CHAPTER 2

POLYURETHANE CHEMISTRY

2.1 Definition

Polyurethanes are a broad class of polymers which have the urethane linkage as the

common feature.

H O
I II
----- N------C----- O------

Urethane linkage

However the urethane linkages constitute only a portion of the total number of

linkages in the polymer chain. Polyurethane cannot be obtained by simple

polymerization o f urethane monomers, nor can they be depolymerized to give the

monomers.

2.2 History of Polyurethane Chemistry

The initial discovery o f polyurethane was made by Otto Bayer and his coworkers of

I.G. Farbenindustrie at Leverkusen, Germany in 1937. This followed as a competitive

response to the work by Caruthers o f Du Point, USA, on the polyamides or nylons.1

The historical discovery o f polyurethane have been reported in a number of standard

works on this subject2,3

2.3 Segmented Polyurethanes

Segmented polyurethanes are block copolymers o f (AB)n type consisting of

alternating rigid and flexible segments. They exhibit properties characteristic o f cross
Chapter 2 5

linked elastomers over a wide temperature range and can be processed by techniques

used for plastics and fibres. They are a unique class o f thermoplastic material. Due to

the different polarity and chemical nature o f the rigid and flexible segments, they tend

to separate into two phases referred to as soft and hard phases. The structure of a

segmented polyurethane molecule and domain formation are schematically drawn in

Fig. 2.1(a) and (b) respectively.

-Soft Segment

Hard Segment T

Fig 2.1(a): The structure o f a segmented polyurethane molecule

Fig. 2.1(b): The two phase structure o f bulk-polymer (polyurethane)

The soft segment is either polyester, polyether or polyalkyl glycol with a molecular

weight between 600-3000. The hard segment is normally an aromatic diisocyanate

that has been chain extended with a low molecular weight diol. The hard segments in

polyurethane block copolymers particularly affect the modulus, hardness, and tear
Chapter 2 6

strength and determine the upper use temperature by their ability to remain associated

at elevated temperatures4. Polyurethanes having highest levels o f modulus, tear and

tensile strengths are obtained by the use of the most rigid, bulky and symmetrical

diisocyanate. The diisocyanate residues in the polymer apparently influence the

ability of the polymer chains to align themselves and will clearly affect the

development o f interchain structure by hydrogen bonding. The low temperature

properties o f polyurethane elastomers are, moderately affected by the diisocyanate

used. 5 The flexible (soft) blocks primarily influence the elastic nature of the product

and its low temperature performance, and they also make important contributions

towards the hardness, tear strength and modulus.4

The extent of phase separation is directly related to the degree of interaction

between the soft and hard segments. It has been reported that in polyester and

polyether-based polyurethanes, some o f the urethane N-H groups could form

hydrogen bonds with the oxygen atoms o f ether or ester linkages causing partial phase

mixing. 6 To avoid the probability of hydrogen bonding between the two segments,

Schneider et a? and Brunette et a t prepared polyurethanes based on hydroxyl

terminated polybutadiene soft segments which possessed a high degree of phase

separation.

2.4 Synthesis of Segmented Polyurethane

The most important and widely used synthetic route for the preparation of

polyurethane is the addition polymerization between a diisocyanate and a diol. As the

polymerization proceeds through a step-wise mechanism, it is often named as step-

growth polymerization.

The direct addition of diisocyanate to the diol requires an elevated

temperature, in order to keep the reactants molten. This method is thus limited to the
Chapter 2 1

synthesis of thermally stable polyurethanes. The development o f polar aprotic

solvents such as dimethylsulphoxide (DMSO) and N,N - dimethylformamide (DMF),

enables the polyaddition o f a variety o f diisoeyanates and diols in solution.9

There are two important methods for its preparation

a) The pre-polymer or two step method

b) The one step method

2.4.1 Pre-polymer method

The widely used pre-polymer method is shown in Fig. 2.2. The diisocyanate and

polyol are reacted to form an intermediate polymer, called the prepolymer. This

prepolymer is then converted into the final polyurethane by reaction with a diol as

chain extender.

Polyol

HO- ■Polyester or Polyether — OH

OCN - + -t- N C O O C N - F........... -I— N C O

Diisocyanate Diisocyanate

H O H
II Polyester or II I
OCN -O - Polyether - O '— C — N — E 3— NCO
Urethane Urethane
group group
Prepolymer

Chain extension Chain extension

with diol with diamine

Polyurethane with
Polyurethane with
urethane linkages
urea linkages

Fig. 2 2 : Prepolymer route for the formation o f polyurethane elastomer

Chapter 2 8

2.4.2 One-step method

The one-step method of polyurethane preparation is schematically represented in Fig.

2.3. In this method the polymerization is carried out by simultaneously mixing

together the polyol, diisocyanate, and chain extender (in the presence o f catalyst). The

major problem here appears to be balancing of the reaction rates of the backbone

polyol and the chain extender.

Big. 2 3 : One-step process for polyurethane elastomer preparation

2.5 Isocyanate Chemistry

The chemistry involved in the synthesis o f polyurethane elastomers centres on the

isocyanate group. The isocyanate group has several resonance structures:

R—N = C = 0 -«------► R— N— C = 0 --------► R— N = C — '& ■ (2.1)

Because of the existence of multiple structures, several classes of reaction involving

the isocyanate group are possible. A detail description o f isocyanate chemistry has

been given by Patai.10

Chapter 2 9

2.5.1 Principal Reactions

The primary reaction is an insertion reaction which proceeds by a nucleophilic attack

at the carbon atom in the isocyanate group, as shown in equation 2.2 for the reaction

of an alcohol with an isocyanate.

V ? (2.2)
R —N = C = 0 R -N C— O R
t t
H _ ° - w

The product of this reaction is a carbamate ester linkage, which is more commonly

known as urethane linkage. Isocyanates can also react with amines in a similar

manner to form urea linkages:

H O H
R—N = c = o + R N H Z ----------► R — N— t!— N—Rf' (23)

The reaction o f water with an isocyanate is a special case o f alcohol/ isocyanate

reaction. Sometimes water is a desirable reaction component, such as in the

production of foams as it yields carbon dioxide as a reaction product (equation 2.4).

H O
R -N C O | II
+ ------------► R —N— C— OH ---------- ► R — NHZ + C02 (2-4)
H-OH

The amine then reacts rapidly with additional isocyanate to form urea linkage.

2.5.2 Side Reactions

Undesirable side reactions in the synthesis o f polyurethanes include both insertion

reactions and oligomer formation, and to a lesser extent, the formation of

carbodiimides. Both the urethane and urea linkages are capable of nucleophilic attack
Chapter 2 10

on the isocyanate, particularly at elevated temperatures. The products o f these

reactions are called allophanates and biurets respectively.

R-— NCO ✓
+ — o — R
(2.5)
H O c=o
/ I II ✓
R— N c— o— R fjt— H

R
Allophanate

R — NCO , ?r , — C— N— R (2.6)
c=o
H O H I
/ 1 1 1 / N— H
R— N — C— N— R
R
Biuret

2JS3 Catalysis of the Hydroxyl-Isocyanate Reaction

The direction and type of urethane reaction is governed by the catalyst used and the

reaction conditions.Tertiary amines and alkyl tin compounds are the most commonly

used catalysts. The tertiary amines catalyse both the hydroxyl-isocyanate reaction as

well as the water-isocyanate reaction. Alkyl tin catalysts, on the other hand, are

specific towards the hydroxyl-isocyanate reaction in their catalytic activity. Tin

catalysts are more effective than amines for producing polyurethane elastomers.

The mechanism for tertiary amine catalysis involves the formation of an

intermediate active complex o f the isocyanate and the tertiary amine. After the

hydroxyl group is added, the intermediate complex rapidly rearranges to the urethane

linkage.
C h a p te r 2 11

=0 + R3N -------- R-N— c — 0 -1- *» R—N=C—

+1 * '
NRj + NRS

h —o —r ^
//
A OR
// / J, / [ _
1— C = 0 + R —OH —*» R-NH— C — 0
| |
+nr3 + NRS + NR,

H O
/ I
R-N— C-OR/ + NR

The divalent tin compounds act catalytically by co-ordinating first the

hydroxyl group and then the isocyanate group. While the exact mechanism is not

known, the following mechanism has been proposed:

R—NCO
4- X ^ + 2 y O —C- =N—R
Sn
R - oh
x / x o-h
+
l
SnXj R

X. +2/ 0 = C = N - r H O
X Sn ( / / I II /
R— N - C - O - R + SnX,
x/v>o^w
i , H
R'
Chapter 2 12

2.6 Basic Building Blocks of Polyurethane

A typical polyurethane block copolymer consists of rigid and flexible alternating

segments. The hard (rigid) segment consists o f a diisocyanate chain extended with a

low molecular weight diol or diamine. The soft (flexible) segment is a long chain

macro glycol. The common materials used in polyurethane synthesis are described

below.

2.6.1 H ard Segments

Two most commonly used isocyanates in polyurethane synthesis are toluene

diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI), O f these two, MDI

has superior reactivity, and polymers based on MDI may possess better physical

properties. Other aromatic diisocyanates, such as naphthalene diisocyanate (NDI) can

also result in high performance polymers, but at a higher cost than MDI based

polymers. The chemical structures o f most commonly used isocyanates in

polyurethane synthesis as hard segments are shown in Table 2.1.

Table 2.1 Aromatic diisocyanate used in polyurethane synthesis

NCO

NCO NCO

2,6- Toluene 2 ,4 - Toluene diisocyanate 1, 5-Naphthalene

diisocyanate (TDI) (TDI) diisocyanate (NDI)

O CN NCO

4,4'-diphenyl methane diisocyanate (MDI) para-Phenylene diisocyanate (PPDI)

Chapter 2 13

2.6 2 Soft Segments

The soft segment polymers are hydroxyl terminated polymers with molecular weights

usually in the range of 600 to 3000 and glass transition temperatures well below

ambient temperature.

Usually, polyurethanes have been produced with polyester and polyether

polyols. Polyester-based urethanes possess relatively good properties. However, they

are susceptible to hydrolytic cleavage o f the ester linkages. The polyether that results

in polyurethane with excellent physical properties is polytetramethylene oxide

(PTMO). Urethanes prepared with this soft segment show a level o f mechanical

strength comparable to that o f polyester polyurethanes and possess relatively good

hydrolytic stability and water resistance.11

The most commonly used polyols (polyether/polyester) as soft segments in

polyurethane synthesis are listed in Table 2.2

Table 2.2: Polyols used in polyurethane synthesis

Polyethylene glycol (PEG) Polypropylene glycol (PPG)

Polytetramethylene glycol (PTMG) Polyethylene adipate

Polytetramethylene adipate Polyisobutylene glycol

1,4-polybutadiene glycol
 Chapter 2 14

2.63 Chain Extenders

The reaction o f equimolar quantities o f a macroglycol and diisocyanate generally

results in a polymer that may not exhibit microphase separation and may possess very

poor physical properties. A low-molecular weight bifunctional chain-extender which,

when reacted with the diisocyanate, results in high molecular-weight hard segment, is

included to produce a polyurethane with a two-phase microstructure and desirable

physical properties.

In general, aliphatic chain extenders yield softer materials than do aromatic

chain extenders.12 Commonly used chain extenders include 1,4-butanediol, ethylene

diamine, 4,4'- methylene bis (2-chloroaniline), ethylene glycol and 1,6-hexane diol.

2.7 Modification o f Polyurethanes

The modification o f polymers has always been attractive. The primary aim o f

modification is to produce materials with new and improved properties. The

modification can be achieved either by

i) Structural modification or

ii) Blending with other polymers.

Polyurethanes can be modified by both the methods.

The structural modification of polyurethane can be achieved by

copolymerization with vinylic monomers, to produce block or graft copolymers.

2.7.1 Modification by Block Copolymerization

Block copolymerization is an attractive method to introduce variety o f functional

groups to a polymer. This can be initiated by various methods like ionic initiators,

transfer reactions, photoirradiation etc.

Chapter 2 15

There is a large number of reported works on block copolymerization of

polyurethane with vinylic monomers. Fildes et a l 13 reported block copolymerization

of polyurethane with styrene, methyl methacrylate and acrylonitrile. The block

copolymerization was initiated through the photolabile disulphide linkage in the

polyurethane backbone.

The formation o f block copolymers containing polystyrene and polyethylene

oxide) or polypropylene oxide) segments was reported by Yuruk et alM

Macroazocarbamates were synthesized by capping polyethylene oxide) glycols

[PEG-4000] or polypropylene oxide) glycols [PPG-4000] and an aliphatic

diisocyanate at 80°C in toluene solution under a blanket o f dry nitrogen and

subsequently by reacting this intermediate with an azobisalcohol. The

macroazocarbamate was further used to obtain block copolymers o f styrene and

ethylene oxide.

In the last 20 years, many studies15"19were carried out with macroazo initiators
AA Ai

(MAI) for preparing various block ' and graft ’ copolymers via conventional

operations of radical polymerization. Chikhalard et a f5 ,26 reported the synthesis o f

block copolymers based on polyurethane and polymethylmethacrylate (PMMA) or

polystyrene (PS) sequences by radical polymerization using a well defined

polyurethane macroazoinitiators (PUMAI). PUMAI with a well defined number of

azo groups per chain were prepared via a two-step reaction procedure using 2,2-

azobis(2-cyanopropanol) (ACP), 4,4-methylene diphenyl diisocyanate (MDI) and

a,w-hydroxypolycaprolactone(PCL).

The polyaddition o f dipropylene glygol and 2,2'-azobisbis(2-cyanopropanol)

(ACP) with hexamethylene diisocyanate results polyurethane type macroazo

initiators (PUMAI) as reported by Kinoshita et al.27PUMAI when heated with vinyl

 Chapter 2 16
monomers e.g methyl methacrylate (MMA), butyl methacrylate (n-BMA),

ethylacrylate (EA) and styrene(St) at 80 °C in nitrogen stream, the radical solution

polymerization o f vinyl monomers through polyurethane chain results PU-PV block

copolymers (Scheme 2.1).

n HO—R1 -N = N — R1— OH + (n + m) OCN— R2— NCO

0-25 °C

nOCN— R2 - 0 _ ri _ N = N — Ri -N C O + (m-n)OCN— R?— NCO

O

mOH-Ra-OH 0-35° C

H H H

PU macroaao Hfiator (PUMA!)

9H) CHj
R1' CH2 6— ; R2 - ; R3 ; — CH^— CH— 0— CH,— CH—
CN

Polymerizabon with vinyi monomers

PUMA! --------------------------------------------------------------------- ► PU — Pdy(vin^)— PU— Pdy(viny!)
80° C,20h Hock Copolymer

Scheme 2.1: PUMAI by ACP

Radhakrishnan G et a l 28'30 synthesized PU iniferter by reacting OH groups of

1,1,2,2-tetraphenyl-l ,2-ethanediol (TPED) with toluene diisocyanate (TDI).

Polyurethane miferter thus prepared were used to polymerize vinyl monomers viz

vinylbenzyl chloride (VBC), styrene (St), acrylonitrile (AN) to produce polyurethane

Chapter 2 17

polyvinyl multiblock copolymers. They showed that due to block copolymerization

both molecular weight and conversion increased with increasing polymerizing time,

and hence the polymerization proceeded via “living” radical mechanism. They also

reported the use of PU iniferter synthesized from equal moles of MDI and TPED, to

polymerize acrylonitrile through a living radical mechanism. Through the use of this

PU, MMA can be polymerized to form PMMA.31 Post polymerization of PMMA in

the presence of MMA and St yielded high molecular weight PMMA homopolymers

and PMMA-PS block copolymers.

Tetraphenylethane based PUMI has also been used to prepare PU-

polymethacrylic acid multiblock copolymers as reported by Tharanikkarasu et al.32

These block copolymers have been converted to the corresponding anionomers by

treating them with triethylamine. PUMI was synthesized from MDI, PTMG and

TPED in presence o f dibutyltindilureate (DBTDL) as catalyst The synthetic route

used is given below (Scheme 2.2).

HO NCO

| eo °c

TPED 30 »C
DBTDL

Ph Ph

PUMI

MMA, 75 ' C

PU - PMMA Multi- block copolymers

Schemed2 : Block Copolymerization by PUMI

Chapter 2 18

The synthesis o f polyurethane macroiniferter by the use of a free radical

initiator, TPED, was also reported by Wang et al.33 Isocyanate terminated prepolymer

was first prepared by reacting MDI and PTMG in DMF at 80-85 °C for 2.5h, which

was then chain extended with TPED solution (in DMF) at room temperature using

DBTDL as a catalyst to obtain PU macroiniferter. In the second step vinyl monomer

was added to the above solution and stirred at 70-75 °C for 5h to synthesize PU-

polyvinyl block copolymers. Three types of PU-polyvinyl block copolymem viz PU-

b-PAN, PU-b-PS and PU-b-PMMA, were reported.

Hiroyuki et a t A reported the synthesis o f a number o f photomacroinitiators

using 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, (HPPK) as a water

soluble photoinitiator. Polyurethane type photomacroinitiator (PTPU) was synthesized

by reaction of HPPK and corresponding polyurethane diisocyanate from

polypropylene glycol (PPG) and hexamethylene diisocyanate (HMDI) in

stoichiometric excess. This macroinitiator was further used for photopolymerization

of styrene and methacrylate to produce block copolymers (Scheme 2.3).

NCO X- Pdymer
OH
HO R<^NCO X: Hydroxy, Amino, etc
OH,
^ //

4-(2-hydroxyethoxy)phenyt2-
(2-hydroxy-2-propyf)ketone(HPPK)

hv
ABA type Blockcopolymers
Vinyl monomers

Scheme 2 3 : Block copolymerization by PTPs

Chapter 2 19

A series o f novel poly(urethane-amide)s were prepared by reaction o f a

polyurethane (PU) prepolymer and a soluble polyamide (PA) containing aliphatic

hydroxyl group in the backbone. 35 PU prepolymer was prepared by a reaction of

polyester polyol and 2,4-toluene diisocyanate and end caped with phenol. Then by a

simple reaction between aliphatic hydroxyl groups in PA and terminal isocyanate in

the PU prepolymer results in poly(urethane-amide).

Polyurethanes containing alkoxyamine units in the main chain were prepared

by addition of diisocyanate to TEMPO-based diol (TEMPO-2,2,6,6-

tetramethylpiperidinyl-1-oxide).36 Radical polymerization of styrene with this

TEMPO- based polyurethane as macroinitiator, results in the segmented copolymer

composed of both urethane and polystyrene segments.

Nair N R Gopinathan et al 37 reported the synthesis o f segmented block

copolymers from hydroxyl terminated natural rubber (HTNR) and polyurethane

oligomers (PU).PUs were synthesized from 1,4-butanediol and toluene diisocyanate

(TDI).

Physically cross-linked novel block copolymer hydrogels were synthesized

through controlled radical polymerization o f polyurethane macroiniferter and (2,2-

dimethyl-l,3-dioxolane) methyl methacrylate. This was as reported by Mequanint et

aL3$ Segmented polyurethane macroiniferter (PUMI) was synthesized by reacting

PTMO 2000 (polytetramethylene oxide) and MDI in 1:2 molar ratio with

stiochiometric amounts o f TPED in presence o f DBTDL. The block copolymers were

converted to hydrogels by selective hydrolysis of poly[(2,2-dimethyl-1,3-

dioxolane)methylmethacrylate] block to poly(glycerol methacrylate).

Runt et al39 synthesized a series o f poly(urethane-urea) multiblock copolymers

via a two-step polycondensation reaction. These were prepared using

Chapter 2 20

polytetramethylene oxide (PTMO), end-capped with MDI and chain extened by

ethylenediamine (EDA). The reactions were carried out in N,N-dimethyl acetamide

(DMAc).

Novel poly (ester-urethane) block copolymer has been synthesized by the use

of telechelic hydroxylated poly-[(R)-3hydroxyoctanoate] (PHO-diol) as soft segment,

telechelic hydroxylated poly-[(R)-3hydroxybutyrate] (PHB-diol) as the crystalline

hard segment and L-Lysine methyl ester diisocyanate (LDI) as the junction unit This

was reported by Andrade et a l +0. Reaction of the PHO diol, PHB diol and LDI at a

ratio of 1:12 in the presence of DBTDL as catalyst formed the block copolymer,

which was confirmed by 'H-NMR, 13C-NMR and IR spectra.

2.72 Modification by Graft Copolymerization

Among the methods o f modification o f polymers, grafting is an important method. In

principle, graft copolymer is a branched copolymer with the main chain and branches

having different compositions. Graft copolymerization can be initiated by chemical

treatment, photoinitiation, high energy radiation technique etc.

A brief review o f the synthesis of grafted polyurethanes is listed below.

Ackelrud and Gomes 41,42 grafted an isocyanate functionalised polyurethane to

a hydroxyl functionalized polymethyl methacrylate. A copolymer of methyl

methacrylate (MMA) and 2-hydroxy ethyl methacrylate (HEMA) was prepared in the

first stage. The hydroxyl groups were the reactive sites for coupling with terminal

isocyanate groups of polyurethane prepolymer, which was prepared in a second stage

by reaction between polypropylene glycol (PPG) and toluene diisocyanate (TDI). The

coupling reaction between the back bone hydroxyl groups and the polyurethane

terminal isocyanate groups was carried out in a third step. The sequence o f these

reactions is depicted below (Scheme 2.4):

Chapter 2 21

REACTION 1

f
i T 3
9 +
H
nX-^
f
CH3

I
^
»
H
- 4j -- Cc
CH,
r
9
H

JmL Y
?H S
I
1 [ c - __o —
1 i
•X

•o-
H 0=0 H c=o ij

O
C=i

II
I I
0 o 0 0
1
CHS I CHj
ch2 ch5
1 1
ch2 CH„
T *
OH OH
MMA
HEMA P(MMA-co-HEMA)

REACTION 2

C H ,^ NCO
y H O .~j~“" c—c—
I I
-O-J-OH
H H
OCN
PPG TDK2.4/2.6 isomer)

(NCO) HO
H1
Ht
•c- ~°4r°" 0H
-N—1^ — c
2n-
H 0
n
V i)
NCO (OH)

PU
Chapter 2 22

REACTION 3

P(MMA-co-HEMA) PU

H CH3 CH,

-c—c- C— C
i i ■ fe t I
H C=0 H C=0
I
0 0
1 1
CHg CH,
I 2
CH,
I
O

c=o

H,c NH

c=o
I
0
I---- 1-----1
HC— CH,
1 3
CH,
o
1______ I
x

(PMMA-g-PU)

S ch e m e 2.4

Sang 43 synthesized isocyanate group terminated polyurethanes by reacting a

stoichiometric excess o f MDI with PPG and BD. Phenoxy polymer was then grafted

onto the polyurethane by coupling the hydroxyl groups on the phenoxy polymers with

isocyanate groups on polyurethanes in the presence of catalyst, dibutyl tin dilaureate

(T12). The reaction scheme is depicted below (Scheme 2.5):

Chapter 2 23

REACTION 1

DMSO
MDi (Sfiochiomebic excess) + BD + PPG — 5----------------- ► OCN -~ ^ s / P U -^ ^ v^ N C O
90°C/4h

REACTION 2

+ OCN •—'^'■v'v'PU ■^-~-v'NCO

Phenoxy polymer
T-12, 50°C/5h, THF

NH
<>
x+y=n PU
<>
NCO
Polyurethane-g-phenoxy polymer

Scheme 2.5

Kuriyama et al 44 grafted polypropylene glycol with butyl methacrylate. A

silane modified polyurethane was then prepared by reaction with isophorone

diisocyanate and isocyanato-propyl triethoxy silane.

Egboh et al 45-48 introduced unsaturation into a polyurethane backbone using

cis-2-butene-l,4-diol as the chain extender. N-vinyl pyrrolidone, methacrylamide,

acrylamide, methyl methacrylate and methacrylonitrile were then grafted onto the

unsaturated sites of the polyurethane backbone. 2, 2'-azobis-isobutyronitrile and

benzoyl peroxide were used as initiators. Gujral49 also reported the grafting of

acrylonitrile and 2-hydroxy ethyl methacrylate onto similar polyurethanes.

Wilson50,51 synthesized unsaturated polyurethanes using unsaturated diol

glyceryl-monomethacrylate. It was then grafted with methyl methacrylate using 2, 2'-

Chapter 2 24

azobisisobutyronitrile (AIBN) as the free radical initiator. W ilson52 also synthesized

segmented polyurethane containing a terminal a- methylstyrene unit using an

unsaturated isocyanate, a, a-dimethyl-isopropyl benzyl isocyanate, together with

polytetramethylene oxide, butane diol and 4, 4 '-diphenylmethane diisocyanate. The

unsaturated polyurethane was subsequently used to form graft-

copolymers,poly(methyl methacrylate-g-urethane), with methyl methacrylate in

presence o f AIBN.

Beachell et a!53-54 synthesized unsaturated polyurethanes by removing the

urethane proton with sodium hydride and then reacting this with an unsaturated alkyl

halide in a nucleophilic substitution. Alkyl halides used were bromomethyl acrylate

and acrylolchloride. These polyurethanes were then grafted with methyl acrylate,

methylmethacrylate or styrene using benzoyl peroxide as initiator.

Adibi et a l 55, also metallated polyurethane with sodium hydride, NaH. This

was followed by grafting o f acrylonitrile on the metallated polyurethane by anionic

polymerization.

Soft segment grafting has been achieved by first synthesizing unsaturated

polyols. Many of the publication in this area are in the patent literature. H itachi56

patented the grafting o f polybutadiene with acrylonitrile and the incorporation o f this

material into a polyurethane. Kuriyama et a f synthesized an unsaturated

polyesterpolyoL, poly (ethylene itaconate), and reacted this with PTMO and MDI to

form the polyurethane. This was then grafted with octyl acrylate. Itaconic acid was

also used as the source o f unsaturation by Takai.58 They synthesized a polyester diol

from adipic acid, itaconic acid and 1,4-butane-diol. Polyurethanes were then

synthesized with this poly-ester diol, MDI and ethylene glycol. It was then grafted

with ethyl acrylate and dimethyl-amino ethyl methacrylate.

Chapter 2 25

Rimmer59 also synthesized polyurethanes with soft-segment grafting. A

polymethyl methacrylate diol was first synthesized by free-radical polymerization of

methyl methacrylate in the presence of a chain-transfer agent, 1-thioglycerol. This

diol was then used to perform a ring-opening polymerization o f e-caprolactone. These

grafted polyols were used as soft segments in the polyurethane synthesis.

Feng et a f° reported selective graft copolymerization o f acrylamide and

hydroxyethyl methacrylate onto different segments of a polyether urethane by using

two different methods: ceric salt initiation and controlled oxidation. With ceric salt

initiation, the grafting took place mainly at the hard segment while controlled

oxidation resulted in grafting at the soft segment

Chujo et al 61 radically polymerized methylmethacrylate in the presence o f a

chain transfer agent thioglycerol. This produced polymethylmethacrylate with the

majority of the chains functionalized at the chain end with a diol-group. This

macrodiol was polymerized with 1,4-butane-diol and toluene-diisocyanate or

hexamethylene diisocyanate to yield P (U-g-MMA) materials (Scheme 2.6).

OH OH

Thioglycerol (TG )

T G /A IB N PM M A
nMMA
EtOH/THF

PM M A
2 + BD P (U -g-M M A )

OH OH

Scheme 2.6
Chapter 2 26
A halogenated polyether urethane was grafted using transition metal
compounds by Bamford and Middleton .62 The urethane proton was replaced with a
halogen atom by reaction with acidified aqueous hypochlorite or hypobromite
solution. Mn2(CO)io and Re2(CO)io were used to graft methacrylic acid, acrylic acid,
hydroxyl propyl methacrylate, hydroxyl ethyl methacrylate and methylmethacrylate to
the polyurethanes.
Kazama et a l 63 reported the synthesis of polyurethane-based graft copolymem
with uniform size polyether and polyamine segments. Polytetrahydrofuran and poly
(N-t-butyl aziridine) having diol end groups were synthesized. The subsequent
polyaddition reaction of poly THF and poly TBA with MDI follwed by chain
extension with BD, produced polyurethane/polyether and polyurethane/polyamine
graft-copolymers possessing uniform-size poly (THF) and poly (TBA) graft segments.
Kazama et a l 64 also reported the synthesis of polyurethane-polysiloxane graft
copolymers using uniform-size poly-dimethyl siloxane (PDMS) with diol end groups.
They synthesized a series of uniform-size poly-dimethyl siloxanes with diol end
groups, by hydrosilylation of PDMS containing a silane end group with 3-allyloxy-
1,2-propane diol. The polyurethane-polysiloxane graft copolymer was then
synthesized by two different methods: polyaddition of uniform-sire PDMS having a
diol end group to MDI, followed by chain extension with BD, and polyaddiation of
BD and MDI followed by chain extension with uniform sire PDMS having a diol end
group.
Mekras et al 65 reported the successful copolymerization of a unsaturated
polyurethane based on MDI, erythrol and BD with acrylic acid in the presence of
AIBN as the initiator.
Chapter 2 27

Zhou66 synthesized and characterized graft copolymer o f the type polymethyl

methacrylate-graft polycarbonate urethane.

Irradiation techniques were also used by several workers to induce grafting

onto polyurethanes. Hayakawa et al 67 reported the graft-copolymerization o f 2-

hydroxyethyl acrylate, 2- hydroxyethyl methacrylate and vinyl acetate onto ether type

polyurethane foams by y-ray irradiation. Sarma et al 68 grafted hydroxyethyl

methacrylate onto polyether-urethane-urea using y-rays from a Co® source.

An unsaturated polyurethane macromonomer was synthesized by the step

growth polymerization o f poly(tetra methylene ether glycol), 1,4-butanediol, glyceryl

monomethacrylate (GMM) and diphenylmethane diisocyale. From this

macromonomer graft copolymers were prepared by copolymerization with MMA in

DMF at 80°C, using various concentration o f 2, 2'- azobisisobutyytronitrile as radical

initiator (Scheme 2.7). This was reported by George et a l.69

PMMA

in itia to r
PUGMM + MMA

PMMA

Scheme 2.7

Li et al 70 synthesized and characterized maleimide terminated polyurethane

grafted epoxy or epoxy graft maleimide terminated polyurethane (EGMPU).

For improving the blood contacting properties of chemically modified

polyurethanes, hydrophilic vinyl monomer has been grafted on to PU by the y

radiation method. Sreenivasan et al 71 reported the grafting of MMA onto PU by y

radiation under nitrogen from a Co60 source to a total dose of 0.5 Mrad. Varied
Chapter 2 28

grafting yields were realized by increasing the exposure time of the polymer to the

monomer rather than increasing the y-ray flux.

Nair PR et a l 72 reported the synthesis o f polyurethane based on polyethylene

glycol (PEG), polyoxy tetramethylene glycol and polybutadiene polyol possessing

polybutylacrylate grafts through the macromonomer method. In this method, the

polyurethane samples were prepared by mixing the polyol and macrodiol polybutyl

acrylate in appropriate ratio in THF. Trimethylol propane was used as the cross

linking agent. A calculated quantity of toluene diisocyanate was added to the system

for an isocyanate index (NCO/OH eq. ratio) o f 1 and mixed well at room temperature

in the presence o f DBTDL as a catalyst

A series of poly (ester urethane urea)s containing pendent methacrylate

functionally has been prepared and formulated into PU methacrylate elastomer using

a prepolymer process which was reported by Oprea et alP

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