp m

Appendix 3.24: ne NMR spectrum poly(exo-CsPhM)- Mo (1)

Appendix 3 96

7 6 5 4 3 2 pp m


I I 1 1 I t 1 1 1 1 1 1 t 1 1 1 t 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 11 1 1 r 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 , 1 1 t 1 1 t 1 1 1 1 1 1 1 1 1 t 1 1 ' 1 1 I' t 1 t 1 1 1 1 1 I' t t 1 1 11

160 140 120 100 80 60 40 pp m

Appendix 3.26: 13C NMR spectrum poly(exo-C6PhM)- Mo (1)

Appendix 3 97

I I

7 6 5 4 3 2 pp m

Appendix 3.27: 1H NMR spectrum poly(exo-PhCM)- Mo (2)

lljllli]llii]iliijllli]lliljllfi]illljlill]iifijiilljflfijllfljtlil]iiiljiili]lli\]lilljilll]lllijlllljtiiljilii]!ill]llll]li

220 200 180 160 140 120 100 80 60 40 20 pp m

Appendix 3.28: 13C NMR spectrum poly(exo-PhCM)- Mo (2)

Appendix 3 98

' I

7 6 5 pp m


220 200 180 160 140 120 100 80 60 40 20 pp m


Appendix 3 99

Appendix 4

Conferences and seminar attended

Appendix4 100

CONFERENCESANDSEMINARSATTENDED

• ProfMarcetta Darensbourg: Dept of Chemistry, Texas A&M University

Functioning Catalyst Inspired by Active Sites in Bio-organometallic Chemistry:

Thew Hydrogenases (23rd October2002).

@ Prof Geoffrey Lawrance: Newcastle University, Australia

Designer L igands: M acrocyclic and alicyclic molecules for metal c omplexation

and biocatalysis (13th November 2002).

8 Dr David Procter: Dept of Chemistry, University of Glasgow

New Strategies and Methods for Organic Synthesis (22"d January 2003).

• Prof Paul Raithby: Dept of Chemistry, University of Bath

Adventures in Organometallic Polymer chemistry (1 ih February 2003).

• Prof Kingsley Cavell: University of Cardiff

(26th February 2003).

8 ProfKevin Shakesheff: The Pharmacy school, University of Nottingham

Polymer materials in tissue engineering (19th March 2003).

• Prof Joe Keddie: Dept of Physics, University of Surrey.

The sticky Business of Waterborne Pressure-Sensitive Adhesives (26th March

2003).

• Royal Society of Chemistry: Dalton division, One day symposium

Metal Mediated Polymerisation (11 1h November 2002).

Appendix 4 0 . ' . ,,'

101

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