Cationic Sufactants in Rubber Compounding

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3/381

CATIONIC

SURFACTANTS IN RUBBER COMPOUNDING

by

MAUYED

SAHIB

MAHDI

BSc

A

Doctoral

Thesis

submitted

in

partial

fulfilment

of

the

requirements

for

the

award of

the

degree

of

Doctor

of

Philosophy

of the

Loughborough University

of

Technology

November

1984

Supervisor: C

Hepburn

PhD

BSc MSc

ANCRT

FRSC FPRI

Institute

of

Polymer Technology

©

by

Mauyed

Sahib Mahdi

1984


4/381

1

ABSTRACT

Cationic

surfactants

have

not

been

previously

known

as

rubber

compounding

ingredients.

This

study

examined

their

use as

processing

aids,

accelerators

and

crosslinking agents.

The following

chemical

classes

have been

investigated,

namely:

i)

Commercially

available

cationic surfactants

having

the

general

formula

[RNH2

(CH2)3

NH3]++ 2

R 000

,

where

R=

tallow

R =

other

long

chain alkyl

groups

derived

from fatty

acids.

ii)

Commercially

available

cationic surfactants

having

the

general

formula RNH-(CH2)3

NH2

where

R=

various

long

chain alkyl groups

derived from

fatty

acids.

iii)

Commercially

available

hydrophobic

materials

having

the

general

formula RCONH

CH2)2

NHCOR

where

R=

long

chain

alkyl

group

derived

from fatty

acid.

iv)

Compounds

specially

prepared as

research

intermediates

and of

general formula [NH3 (CH2)3 NH3]++2[R000]

.

Much

of

the

research

has been

concentrated on

truck tyre

sidewall

rubber compounds

based

on

NR/SBR

blends; however,

the

effects

of

the

above materials,

i.

e.

the

surfactants,

diamide

compounds and

the

research

intermediate

materials, on other

rubbers such as

NBR,

CR,

BR,

NR

and

SBR

have

also

been

examined.

It

was

discovered

that

surfac-

tants

(i)

act as excellent

processing

aids

and

were superior

in

performance

to

six conventional

plasticisers

and

processing

aids.

It

was also

found

that

the

other

materials

(ii),

(iii)

and

(iv)

act

as

excellent processing

aids

and

behave

similar

to

(i).


5/381

11

Also,

and

unexpectedly,

they

can

function

as cure accelerators

without the presence of the conventional cure activation system

of

zinc

oxide

and

stearic

acid.

Indeed

the

use of

zinc

oxide

with

surfactants

class

(i)

and

research compounds

(iv)

retarded

cure

rate.

Hydrophobic

compounds

in

class

(iii)

were

found

to

be

cure

activated

by

the

addition

of

triethanolamine.

Another

new

finding

was

that

the

surfactants

in

classes

(i)

and

(ii)

and

the

research

materials

(iv)

act as good

crosslinking

agents

for

polych.

loroprene

(CR)

rubber

and

the

mechanical

properties

of

the

resulting vulcanisate

are

excellent.

The

mechanical properties

of

vulcanisates

cured with

a

surfactant

or

a

research

intermediate

material-accelerator

and sulphur

were

found

to

be

superior

to

those

based

on

conventional

thiazole

and sul-

phenamide accelerators

in

NR, SBR

and

BR; NBR

and

CR

surfactant

con-

taining

formulations did

not

show any

significant

improvement in

vulcanisate properties.

Stress-relaxation

and

hot

air

oven

techniques

were used

to

study

the

elevated

temperature

(100°C)

ageing

behaviour. Over

a period of one

week no significant

difference

with

conventional

curing systems was

found.

However

for

ageing periods

of

more

than

one week

surfactant

containing vulcanisates

(without

ZnO)

were

found

inferior

to

conven-

tional

rubber

cure systems.

However

addition

of

zinc

oxide was

found

to

be beneficial in improving

their

ageing

behaviour,

an unexpected

observation.

The

chemical mechanisms

involved

were

investigated

by

use of

the

following

techniques:

infrared

spectroscopy,

differential

scanning

calorimetry,

scanning

electron microscopy,

solvent

swelling

and

extraction,

in

order

to

obtain

an

insight into

the

behaviour

of

surfactants

when

incorporated

into

a rubber

formulation.


6/381

111

ACKNOWLEDGEMENTS

I

wish

to thank

Dr C Hepburn

my

supervisor

who

has devoted

many

hours

to

this

work.

His

effective

guidance constructive

criticisms

and constant encouragement

throughout

this

work

is

very

much appre-

ciated.

I

would

also

like

to

extend

my

thanks

to

Professor AW Birley

and

Dr

M

Gilbert.

Last

but

not

least

my

thanks

go

to

all

the teaching

staff

techni-

cians and

colleagues at

the

Institute

and

to

my excellent

typist

Janet

Smith.


7/381

iv

Dedicated to

the

ones

I

Love

My

parents

My

sisters

My

wife

and our

daughter

Russell


8/381

vi

rnNTFNTC

Page

No

CHAPTER

:

RUBBER

COMPOUNDING

..... .....

1

1.1 Surfactants

..... .....

1

1.1.1

Classification

of

Surfactants

2

1.1.1.1 Anionic

surface active

agents

.....

2

1.1.1.2 Nonionic surface active

agents

.. ..

3

1.1.1.3

Amphoteric

surface active

agents

.....

3

1.1.1.4

Cationic

surface active

agents

.....

7

1.1.2 Methods

of

Evaluating

the

Proper-

ties

of

Surfactants

.....

16

1.1.3

Some

Miscellaneous

Applications

of

Surfactants

..... .....

18

1.1.4

Rubber

and

Plastic Industries

18

1.2

Plasticisers

and/or

Processing

Aids

22

1.2.1

Methods

of

Plasticisation

23

1.2.2

Types

of

Physical Plasticisers

28

1.2.2.1

Petroleum Products

28

1.2.2.2

Natural

Fats

and

Oils

33

1.2.2.3

Naturally Occurring

Plas-

ticisers

. ...

35

1.2.2.4

Plasticisers

Based

on

Coal

Tar

.....

.....

36

1.2.2.5

Synthetic

Organic

Plasti-

cisers

.....

39

1.2.3

Parameters Involved

in

Selection

of

Plasticisers

.....

.....

40

1.3

Sulphur Vulcanisation

.....

51

1.3.1

Unaccelerated

Sulphur Curing

51

1.3.2 Accelerated Sulphur Vulcanisation 53

1.4

Object

ives

of

the

Research

... 1.

60


9/381

Vil

Page

No

CHAPTER: CONVENTIONALLASTICISERANDCATIONIC

SURFACTANT

.....

.....

62

2.1 Performance

of

Individual

Pla

sticisers

in

a

Truck Tyre Sidewall

Rubber

Compound

63

2.2

Optimisation

of

Plasticisers

Proportion

for

NR/SBR Compound

.....

.....

73

2.3

Effect

of

SAPA

1/1

and

Variou

s

Plastici-

sers

on

the

Processability

of

a

Truck

Tyre

Sidewall

Compound

.....

74

2.3.1 Methods Used to Study Process-

ability

..... .....

74

2.3.2

Experimental

..... .....

79

2.3.3

Results

and

Discussion

.....

81

2.4

Conclusions

.....

...

92

CHAPTER

:

CATIONIC SURFACTANTS

S

PROCESSING

IDS

FOR RUBBERCOMPOUNDS

.....

.....

93

3.1

Synthesis

of

Diamine

Salts

.....

93

3.1.1 Materials

..... .....

95

3.1.2

Preparation

of

Diamine

Fatty Acid

Salts

..... .....

96

3.1.3

Identification

of

the

Reaction

Product

..... .....

97

3.2

Performance

of

Surfactants, Prepared Salts

and

Diamide Material

as

Processing

Aids

for

an

NR/SBR

Compound

.....

99

3.3

Examination

of

Surfactants,

Prepared Salts

and

Diamide

Material in Natural

and

in

Some Further Synthetic Rubbers

.....

107

3.3.1

Unfilled

Gum)

and

Filled Natural

Rubber

.....

,. e,.

107

3.3.2

Chloroprene Rubber

CR)

.....

121

3.3.3

Nitrile

Rubber

NBR)

.....

129

3.3.4 Sytrene-Butadiene

Rubber

SBR)

134

3.3.5 Polybutadiene

Rubber

BR-cis)

146

3.4 Conclusions 151


10/381

viii

CHAPTER: SURFACTANTSS A CUREACCELERATOROR

TRUCKTYRE

SIDEWALL

COMPOUNDS

.....

4.1

Elimination

of

the

Cure

Activation

and

Acceleration

Systems

from

a

Rubber

Formu-

lation

.....

.....

4.2

SAPA

1/las

a

Combined

Cure

Activator

and

Accelerator

System

for

NR/SBR Compound

4.3

Zinc Oxide

as

a

Scorch

Control

Additive

in

an

NR/SBR Compound

Accelerated

by

the

SAPA

1/1

system only

..... .....

4.4

Zinc

Oxide Versus Benzoic

Acid

as

Cure

Retarders

for

SAPA

1/l/Sulphur

Curing

System

in NR/SBR Compound

.....

4.5

SAPA

1/1

as a

Combined

Processing

Aid

and

Accelerator

System

for

Truck Tyre Side-

wall

Compound Based

on

4.6

Examination

of

Various Surfactants

Prepared

Salts

and

Diamide

Material

as

Cure

Activa-

tor/Accelerator

Systems in

the

NR/SBR

Compound

..... .....

4.7

Effect

of

Various Concentrations

of

SAPA

1/1

and

Some

of

the

NS Series

on

Cure Charac-

teristics

.....

.....

4.8

Effect

of

Antioxidants

on

the

SAPA

1/l/Sul-

phur

Curing System

in

the

NR/SBR Compound

4.9

Conclusions

.....

.....

Page

No

153

154

160

165

169

173

179

189

194

197

CHAPTER : SURFACTANTSS CUREACTIVATOR/ACCELERATOR

FOR NATURALAND

SOME

SYNTHETICRUBBERS

199

5.1

SAPA

1/1

as a

Cure

Activator/Accelerator

System

for

Natural

Rubber

199

5.1.1

Effect

of

Zinc

Oxide

and

Stearic

Acid

on

the

Performance

of

SAPA

1/1 in

204

Natural

Rubber

.....

5.1.2

An Acceleration

Study: SAPA

1/1 Vs

a

Sulphenamide

Accelerator.

in NR

207

5.2

Surfactants and SBR Rubber .....

212

5.2.1

Surfactants

Prepared

Salts

and

Diamide

Materials

Systems Vs

212

Sulphenamide

System

.....


11/381

ix

Page

No

5.2.2

SAPA

1/1 Vs Thiazole

Accelerator

Systems

in

SBR

.....

224

5.2.3

Effect

of

Zinc

Oxide

on

the

Per-

formance

of

Two Different Surfac-

tants/Sulphur

Curing

Systems

228

5.2.4

Ethylene

bis

Stearamide

(EBF-S)

as

a

Secondary

Accelerator

for

SBR

Rubber

.....

.....

231

5.2.5

Effect

of

Triethanolamine

on

the

Curing Behaviour of Various Ethy-

lene bis Fatty Amides in

SBR

Rubber

.....

.....

234

5.3

Surfactant/Sulphur

Curing

System

for

BR

Rubber

.....

.....

243

5.4 The

Surfactant/Sulphur

Curing

System

in

NBR

.....

.....

247

5.5

Interpretation

of

Cure

Acceleration by

Surfactants

..... .....

251

5.5.1

Proposed

Mechanism

for

the

Multi-

plicity of

Functions

of

SAPA1/1

in

Rubber Compounds

.....

251

5.5.2

Proposed

Hypothesis

to

Account for

the

Cure Retardation

that

Occurs

When ZnO

is

Used

.....

255

5.5.3

Acceleration

Effect

of

Ethylene

bis

Stearamide

and

Similar Compounds

256

5.5.4

Vulcanisation

Acceleration

Mechanism

of

SAPA

2/A

and

Similar

Compounds

258

5.6 Conclusions

..... .....

259

CHAPTER

:

SURFACTANTS

S

CROSSLINKING

GENTS

FOR

POLYCHLOROPRENE

CR)

RUBBER

..,..

261

6.1

Vulcanisation

of

CR

with

Only

a

Surfactant

264

6.2

Surfactants

as

Vulcanising

Agents

in

the

Presence

of

ZnO

and/or

MgO

.....

268

6.3 A Mechanism to Explain the Dual Role Func-

tion

of

Surfactants

and

Similar

Materials

as

Combined

Vulcanisation

Agents

and

Pro-

cessing

Aids

.

273

6.4

Conclusions

276

.....

.....


12/381

X

Page No

CHAPTER

:

SOME

RUBBER

GEINGCHARACTERISTICS

ND

SURFACTANTS

.....

.....

278

7.1 Ageing

Behaviour

of

the Surfactant/

Sulphur

Curing

Systems in

SBR Rubber

278

7.1.1

Experimental

.....

.....

280

7.1.2

Effect

of

Antioxidants

on

Ageing

Behaviour

.....

.....

281

7.1.3

To Explore

the

Use

of

Zinc

Oxide

as a

Means

of

Improving Ageing

Behaviour

..... .....

300

7.1.4

Conclusions

.....

.....

305

7.2

Surfactants

of

Improved

Physical

Form

307

7.2.1

Experimental

..... .....

307

7.2.2

Results

and

Discussion

.....

309

7.2.3

Conclusions

.....

.....

309

CHAPTER :

DISCUSSION1CONCLUSIONSND

RECOMMENDATIONS

12

8.1 Discussion and Conclusion ..... 312

8.2

Recommendation

..... .....

324

APPENDICES:

I: Surface

Activity

of

Surfactant

.....

327

II:

Analytical

Methods Used for

the

Analysis

of

Cationic

Surfactants

.....

329

III:

Commercially Available

Rubber

Processing

Petroleum

Oils

..... .....

332

IV:

List

of

Materials Used in

the

Research

Work

with

their

Technical

Information

333

V:

A

Short Account

of

the

Processing Vulcani-

sation and

Physical Tests

Used Throughout

the Research

Work

.....

.....

338

REFERENCES

..... .....

345


13/381

xi

LIST

OF

FIGURES

Page No

FIGURE

1.0 Effect

of milling

on viscosity

of

NR,

IIR,

CR

and

SBR

rubbers

.....

.....

23

FIGURE 1.1

Breakdown

of

NR

after

30

mins mastication

at

different

temperatures

,,...

25

FIGURE

1.2

Effect

of

chemical plasticiser,

pentachlo-

rothiophenol,

on

the

Mooney

viscosity and

mixing time of SBRrubber

.....

26

FIGURE

1.3:

Carbon

atom analysis nomograph

used

for

rubber processing oil characterisation

31

FIGURE 1.4:

Raw

materials

for

coal

tar

resins

38

FIGURE

1.5:

Rate

of oil

take-up

as a

function

of

VGC

and molecular weight

..... .....

44

FIGURE 1.6:

Processability

characteristics at

the

extrusion stage for compounds of Table

1.12 formulation

as a comparison

between

dehydrated

castor oil

DCO)

and naphthe-

49

nic mineral oil

.....

.....

FIGURE1.7:

Typical

chemical groups

present

in

an

unaccelerated sulphur

NR

vulcanisate

network

..... .....

52

FIGURE 1.8:

Structural

feature

of

an accelerated

sulphur vulcanisate of natural

rubber

57

FIGURE2.1: Effect of the Iraqi aromatic oil concen-

tration

on

the

Curing

Behaviour

of

the

NR/SBR

compound

.....

.....

69

FIGURE

2.2:

Effect

of

the

Dutrex

729,

aromatic

oil,

concentration

on

the

curing

behaviour

of

69

the

NR/SBR

compound

..,.. .,...

FIGURE 2.3:

Effect

of

the Sudex

790,

aromatic

oil,

concentration

on

the

curing

behaviour

69

of

the

NR/SBR

compound

.....


14/381

xii

Page No

FIGURE

2.4

Effect

of

the

Circosol

4240,

naphthenic

oil

concentration

on

the

curing

behaviour

of

the

IIR/SBR

compound

..... .....

70

FIGURE

2.5:

Effect

of s.

earic

acid,

Struktol WB

212

and

their

combination

with

the Iraqi

oil

concentration

on

the

curing

behaviour

of

the

NR/SBR

compound

.....

.....

70

FIGURE

2.6:

Effect

of

SAPA

1/1

concentration

on

the

curing

behaviour

of

the NR/SBR

compound

70

FIGURE2.7:

Shows

the

basic

mode of

use

of

the

Daven-

port extrusion

rheometer

.....

76

FIGURE2.8:

Cross-section

of

Garvey die

.....

78

FIGURE2.9:

Davenport

capillary

rheometer shear stress

Vs

shear

rate

for

truck tyre

side

well

compound mixed

with mineral

oils,

combi-

nation of

mineral oils and

processing aids,

and

SAPA

1/1;

also

a

compound without

any

plasticiser

..... .....

90

FIGURE

2.10:

Extrudates

produced

through

Garvey

die

91

FIGURE

3.1:

Infrared

spectrum of

1,3

propane

diamine-

di-oleate

laboratory

prepared salt)

98

FIGURE

3.2:

Infrared

spectrum of

SAPA

1/1

in

viscous

liquid form)

of

Akzo

Chemie

Duomeen

TDO)

98

FIGURE3.3:

Infrared

spectrum

of

SAPA

1/1

in

paste

form)

of

AOCM

hemicals

.....

98

FIGURE3.4: Infrared spectrum of SAPA1/1 in viscous

liquid form)

of

AOCM

hemicals

.....

98

FIGURE

3.5:

Infrared

spectrum

of

a

typical

member

of

the

SAPA

2

series

represented

by

oleyl

1-3

propane

diamine

SAPA

2/B)

in

liquid

98

form)

..... .....

FIGURE

3.6:

Curing

behaviour

of

SAPA

1/1,

SAPA

2/A,

102

NSA/l

and

EBF-S in

NR/SBR

compound

FIGURE

3.7: Curing behaviour of various ethylene bis

fatty

amides

on

NR/SBR

compound

103

FIGURE

3.8: Curing behaviour

of

SAPA

2/A

and

NS

type

104

substances

with

different

alkyl

group.


15/381

xiii

Page

No

FIGURE

3.9(a):

Effect

of

SAPA

1/1

on

the

extrudate

appearance of carbon

black

filled

NR

113

FIGURE

3.9(b): Effect

of

SAPA

1/1

on

the

extrudate

appearance

and

dimensional

stability

of

silica

filled NR

.....

.....

113

FIGURE

3.10: The

effect of

SAPA

1/1

on

the

curing

beha-

viour of

gum

NR

mixes

.....

116

FIGURE 3.11:

The

effect

of

SAPA

1/1

on

the

curing

beha-

viour

of carbon

black

filled

NR

mixes

117

FIGURE3.12: SEMmicrographs (x 7000 magnification)

of a

torn

vul can

i

sate surface

illustra-

ting

the

effect

of

SAPA

1/1

as

a

filler

dispersion

and wetting agent

in

NR

rubber

.....

.....

118

FIGURE3.13:

Effect

of

SAPA

2/A,

NSI,

and

EBF-S

on

the

curing

behaviour

of

gum

NR

rubber

in

comparison

with

SAPA

1/1

surfactant

120

FIGURE3.14:

Effect

of

SAPA

1/1

on

curing

properties

of gum and carbon black filled CR rubber

126

FIGURE 3.15:

Effect

of

SAPA

1/1

and

NSI

on

the

curing

behaviour

of carbon

black filled CR

rubber

.....

128

FIGURE

3.16:

Curing

behaviour

of

SAPA

1/1

and

NSA/l

133

in

NBR

rubber

.....

.....

FIGURE 3.17:

Effect

of

SAPA

1/1,

SAPA

2/B,

NSA/l

and

EBF-S

as processing

aids

on

SBR

rubber

vulcanisation .,... .....

142

FIGURE

3.18:

Curing

behaviour

of

EBF-S

and

EBF-O

materials

in

comparison with

aromatic

oil

and

Struktol

WB

212

.....

144

FIGURE

3.19:

Effect

of

SAPA

1/1

and

NSA/l

on curing

properties of

BR

rubber

,...,

150

FIGURE

4.1:

Effect

of

PVI

prevulcanisation

retarder

on

the

curing

behaviour

of

NR/SBR

com-

159pound containing

.....

.

...


16/381

xiv

Page

No

FIGURE

4.2:

Cure

behaviour

of

NR/SBR

compound

containing

7.5

phr

SAPA1/1

and

the

effect

of eliminating

the

activators

and accelerators

systems

.....

159

FIGURE

4.3:

ODR

races

of

the

NR/SBR

compound con-

taining

various

levels

of

SAPA

1/1

as

a

combined cure activator/accelerator

system

164

FIGURE4.4:

Zinc

oxide as

a scorch

control additive

in

NR/SBR

compound cured with

SAPA

/1/

168sulphur curing system

.....

FIGURE

4.5:

Benzoic

acid

Vs

zinc

oxide

in

NR/SBR

compound cured

with

SAPA

1/1/sulphur

curing

systems

171

FIGURE

4.6:

Comparative

cure properties

of

the

SAPA

1/1/sulphur

system

with

sulphe-

namide/sulphur

system plasticised with

various plasticisers

and

processing

aids

174

FIGURE4.7: Cut growth resistance of a conventional

curing

system

vulcanisate

compared with

SAPA

1/1/sulphur

curing system

vulcani-

178

sates

.....

.....

FIGURE

4.8:

Curing

behaviour

of

SAPA

1/2

NSC/

SAPA

2/B

and

EBF-S

substances as cure

activator/accelerator

systems

compared

with a

conventional sulphenamide

curing

185

system

in

the

NR/SBR

compound

FIGURE

4.9:

Effect

of

various alkyl

groups

of

SAPA

2

series on the

curing

behaviour

of

the

186

NR/SBR

compound

.....

.....

FIGURE4.10:

Effect

of

ZnO

on

NCS/l/sulphur

and

SAPA

2

B/sulphur

curing systems

in

NR/SBR

com-

pound

..... .....

188

FIGURE

4.11:

Effect

of

SAPA

1/1

and

NSC/1

systems

on

t90

and

t95

of

the

NR/SBR

compound

191

FIGURE

4.12:

Effect

of

NSI

and

NSA/3

systems

on

t

and t95 of the NR/SBRcompound

90

192

FIGURE

4.13:

Effect

of

concentration

of

SAPA

1/1

NSC/1

NSI

and

NSA/3

systems on

the

Mooney

scorch

time

t5

of

the

NR/SBR

compound

... .

.....

193


17/381

xv

Page

No

FIGURE5.1: Curing behaviour of NR rubber cured by

SAPA

1/l/sulphur

system

.....

202

FIGURE

5.2:

Effect

of

various

levels

of

ZnO

and

stearic acid

on

the

performance of

NR

rubber cured

with

0.5

phr

SAPA 1/1/2

phr

sulphur

curing

system

.,...

205

FIGURE

5.3: Effect

of

various

levels

of

ZnO

and

stearic acid

on

the

performance

of

NR

rubber

cured

by

the

1.5

phr

SAPA/l/

2 phr sulphur curing system .....

205

FIGURE

5.4:

SAPA

1/1 Vs

the

sulphenamide

MOR)

211

n

NR

rubber

..... .....

FIGURE5.5:

Effect

of

various

substances

as cure


in

comparison with

a

conventional sulphenamide

CBS)

system

217

in

NR

rubber

..... .....

FIGURE5.6:

SEM

micrograph

x

7000

magnification)

of

a

torn

surface

to

illustrate

the

ability

of the SAPA1/1 surfactant

as

a

filler

dispersion

and

wetting agent

in

addition

to

being

a cure


system

in

SBR

rubber

.....

220

FIGURE

5.7:

Illustrating

stress-relaxation

behaviour

of

NSA/l

vulcanisate

in

comparison with

a conventional

sulphenamide

vulcanisate

221

ased

SBR

rubber

..... .....

FIGURE

5.8:

Effect

of

SAPA

2

series cationic

surfac-

tants as cure activator/accelerator

222

systems

in

SBR

rubber

.....

FIGURE

5.9:

Cure

properties

of

SAPA

1/1

Vs

Thiazole

accelerator

systems

in

SBR

black

Vs

227

silica

fillers)

...,.

....,

FIGURE

5.10:

Effect

of

ZnO

and stearic

acid on

the

curing

behaviour

of

SAPA

1/1/sulphur

and

SAPA

2/C/sulphur

curing

systems

in

229

SBR

rubber

.....

.....

FIGURE

5.11:

EBF-S

as

a secondary

accelerator

in

SBR

232

rubber

..... .....


18/381

xvi

Page

No

FIGURE5.12: Curing behaviour of EBF-S and EBF-0

materials

as

accelerators activated

by

TEA

without

and with

ZnO

compared

with

a

conventional

accelerator system

240

FIGURE

5.13:

SAPA

1/2/sulphur

as

a curing system

for

BR

rubber

compared

with

a

conventional

curing system

..,..

,....

246

FIGURE

5.14:

SARA

1/l/sulphur, NSC/2/sulphur

and

NSA/

3/sulphur

as

curing systems

for

NBR

rubber

in

comparison with

ZnO/stearic

acid/CBS/sulphur

curing system

249

FIGURE5.15:

DSC

evidence

for

the

decomposition

of

SAPA

1/1

.....

.....

253

FIGURE

5.16 a):

Infrared

spectrum

of

SAPA

1/1

unheated

253

FIGURE

5.16 b):

Infrared

spectrum of

SAPA

1/1 heated

for 5

minutes

at

150°C

under

vacuum)

253

FIGURE 5.17: Proposed

mechanism

to

account

for the

multiplicity of

functions

of

SAPA

1/1

254

and similar

compounds

.....

FIGURE6.1 a):

Progressive

influence

of metal

oxides

on

vulcanisation

properties

of ethy-

lene

thiourea

crosslinked

chloroprene

263

rubber

.....

.....

FIGURE

6.1 b):

Effect

of metal oxides on chloroprene

vulcanisation

without

and

with ethylene-

263

thiourea

ETU)

..... .....

FIGURE

6.2:

Curing behaviour

of surfactants and

prepared

diamine

salts as

crosslinking

agents

for

CR

rubber

in

comparison

with

a

conventional

ETU)

crosslinking

system

.....

.....

266

FIGURE

6.3:

Crosslinking

properties of

CR

rubber

270

mixes ..... .....

FIGURE

7.1:

Effect

of various

carrier/absorbant

powders

for

SAPA

1/1

on

cure

properties

310

of

NR/SBR

mix

..... 0 ...


19/381

xvii

Page

No

FIGURE7 2: Curing behaviour

of

NSA/l

activator/

accelerator

system

without

and

with

carrier

in

an

NR/SBR

compound

310


20/381

xviii

LIST

OF TABLES

Page No

TABLE

1.0:

Representative

commercial

anionic

surfactants,

their

properties

and uses

4

TABLE

1.1: Typical

commercially available nonionic

surfactants

..... .....

5

TABLE 1.2:

Typical

commercially

available

ampho-

teric

surfactants

..... .....

6

TABLE

1.3:

Some

commercially

available

cationic

surfactants

.....

.....

9

TABLE

1.4:

Commercially

available

diamide

and

their

uses

.... .....

13

TABLE 1.5:

Application

of surfactants

in

the

pro-

cessing

industries

..... .....

19

TABLE 1.6: Some

commercially

available peptisers

27

TABLE 1.7:

Typical

properties

for

various

types

of

process oils

..... .....

32

TABLE

1.8 a):

Typical

aniline points

of coal

tar

resins

...,.

.....

37

TABLE

1.8 b):

Effect

of

plasticiser

aromaticity

and

its

reinforcing

effect

in

rubber when

15

phr are

used

in

mineral

filled

SBR

3ý

TABLE

1.9:

Some

polymerisable

ester

plasticisers,

40

their trade

names and

suppliers

TABLE

1.10:

Solubility

parameters

for

some rubbers

42

and

plasticisers

.....

.....

TABLE

1.11:

Effect

of

different

processing

aids on

extrusion

characteristics

of cis poly-

46

butadiene

rubber

.....

.....

TABLE

1.12:

Formulation used to study the effect of

various

levels

of

dehydrated

castor

oil

DCO)

and naphthenic

oil

in

comparison

with

a control

mix

where

there

is

no

4ý

plasticiser

.....

.....


21/381

xix

Page

No

TABLE

1.13:

Processing,

curing and

physical

prop-

erties of

SBR

rubber

based

on

formu-

lation

of

Table

1.12

.....

48

TABLE

2.1:

Plasticisers,

processing

aids and

SAPA 1/1

proportions studied

.....

64

TABLE 2.2:

Truck

tyre

sidewall

compound

formu-

lation

studied

..... ,....

65

TABLE

2.3:

Effect

of commonly

used plasticisers

and processing

aids on

processing,

curing

and physical

properties of

truck tyres

sidewall

compound

based

on

NR/SBR

rubber

..... .....

71

TABLE 2.4:

Showing

the

level

selected

for

each

plasticiser,

plasticiser/processing

aid

combination and

SAPA

1/1

for

pro-

cessability

testing

.....

73

TABLE 2.5:

Formulation

used

to

assess

SAPA

1/1

as a plasticiser

in

NR/SBR

compound

79

TABLE 2.6:

Internal

mixing

studies of

SAPA

1/1

compared

with

hydrocarbon

mineral oils,

processing

aids and

a

control

mix

where

there

is

no plasticiser

.....

85

TABLE 2e7:

Milling

behaviour

of

SAPA

1/1

compared

with

mineral

oils,

processing

aids and

a control mix without plasticiser) 86

TABLE

2.8:

Extrusion

characteristics measured

by

Davenport

capillary

rheometer

for

SAPA

1/1

containing mixes, mineral

oil

containing

mixes, combination of

mineral oil and processing

additive

containing

mixes

and a control mix

87

without

plasticiser

.....

TABLE

2.9:

Extrusion,

processability evaluation

by the

use of

Garvey type die

of

SAPA

1/1,

mineral

oil,

mineral

oil/

processing

aid

and

a control mix

88

without

plasticiser

0

...


22/381

xx

Page

No

TABLE

2.10:

Processing

properties at

the

moulding

stage

of

mineral

oils,

combination

of

mineral

oil and

processing

aid,

SAPA

1/1

and a

control

mix with no

plasticiser

..... .....

89

TABLE

3.1:

General

formula

and structure

of

the

surfactants,

diamide

materials and

the

prepared

salts, studied

through-

out the research work 94

TABLE 3.2:

Formulations

used

for

evaluating

the

effect of

the

surfactants,

diamide

and

the

prepared salt

in

an

NR/SBR

compound

100

TABLE

3.3: Effect

of

the

surfactants,

diamide

material

and

the

prepared salt as

processing

aids on

the

processing

and

vulcanisate

properties

of

the

Table

1053.2 compounds

.....

.....

TABLE

3.4:

The

(A)

formulation

series

used

to

107

examine

SAPA

1/1

as a processing

aid

TABLE

3.5:

The

(B)

formulation

series used

to

108

examine

SAPA

1/1

as a processing

aid

TABLE

3.6: Effect

of

SAPA

1/1

on

gum

and carbon

black filled

NR;

(SMR5)

processing,

114

curing

and physical

properties

TABLE

3.7:

Effect

of

SAPA

1/1

on gum

and carbon

black filled

NR;

(SMR

20)

processing,

115

curing

and physical

properties

TABLE

3.8:

Swelling

and acetone

extract results

for

NR

rubber

with

and without

sur-

factant

(SAPA

1/1)

.....

.....

TABLE

3.9:

The

(I)

examine

TABLE

3.10: The

(II

examine

aids

formulation

series

used

to

121

SAPA

1/1

as

a processing

aid

formulation

series used

to

SAPA

1/1

and

NSI

as

processing

.e

122


23/381

xxi

Page

No

TABLE

3.11: Comparison

of

effects of a

conventional

DOP)

plasticiser

and

SAPA

1/1

upon pro-

cessing,

curing

and

physical

properties

of

gum

and carbon

black

filled

CR

125

rubber

..... .....

TABLE 3.12: Effect

of

SAPA

1/1

and

NSI

as

processing

aids

on

CR

rubber

.....

,....

127

TABLE

3.13: Recipe

used

to

examine

the

behaviour

of

SAPA1/1 and NSA/1 as processing aids

in

NBR

rubber

.....

.....

129

TABLE 3.14:

Effect

of

SAPA

1/1

and

NSA/l

as proces-

sing

aids

on

the

processing, curing

and physical properties of

the

NBR

compound

..... .....

132

TABLE

3.15:

Formulations

used

to

study

the

perfor-

mance

of

SAPA

1/1,

NSA/1,

SAPA

2/B,

and

EBF-S

as

processing aids

in

SBR

rubber ..... .....

134

TABLE

3.16:

Formulations

used

to

examine

the

perfor-

mance of

EBF-0

and

EBF-S

versus

aroma-

tic

oil and

Struktol

WB

212

.....

135

TABLE

3.17:

Effect

of

SAPA

1/1,

SAPA

2/B,

NSA/1

and

EBF-S

as processing additives

in

SBR

rubber

..

141

TABLE

3.18:

Effect

of

EBF-S

and

EBF-0

as proces-

sing aids for SBRrubber in comparison

with aromatic oil

and

Struktol WB

212

143

TABLE

3.19: Ageing

behaviour

of

EBF-S

and

EBF-0

in

comparison with

aromatic

oil and

145

Struktol

WB

212

..... .,...

TABLE

3.20:

BR

recipes used

to

examine

the

effect

of

SAPA

11

and

NSA/1

as

compounding

146

ingredients

..... .....

TABLE3.21: Effect of SAPA1/1 and NSA/l on proces-

sing,

curing and physical

properties

of a

cis-polybutadiene

compound

149


24/381

xxii

TABLE

4.1:

Formulations

used

to

examine

the

effect

of

PVI

retarder

in

the

NR/SBR

compound

containing

SAPA

1/1

;.,..

TABLE

4.2: Formulations

used

to

examine

the

effect

of

eliminating

the

cure

activators and

accelerators

systems

from

rubber

TABLE

4.3:

Effect

of

PVI

retarder

on

optimum

curing

time, t,

and

Mooney

scorch of

an

NR/

SBRcomýöund containing 7.5 phr SAPA1/1

TABLE

4.4:

Effect

of

eliminating

the

cure

activa-

tors

and accelerator systems

for

NR/SBR

compound containing

7.5

phr

SAPA

1/1

TABLE

4.5:

Formulations

used

to

examine various

levels

of

SAPA

1/1

as a

cure

activator/

accelerator system

.....

... es

TABLE

4.6:

Elimination

of

the

conventional cure

activator and accelerator system from

SAPA

1/1

containing

rubber

formulations

TABLE

4.7:

Effect

of

ZnO

and

stearic

acid on

the

properties of

the

SAPA

1/l/sulphur

curing system

.....

,....

TABLE

4.8:

Zinc

oxide

as

a scorch

retarder

for

the

SAPA

/l/sulphur

curing system

in

the

NR/

SBR

compound

......

.....

TABLE 4.9: Formulations

used

to

study

the

effect of

benzoic

acid

as

a

retarder

in

comparison

with

ZnO

on

SAPA /1/sulphur

curing

system

.....

,....

TABLE 4.10:

Effect

of

ZnO

and

benzoic

acid

on

proces-

sing,

curing and physical properties of

NR/SBR

compound cured with

SAPA

1/1/

sulphur

system

.

...

.....

TABLE4.11:

Effect

of

SAPA

1/1

as a

plasticiser

and

_a

combined

cure.

activator_accelerator

system

compared

with

a

conventional

system

in

an

NR/SBR

compound

plasticised

with

various

plasticisers

.....

Page

No

156

157

158

158

160

163

165

167

169

172

175


25/381

xxiii

Page

No

TABLE

4.12: Processing

curing

and

vulcanisate

properties

of

NR/SBR

compound contai-

ning

3

phr

SAPA

1/1

as

a

plasticiser

and

accelerator

system

compared

with

a

conventional

accelerator and plasticiser

system

.....

.....

177

TABLE 4.13:

Formulations

used

to

examine various

surfactants

diamide

material and a

prepared salt as

cure

activator/

accelerator

system in

comparison with

a conventional

sulphenamide system

180

TABLE 4.14:

Performance

of

SAPA

1/2

NSC/l

SAPA

2/B

and

EBF-S

as

a

combined cure acti-

vator/accelerator

system

compared with

a

conventional activator/accelerator

183

system

in

NR/SBR

compound

....

TABLE 4.15:

Effect

of

various

alkyl

groups

of

SAPA

2

series


system

on

the

curing

and

physical properties

187

of

the

NR/SBR

compound

.....

TABLE

4.16:

Formulations

used

to

examine

the

effect

of

antioxidants on

the

SAPA

1/1

system

in

comparison

with a

sulphenamide

194

system

in

the

NR/SBR

compound

TABLE

4.17:

Effect

of antioxidants

on

the

ageing

properties

of

the

vulcanisate

cured

by

the

SAPA

1/l/sulphur

curing system

compared

to those

obtained

from

a sul-

196

phenamide/sulphur system

.....

TABLE

5.1:

Recipes

used

to

examine

SAPA

1/1

as a

cure

activator/accelerator system

for

NR

rubber

.....

.....

200

TABLE

5.2:

Processing

curing and

physical

proper-

ties

of

NR

rubber cured with

the

SAPA

1/l/sulphur

system ..... .....

203

TABLE

5.3:

Compound

recipes used

to

examine

the

effect

of

ZnO

and

stearic

acid

on

SAPA

204

l/1/sulphur

curing

system

.....


26/381

xiv

I Sv

Page

No

TABLE

5.4: Effect

of

ZnO

and

stearic

acid

on

the

performance

of

the SAPA

1/1/sulphur

curing

system

in NR

rubber

.....

206

TABLE

5.5:

Recipes

used

to

examine

SAPA

1/1

as

a

cure

accelerator

in

comparison

with

a

sulphenamide

accelerator

in

NR

rubber

208

TABLE

5.6:

Effect

of

SAPA

1/1

as accelerator

in

comparison with

a sulphenamide

accele-

rator on the processing, curing and

physical

properties of a

truck tyre

tread

compound

,.,..

.....

210

TABLE

5.7:

Formulation

used

to

examine

various

surfactants,

diamide

material

and

prepared salts

as cure activator/acc-

elerator

systems

in

comparison with

a suiphenamide

system

in

SBR

rubber

216

TABLE

5.8:

Effect

of

various

substances

as cure

activator/accelerator systems for SBR

rubber

in

comparison

with

a conven-

tional

sulphenamide

CBS)

system

218

TABLE

5.9:

Effect

of

SAPA

2

series systems

as

cure


for

SBR

compared with

a

conventional

sulphe-

namide accelerator system

.....

223

TABLE

5.10:

Recipes

used

to

examine

SAPA

1/1

as a

cure activator/accelerator

for

SBR

in

comparison with a thiazole accelerator

system

.....

.....

224

TABLE

5.11:

SAPA

1/1

Vs MBT/DPG

accelerators

in

carbon

black

and

silica

filled

SBR

rubbers

226

TABLE

5.12:

Effect

of

ZnO

and

stearic acid

on

the

performance of

SAPA

1/1/sulphur

and

SAPA 2/C/sulphur

systems

in

SBR

rubber

230

TABLE5.13: Effect of the EBF-S diamide material

when

used

as a

secondary

accelerator

233

for

SBR

rubber

.....

.....

TABLE

5.14:

Formulations

used

to

examine

EBF-S/

TEA

and

EBF-O/TEA

combination

as cure


system with and

without zinc

oxide

in

SBR

rubber

in

comparison

with

a conventional

curing

235

ystem

.,.......


27/381

xxv

Page

No

TABLE

5.15:

Effect

of

EBF-S

and

EBF-0

sy

accelerator

activated

by

TEA

and

with

ZnO

compared with

a

tional

MOR/DPG)

accelerator

compound

6 ...

stems as

without

conven-

based

... SS

241

TABLE

5.16:

Formulations

used

to

examine

the

ability

of

the

surfactant

SAPA

1/2)1

sulphur

as a curing

system

for

solu-

tion

polymerised

BR

rubber

in

compa-

rison with a conventional curing

system

....

.....

243

TABLE

5.17:

Processing,

curing

and physical prop-

erties

of

BR

compound cured

by

sur-

factant/sulphur

curing

system

in

comparison

with

a conventional

DPG/

sulphur

curing

system

,....

245

TABLE

5.18:

Recipes

used

to

evaluate

a surfactant

and

various prepared

salts as activator/

accelerator systems for NBR compared

with

a conventional

activator/accelera-

tor

system

.....

.....

247

TABLE

5.19:

Effect

of a surfactant and prepared

salts as cure activator/accelerator

systems

on

the

processing, curing

and

physical

properties

of

NBR

compound

compared

with

a

conventional

system

250

TABLE6.1: Surfactants and some prepared diamine

salts

used as crosslinking agents

to

vulcanise chloroprene rubber

.....

265

TABLE

6.2:

Properties

of

unvulcanised

and vul-

can.

sed

chloroprene rubber

cured

with

surfactants

and prepared

diamine

salts

267

TABLE

6.3:

Chloroprene

rubber

cured with

surfac-

tants

and

prepared

diamine

salts

in

combination with

metal

oxides

271

TABLE

6.4:

Comparison

of pH changes

in

chloroprene

vulcanisates

crosslinked

with

surfac-

tant

and prepared

diamine

salts

276


28/381

xxvi

Page

No

TABLE

7.1:

The

surfactants

and

the

EBF-S/TEA

systems

used

in

this

ageing

investi-

gation

...... ,....

280

TABLE

7.2:

Formulation

of

SBR

rubber

used

through-

out

the

investigation

.....

282

TABLE

7.3:

Ageing behaviour

of

a conventional

curing system

ZnO/stearic

acid/MPT/

DPG/sulphur)

without antioxidant

in

carbon black filled SBRvulcanisates 284

TABLE 7.4:

Ageing

behaviour

of a

conventional

ZnO/stearic

acid/MBT/DPG/sulphur)

curing system

with

antioxidant

[Flectol-H] in

carbon

black filled

SBR

vulcanisates

a....

.....

285

TABLE

7.5: Ageing

ebehaviour

of a

conventional

ZnO/stearic


curing system

without

antioxidant

in

silica filled SBRvulcanisates 286

TABLE

7.6:

Ageing behaviour

of a conventional

ZnO/stearic


curing

system

with

antioxidant

[Flectol-H]

in

silica

filled SBR

vulcanisates

.....

.....

287

TABLE

7.7:

Ageing behaviour

of

SAPA

2/C

surfactant

system

without

antioxidant

in

carbon

black

filled

SBR

vulcanisates

288

TABLE

7.8: Ageing

behaviour

of

SAPA

2/C

surfactant

system

with

antioxidants

[Flectol-H]

in

carbon

black filled

SBR

vulcanisates

289

TABLE

7.9:

Ageing

behaviour

of

SAPA

2/C

surfactant

system

without

antioxidant

in

silica

filled

SBR

vulcanisates

.....

290

TABLE

7.10:

Ageing

behaviour

of

SAPA

2/C

surfactant

system

with

antioxidant

[Flectol-H] in

291silica filled SBRvulcanisates

TABLE

7.11:

Ageing behaviour

of

IM

surfactant

sys-

tem

without antioxidants

in

carbon

black

292

filled

SBR

vulcanisates

.....


29/381

xxvii

Page

No

TABLE7.12: Ageing behaviour

of

IM

surfactant

system with

antioxidant

[Flectol-H]

in

carbon

black filled

SBR

vulcanisates

293

TABLE

7.13: Ageing

behaviour

of

IM

surfactant sys-

tem

without

antioxidants

in

silica

filled

SBR

vulcanisates

.....

....

294

TABLE 7.14:

Ageing

behaviour

of

IM

surfactant sys-

tem

with antioxidant

[Flectol-H] in

silica

filled

SBR

vulcanisates

295

TABLE 7.15:

Ageing

behaviour

of

EBF-S/TEA

activator/

accelerator

system

without

antioxidant

in

carbon

black filled

SBR

vulcanisates

296

TABLE 7.16:

Ageing behaviour

of

EBF-S/TEA

activator/

accelerator

system

with

antioxidant

[Flectol-H] in

carbon

black

filled

SBR

vulcanisates

..... .....

297

TABLE

7.17: Ageing behaviour

of

EBF-S/TEA

activator/

accelerator

system without antioxidants

in

silica

filled

SBR

vulcanisates

298

TABLE

7.18:

Ageing

behaviour

of

EBF-S/TEA

activator/

accelerator system with antioxidant

[Flectol-H]

in

silica

filled

SBR

vulcanisates

.....

.....

299

TABLE

7.19:

Effect

of

ZnO

on

the

ageing

behaviour

of

SAPA

2/C

surfactant

system without

antioxidants in carbon black filled SBR

vulcanisates

301

TABLE

7.20:

Effect

of

ZnO

on

the

ageing

behaviour

of

SAPA

2/C

surfactant system without anti-

oxidants

in

silica

filled SBR

vulcanisates

302

TABLE

7.21:

Effect

of

ZnO

on

the

ageing

behaviour

of

IM

surfactant

system without antioxidants

in

carbon

black

filled

SBR

vulcanisates

303

TABLE7.22: Effect of ZnO on the ageing behaviour of

IM

surfactant system

without

antioxidants

304

in

silica

filled

SBR

vulcanisates

TABLE

7 23:

Effect

of

various

levels

of

ZnO

on

the

ageing

behaviour

of carbon

black filled SBR

vulcanisates

obtained with

EBF-S/TEA/

sulphur

curing system aged

for 3

weeks

at

100°C

..... .....

306


30/381

1

CHAPTER

1

RUBBER

COMPOUNDING

Introduction

The

mixture

of rubber

and

ingredients

used

in

rubber

manufacture

is

known

as

a

compound

and

the

process of

making such a compound as

compounding.

The

principal raw materials

of

a compound

are: rubber

or

blend

of

rubbers,

curing

system,

fillers,

plasticiser

and/or

processing

aid.

Each

one of

these

components plays an

important

part

in both

the

processing

behaviour

and

vulcanisate properties of a compound.

The

author's research work was

to

study

the

behaviour

of a cationic

surface active

agent

as

plasticiser

and/or processing aids for rubber

compounds.

In

the

course of

the

study

it has been discovered

that this type

of

surfactant

has

multiple

functions

and

can

act as

both

processing

aid

and

cure activator/accelerator

for

natural

and synthetic rubbers,

additionally

they

can

function

as crosslinking

agents

for

CR

rubber.

This

chapter

describes the

present

technology

of surfactants, plasti-

cisers

and/or processing

aids,

and a

brief

summary of

current

rubber

vulcanisation

theory.

Finally the

objectives

of

the

present research

are

stated.

1.1

Surfactants

Some

solutes,

even

present

in

very

low

concentration,

have

the

ability

of

changing

the

surface energy

of

their

solvents

to

a considerable

degree.

The

effect

is

always a

lowering

rather

than

an

increase

of


31/381

2

the

surface

energy.

Such

materials

have

come

to

be known

as

Surface

Active Agents,

and

their

effect

is known

as surface

activity.

A

detailed

consideration

of

this

effect

is

given

in Appendix

1.

Surface

active

agents

are

characterised

by

their

linear

structure.

One

end

of

this

linear

structure

is

composed of

radicals

which are

compatible

with

the

solvent, and

the

opposite

end

of

incompatible

radicals.

For

example,

fatty

amines are composed

of a

hydrophobic

non-polar,

water

insoluble), hydrocarbon

chain, characterised

by

weak

residual valence

forces

in

one end and a

hydrophilic

polar,

water soluble) cationic nitrogen

group which

has

strong

residual

valence

forces

on

the

other

end as

shown

below:

i\/\

CH2

H2 CH2

CH2

CH2

CH3

2

CH2

CH2

CH2 CH2

CH2

N+H3

Hydrophil is

Ammonium

Hydrophobic hydrocarbon

chain

-

group

1.1.1

Classification

of

Surfactants [1][2][3]

The

most

common system

used

to

classify surfactants

is

one

which

depends

on

the

distribution

of electrical

charge

on

the

molecules

and

this

system

will now

be described.

1.1.1.1

Anionic

Surface

Active

Agents

This class of surfactant is characterised by the inclusion of a low-

affinity

hydrocarbon

chain adjacent

to

anion and

is

usually

soluble

in

aqueous

solution.

Sodium

stearate

C17

H35COONa) s

a

typical

anionic

surfactant

since

it ionises

in

solution

to

form

Na+

and

the

long-chain


32/381

3

stearate

anion,

C17H35C00

,

which

is

considered

to

be

responsible

for

its

surface activity. In this class some of

the

most

important

end

groups

are

Carboxy

-COOH),

Sulphonic

acid

-SO3H),

and

Sulphuric

ester

-OSO3H).

Table

1.0

shows some

typical

commercially

available

anionic

surfactants

[3].

1.1.1.2 Nonionic Surface Active Agents

The non-ionic class has non-ionisable high-affinity end group i. e. no

residual

electrical charge

as

for

example

Dodecylalcohol

ethoxylate:

CH3 CH2)10

CH2 OCH2CH2)n

OH.

Usually

the

non-ionic surfactants

con-

tain

a

number

of oxygen, nitrogen, or

sulphur

atoms

in

non-ionising

configurations.

Table

1.1

shows some

commercially available non-

ionic

surfactants,

their

properties,

with

their

main

suppliers

[3].

1.1.1.3

Amphoteric

Surface

Active Agents

This

class

is

characterised

by

the

presence of

both

positive

and

negative

centres

in

one molecule.

Cetylamine

acetic acid,

for

example,

comes

to the

following

equilibrium

in

aqueous

solution:

C16H33NH

-

CH

2000H

=

C16H33N+H2

-

CH2000 1.1)

depending

on

the

pH of

the

medium, cationic, anionic, or nonionic

type

properties

may

be

exhibited.

Table

1.2

shows some

commercially

avai-

lable

amphoteric surfactants

[3].


33/381

I.

u

N

W

V)

N

W

º

-4

H

W

CL

O

of

r- I

W

2

F-

a

N

o

r-

U

Q

W Li

J

QN

U

O

Q

J

Q

r-ý

U

W

Z

Z

O

U

W

I--

W

N

W

0-1

CL

W

i

V

N

Q)

'ý f0

%ý

q

J

C

+)

O Q)

O

+

'r

i

^EN

r

XrN

U)

r

ý

v)

Q ý

-

4-

O

'--'

4-.

+.

>

3

Li

-

-

N

O

+J

XN

aO

tio

r

Cl.

N

01

(a

L

=rN

OQa

a)

4-

U

co

o

ON

3

(C

N ^

tO

+>

>O

4-1

O r'

-0

r-

3

4

r-4)

U

4)

Nt a)

r-0

Q)

r

Cr-

t

C

=O

N

OV^

CD- Cl.

0Oi. S-

(1)

CL

eu CO

N

Q)

NO

0

-0

NC

B=

Si

(A

ru

4-)

r

fl.

r-

Q)

(

0)

ONO

0

r- rö

N c

a¢ >, ^ -0 s.. 3L 0- a) 0. s.

-lc

.^U ^N

0

E

>>,

N

.w

E4-

E

(1) +-) N

N(1)-a

(L)

113

4-

00

4) -0

4--1

N

4-)

co

N

(CS

4-'

r

CO

a) '0

rXa

C

XO Q)

OC

(2) . r-

QJ

c Or Q1

r^

C

r

ro

r-

O

W

= Zi

CO

O

C)

'a

V)

QN

C]

MrS..

rö

O33

U

Q)

\

I

O

cý

N

rý

C

^

Q1

N

4--) IU

fý

Q7

r

a1

4-)

O

Q1

U

NN

+j

'

0 O

3

O.

N

N

(v

C +3

E

+-)

'

r

S-

. r'

N

M$

C

(ö

C :4-

)0(

rC

4-

N

=

0

rO

S-

U

0)

-

a1

S

3

4-

4-)

(v

L

M

L

r

S-

r

i

i-)

-

QO

4- O

.CN

0)-C

Q)

-a

41 CU

O

s.

+'

rnU

C-I-'4-'

CO

3Nc

O

S.

-

n

ö

ý ä ý

c U)a iC33 MS(1)

0) 0

0)

W

Cr

NCC

})

r-

r

N

'r

r

r

O

r'

3N

N3

RS

N 4.

)

N

O >>

rOC

UE

r'

3

r-

r^

rO r

f

L

3V

i.

3

4-

i.

>,

i.

4-

r-

\0

NO

O

r'

N

^

4)

O 4)

IOr

: +-)

i

..

C

LL

rO

+) di

V

r

-ý

41 O

_]G

0C CU 0

t

r0N

C3

rN

(1)

3

co

r---

()

r

+ )

U

n-

N-

to

O

O

RS

LOO

O

S-

O

(10

r

>rQ

IL

t)- >-

d

IL

Q3 U 4-

N

3

RS

> o 0

0

00

Un

'r

U) al

L()

0)

4-)

UU

^

>j

I

U)

a) 00

+-)

0I

4-'

S=

>j

r

+.

=O-^

4)

4

-3

IU

c

CU O-

ro

-0

00

rO

C

N

4-'

i-

I

4-

r-

(0

r

>'

-

O

O

4J

«s

CV

CiU +-)

U

(

4-

N

r-

U

^.

C

NI

:U

C

.0

co

U

r-

00

0-

rU

LO

.0:

r-

a 4-)

r

.

-J

r- r--r-

(Cr IN

>,

0

OO

a)

OU:

COU

00

U.

C

C..

C N

-C

.IN

r-

Nr-

_I_-

(2)

0.

00

+- +-)

0

ILO

4-

a)

>> O-

T3r

UU (0 CU

r0

C)

4->-lLr I

r-

0: Or.

>r

C-)

W

r (0 r-

(0 r^

:

C] N U

(z

Cl. (/) (- CV OC

to

U C

(A

a

E

E

I

E

E

0

N

O

r- I-

'r-

E

r

r

i-)

-a -v

I-.

:

-v -a

(0

0

0 O

r-

0

0

U

V)

(/)

Cl-

(n

V) V)

N

S-

V)

Z

a1

4)

O

Y

(1)

'ß

V

'ß U

O

s-

03 cv

3

ö

U

¢n

co 0

(/

)00

(/)0

CO 0

LO

3cn

c\j

a

zt.

p

Oa

OUP

r

0.

O

O

C O O

(0

fl-

-a

qý

to

(0

(0

0

ro

E

4-

4-

4-

N

U

S-

0

r- r- r

O

r

I--

Z W

W

W

2

¢

S-

(A

41

i.

V

r

'r'

+) i 43

NO

0.

O

EJ

UJ

r r

Q

N

(D Q)

rr-0

:3

-lid

0

ie

4-)

(/)

¢U=

==)

¢UJ


34/381

5

r

i--

w

m

M

v;

F-

z

I-

U

L

N

U

H

L

L

LLI

J

m

J

H

Q

J

Q

U

LU

cD

U

J

U

H

>--

I--

I

^

N

Ni

p)

1

1

Q

1

W

Q

O

1

^

r

N C

I

r

I

a)

^

S.

'II

r

1

'r

(0

X

+) 1 iNi

41

O

O

1

+-)

Q

Q) 4-

O +-

0

E

(3)

0

U

4-)

I

XU

+- 4)

C c-

Li_

d-)

E

.,

C

4)

I

+)

O

Q1

^

+ý

(V

0)

N

0

C

i

1

i

NN

4-

(0

O CL

U

4-

Ü

r

1

^ON 1

=r

F)

O

i

r

4-)

I

U

+ý

Q)

a Q

I

OES.

-

aU

r-

-F-)

N

U

1

r

r

>

a)

I

(0(0

(0

O

N

II. co

d-)

r

M^

I

EQ

r r

C

rQ

E

i 4--

NUN

S-

(A

I

4-.

r-

NO

QQ Q Q) 1 ý r 4) Q) Q) 1 Q r r r- r

E

4)

-

O

N

i-C

4)i-

U I

}-

X

-P

(CS

4-

+-)

(0

0

0)

-0 N

r

4J

1

r-

O

E

XO

W

E

)

«f

(0

Cl

-N

N

C3

(o (o

N

V)

L

\ i) 1

iI

r

O

d)

I

Q

r

>,

a)

1

0-

r-

4- C>:

Q)

1

4-

Q

f0

CO

I

N r r

CO

>

1

O

>

N

Q)

ý

-

r-

N

-in

0

I

N

0

N

U)

C

i

1

-0

r

U

..

Q

1

O

4-)

QN

r

Q

I

r r

(0

I 0)

O

(0

r-

_

I- )

1

^0E+.

)

I

cm

4-3

N

(A

(0

1

Q)

NQ

(0

N

I

f0

N

N

S.

-

4-

(0

4-3

E

I

O +'

«3

1

iU

«s

(DO

O

1

r

^^ (/)

Q..

a) N

+-

0

C7)-r- d)

I

N

4-

(1)

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7

1.1.1.4

Cationic

Surface

Active Agents

Cationic

surface active

agents

consist of a cation

attached

to

a

low

water

affinity

hydrocarbon

chain.

Cetyltrimethyl

ammonium

bromide

is

an example

of

this

class.

In

aqueous solution

it ionises

accor-

ding

Documents

Cationic Sufactants in Rubber Compounding