Fluoropolymers - Technology, Markets and Trends

133 Pages·2001·1.778 MB·English

by  Scheirs, John

Fluoropolymers
Technology, Markets and Trends
A Rapra Industry Analysis Report
by
John Scheirs
ExcelPlas Australia
April 2001
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
Tel: [phone] Fax: [phone] http://www.rapra.net
The right of John Scheirs to be identified as the author of this work has been asserted by
him in accordance with Sections 77 and 78 of the Copyright, Designs and Patents Act
1988.
© 2001, Rapra Technology Limited
ISBN: 1-85957-273-1
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means—electronic, mechanical,
photocopying, recording or otherwise—without the prior permission of the publisher,
Rapra Technology Limited, Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK.
Contents
1. Introduction ............................................................................................................. 1
2. Executive Summary ................................................................................................ 3
3. Fluoroplastics ......................................................................................................... 5
3.1 Introduction ................................................................................................................... 5
3.2 Consumption and Growth Statistics .............................................................................. 6
3.3 Fluoroplastics by Type .................................................................................................. 8
3.3.1 Polytetrafluoroethylene (PTFE) ......................................................................... 8
3.3.2 Fluorinated Ethylene Propylene Copolymer (FEP) ........................................... 19
3.3.3 Polyvinylidene Fluoride (PVDF) ........................................................................ 24
3.3.4 Tetrafluoroethylene-ethylene Copolymers (ETFE) ............................................ 28
3.3.5 Tetrafluoroethylene and Perfluoroalkyl Vinyl Ether (PFA) ................................. 33
3.3.6 Tetrafluoroethylene and Perfluoromethyl Vinyl Ether Copolymer (MFA) .......... 38
3.3.7 Polyvinyl Fluoride (PVF) .................................................................................... 42
3.3.8 Chlorotrifluoroethylene-ethylene Copolymer (ECTFE) ...................................... 45
3.3.9 Polychlorotrifluoroethylene (PCTFE) ................................................................. 50
3.3.10 Tetrafluoroethylene-hexafluoropropylene-vinylidene Fluoride
Terpolymer (THV) .............................................................................................. 52
3.3.11 Amorphous Fluoroplastics ................................................................................. 54
3.4 Application Areas for Fluoroplastics .............................................................................. 56
3.4.1 Chemical Processing ......................................................................................... 56
3.4.2 Semiconductor Manufacture ............................................................................. 61
3.4.3 Wire and Cable .................................................................................................. 63
3.4.4 Coatings and Surface Treatments ..................................................................... 65
3.4.5 Automotive/Transportation ................................................................................ 67
3.4.6 Electrical/Electronic ........................................................................................... 67
3.4.7 Architectural ...................................................................................................... 69
3.4.8 Mechanical ........................................................................................................ 70
3.4.9 Medical .............................................................................................................. 70
3.4.10 Aviation/Aerospace ........................................................................................... 70
3.4.11 Other Applications ............................................................................................. 71
3.5 Fluoroplastic Developments .......................................................................................... 72
3.5.1 Polymerisation Developments ........................................................................... 72
3.5.2 Processing Developments ................................................................................. 72
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vi Contents
3.5.3 Material Developments ...................................................................................... 73
3.5.4 Coating Developments ...................................................................................... 73
3.6 Health and Safety Considerations with Fluoroplastics .................................................. 74
3.7 Fluoroplastic Company Profiles .................................................................................... 75
3.7.1 Asahi Glass Co. ................................................................................................. 75
3.7.2 Atofina ............................................................................................................... 75
3.7.3 Ausimont ........................................................................................................... 76
3.7.4 Daikin Industries Ltd. ......................................................................................... 76
3.7.5 DuPont .............................................................................................................. 76
3.7.6 Dyneon .............................................................................................................. 77
3.7.7 Honeywell .......................................................................................................... 78
3.7.8 JSC Halogen ..................................................................................................... 78
3.7.9 Kureha Chemical Co., Ltd.. ............................................................................... 78
3.7.10 Solvay ................................................................................................................ 78
3.7.11 Recent Acquisitions and Mergers ...................................................................... 79
References ............................................................................................................................. 79
4. Fluoroelastomers .................................................................................................... 81
4.1 Introduction ................................................................................................................... 81
4.2 Consumption and Growth Statistics .............................................................................. 85
4.3 Fluoroelastomers by Type ............................................................................................. 88
4.3.1 VDF-HFP Fluoroelastomers .............................................................................. 88
4.3.2 VDF-HFP-TFE Fluoroelastomers ...................................................................... 90
4.3.3 VDF-PMVE-TFE Fluoroelastomers ................................................................... 92
4.3.4 TFE-P Fluoroelastomers ................................................................................... 92
4.3.5 E-TFE-PMVE Fluoroelastomers ........................................................................ 96
4.3.6 TFE-VDF-HPFP Fluoroelastomers .................................................................... 98
4.3.7 TFE-VDF-HFP-E Fluoroelastomers .................................................................. 98
4.3.8 TFE-PMVE Perfluoroelastomers ....................................................................... 98
4.3.9 VDF-CTFE Fluoroelastomers ............................................................................ 103
4.3.10 Fluoroelastomer-acrylic Alloys .......................................................................... 104
4.3.11 Fluorinated Thermoplastic Elastomers (FTPE) ................................................. 105
4.3.12 Liquid Fluoroelastomers .................................................................................... 107
4.3.13 Fluorosilicone Elastomers ................................................................................. 109
4.3.14 Fluorophosphazene Elastomers ........................................................................ 112
4.4 Application Areas for Fluoroelastomers ........................................................................ 114
4.4.1 Automotive Industry ........................................................................................... 114
4.4.2 Industrial Applications ....................................................................................... 115
4.4.3 Oil and Gas Recovery ....................................................................................... 117
4.4.4 Aviation/Aerospace Industry .............................................................................. 118
4.4.5 Semiconductor Manufacture ............................................................................. 119
4.4.6 Environmental Protection .................................................................................. 120
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Contents vii
4.5 Fluoroelastomer Developments .................................................................................... 121
4.5.1 Polymer Processing Additive Developments ..................................................... 121
4.5.2 Material Development ....................................................................................... 122
4.5.3 Future Outlook ................................................................................................... 124
4.6 Health and Safety Considerations with Fluoroelastomers ............................................ 125
4.7 Fluoroelastomer Company Profiles ............................................................................... 126
4.7.1 Asahi Glass ....................................................................................................... 126
4.7.2 Ausimont ........................................................................................................... 126
4.7.3 Central Glass Co., Ltd. ...................................................................................... 127
4.7.4 Daikin Kogyo ..................................................................................................... 127
4.7.5 Dow Corning ...................................................................................................... 127
4.7.6 DuPont Dow Elastomers ................................................................................... 127
4.7.7 Dyneon LLC ...................................................................................................... 127
4.7.8 Kureha Chemical Co. ........................................................................................ 127
4.7.9 Nippon Mektron Co. .......................................................................................... 128
4.7.10 Precision Polymer Engineering ......................................................................... 128
References ............................................................................................................................. 128
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Fluoropolymers – Technology, Markets and Trends
1 INTRODUCTION
This report gives an overview of commercial fluoropolymers, their properties and end-use
markets, and of the developments and trends within the industry. The increasing use of
fluoroplastics in such dynamic industries as wire and cable insulation, automotive,
aerospace, oil and gas recovery and semiconductor manufacture has led to significant
fluoropolymer developments and trends in the last few years.
New fluoropolymers have been introduced to the market in the last few years, expanding
the already broad slate of applications. Major fluoroplastic developments in the past five
years include:
• amorphous fluoroplastics (e.g., Teflon AF by DuPont),
• tetrafluoroethylene hexafluoropropylene vinylidene fluoride terpolymers (by Dyneon),
• modified polyethylene terephthalate (PTFE) (e.g., Teflon NXT by DuPont), and
• copolymers of tetrafluoroethylene and perfluoromethyl vinyl ether (by Ausimont).
Major fluoroelastomer developments in the past five years include:
• specific low-temperature grades (e.g., Viton GLT by DuPont),
• amine-resistant grades (e.g., Viton Extreme, Viton ETP-500), and
• improved rheology grades (e.g., Viton A210C and B201C).
The objectives of the report are:
• to describe the properties, attributes and limitations of the major fluoropolymer resins,
and their future prospects,
• to describe the many different types of end-use markets for fluoropolymers and the
end-use market share in the USA and worldwide,
• to analyse and estimate fluoropolymer industry production figures and trends,
• to describe manufacturing methods used for processing of fluoropolymer resins,
dispersions and additives,
• to describe fluoropolymer technology and trends and identify reasons for the growth
or decline in demand for materials used and markets,
• to discuss some of the environmental, health and safety aspects of fluoropolymer
production and processing, and
• to identify and profile the major suppliers of fluoropolymers.
The author would like to acknowledge the help of the following people for supplying
written market data, for telephone conversations and for product literature:
Ms. Alison Deutsch (Ausimont, USA) for supplying fluoroplastic and fluoroelastomer
pricing and market information.
Mr. K. Tokuhira (Daikin Industries, Japan) for supplying photographs of fluoroplastic
applications as well as worldwide production and consumption data.
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Fluoropolymers – Technology, Markets and Trends
Mr. Peter-Karl Eichhorn (Dyneon, Germany) for supplying product literature and
application information (by telephone).
Mr. Shin Kato (Asahi Glass Company, Japan) for supplying product literature and
technical brochures.
Dr. Hiroki Kamiya (Asahi Glass Company, Japan) for supplying technical literature on
AGC's range of fluoroplastics.
Dr. Bruce Smart (DuPont, USA) for supplying technical information on DuPont’s range of
fluoroplastics.
Mr. John Fortey (Sythree, Australia) for supplying technical information on DuPont
Fluoroplastics.
Dr. Sarah Ward (Rapra Technology Limited, UK) for supplying a Rapra Abstracts search
on fluoroplastics and fluoroelastomers.
Ms. Darlene Dase (Ausimont, USA) for supplying technical information on fluoroplastics.
Mr. N.S. Murthy (Honeywell, USA) for supplying technical information on Aclar PCTFE.
Mr. Yoshihisa Yamamoto (Daikin Industries, Japan) for supplying technical information on
Daikin fluoroplastics and fluoroelastomers.
Mr. Graham Deavin (AtoFina, USA) for supplying technical information on PVDF resins
and applications.
Mr. J.P. Ventura (Dow Corning, UK) for supplying information on Dow Corning and
fluorosilicones.
Dr. Tim Maxson (Dow Corning, USA) for supplying technical information on
fluorosilicones.
Mr. Pascal Ferrandez (DuPont Dow Elastomers, USA) for supplying technical information
on fluoroelastomers.
Mr. Torkel Rhenmann (DuPont Dow Elastomers, Belgium) for supplying technical
information on Kalrez fluoroelastomer.
Mr. Klas Zetterman (DuPont Dow Elastomers, Switzerland) for supplying product
information on fluorolastomers.
The Fluoroplastic Division of the Society of Plastics Industry for supplying copies of its
newsletter FluoroNews.
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Fluoropolymers – Technology, Markets and Trends
2 EXECUTIVE SUMMARY
Fluoropolymers is the term used to describe both fluoroplastics and fluoroelastomers.
Collectively, these high-performance polymers are used in diverse applications where the
incorporation of fluorine into the polymer structure confers enhanced thermal, chemical
and oxidative stability, reduced adhesion, increased hydrophobicity and improved
biocompatibility. This comprehensive report provides current information on the chemistry,
properties and applications of commercially available fluoropolymers including new and
emerging trends and technologies.
Fluoropolymers in the past few years have matured to give a family of polymers which are
suited to almost any application. Traditional weaknesses of both fluoroplastics and
fluoroelastomers have been overcome through structural modification to give a range of
new grades. PTFE is no longer plagued by the traditional shortcomings of poor
processibility and high creep. Modified PTFE, which combines ease of processing with
the inertness, stability and chemical resistance of regular PTFE, is now available. New
fluoroelastomers are no longer susceptible to attack by organic amines or polar solvents.
The incorporation of specific comonomers and specialised cure systems has enabled
fluoroelastomers to be produced with unrivalled fluid and heat resistance.
The growth in fluoropolymer production and consumption has been a healthy 5%–7% per
annum spurred on by applications such as wire and cable insulation for the booming
information technology revolution. Semiconductor manufacture applications have
provided another major market for fluoropolymers which are characterised by unparalleled
purity and inertness. Fluoropolymers also contribute greatly to environmental
management and cleaner production as their use curbs fugitive emissions, e.g., vapour
emissions from components such as automotive fuel hoses.
The workhorse fluoropolymer is still PTFE accounting for some 70% of the total
fluoroplastic market which exceeded $2.0 billion in 2000. DuPont retains it position as the
dominant fluoropolymer producer supplying about half of global capacity. Most
fluoroplastics lie in the price range $13/kg (for PTFE) to $45/kg (for PFA).
Fluoroelastomers, like fluoroplastics, are characterised by chemical stability and
resistance to high temperatures. Fluoroelastomers are the materials of choice for
demanding applications where conventional elastomers would prematurely fail. The
majority of commercial fluoroelastomers are based on just three main monomers (namely
vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene). However, the
incorporation of low levels of other fluorinated monomers as cure sites allows the
production of a whole range of different fluoroelastomers with tailored properties such as
low-temperature resistance or specific resistance to certain aggressive chemicals. Such
fluoroelastomers find use in a diverse range of applications ranging from O-rings, valve
stem seals, shaft seals, gaskets and fuel hoses in automotive applications to seals and
packing for oil wells.
Worldwide demand for fluoroelastomers has increased considerably during recent years
from 30,000 tonnes in 1996 to in excess of 40,000 tonnes in 2000 representing an
increase in demand of 8% per annum. Increased supplier economies of scale have
resulted from industry rationalisation and joint ventures such as that by DuPont and Dow
(to create DuPont Dow Elastomers) and by 3M and Hoechst (to create Dyneon). North
America is the dominant producer and consumer of fluoroelastomers accounting for some
50% of global production, followed by Western Europe, Japan and the remainder of Asia.
DuPont Dow Elastomers is the largest fluoroelastomer producer with five manufacturing
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Fluoropolymers – Technology, Markets and Trends
sites in 3 continents. The automotive industry is by far the largest consumer of
fluoroelastomers accounting for 65% of all consumption with applications including O-
rings, valve stem seals, shaft seals, and extrusion for fuel hosing and tubing. Compared
to conventional elastomers, the price of some fluoroelastomers and perfluoroelastomers
seems incredibly expensive yet when consideration is given to cost savings in terms of
replacement costs, downtime and lost production costs and maintenance costs, price is
not the dominant selection criteria.
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Fluoropolymers – Technology, Markets and Trends
3 FLUOROPLASTICS
3.1 Introduction
Fluoroplastics are high-performance polymers that occupy a myriad of diverse end-use
applications, many of which cannot be satisfied by any other materials. Typical uses for
fluoroplastics are given in Table 3.1. These applications depend on one or more of the
unique features displayed by respective fluoroplastics.
Table 3.1 Typical Applications for Fluoroplastics
Industry Segment Applications
Automotive O-rings, gaskets, valve stem seals, shaft seals, linings for
fuel hoses
Chemical industry chemically resistant coatings, heat exchangers, pumps,
diaphragms, impellers, tanks, reaction vessels, autoclaves,
drums and containers, flue duct expansion joints, heavy-wall
solid pipe and fittings, processing aids for polyethylene film
extrusion, sight glasses, flowmeter tubes, laboratory ware
Electrical/electronic electrical insulation, flexible printed circuits, ultra-pure
components for semiconductor manufacture
Engineering seats and plugs, bearings, non-stick surfaces, coatings for
pipes, fittings, valve and pump parts, gears
Architectural and domestic water-repellent fabric, architectural fabric, non-stick
coatings for cookware
As a group, fluoroplastics are characterised by chemical inertness, a low coefficient of
friction, anti-stick properties, excellent dielectric properties and outstanding weatherability.
These properties are the result of the strong carbon-fluorine valence bonding and the
relative sizes of the carbon and fluorine atoms which enable compact packing of the
molecular chains.
Most commercial fluoroplastics are homopolymers and copolymers derived from free-
radical polymerisation of a relatively limited number of fluorinated monomers such as
tetrafluoroethylene (TFE), vinyl fluoride (VF), vinylidene fluoride (VDF),
chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), perfluoropropylvinylether
(PPVE) and, more recently, perfluoromethylvinylether (PMVE).
Traditional markets for fluoroplastics have been the construction and automotive
industries. In the late 1990s, two strong growth areas for fluoroplastics emerged:
communications and semiconductor manufacture.
One of the largest application areas for fluoroplastics is in communications wire and cable
insulation, where the information technology explosion and conversion to fibre optics is
completely changing the form of wiring used for communication and information
transmission. Furthermore, the greater use of plenum cabling (i.e., cable placement in air-
conditioning ducts and open spaces between ceiling and floors), which must meet
stringent electrical and building code requirements for low smoke generation and low
flame spread, has increased demand. There is also greater use of fluoroplastics for wire
and cable insulation due to the growth of local area networks (LANs), the increased use
of cellular telephones and the introduction of high definition television (HDTV) and digital
satellite systems (DSS).
5