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A
Concise Introduction
to Additives
for
The
r
m
o
p
I
as
t
i
c
Po
I
y m
e
rs
Johannes Karl Fink
Montanuniversitat Leoben, Austria
S/c
r
ive
n
er
@WILEY
This Page Intentionally Left Blank
A
Concise Introduction
to Additivesfor
Thermoplastic Polymers
Scrivener Publishing
3
Winter Street, Suite
3
Salem, MA
01970
Scrivener Publishing Collections Editors
James
E.
R.
Couper
Rafiq Islam Pradip Khaladkar
Norman Lieberman Peter Martin
W.
Kent Muhlbauer Andrew
Y.
C. Nee
S. A. Sherif James
G.
Speight
Richard Erdlac
Publishers
at
Scrivener
Martin Scrivener
(rnartin@scrivenerpublishing.com)
Phillip Carmical
(pcarmical@scrivenerpublishing.com)
A
Concise Introduction
to Additives
for
The
r
m
o
p
I
as
t
i
c
Po
I
y m
e
rs
Johannes Karl Fink
Montanuniversitat Leoben, Austria
S/c
r
ive
n
er
@WILEY
Copyright
Q
2010 by Scrivener Publishing, LLC. All rights reserved.
Co-published by John Wiley
&
Sons, Inc., Hoboken, New Jersey and Scrivener Publishing, LLC, Salem,
Massachusetts.
Published simultaneously in Canada.
No
part of this publication may be reproduced, stored in a retrieval system,
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Cover designed by Russell Richardson.
Library
of
Congress Cataloging-in-Publication Data is available.
ISBN 978-0-470-60955-2
Printed in the United States of America.
10987654321
Contents
Preface
xiii
1
Introduction
1.1
Classification
References
2
Plasticizers
2.1 Principle of Action
2.2 Principle of Selection
2.3 Characterization
2.4 Risks and Drawbacks
2.4.1 Leaching
2.4.2 Inherent Toxicity
2.5 Classes of Plasticizers
2.5.1 Phthalate Plasticizers
2.5.2 Cyclohexanoic Diesters
2.5.3 Phophate Plasticizers
2.5.4 Aliphatic Esters
2.5.5 Polymeric Plasticizers
2.5.6 Ionic Liquids
2.6 Specific Examples of Application
2.6.1 Heat Shrinkable Films
2.6.2 Adhesive Compositions
2.6.3 Interlayer Films for Safety Glasses
2.6.4 Electrolyte Membranes
2.6.5 Porous Electrodes
2.6.6 Biodegradable Polymers
2.6.7 Plasticizers for Energetic Polymers
References
1
1
3
5
6
6
7
8
8
9
9
9
12
13
13
14
15
16
16
17
17
18
18
19
20
21
V
vi
Contents
3
Fillers
3.1
Surface Modification
3.1.1
Siloxanes
3.1.2
Dispersion and Coupling Additives
3.2
Special Applications
3.2.1
Flame Retardant Fillers
3.2.2
Conductive Fillers
3.2.3
Solder Precoated Fillers
3.2.4
Nan0 Clays
3.2.5
Mixed Matrix Membranes
References
4
Colorants
4.1
Physics Behind a Color
4.1.1
Human Eye
4.1.2
Tristimulus Values
4.1.3
Color Spaces
4.2
Color Index
4.3
Test Standards
4.4
Pigments
4.5
Organic Colorants
References
5
Optical Brighterners
5.1
Basic Principles
5.2
Measurement
5.3
Inorganic Brighteners
5.4
Organic Optical Brighteners
5.4.1
Reactive Optical Brighteners
5.4.2
Melt Extrusion
5.4.3
Photographic Supports
References
6
Antimicrobial Additives
6.1
Modes of Action
6.2
Plasticizers
6.1.1
Types of Irritations
25
25
25
25
29
29
30
32
33
34
34
37
37
37
37
39
40
41
43
43
47
49
50
51
52
52
52
54
55
56
59
59
60
60
Contents
vii
6.3 Special Formulations
6.3.1 Contact Lenses
6.3.2 Food Packaging
6.3.3 Polymers with Inherent
Antimicrobial Properties
References
7
Flame Retardants
7.1 Mechanisms of Flame Retardants
7.2 Smoke Suppressants
7.3 Admixed Additives
7.4 Bonded Additives
References
7.1.1 Flame Cooling of Halogens
7.4.1 Examples of Polymers
8 Lubricants
8.1
Principle of Action
8.2 Methods of Incorporation
8.2.1 Conventional Method
8.2.2 Separate Delivery of the Lubricant
8.3 Types of Lubricants
8.3.1 Alcohols
8.3.2 Fatty Acids, Esters and Amides
8.3.3 Waxes
8.3.4 Polymeric Lubricants
8.4.1 PVC
8.4.2 Chlorinated PVC
8.4.3 Electically Conductive Polymers
8.4 Special Applications
References
9
Antistatic Additives
9.1 Types of Additives
9.2 Areas of Application
9.3 Additives in Detail
9.3.1 Conventional Additives
9.3.2 Polymeric Additives
65
65
66
67
68
71
71
71
73
74
77
77
83
87
87
88
88
88
89
89
90
90
91
91
91
91
92
92
95
95
96
98
98
100
viii
Contents
9.3.3 External Antistatic Additives
9.3.4 Intrinsically Antistatic Compositions
9.3.5 Conductive Fillers
References
10 Slip Agents
10.1
Basic Principles
of
Action
10.2 Compounds
10.3 Special Formulations
10.3.1 Poly(ethy1ene terephthalate)
10.3.2 Formulations for Poly(ethy1ene)
References
11
Surface Improvers
11.1
Additives
11.1.1
Fluorocarbon Compounds
11.1.2 Acrylics
11.1.3
Modified Pigments
11.1.4 Organic Salts
References
12 Nucleating Agents
12.1 Crystalline Polymers
12.1.1 Crystal Structures
12.1.2 Modification
of
Properties by
Crystallinity
12.2 Experimental Methods
12.2.1 Nucleation Technologies
12.2.2 Characterization
of
Polymer
Crystallization
12.3 Classes
of
Nucleating Agents
12.3.1 Inorganic Nucleating Agents
12.3.2 Sorbitol Compounds
12.3.3 Phosphates
12.3.4 Carbon Nanotubes
12.3.5 Coupled Nucleating Agents
101
101
101
104
107
107
109
110
110
111
111
113
114
114
114
115
116
116
119
120
120
120
121
121
121
122
122
123
124
124
124
[...]... for Safety Glasses Poly(viny1acetal) (PVAL)based formulations are used as interlayer films for laminated glass, as binders for ceramic forming, as binder for ink or paint and as thermally processable photographic materials (36) Important issues are improved waterproofness and the compatibility with a plasticizer For example, when laminate glass is exposed to high humidity fora long time, it may face... for Thermoplastics Table 1.1:Classification of AdditivesforPolymers Type Usage for Antioxidant Light stabilizer Acid scavenger Lubricant Processing aid Antiblocking Slip additive Antifogging additive Antistatic additive Antimicrobial agent Flame retardant Blowing agent Modifier Controlled degradation additive Crosslinker Colorant Filler Reinforcement Optical whitener Coupling agent Nucleating agent... into the polymeric matrix, but they will become chemically reactive when they are starting with their protective action The same is mostly true fora flame retardant, but this not a general rule In addition, there is a basic difference between additivesforthermoplastic material and additivesfor thermosetting resins Likewise, a curing agent and an accelerator may be considered as an additive However,... evaporation and degradation of plasticizers have been developed, with the aim of formulating long-lasting flexible plastics and minimizing the ultimate environmental impact of these chemicals Also, fire-retardant plasticizers and plasticizers for use in biodegradable plastics have been developed (2) Several monographs have been prepared with regard to the topic (3-7) Plasticizers are used for several... seems to be a good alternative to phthalates in flexible toys due to its ease of processing, final product performance, low toxicity and fast biodegradation Toxicity tests showed a low acute toxicity and no evidence of reproductive toxicity (2) 2.5 Classes of Plasticizers Plasticizers can be classified according to their chemical structure as shown in Table 2.1 Plasticizers may be also classified into... Flame retardant, not suitable for food applications Phosphates Low viscosity, high gelling capacity, relatively volatile Adipates and extractable, superior low temperature flexibility Good low temperature flexibility, less water sensitive Azelates than adipates Good low temperature performance Sebacates Very low volatility, highly resistant to extraction and Polymers migration Trimellitates Low volatility,... Plasticizers Phosphates have been long known as PVC plasticizers Phosphate based plasticizers are summarized in Table 2.4 Most common is tricresyl phosphate Commercial tricresyl phosphate is a mixture of the ortho, meta, and para isomers Phosphate based plasticizers impart flame retardant properties The flame retardant action arises because they are capable to form polyphosphoric acids by condensation... summarize a few examples of the application and usages of plasticizers in polymeric materials Among all kinds of additives, plasticizers are the most important class of additivesforpolymers The global demand for plasticizers was 4,647 thousand metric tons in 2000 (31) According to another study, in 2007, the global plastic additives industry grew to 12.2 million tomes This is justified by the rapidly... (multipurpose action), or Commercial importance The most comprehensive classification is the classification with respect to its field of application This kind of classification is summarized in Table 1.1 Additives can be subdivided into chemically inert additives and chemically reactive additivesFor example, plasticizers, or lubricants are not chemically reactive On the other hand, antioxidants 1 2 Additives for. .. that water may penetrate into it through its edges and it may whiten as its compatibility with plasticizer is not good Special formulations have been developed to overcome these drawbacks When the PVAL is used for interlayer films for laminated glass, a plasticizer may be added to it A preferred plasticizer is triethylene 28 Additivesfor Thermoplastics glycol For ceramic green sheets, dioctyl phthalate . cants are not chemically reactive. On the other hand, antioxidants 1 2 Additives for Thermoplastics Table 1.1: Classification of Additives for Polymers Type Usage for Antioxidant. between additives for ther- moplastic material and additives for thermosetting resins. Likewise, a curing agent and an accelerator may be considered as an additive. However, these types of additives. teaching material on additives for thermoplastic polymers so I have tried to fill the gap. The goal of the book is to offer a general and concise introduction into plastics additives. For students