Synthesis and Characterization of Novel Silicone Graft Copolymers

by

Pummy Singh

A Thesis Presented in Partial Fulfillment

of the Requirements for the Degree
Master of Science

Approved May 2016 by the

Graduate Supervisory Committee:

Matthew Green, Chair

Ximin He
Mary Lind

ARIZONA STATE UNIVERSITY

August 2016
 ABSTRACT

Silicone compounds have a very low surface energy due to highly flexible Si-O-Si

backbone and large number of –CH3 groups, but these compounds are extremely hydrophobic

and thus have limited applications in aqueous formulations. Modification of such silicone

compounds by grafting hydrophilic chains provides a wide range of silicone products called

"Silicone Surfactants". Silicone surfactants are surface active agents which get adsorbed at the

air-water interface thereby, reducing the interfacial tension. Some of the larger applications of

silicone surfactant are in the manufacture of plastic foams, in personal care products and as

spreading and wetting agents (Hill, R.M, 2002).

In this thesis, a series of silicone surfactant graft copolymers were synthesized via

hydrosilylation reaction. Poly(ethylene glycol) (PEG) of different chain length was grafted to a

hydrophobic Poly(methylhydrosiloxane) (PMHS) backbone to improve the final hydrophilicity.

Also, a positively charged quaternary ammonium salt (allyltriethylammonium bromide) was

grafted to the PMHS backbone. The objective of this thesis was to synthesize polymers in

predefined ratios of the above mentioned side groups and utilize these polymers to-

1) Study the effect of PEG chain length and its composition on the hydrophilicity of the polymer.

2) Study the effect of PEG: ammonium salt ratio on the surface tension of aqueous systems.

Analysis of FT-IR and H NMR spectra of the polymers confirmed the predicted structure.
1

The absence of characteristic Si-H absorbance peak at 2160 cm in FT-IR spectra indicates
-1

consumption of silane groups along the polymer backbone. The actual moles of the side chain

grafted on the backbone are calculated by H NMR peak integration. The results of contact angle
1

studies indicated an increase in hydrophilicity with an increase in the composition of PEG in

molecule. A 2*2 factorial DOE analysis reported that the fraction of Si-H bonds converted to PEG

grafts was the critical factor towards increasing the hydrophilicity (p value of 0.015). Surface

tension studies report that the air-water interfacial tension of the synthesized polymers is between

28mN/m – 45mN/m. The amount of Si-H was concluded to be the deciding factor in lowering the

surface tension.

i
DEDICATION

To my parents

S. S. Singh

Suchita Singh

ii
 ACKNOWLEDGMENTS

First of all, I express my sincere gratitude to my thesis advisor and chair Dr. Matthew Green

without whom this thesis would not have been possible. Thank you, for your continuous advice

and support during my research. I extend my appreciation to Dr. Mary Laura Lind and Dr. Ximin

He for agreeing to be on my committee. I am also very thankful to all my colleagues (labmates) at

The Green Research group with whom I had the pleasure to work, Yi Yang, Jack Felmly, Felicia

Romero and Heeran Hong .Thanks for their help, support and friendship and providing a fun and

learning environment for the tremendous growth. I would also like to thank my roommates Taruna

Saini and Akanksha Mann for always being there for me.

Finally, I extend my utmost gratitude to my parents and my entire family who have always

encouraged and believed in me at every step of my life. Thanks for their unconditional love and

support throughout this beautiful journey of life.

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 TABLE OF CONTENTS

Page

LIST OF TABLES ...................................................................................................................................vi

LIST OF FIGURES ................................................................................................................................ vii

CHAPTER

1 INTRODUCTION ................. ...................................................................................................... 1

1.1 Motivation ............................................................................................ ………..1

1.2 Silicone Polymers ............................................................................................ 3

1.3 Problem Statement .......................................................................................... 4

1.4 Organisation Of Thesis .................................................................................... 5

2 SYNTHESIS OF POLYMERS .................................................................................................... 6

2.1 Introduction................................................................................................. …..6

2.2. Hydrosilylation ................................................................................................. 8

2.3 Reaction Scheme And Polymers Sunthesized ............................................. 10

2.4. Experimental Section .................................................................................... 12

2.4.1 Materials ................................................................................................. 12

2.4.2 Synthesis Of Unsaturated Polyethylene Glycol (Alpeg)………….……12

2.4.3. Synthesis Of Allyltriethylammonium Bromide (Alquat)………………. 14

2.4.4 Synthesis Of Polymers…………………………………….…….…….…14

2.5.Synthesis Challenges………………………………………………………..…16

3 STRUCTURAL CHARACTERIZATION …………………………………………………………….18

3.1. H NMR Spectroscopy …. ……………………………………………………..18

1

3.1.1. H NMR Spectroscopy Introduction…………..……………….…………18

1

3.1.2. Methods And Measurements………..…………………..……………….19

3.1.3. H NMR Analyses……………………………………….……...…………19

1

3.2. Fourier Transform Infrared Spectroscopy .................................. …………..26

3.2.1 Introduction …….…………….……………………………………………26

3.2.2 Methods And Measurements ................................................................ 26

iv
CHAPTER Page

3.2.3 Results ................................................................................................... 27

4 PHYSICAL CHARACTERIZATION ......................................................................................... 29

4.1. Contact Angle Study ..................................................................................... 29

4.1.1. Introduction ............................................................................................. 29

4.1.2.Sample Preparation ................................................................................. 30

4.1.3.Contact Angle Measurement ................................................................... 31

4.1.4.Results And Discussion ........................................................................... 32

4.2.Surface Tenshion ........................................................................................... 35

4.2.1. Introduction ............................................................................................. 35

4.2.2.Sample Preparation ................................................................................. 36

4.2.3. Measurement Method............................................................................. 37

4.2.4.Results And Discussion ........................................................................... 38

5 CONCLUSION AND FUTURE WORK .................................................................................... 42

REFERENCES....... ............................................................................................................................ 45

v
 LIST OF TABLES

Table Page

1.1. Cosmetic Ingredient Functional Properties And Consumer Benefits ......................................... 02

2.1. Naming Of Synthesized Polymers ............................................................................... ……….15

2.2. Synthesis Of Series I Polymers ................................................................................................... 16

2.3. Synthesis Of Series II Polymers .................................................................................................. 16

3.1. Quantitative H NMR Spectroscopy Analysis For Series I Polymers ......................................... 20

1

3.2. Quantitative H NMR Spectroscopy Analysis For Series II Polymers ........................................ 24

1

3.3. FT-IR Peak Assignment ............................................................................................................... 28

4.1. Contact Angle Sample Preparation ............................................................................................. 30

4.2. Static Contact Angle For Series I Copolymers ............................................................................ 32

4.3. High And Low Levels Of Factors ................................................................................................. 33

4.4. Treatment Combinations And Contact Angle Data For Series I Polymers ................................ 33

4.5. Effect Estimates For Factors........................................................................................................ 34

4.6. Static Contact Angle For Series II Copolymers ........................................................................... 35

4.7. Surface Tension Sample Preparation ......................................................................................... 37

4.8. Surface Tension For Series I Polymers....................................................................................... 39

4.9. Surface Tension For Series II Polymers...................................................................................... 39

4.10. Trend Analysis For Series II Polymers With Respect To PMHS Content ................................ 40

4.11. Trend Analysis For Series II Polymers With Respect To PEG Content ................................... 40

5.1. General Relationship Between Molecular Weight Of Polymer And Its Function ...................... 43

vi
 LIST OF FIGURES

Figure Page

2.1. Hydrosilylation Reaction Mechanism ......................................................................................... 9

2.2. H NMR Spectrum Of PMHS .................................................................................................... 11

1

2.3. Overall Reaction Scheme ......................................................................................................... 11

2.4. H NMR Spectra Of A) ALPEG3 And B) ALPEG 11 ............................................................ 13

1

2.5. H NMR Spectrum Of ALQUAT ................................................................................................ 14

1

2.6. Schematic Of Synthesis Challenges ........................................................................................ 17

3.1. H General Region Of Chemical Shift In Organic Molecules .................................................. 18

1

3.2. H NMR Spectrum Of 1:10(3) ................................................................................................... 21

1

3.3. H NMR Spectrum Of 1:20(3) ............................................................................................... 21

1

3.4. H NMR Spectrum Of 1:10(11) ............................................................................................. 22

1

3.5. H NMR Spectrum Of 1:20(11) ............................................................................................. 22

1

3.6. H NMR Spectrum Of 1:5:15(3) ............................................................................................ 24

1

3.7. H NMR Spectrum Of 1:5:15(11) .......................................................................................... 25

1

3.8. H NMR Spectrum Of 1:10:10(3) .......................................................................................... 25

1

3.9. H NMR Spectrum Of 1:10:10(11) ........................................................................................ 26

1

3.10. FT-IR Spectra For Series I Polymers ................................................................................. 27

3.11. FT-IR Spectra For Series II Polymers ................................................................................ 28

4.1. Main Effect And Interaction Plots From JMP ............................................................................ 34

4.2. Air- Water Interfacial Tension (IFT) As A Function Of PMHS Content .................................. 41

4.3. Air- Water Interfacial Tension (IFT) As A Function Of PEG Content ..................................... 41

vii
 CHAPTER 1

INTRODUCTION

1.1 Motivation

Polymers are commonly used in the personal care and cosmetic industry, as surfactants,

emulsifiers, rheology modifiers, film formers and thickeners. They can perform these functions

while providing additional consumer benefits such as extended product wear, improved product

aesthetics, ease of application, enhanced skin, hair and nail protection etc. Within a series of

polymers, structural variations and modifications, such as, degree of polymerization, branching,

type of substituent group, and ratio of different blocks within copolymers, highly affect the nature

of the polymer and thus dictate the applications they are designed for.

Several articles have been published relating the advancements and structure–function

relationship of polymers specific to personal care and cosmetic industry (Gruber, J. V, 1999;

Lochhead, R. Y, 2007; Clarke, T. M, 1993; Butuc, G., Morrison, D. S, 2007). A book based on the

international symposium on “Polymers for cosmetic and Personal care” provided significant

motivation for this work (Patil, A., et al; 2013). The book covers multiple facets of the use of

polymers in personal care industry and recent advances in how specific properties of polymers

have been used to provide some unique benefits in personal care products. An understanding of

the polymer structure-function relationship and the ability to alter these structures for specific

applications translated into the present work.

As mentioned, polymers can be used for various functions in personal care industry. A

large variety of polymers such as poly(α-olefins), acrylate copolymers, silicone-acrylate

copolymers, polyester resins and polyurethanes are used as film formers, these polymers do not

necessarily form a self-standing film but can improve the spreadability of cosmetic formulation.

The films formed can serve various functions such as extend sunscreen protection, impart oil or

water resistance and improve product aesthetics. Polymers are also used in cosmetic products

such as lipsticks and lip-gloss as transfer resistance agents. When a cosmetic product does not

deposit on food or cloth or when it resists removal, it is called “transfer- resistant”. A

trimethylsiloxysilicate polymer, due to its highly cross-linked structure is an extremely efficient

1
transfer resistant. In shampoos, soaps and detergents, polymers are used as surface active

agents. Poly(ethylene oxide) (PEO), poly (propylene oxide) (PPO) and their copolymers are some

examples of surface active polymers commonly used in personal care industry. Though PEO and

PPO differ only in a single methyl group, this small difference has high implications. PEO

homopolymers are soluble in water at all molecular weights; in contrast, PPO is hydrophobic.

Block copolymerization of EO/PO produces an entire range of amphiphilic nonionic surfactants.

Though such surfactants are conventionally used, they are less surface active as compared to a

comparatively new class of surfactants called “silicone surfactants” which have low surface

energy –CH3 groups attached to a highly flexible Si-O-Si backbone. The above mentioned

polymers along with additional examples are tabulated in Table 1.1 which relates functional

properties of the polymers to the consumer benefits.

Table 1.1: Cosmetic Ingredient Functional Properties and Consumer benefits

(Patil, A., Sandewicz, R.W., 2013, p 17)

Functional Property Consumer benefits Polymeric examples

Film formation Extended product wear; Nitrocellulose, polybutene,

enhanced skin protection; polyester resins, acrylates

improved product aesthetics copolymers, silicone acrylate

copolymers, polyurethanes

Transfer resistance Tenacious product adhesion; Trimethylsiloxysilicate

enhanced skin protection; (MQ resins), silicone

reduction in number of elastomers

product application cycles

Surface activity Ease of application; enhanced PEG/PPG block copolymers

product shelf life

Rheological control Ease of application; enhanced Hydroxypropylmethylcellulose,

product shelf life hydroxyethyl cellulose,

polyacrylic acid, polyamides

2
Gloss reduction Mitigation of appearance Polyurethane crosspolymers

of undesirable skin surface

defects

Pigment surface Ease of application; novel Reactive silanes

treatment visual aesthetics

1.2 Silicone Polymers

Silicone polymers are a class of inorganic polymers with a Si-O-Si backbone. In the past,

silicones frequently used in personal care applications were homopolymers of dimethylsiloxanes

known as poly(dimethylsiloxane) (PDMS). The highly flexible silicone and oxygen backbone of

PDMS has the ability to orient itself in such a way, so as to allow maximum adsorption of low

surface energy methyl groups attached to it, thus having a very low surface tension. Moreover,

due to a very low glass transition temperature (T g) PDMS is liquid at room temperature and is

thus not sticky, therefore, having a desired dry feel character associated with it. In order to take

advantage of these numerous properties desirable for various personal care products, alternative

silicone compounds for various applications were explored. The use silicone compound as

surface active agents is one such application. These surface active agents called “surfactants”

consist of a hydrophilic and hydrophobic part which when dissolved in liquid reduces its surface

tension. The first silicone surfactant was introduced to the marketplace in 1950s for

manufacturing of polyurethane foam (Herrington et al., 1991); the surface activity of silicones in a

non-aqueous medium formed the basis of their use in polyurethane manufacture. Though

silicones are surface active even in an aqueous medium, its strong hydrophobic nature limits its

applications. Poly(ethylene glycol) is grafted to the silicone to form amphiphilic silicone

surfactants. These silicone surfactants have certain unique properties, since their hydrophobic

group is silicone; they are able to lower the surface tension to ≈20mN/m as compared with

≈30mN/m for conventional hydrocarbon surfactants causing them to be surface active in both

aqueous and non-aqueous media. Though silicone surfactants are superior to hydrocarbon

surfactants, the two show similarities in many common features of surfactants. For both types of
3
surfactants, micelle formation is represented by a break in their surface tension versus log

concentration curve. Moreover, the variation in critical micelle concentration (cmc; defined as the

concentration of surfactant above which micelles forms and there is no further decrease in

surface tension) with molecular structure is similar for both types of surfactants, that is, within a

homologous series larger hydrophobic groups lead to smaller cmc value.

1.3 Problem Statement

This thesis is focused on synthesizing silicone surfactant polymers. Poly(ethylene

glycol)mono methyl ether( PEG11, Mn 550) or triethylene glycol mono methyl ether (PEG3) and a

quaternary ammonium salt (N,N,N- triethylprop-2-en-1-ammonium bromide) is grafted on to the

silicone backbone via hydrosilylation reaction. Poly(ethylene glycol)s and quaternary ammonium

salt are attached to impart hydrophilic characteristics in a surfactant, also, the positive charge on

the quaternary ammonium salt provides conditioning nature (Kollmeier, B. J, 1986).

Since, these polymers were designed for personal care products; the area of application

for the polymers is skin and hair. The function of a conditioner is to improve the quality (condition)

of the biological surface with which it interact thus reducing the surface damage. Cationic

polymers such as quaternary ammonium silicones are very effective conditioning agents because

of their substantivity to the respective substrate, directly attributable to electrostatic interactions

between the negatively charged damaged sites on the hair shaft and positive charge on the

polymer. Moreover, the germicidal properties associated with quaternary ammonium salts (Lu et

al., 2007) and their ability to reduce surface tension made them a suitable source of positive ions.

In the past, in order to take advantage of the various desirable properties offered by otherwise

hydrophobic silicones, they were used as emulsion in aqueous medium in addition to

conventional anionic surfactants being primary surfactants. However, the presence of anionic

surfactants shifts the hydrophilic-lipophilic balance (HLB) and splits the emulsion thus reducing

the shelf life of the product. Modification of silicone by grafting PEG results in a surfactant that is

soluble in aqueous formulations and thus can be used with anionic surfactants. Moreover, since

silicone surfactants have high surface activity they are used in lesser quantities in the

formulations.
4
The objective of this thesis was to synthesize polymers in predefined ratios of the above

mentioned side groups and utilize these polymers to-

1) Study the effect of PEG chain length and its composition on the hydrophilicity of the polymer.

2) Study the effect of PEG: ammonium salt ratio on the surface tension of aqueous systems.

1.4 Organization of Thesis

This thesis is structured into 5 chapters. Chapter 1 provides an introduction to the use of

polymers in personal care industry, particularly silicone polymers and delivers an overview of the

objective of this thesis. Then, chapter 2 delves deeper into silicone surfactants; it gives an

overview of the commonly used methods to synthesize such polymers with special emphasis on

hydrosilylation mechanism. The reaction scheme adopted to synthesize these polymers is

discussed with detailed experimental procedure. Furthermore, the two series of polymers

synthesized are introduced at the end of chapter 2.

Chapter 3 discusses the characterization techniques adopted to confirm the structure of

the synthesized polymers. Fourier Transform Infrared spectroscopy (FT-IR) is utilized for

qualitative analysis of the polymers. However, it is not sufficient to quantitatively analyze the

structure. H Nuclear Magnetic Resonance (NMR) Spectroscopy is used to calculate the actual
1

number of repeating units in the backbone grafted with side chains. The combination of these

analyses is used to calculate the molecular weight of the polymers and the composition of

unreacted hydrosilane and grafted side chains.

Chapter 4 presents techniques of physical characterization of polymers. Contact angle

and surface tension studies are conducted to determine the wettability and surface activity

properties of the polymers. The theory of both these techniques is discussed along with

laboratory procedures for sample preparation and measurement methods. Results are analyzed

and discussed at the end of chapter 4.

Chapter 5 summarizes and concludes the results of this thesis and explores the future

scope of research.

5
 CHAPTER 2

SYNTHESIS OF POLYMERS

2.1 Introduction

Silicone surfactants are prepared by attaching one or more polar groups to the

permethylated siloxane backbone. The three most widely used methods of attaching these polar

groups are discussed below. However, the first step in the synthesis of siloxane surfactants is to

prepare a siloxane backbone containing reactive sites such as SiOH, SiOR (where, R is usually

–CH3 or –CH2CH3) and SiH. Ionic and nonionic groups are then attached to these reactive sites

by the techniques described below. Non-ionic surfactants are prepared usually by the direct

synthesis routes of transesterification and hydrosilylation whereas, the indirect method involving a

two step synthesis, is used for attaching ionic species to the backbone. The three routes are

(Randal M.Hill, Silicone surfactants: Vol. 86; p 7-13):

1) Transesterification – Directly by reaction of SiOR and R OH

1 2

The method of transesterification involves coupling of alkoxymethylsiloxane polymers and

hydroxyl-terminated polyoxyalkylenes to form siloxane polymers. The following reaction

represents the same;

SiOR1 + R2OH SiOR2 + R1OH

Where R1 is usually -CH3 or – CH2CH3 and R2 is polyalkylene oxide.

Siloxane surfactants prepared by this method contain Si-O-C linkages, which hydrolyze in

water to generate a silanol and alcohol. Therefore, the products of this reaction are suitable for

non-aqueous applications such as polyurethane foam manufacturing. Since, in the current work,

designing polymers for aqueous formulations was of interest, alternative approaches were

explored.

2) Hydrosilylation – Directly by reaction of Si-H and CH2=CHCH2R; where R is a polar group

Hydrolytically stable siloxane surfactants can be prepared by hydrosilylation. This method

involves the reaction of reactive Si-H bonds, such as; poly(methyl hydrosiloxane) with allyl-

6
functionalized polar groups to form siloxane surfactants. Numerous works involving amphiphilic

polymers with polar groups attached to siloxanes using hydrosilylation have been reported in

past. These polymers are designed and modified for various applications. A poly(dimethyl

siloxane) modified by grafting a poly(ethylene glycol) (PDMS-g-PEG), has the ability to form nano

tanks of self-assembled vesicles for hydrophobic drugs (Li et al., 2010); novel synthesis

techniques involving hydrosilylation are used to generate PMHS-g-PEG-co-PMVS copolymer

membranes with enhanced water cohesion and lubrication properties (Ding et al. ,2012).

Moreover, due to the extraordinary flexibility of siloxanes, synthesis of such polymers as solid

polymer electrolytes has also been reported.

3) Two step synthesis using reactive intermediate- Indirectly by attaching a reactive group such

as epoxy via hydrosilylation and then using that reactive group to attach the polar group.

Two step synthesis routes via formation of reactive intermediate are used to attach polar

groups that are incompatible with hydrosilylation reaction conditions. This process involves the

addition of a reactive group to the backbone and then a subsequent reaction to attach polar

groups. A detailed literature review showed most of the work for attaching quaternary ammonium

groups to the siloxanes followed this synthesis technique. Hou and Kan synthesized

polysiloxanes with quaternary ammonium groups using allyl glycidyl ether as the reactive

intermediate, followed by a ring opening reaction of the epoxide group with diethyl amine and

quaternization with benzyl chloride (Hou, Z. and Kan, C., 2015). However, literature also supports

the use of hydrosilylation for attaching such reactive ionic groups (Tong et al., 2003).

In this thesis, novel siloxane polymers were grafted with either allyl functionalized

poly(ethylene glycol)mono methyl ether( PEG11, Mn 550) or triethylene glycol mono methyl ether

(PEG3, Mn 164) and a quaternary ammonium salt (N,N,N- triethylprop-2-en-1-ammonium

bromide) via hydrosilylation and, thus, this method is discussed in detail in the following section.

To our knowledge, there have been no earlier attempts to simultaneously graft these groups to

the PMHS backbone.

7
2.2 Hydrosilylation

Hydrosilylation describes the addition of hydrosilanes across carbon-carbon multiple

bonds under catalysis by transition metal complexes. A simple model of this reaction is given

below where heptamethyltrisiloxane is used to hydrosilylate allyl alcohol in presence of Pt

catalyst.

A group VIII transition metal complex is used to catalyze the hydrosilylation reaction.

Numerous reports on hydrosilylation and various forms of catalysis have been published and

summarized in articles (Patai, S. and Rappoport, Z., 1989). Complexes of Ni, Pt, Pd and Rh have

been widely studied for hydrosilylation. A Pt compound such as hexachloroplatinic acid (H2PtCl6),

platinumdicyclopentadienyldichloride [Pt(dcp)] and platinumdivinyltetramethyldisiloxane [Pt(dvs)]

are most commonly used. Hydrosilylation is an exothermic reaction with heat of reaction of

117.15 KJ/mol. Various solvents, such as tetrahydrofuran (THF), isopropyl alcohol (IPA), and

toluene, are used depending upon the compatibility of the reactants. These solvents act as heat

sink for energy generated during the reaction. The work of Zhang and Laine provides a

comparison between different combinations of the aforementioned Pt complexes and solvents for

these reactions (Zhang, C., Laine, R.M., 2000).

The mechanism for hydrosilylation of unsaturated olefins or polyethers by homogenous

catalysis using transition metal complex is described by Chalk and Harrod (Chalk, A.J., Harrod,

J.F, 1964). Oxidative addition of the hydrosilane to a metal complex, which is low in oxidation

state activates the hydrosilane and is the most important step in hydrosilylation. This leads to the

formation of hydrido-silyl complex (I) coordinated with substrate alkene. The complex I undergoes

insertion of alkene into M-H bond forming alkyl-silyl species (II) .Reductive elimination of the alkyl

and silyl ligands from complex II results in the formation of final product. The following sequence

shows elemental reactions in a transition metal complex catalyzed hydrosilylation.

8
Figure 2.1.Hydrosilylation reaction mechanism

(Ojima, I, Yamamoto, K. ,Kumada, M. Aspects of homogeneous catalysis: A series of advance,

2012, Vol 3, p 188)

Although, the mechanism of the hydrosilylation reaction is usually depicted as shown in

Figure 2.1, it is often accompanied with competing side reactions. Isomerization of the terminal

olefinic groups is favored at high temperatures (> 80 C) resulting in retardation/termination of

o

hydrosilylation reaction. Since, this reaction has been well studied over the years; it was

determined that the addition of excess of allyl-containing compounds will reduce the propensity

for the competing isomerization reaction. Another side reaction that can occur is silylation,

9
wherein the hydrosilane reacts with hydroxyl group on terminal carbons in polyethers to form

alkoxysilane. This can be controlled by protecting the active hydrogen in unsaturated alcohols.

For this work, methyl terminated poly(ethylene glycols) were used to eliminate the possibility of

silylation byproducts. Furthermore, residual hydrosilane functionalities can lead to hydrolysis of

Si-H in presence of moisture to form silanol and hydrogen gas.

2.3 Reaction Scheme and Polymers Synthesized.

The process of hydrosilylation requires three steps:

1) Preparation of hydrosilane intermediate

2) Preparation of allyl substituted derivatives of polar groups.

3) Hydrosilylation of second compound to first one to form final polymer

Hydrosilane intermediates can be synthesized by several different processes. The most

popular method involves hydrolysis of hydridochlorosilanes. Hydridomethyl siloxanes are

prepared commercially by hydrolysis of HMeSiCl2 in presence of Me3SiCl as shown in equation

2.1. Trimethylchlorosilane serves as end groups to control the molecular weight of the polymer

during the polymerization reaction.

Excess H2O
2Me3SiCl + (ѡ + Χ)HMeSiCl2 Me3SiO(HMeSiO)ΧSiMe3 + ѡ( HMeSiO)y

+2(ѡ + 1 +Χ) HCl ……………………2.1

For the current work, poly(methylhydrosiloxane) (PMHS) end capped with trimethylsilane

was directly obtained from Gelest. H NMR spectroscopy (Figure 2.2) of the sample indicated 20
1

repeating units (n= 20). The allyl substituted derivatives of the polar groups were prepared in the

laboratory, and then attached subsequently to the PMHS according to the procedure described in

section 2.4. The overall reaction scheme is shown in figure 2.3.

10
Figure 2.2. H NMR spectrum of PMHS
1

Figure 2.3. Overall Reaction scheme

11
2.4. Experimental Section

2.4.1 Materials

Poly(methylhydrosiloxane) (PMHS, Mn-1700-3200) was obtained from Gelest.

Poly(ethyleneglycol)mono methyl ether( PEG11, Mn 550) and triethylene glycol mono methyl ether

were obtained from Sigma- Aldrich. Platinum divinyltetramethyldisiloxane [Pt(dvs)] (also known as

Karstedt’s catalyst ), 3% in xylene solution, allyl bromide, 60% dispersion of sodium hydride

(NaH) in mineral oil, triethylamine and NMR grade deuterated chloroform were also supplied by

Sigma-Aldrich. Diethyl ether, chloroform, THF, toluene and acetone were ACS reagent grade,

obtained from Fisher Scientific, and used without any further purification.

2.4.2 Synthesis of unsaturated polyethylene glycol (ALPEG)

Poly(ethylene glycol)allyl methyl ether (ALPEG11) was synthesized according to literature

protocol (Hooper et al.,2001). A solution of 0.06 mol of poly(ethylene glycol) methyl ether

(Mn=550 g/mol) was added drop wise to a suspension of NaH (0.12 mol) in THF (50 mL)

maintained at 0ºC. The mixture was stirred at 180 rpm for 3 h followed by dropwise addition of a

solution of allyl bromide (0.06 mol) in THF (50 mL). The resulting mixture was warmed to room

temperature and stirred for 18 h. The solution was concentrated using rotatory evaporation to

yield an orange oil. This orange oil was then dissolved in water and unreacted PEG was removed

by washing with 50 mL of toluene three times. The desired product was then extracted from the

water layer using chloroform (3*200 mL). The organic layer was then dried with MgSO 4 and

concentrated using rotatory evaporation followed by vacuum drying. 14.85 g of pale yellow

colored product (ALPEG11) was obtained. H NMR spectroscopy of the product confirmed the
1

structure and the conversion of PEG11 to ALPEG11 was determined to be 81%.

Triethylene glycol allyl methyl ether (ALPEG3) was synthesized by the same procedure

where 0.06 mol of triethylene glycol mono methyl ether was used instead of poly(ethylene glycol

methyl ether). The final yield was11.32 g. H NMR spectroscopy of the product confirmed the
1

structure and the conversion was determined to be 78%. Figure 2.4 shows the H NMR spectra
1

for ALPEG3 and ALPEG11.

12
 H NMR (CDCl3),δ (ppm): 5.85 (m,1H) , 5.15 (dd,2H), 3.95(d,2H), 3.45-3.65(m,12 H), 3.35(s,3H).
1

Figure 2.4. H NMR spectra of A) ALPEG3 and B) ALPEG 11

1

13
2.4.3. Synthesis of Allyltriethylammonium bromide (ALQUAT)

ALQUAT was synthesized by the method described by Tong et al. (Tong et al., 2003).

Allyl bromide (6.0 g, 0.05 mol) was added dropwise to a solution of triethylamine (10 g, 0.07 mol)

in acetonitrile (70 mL). The mixture was allowed to reflux for 10 h. After the reaction was

completed, the product was precipitated in 50 mL of diethylether. The precipitate was filtered and

dried under vacuum to yield 9.28 g of white solid. The structure was confirmed by H NMR
1

spectroscopy and the spectrum of the product is shown in Figure 2.5.

H NMR (CDCl3),δ (ppm):6 (m,1H) , 5.8 (dd,2H), 4.15(d,2H), 3.45(q,6 H), 1.4(t,9H).
1

Figure 2.5. H NMR spectrum of ALQUAT

1

2.4.4 Synthesis of polymers

Two series of polymers were synthesized. Series I include, ALPEG3 or ALPEG11 grafted

to the PMHS backbone. Whereas, series II includes ALPEG3 and ALQUAT or ALPEG11 and

ALQUAT attached to the PMHS backbone. Table 2.2 and 2.3 shows the amounts of these

14
reactants required to synthesize the polymers of the desired ratio. A general procedure for the

synthesis of polymers is outlined here.

A solution of PMHS in toluene (10 mL) was placed in a two neck round bottomed flask

equipped with a reflux condenser. The desired quantities of ALPEG3, ALPEG11 and ALQUAT was

added to the reaction vessel. The contents of the reactor were mixed for 15 min to dissolve the

reactants in solvent. The reactor was carefully degassed and backfilled with nitrogen three times

using the freeze-pump-thaw cycle. Then, the reactor was heated to 75ºC and 250 μL of Pt(dvs)

catalyst was added via syringe. Hydrosilylation is an exothermic reaction and slight effervescence

was observed following the addition of the catalyst. The reaction was allowed to run for 18 h

under reflux. Volatiles were evaporated under vacuum to obtain final product. The structure of all

synthesized copolymers was confirmed by H NMR spectroscopy and fourier transform infrared
1

spectroscopy (FT-IR). A detailed analysis of graft copolymer structures is given in chapter 3.Table

2.1 gives the nomenclature for both series of polymers. This nomenclature will be used

throughout this thesis.

Table 2.1: Naming of synthesized polymers

Series PMHS: Ammonium: PEG Sample code

Ratio

PEG Chain Length PEG (3) PEG (11)

Series I 1:0:10 1:10 (3) 1:10 (11)

1:0:20 1:20 (3) 1:20 (11)

Series II 1:5:15 1:5:15 (3) 1:5:15 (11)

1:10:10 1:10:10 (3) 1:10:10 (11)

15
Table 2.2: Synthesis of Series I polymers

Sample code PMHS ALPEG ALPEG

(mol) (mol) (g)
Req M Req M Req M
1:10 (3) 0.0005 0.00055 0.005 0.0058 1.02 1.20

1:20 (3) 0.0005 0.00051 0.010 0.010 2.04 2.04

1:10 (11) 0.0005 0.00050 0.005 0.0051 2.78 2.80

1:20 (11) 0.0005 0.00053 0.010 0.0112 5.56 6.23

*Req = Required *M= Measured

Table 2.3: Synthesis of Series II polymers

Sample PMHS ALPEG ALPEG ALQUAT ALQUAT

code (mmol) (mmol) (g) (mmol) (g)
Req M Req M Req M Req M Req M

1:5:15 0.05 0.055 0.75 0.85 1.53 1.74 0.25 0.27 0.555 0.59
(3)
1:10:10 0.05 0.05 0.5 0.51 1.02 1.02 0.50 0.51 1.11 1.13
(3)
1:5:15 0.05 0.05 0.75 0.75 4.17 4.19 0.25 0.24 0.555 0.54
(11)
1:10:10 0.05 0.05 0.5 0.5 2.78 2.78 0.50 0.50 1.11 1.11
(11)

*Req = Required *M= Measured

2.5. Synthesis challenges

Though literature reports hydrosilylation reaction conditions for attaching polar groups

such as poly(ethylene glycol) or, separately, for attaching quaternary ammonium compounds, to

our knowledge there have been no earlier attempts to simultaneously graft these groups to the

PMHS backbone. Thus, the biggest challenge during the synthesis phase was the selection of the

reaction conditions, including the amount of catalyst, temperature of the reaction and time

16
required for the reaction to go to completion. For the graft copolymers with the nomenclature

1:5:15 (3 or 11), the process conditions selected were similar to those reported in literature for

grafting allyl PEG to the PMHS. Due to unavailability of in-situ FT-IR, the reaction was allowed to

run for 24 h (i.e., the maximum duration reported in literature for similar hydrosilylation reactions).

Lastly, it is required to follow laboratory safety protocols while dealing with hazardous chemicals

such as NaH, triethylamine and allyl bromide. According to Globally Harmonized System (GHS)

of classification these chemicals are highly flammable, corrosive and toxic. NaH reacts violently

with moisture to produce hydrogen gas, which can ignite from the exothermic reaction. Thus, a

good understanding of possible dangers and a thorough knowledge of the standard operating

procedures while dealing with such chemicals are required.

Figure 2.6 - shows a schematic of the various challenges encountered during the synthesis of the

PMHS graft copolymers.

Figure 2.6. Schematic of synthesis challenges

17
 CHAPTER 3

STRUCTURAL CHARACTERIZATION

3.1 H NMR Spectroscopy

1

3.1.1. H NMR Spectroscopy Introduction

1

An accurate quantitative analysis of polymers can be performed by elucidating molecular

structures using nuclear magnetic resonance spectroscopy. NMR spectroscopy is a technique

that studies the magnetic properties of the nuclei and thus provides useful information required

for identifying organic molecules. The NMR spectrum is produced by absorption of

electromagnetic radiations in radio–frequency region at frequencies defined by the structure of

the sample. All nuclei carry a charge; however, in some nuclei this charge spins along the nuclear

axis generating a magnetic dipole moment. During NMR spectroscopy experiments this magnetic

dipole moment is analyzed. Isotopes such as C, O, S have no spin and thus cannot be
12 16 32

analyzed by NMR. Whereas, nuclei with positive or negative spin like H, C, F, Si can be
1 13 19 29

easily studied.

Since almost all organic molecules have H isotopes, H is the most studied nucleus.
1 1

Figure 3.1 shows the chemical shifts for common proton functional groups in ppm.

Figure 3.1.General region of H chemical shift in organic molecules.

1

(Enrique, S.G; Eduardor, V.L . Handbook of Polymer Synthesis, Characterization, and Processing (1); Wiley: Somerset,

2013; p 344)

18
In this thesis, H NMR spectroscopy was used to quantitatively analyze the two series of
1

polymers synthesized. H NMR spectra were obtained using a Bruker FT-NMR spectrometer
1

(400 MHz) using CDCl3 as the solvent. Tetramethylsilane (TMS) was used as reference for all

reported NMR spectra.

3.1.2 Methods and measurement

H NMR spectroscopy samples were prepared by dissolving 20-22 mg of polymers in

1

CDCl3 solvent and introducing these polymer solutions in NMR tubes. Based on the molecular

nature, some samples dissolved easily in the solvent while others were stirred for 30 min. All the

samples prepared were clear solutions and free from suspended dust and impurities. These

samples were injected into clean, dried NMR tubes through filters.

3.1.3. H NMR analyses

1

3.1.3.1 Series I polymers

As described in Chapter 2, two series of polymers were synthesized. Polymers in series I

include either PMHS-g-ALPEG3 or PMHS-g-ALPEG11 with predefined ratios of PMHS: PEG. H

1

NMR spectra were used to calculate the number of Si-H repeating units grafted with side chains.

The calculations for sample 1:10(3) are discussed in detail below. Similar calculations were

performed for all series I polymers, the results are listed in Table 3.1. Based on these analyses,

the amount of hydrophilic poly(ethylene glycol) in the copolymer and number average molecular

weight (Mn) of the synthesized polymers was calculated. This information was used for analyzing

the contact angle and surface activity of the graft copolymers.

From table 2.2,

We have,

Actual moles of PMHS added= 0.00055 moles

Moles of ALPEG3 added = 0.00588 moles

Also,

H NMR spectrum of ALPEG3 (Figure 2.4- A) shows conversion of 78%

1

19
 Thus,

actual moles of allyl PEG added = 0.78 (0.00588)

= 4.58*10
-3

Therefore,

The ratio of PMHS: Allyl PEG is 1:8.5 . It is worth noting here, that the target ratio for this

polymer was 1:10.

According to the H NMR spectrum of 1:10 (3) shown in Figure 3.2.

1

16/2
∗= = 8.188
76.2/78

Where, 16 and 76.2 are the integration corresponding to peak c and a respectively.

= 20 − ∗ = 11.81

H NMR spectra for 1:20(3), 1:10(11) and 1:20(11) are shown in figures 3.3, 3.4 and 3.5
1

respectively.

Table 3.1: Quantitative H NMR spectroscopy analyses for Series I polymers

1

Sr. Code Structure of PMHS-PEG PEG PEG Mn (g/mol)

no. chain Content
Target Obtained Length (wt%)
D* D D* D (n)
1 1:10 (3) 10 10 8.18 11.81 3.2 55.63 3,010.0

2 1:20 (3) 20 0 16.97 3.03 3.2 72.35 4,810.0

3 1:10 (11) 10 10 7.9 12.91 11.1 76.03 5,790.0
4 1:20 (11) 20 0 15.6 4.4 11.1 86.72 10,020.0

20
Figure 3.2. H NMR Spectrum of 1:10(3)
1

Figure 3.3. H NMR spectrum of 1: 20(3)

1

21
 Figure 3.4. H NMR spectrum of 1:10 (11)
1

Figure 3.5. H NMR spectrum of1:20(11)

1

22
 3.1.3.2 Series II Polymers

H NMR spectra for series II polymers were also studied. An analysis similar to series I
1

polymers was performed to obtain the values of D, D* and unreacted hydrosilane.

Detailed analysis for one of the series II graft copolymer (1:5:15(3)) is discussed below.

From table 2.3,

Actual moles of PMHS added= 0.00055 moles

Moles of ALPEG3 added = 0.0085 moles

Moles of ALQUAT added = 0.0027 moles

H NMR spectrum of ALPEG3 (Figure 2.4- A) shows conversion of 78%

1

Thus, actual moles of allyl PEG added = 0.78 (0.0085)

= 6.63*10
-3

Therefore, the ratio of PMHS : Allyl PEG is 1:12.03. It is worth noting here, that the target ratio

for this polymer was 1:15.

Also, H NMR spectrum of ALQUAT (Figure 2.5) shows 99 % conversion,

1

Thus, actual moles of quaternary ammonium added = 0.99 (0.0027)

= 2.66*10
-3

Therefore, the ratio of PMHS: Allyl Substituted quaternary ammonium salt is 1:5.3. The desired

ratio here was 1:5.

According to the H NMR spectra of 1:5:15 (3) shown in figure 3.6.

1

12.61/12
∗= = 12.035
6.81/78

Where, 12.61 and 6.81 are the integration corresponding to peak b and a respectively.

Also,
2.09/6
= = 3.98
6.81/78

Where, 2.09 is the integration corresponding to peak d.

Similar analyses were performed for all the series II copolymers and the results are listed in

table 3.2.

23
Figure 3.6. H NMR spectrum of of 1:5:15(3)
1

Table 3.2: Quantitative H NMR spectroscopy analysis for Series II polymers

1

Code Structure of PMHS-PEG * (n) *X *Y Si-H Mn

Target Obtained (wt%) (wt%) content (g/mol)
D* D D* D Si-H
1:10:10 10 10 9.1 6.5 4.4 3.2 46.92 23.37 29.71 3976.0
(3)
1:5:15 15 5 12.0 3.98 3.98 3.2 51.27 8.8 39.93 3826.0
(3)
1:10:10 10 10 8.1 5.6 6.3 11.1 68.32 12.12 19.56 6603.0
(11)
1:5:15 15 5 11.0 2.15 6.85 11.1 70.32 2.83 26.85 7550.0
(11)
*X= PEG content *Y = Ammonium content *n= PEG Chain length

24
Figure 3.7. H NMR spectrum of 1:5:15(11)
1

Figure 3.8. H NMR spectrum of 1:10:10 (3)

1

25
Figure 3.9. H NMR spectrum of for 1:10:10(11)
1

3.2 Fourier Transform Infrared spectroscopy (FT-IR)

3.2.1. Introduction

Infrared spectroscopy is a technique used for the structural characterization of samples

based on the absorbance of the IR-frequency energy by the bonds between the atoms. In this

technique, the sample is placed in a sample holder and infrared rays are passed through it. The

sample absorbs energy at a frequency specific to the structure of the molecule. The use of

Fourier transform to process the results of interferogram led to the development of FT-IR. For

most organic molecules, infrared rays interact with atoms in a chemical bond in mid IR region

(4000 cm -400 cm ) to give an absorption band. These interactions involve changes in molecular
-1 -1

dipoles associated with vibrations and rotations.

3.2.2. Methods and measurement

The product of hydrosilylation was vacuum dried for 12 h at 40ºC to obtain completely dry

white solid polymer. Mortar and pestle was used to obtain fine powder of the sample which was

then placed in a sample holder filled to the brim. Thermal Fisher 1S50 FT-IR Nicolet was used to
26
obtain FT-IR spectrum at room temperature in the range of 4000 cm to 400 cm and averaged
-1 -1

over 16 scans.

3.2.3. Results

FT-IR absorption spectra were obtained for both series I and series II polymers. For

samples 1:10(3) and 1:10(11) a characteristic Si-H stretching peak was observed at 2160 cm ,
-1

however no such peak was observed for 1:20 type polymers .The O—HO stretching from water at

3480 cm , asymmetric C-H3 stretching at 2906 cm , Si-CH3 stretching at 1960 cm and C-O-C
-1 -1 -1

bending at 1100 cm were visible in both series I and series II polymers. In addition, series II
-1

polymers also showed C-H2 stretching from amine at 2492 cm indicating the presence of
-1

ammonium groups. Qualitative analysis of the samples was done using FT-IR to better

understand the structural composition of the synthesized polymers.

Figure 3.10. FT-IR spectrum of series I polymer

27
Figure 3.11. FT-IR spectrum of series II polymer

Table 3.3. FT-IR peak assignment

Assignment
-1
Frequency(cm )

2160 Si-H bending

1957 CH deformation in SiMe2

3

1160 C-O-C stretching

2967 Asym CH stretching

3

2492 CH stretching in amine

2

3480 OH---O stretching from water

28
 CHAPTER 4

PHYSICAL CHARACTERIZATION

4.1 Contact angle Study

4.1.1 Introduction

Contact angle is the measure of wettability of solid surface by a liquid. For a drop of liquid

resting on a flat horizontal solid surface, the contact angle (θ) is defined as the angle formed by

the intersection of liquid–vapor interface and liquid-solid interface. If a liquid spread over the solid

surface, the measured contact angle is small and the wetting of the solid surface is favorable,

such surfaces for which θ<90 are considered hydrophilic surfaces. Whereas, for hydrophobic
0

surfaces with θ>90 wetting of the surface by liquids is unfavorable, therefore; the liquid
0

minimizes its contact with solid by forming compact liquid droplets on the surface.

Contact angle is determined by a combination of surface tension and external forces

(usually gravity) acting on the liquid drop. The phenomenon of surface tension or surface free

energy is discussed in detail in section 4.2. Thomas Young in 1805 first defined the contact angle

of a liquid drop on a solid surface as the mechanical equilibrium of drop under three interfacial

tensions (Young, T, 1805). Equation 4.1 shown below is referred to as Young’s equation.

lv cos θγ = sv− sl ………………………………………. 4.1

Where,

γlv = liquid vapor interfacial tension

γsv = solid-vapor interfacial tension

γsl = solid-liquid interfacial tension

θγ = Young’s contact angle

PMHS is extremely hydrophobic with the water contact angle of 103º, whereas the C-O-C

ether linkages present on the poly(ethylene glycol) form hydrogen bonds with water resulting in

complete spreading and consequently very low contact angle. In this work, PEG chains were

grafted on the PMHS backbone to impart hydrophilicity to the designed polymer and the effect of

two factors a) concentration of PEG and b) PEG chain length, on the hydrophilicity of the
29
copolyme were studied by measuring contact angle. Similar studies performed in the past by Ding

et al. and Chung & Lim, reported an increase in hydrophilicity with an increase in the

concentration of PEG attached to the molecule when the PEG chain length is kept constant. Ding

et al. studied these effects using a shorter PEG (n=7) whereas, Chung & Lim studied a longer

PEG of 16 repeating units. No work in literature was found where both these factors were altered

simultaneously. A 2 full factorial experiment was performed on series I polymers to study the
2

effects of main factors and their interaction. The results are discussed in detail in the section

4.1.4.

4.1.2 Sample Preparation

The polymeric products obtained from the hydrosilylation reaction were in the form of

white solid powder. Since a smooth continuous solid film is required for contact angle

measurements, thin films of these polymeric samples were prepared over glass substrate. To

cast a typical film, 0.05 g of each sample was dissolved in 0.66 g of THF to obtain 7 wt%

solution of sample in THF which were then stirred at 320 rpm for 24 h to ensure maximum

dissolution. Table 4.1 below shows the exact quantities measured while preparing the samples.

Air free drops of these solutions were deposited very carefully by pipette, on to the thin glass

cover slip. The THF was evaporated by drying in air for 12 h, leaving thin, smooth polymeric

films. These films were then used as solid surface for contact angle measurements. Easy drop

from Kruss was used to measure contact angle.

Table 4.1: Contact angle sample preparation

Sample code Sample measured (g) Sample + THF (g) Sample Wt%
1:10(3) 0.049 0.690 7.10
1:20(3) 0.054 0.722 7.47
1:10(11) 0.051 0.687 7.42
1:20(11) 0.048 0.646 7.43
1:5:15 (3) 0.054 0.701 7..70
1:5:15 (11) 0.052 0.697 7.46
1:10:10 (3) 0.050 0.714 7.00
1:10:10(3) 0.049 0.706 6.94

30
4.1.3 Contact angle Measurement

The interface where liquid, solid and vapor coexist is called a three phase contact line.

Depending on the nature of the contact line, contact angle can be defined as static or dynamic. If

the contact line is stationary, Young’s equation can be directly applied to determine the unique

contact angle called Young’s contact angle (θγ). However, in practice, the phenomenon of

wetting is dynamic in nature and a single contact angle is no longer entirely sufficient to

characterize the wetting behavior of the solid, though it is still considered a good approximation

for smooth homogenous surfaces (Yuan,Y.; Lee, T.R. 2013).

In such case, when the three phase contact line is in motion, dynamic contact angle in

the form of advancing and receding contact angles are usually measured. Advancing and

receding contact angles are represented as θa and θr respectively and are determined by

expanding or contracting the liquid drop on the solid surface. The difference between θ a & θr is

called hysteresis and is the measure of surface roughness and heterogeneity of the sample.

Ideally, dynamic contact angles should be measured to completely characterize the wetting

behavior of the solid surface. Advancing contact angle is a good approximation of θ γ for rough or

chemically homogenous surfaces, while the receding contact angle has low reproducibility due

to solid swelling or liquid sorption (Sedev et al., 1996).However, in this thesis, due to the

limitations of the instrument, static contact angles were measured for a drop of pure water

resting on the polymeric film. As mentioned earlier, advancing and receding contact angles are

measured by expanding and contracting the liquid drop while the needle is still in contact with

the drop. Kruss’s Easy Drop limits such measurements and is designed to report a value of

static contact angle when needle is out of the liquid drop. Due to such limitations, utmost care

was taken while preparing the solid polymeric films, such that the films were free from air

bubbles and cracks and, thus, had the least surface roughness possible.

The measurement of contact angle relies significantly on the consistency of the operator.

To reduce experimental errors due to such factors, a standard operating procedure for contact

angle measurement was determined. A 3 μL sessile drop was formed on the polymer surface

and a live image of the drop was obtained. Initially, the solid polymeric film was focused to
31
 determine the baseline of the drop image which is the boundary between solid surface and the

drop. The focus was then shifted to the drop image and Tangent Method 1 was used to calculate

the contact angle which involves aligning a tangent line to the sessile drop profile at solid-liquid

interface. The complete profile of the sessile drop is then fitted to a general conic section

equation and the derivative of this equation at the baseline gives the slope at three phase

contact point and thus the contact angle. For every sample, contact angle was measured at 3

locations on the sample surface at the end of 10 seconds. The measured values of contact

angle given in the last column of the table 4.2 & 4.6 represent an average of the contact angle

measured at three locations for each sample.

4.1.4 Results and Discussion

Grafting PEG to PMHS backbone is a technique to improve hydrophilicity of the resulting

copolymer. Contact angle studies for both series I polymers and series II polymers were

performed according to the procedure described above. Tables 4.2 & 4.6 show the average

value of static contact angle for series I and series II copolymers respectively.

Table 4.2: Static Contact angle for series I copolymers

Code Structure of PEG PEG Content Mn (g/mol) Static

PMHS-PEG chain (wt%) Contact
Obtained Length angle
D* D (n)

1:10 (3) 8.18 11.81 3.2 55.63 3,010.0 45.3

1:20 (3) 16.97 3.03 3.2 72.35 4,810.0 38
1:10 (11) 7.9 12.91 11.1 76.03 5,790.0 41
1:20 (11) 15.6 4.4 11.1 86.72 10,020.0 38.5

The primary objective of the contact angle study for series I polymers was to determine

the effect of PEG chain length and number of repeating units in the copolymer containing PEG on

the hydrophilicity of the polymers. Since PEG is polar in nature, an overall increase in its

32
composition is expected to increase the hydrophilicity of the polymer. However, the individual

effect of the contributing factors on the water contact angle is not much studied.

In this work, principles of design of experiments and analysis software like JMP were

used to study the individual factor effects. A 2 full factorial design was constructed with two
2

factors A and B each at two levels. These levels are arbitrarily called low and high levels. The +1

and -1 represent high and low level of the factors respectively. PEG chain length was selected as

Factor A, whereas, the number of repeating units in the copolymer containing PEG was factor B.

Table 4.3 shows low and high levels of these factors. For factor B, the values of the target

structure were taken as low and high level. A full factorial 2 design consists of 4 runs at all
2

possible combinations of low and high level of both factors. The four treatment combinations are

shown in table 4.4. Series I polymers are the polymers generated from these treatment

combinations. For example, in sample 1:10(3), both factor A and factor B are at their low levels of

3 and 10, respectively.

Table 4.3: High and low levels of factors

Factor Low High

A 3 11
B 10 20

Table 4.4: Treatment combinations and contact angle data for Series I polymers
S A (PEG B(PEG A*B Run 1 Run 2
no length) composition)
1 -1 -1 +1 44.6 46
2 -1 +1 -1 40 36
3 +1 -1 -1 42 40
4 +1 +1 +1 38 39

Since the polymers obtained were solid powders, they were dissolved in THF to obtain 7

wt% solutions which were then used to prepare films. Two films were prepared for each sample

from the same 7 wt% solution of the sample. Contact angles were measured at 3 different points

at the end of 10 seconds for both films of every sample. The data given in run 1 and run 2
33
columns of the table 4.4- is the average of contact angle measured at three points on each film.

Two runs were performed for each sample to reduce variability of the system. Effect estimates of

the main factors A and B and their interaction AB were calculated. The magnitude of the effect

estimate identifies significant factor whereas the sign (+ or -) indicates increase or decrease in

response variable with change in factor levels. These estimates are reported in table 4.5.

Table 4.5: Effect estimates for factors

Factor Effect
A -1.9
B -4.9
A*B 2.4

Since the magnitude of factor B (4.9) is larger than that of factor A and AB, the number of

repeating units grafted with PEG has larger effect on the hydrophilicity than the PEG chain length.

The Negative sign indicates that the contact angle decreases with the increase in the number of

repeating units grafted. In other words, hydrophilicity increases considerably if the increase in

PEG content in the polymer is due to the increase in number of Si-H units grafted with PEG rather

than due to an increase in the PEG chain length. This important conclusion gives immense power

to control the wettability of siloxane polyether copolymers.

Figure 4.1 shows the main factor plots and interaction plots from JMP. A low P value of 0.015 for

factor B indicates that it is highly significant.

Figure 4.1: Main effect s and Interaction plots from JMP

Also, static contact angles were measured for series II polymers, and these results are

shown in Table 4.6. It was observed that for pairs of copolymers with same chain length, the
34
contact angle increased in spite of an increase in PEG content. This unexpected effect can be

attributed to the simultaneous increase in SiH content for both pairs of copolymers. For example

between 1:10:10(3) and 1:5:15(3), in spite of a 5% increase in PEG content, the contact angle

increases by 4 ; this may be attributed to a 10% increase in Si-H (from 29.71 to 39.93 ). This
0

suggests that between the following two factors: a) amount of PEG and b) amount of Si-H

hydrophobe; the second factor determines the hydrophilicity of the copolymer.

Table 4.6: Static Contact angle for series II copolymers

Code Structure of PMHS-PEG *X *Y *Z (wt%) Static
Target Obtained (wt%) (wt%) Contact
D* D D* D Si-H angle
1:10:10 10 10 9.1 6.5 4.4 46.92 23.37 29.71 38
(3)
1:5:15 15 5 12.0 4.0 4.0 51.27 8.8 39.93 42
(3)
1:10:10 10 10 8.1 5.6 6.3 68.32 12.12 19.56 33
(11)
1:5:15 15 5 11.0 2.15 6.85 70.32 2.83 26.85 37.5
(11)
*X= PEG Content *Y= Ammonium Content *Z= Si-H content

4.2 Surface Tension

4.2.1 Introduction

Contact angle depends upon the shape of liquid droplet on solid surface which in turn is a

function of unbalanced intermolecular forces. Every molecule in the bulk of the liquid,

experiences equal amount of pull in all the directions resulting in net zero force. However due to

unbalanced intermolecular forces, the molecules on the surface are pulled inward thereby

attaining a state of minimum energy. This intermolecular force which leads to contraction of

liquid surface is called surface tension of the liquid.

Surfactants are the surface active agents consisting of a hydrophilic and hydrophobic part

which when dissolved in a liquid reduces its surface tension. For a surfactant dissolved in water,

35
the hydrophilic group of surfactant is solvated by water molecules while the hydrophobic group is

forced towards air-water interface (away from the water molecules), this is called the

hydrophobe effect and is the reason for strong adsorption of surfactant on the water surface.

According to Gibb’s adsorption isotherm, given in equation 4.2, the adsorption of any molecule

on the surface leads to a decrease in surface tension.

− = Г ln ………………………………………..….4.2

Where,

σ = Surface tension of the solution

Г = Surface concentration of adsorbed molecules

C = Concentration of adsorbed sample in the bulk phase

Initially, an increase in the bulk concentration of the surfactant (C) decreases surface

tension until a point when no further decrease in surface tension is observed with increase in

surfactant concentration. This is known as the critical micelle concentration (cmc) and defines

the effectiveness of the surfactant.

Silicone surfactant solutions can have very low surface tension between 20-30 mN/m due

to the large number of methyl groups and small intermolecular attraction between the siloxane

hydrophobe. The siloxane backbone is highly flexible and can lie flat on the surface, allowing

maximum orientation of the –CH3 groups at the interface, leading to a very dense packing of low

surface energy methylene groups on the surface. Since surface energy is mostly dependent on

the composition of the hydrophobe, for silicone surfactants (silicones modified with hydrophilic

groups) an increase in the composition of the hydrophilic group in the molecule is expected to

increase the surface tension. Specifically, for this work, an increase in PEG composition in

PMHS-g-PEG was hypothesized to increase the air-water interfacial tension. Furthermore,

depending upon the type of the grafted group and size of the PEG chain, different packing

densities can be obtained which can also affect surface tension.

36
4.2.2. Sample preparation

The polymers obtained from hydrosilylation reaction were dissolved in water to form a 2

wt% aqueous solution of samples. 0.02 g of each sample was dissolved in 1.2 g of water. Table

4.7-, shows the actual measurements for the samples prepared. All solutions were mixed for 12

h at 280 rpm to ensure formation of a homogenous solution. Samples with a higher

concentration of PEG formed clear solution in water; whereas, samples with a lower PEG

composition, or higher number of unreacted Si-H (non polar) groups and quaternary ammonium

groups formed a white turbid suspension. These 2 wt% aqueous solutions were used to analyze

the air-water interfacial tension using Kruss Easy Drop. The values obtained were compared

with the surface tension of pure water (without surfactant).

Table 4.7: Surface tension sample preparation

Sample code Sample measured (g) Sample + Water (g) Sample Wt%
1:10(3) 0.024 1.219 1.97
1:20(3) 0.025 1.260 1.98
1:10(11) 0.023 1.156 1.99
1:20(11) 0.023 1.120 2.05
1:5:15 (3) 0.022 1.120 1.96
1:5:15 (11) 0.027 1.340 2.01
1:10:10 (3) 0.024 1.210 1.98
1:10:10(3) 0.023 1.20 1.92

4.2.3 Measurement Method

Surface tension of the 2 wt% aqueous solution was obtained by fitting the Young-Laplace

equation to the contour profile of a pendant drop. A 3 μL pendant drop was formed at the tip of

the syringe needle. The drop assumes a characteristic shape and size which is used to calculate

surface tension. A requirement is that the drop is in hydromechanical equilibrium. In such an

equilibrium, the force of gravity acting on the drop equals the Laplace pressure drop below and

above the curved section of the drop. This is represented mathematically as:

∆ = + = ∆ ………………………………………4.3

Where,

37
 r1 and r2 are the principle radii of curvature

∆ = density difference between liquid drop and its surroundings

= acceleration due to gravity

The contour profile of the drop was extracted and the Young-Laplace equation was fitted

to the profile. An inbuilt model from Easy Drop directly computes the air- water interfacial tension

for each surfactant solution. Four drops were formed for every sample and the error of fit between

the actual drop curvature and the model was found to be very small. The small values of fit error

are indicative of this method as an efficient method for measuring surface tension.

4.2.4 Results and discussion

Low surface energy is a characteristic of the siloxane backbone. The methyl groups

attached to the siloxane chain has lower surface energy as compared to the –(CH2 )- moiety in

the surfactant having hydrocarbon chain. Moreover, the siloxane backbone is highly flexible due

to the easy rotation of Si-O-Si bonds resulting in improved film forming properties at the air- water

interface. Due to such advantages, the use of silicone backbone is gaining importance over the

conventional hydrocarbon backbone. Poly(ethylene glycol)s are attached as hydrophilic part of

the siloxane surfactants forming silicone polyether copolymers mentioned in chapter 2.However,

it has been previously reported that the surface tension of air-water interface increases with an

increase in PEG concentration in the molecule (Ding et al.,2012).

Quaternary ammonium derivatives of siloxanes have also been reported to have surface

active properties. Vaidhya and Kumar studied the surface active properties of olefinic quaternary

amino siloxanes and concluded that lowering in surface tension by oligomeric quaternary siloxane

for air-water interface was more than that observed for monomeric quaternary siloxanes.

Furthermore, because of the positive charge, these surfactants have excellent binding properties

to negatively charged substrates like hair and skin, thus, providing the conditioning effect.

In this thesis, surface active properties of the synthesized polymers were studied. Air-

water interfacial tension (IFT) for the polymers was measured according to the procedure

38
discussed above. Table 4.8 and 4.9 shows the IFT values for series I and series II polymers

respectively.

Table 4.8: Surface tension for series I polymers

Code PEG Ammonium PMHS Mn (g/mol) Avg. IFT

Content Content content
(wt%) (wt%)
1:10 (3) 55.63 ----- 44.37 3,010.0 28
1:20 (3) 72.35 ----- 27.65 4,810.0 32
1:10 (11) 76.03 ----- 23.97 5,790.0 44.95
1:20 (11) 86.72 ----- 13.28 10,020.0 38

Table 4.9: Surface tension for series II polymers

Code PEG Ammonium PMHS Mn (g/mol) Avg. IFT

Content Content content
(wt%) (wt%)
1:10:10(3) 46.92 23.37 30 3976.0 38
1:5:15 (3) 51.27 8.8 39.93 3826.0 33
1:10:10 (11) 68.32 12.12 20 6603.0 44
1:5:15 (11) 70.32 2.83 26.85 7550.0 40

Considering table 4.8, the PEG content increases while the PMHS content decreases

(moving down the table). Since both these trends favor an increase in surface tension, the

average value of IFT (last column of table 4.8) was expected to increase. Though this value

increases from 28 mN/m to 44.95 mN/m for 1:10(3) to 1:10(11), there is a decrease in IFT for

1:20(11) in spite of a 10% favorable change in PEG and PMHS content as compared to 1:10(11).

The reason for this unusual behavior is not completely understood.

For series II polymers, (last column of table 4.9) the IFT value increases with decrease in

PMHS content. This means that less lowering in surface tension is obtained for small amount of

39
PMHS in the molecule. For easy comparison, the data from table 4.9 is reproduced below in table

4.10 in decreasing order of PMHS composition.

Table 4.10: Trend analysis for series II polymers with respect to PMHS content

Code PMHS content Avg. IFT (mN/m)

1:5:15 (3) 39.93 33

1:10:10 (3) 30 38

1:5:15 (11) 26.85 40

1:10:10 (11) 20 44

In order to determine the effect of PEG concentration on IFT for series II polymers, the data was

arranged as shown in table 4.11.

The comparison between two pairs of samples having same PEG chain length (i.e.

[1:10:10(3) & 1:5:15(3)] and [1:10:10(11) & 1:5:15(11)] shows an increase in air- water interfacial

tension in spite of a decrease in PEG content. This observation suggests that the PMHS

composition of a molecule is the deciding factor for IFT calculations.

Table 4.11: Trend analysis for series II polymers with respect to PEG content

Code PEG content Avg. IFT (mN/m)

1:5:15 (3) 51.27 33

1:10:10 (3) 46.92 38

1:5:15 (11) 70.32 40

1:10:10 (11) 68.32 44

Figure 4.2 and 4.3 plots the IFT value as a function of PMHS content and PEG content for both

series I and series II polymers. Ideal behavior was observed for series II polymers where the IFT

values decreases with decrease in PMHS content.

40
 92
82
PMHS content (wt%)
72
62
52
42 Series2
32
22 Series1
12
2
0 10 20 30 40 50
IFT (mN/m)

Figure 4.2. Air- water interfacial tension (IFT) as a function of PMHS content

82
PEG content (wt%)

62
42
Series2
22
Series1
2
20 40 60 80 100
IFT (mN/m)

Figure 4.3. Air- water interfacial tension (IFT) as a function of PEG content

41
 CHAPTER 5

CONCLUSION AND FUTURE WORK

In this thesis, series of silicone graft copolymers were successfully synthesized by

hydrosilylation. Two series of polymers were synthesized. Series I include, allyl-PEG of different

chain length grafted to the PMHS backbone. Whereas, series II includes allyl-PEG and a

quaternary ammonium salt attached to the PMHS backbone. The structure of the polymer was

characterized by H NMR spectroscopy and FT-IR, and the contact angle and air-water interfacial
1

tension of the polymers was studied.

Principles of Design of Experiment were used to determine the effect of two factors ; a)

PEG chain length b) number of repeating units in the copolymer containing PEG; and their

interaction on the hydrophilicity for series I polymers . Analyses of the results show an expected

increase in the hydrophilicity with increase in PEG content. However, the increase in

hydrophilicity is considerably larger if the increase in PEG content in the polymer is due to the

higher number of Si-H units grafted with the poly(ethylene glycol) rather than due to increase in

PEG chain length. Similar results were obtained for series II polymers.

Since lowering in surface tension is a characteristic of silicone backbone, the IFT value

decreases with decrease in PMHS content. Results of the study were suggestive of hydrophobe

content to be the deciding factor in IFT calculations as compared to the PEG content.

These important conclusions give a good control over surface properties (wettability and

spreadability) while designing such polymers.

Polymers synthesis and structural characterization formed a major fraction of the current

work. Though some surface characterization techniques like contact angle and surface tension

studies were conducted, a lot can still be done to fully understand the nature of these polymers

.The thermal and rheological behavior of the polymers can be studied to characterize the physical

properties of polymers. The glass transition temperature (T g) and melting points of the polymers

can be obtained from Differential Scanning Calorimetry (DSC) curves in order to study polymer

morphologies.
42
Also, solution rheology can be studied to obtain the viscosity of the polymers which depends

upon molecular weight and level of crosslinking within the polymer. Since such polymers usually

constitute 1%- 2% by weight of cosmetic formulation which have water as major component

(around 85%), knowledge of rheological behavior of 1 wt% -2 wt% aqueous solutions of these

polymers helps in determining the flow behavior of the final product. Also, the charge density on

the polymer can be determined, as a measure of the conditioning effect provided by the polymer.

From a consumer’s point of view, the ability to form foam is perceived as a test for good

surfactant. In silicone polymers, foam forming ability depends upon the balance of Si composition

in the polymer and the amount of water in the formulation. In order, to test the consumer appeal

of the synthesized polymers, such foam forming tests can be performed. Also, as these polymers

are designed for personal care products, they are required to be gentle to sensitive organs like

skin and eyes. Smaller molecular weight polymers can penetrate in the eyes and cause irritation;

therefore larger molecular weight polymers are preferred. However, as molecular weight of the

polymer increases its ability to function in different capacities changes, thus a good

understanding of all these factors is required while designing polymers for specific applications.

Table 5.1 relates molecular weight of the polymer to the function they are most suitable for.

Table 5.1 General relationship between molecular weight of polymer and its function.

(Patil, A., Sandewicz, R.W, 2013, p 17)

Molecular weight (Daltons) Function

500 Wetting

2,500 Emulsification

10,000 Conditioning

50,000 Water proofing

43
 In conclusion, in this work, an attempt was made to design and synthesize novel

polymers for specific applications, though the target structures were obtained and important

structure-function relationships discovered, further analyses are required to completely comment

on the utility and future of these polymers.

44
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