Flame Retardants. Practical Applications

306 Pages·4.205 MB·306\306

by  Edward D. Weil and Sergei V. Levchik (Auth.)

Weil, Levchik
Flame Retardants for Plastics and Textiles
Edward D. Weil
Sergei V. Levchik
Flame Retardants for
Plastics and Textiles
Practical Applications
Hanser Publishers, Munich Hanser Publications, Cincinnati
The Authors:
Prof. Edward D. Weil, 850 Sumner Parkway, Apt. 301, Copley, OH 44321, USA
Dr. Sergei V. Levchik, Supresta LLC, Saw Mill River Road 430, 10502 Ardsley, NY, USA
Distributed in the USA and in Canada by
Hanser Publications
6915 Valley Avenue, Cincinnati, Ohio 45244-3029, USA
Fax: [phone]
Phone: [phone] or 1-800-950-8977
www.hanserpublications.com
Distributed in all other countries by
Carl Hanser Verlag
Postfach 86 04 20, 81631 München, Germany
Fax: [phone]
www.hanser.de
The use of general descriptive names, trademarks, etc., in this publication, even if the former are
not especially identified, is not to be taken as a sign that such names, as understood by the Trade
Marks and Merchandise Marks Act, may accordingly be used freely by anyone.
While the advice and information in this book are believed to be true and accurate at the date
of going to press, neither the authors nor the editors nor the publisher can accept any legal
responsibility for any errors or omissions that may be made. The publisher makes no warranty,
express or implied, with respect to the material contained herein.
Library of Congress Cataloging-in-Publication Data
Weil, Edward D.
Flame retardants for plastics and textiles / Edward D. Weil, Sergei V.
Levchik.
p. cm.
Summary: „For several years, the authors have taught a short course on
flame retardancy under the auspices of the Business Communications Corp.
This course has been found useful by persons entering the field of flame
retardancy or who were facing particular problems of flame retarding
plastics“--Provided by publisher.
ISBN 978-1-56990-454-1
1. Fireproofing agents. 2. Fire resistant plastics. 3. Fireproofing of
fabrics. I. Levchik, Sergei V. II. Title.
TP266.5.W45 2009
628.9‘223--dc22
2009014081
Bibliografische Information Der Deutschen Bibliothek
Die Deutsche Bibliothek verzeichnet diese Publikation in der Deutschen Nationalbibliografie;
detaillierte bibliografische Daten sind im Internet über <http://dnb.d-nb.de> abrufbar.
ISBN 978-3-446-41652-9
All rights reserved. No part of this book may be reproduced or transmitted in any form or by
any means, electronic or mechanical, including photocopying or by any information storage and
retrieval system, without permission in wirting from the publisher.
© Carl Hanser Verlag, Munich 2009
Production Management: Steffen Jörg
Coverconcept: Marc Müller-Bremer, www.rebranding.de, München
Coverdesign: Stephan Rönigk
Typsetter: Hilmar Schlegel, Berlin
Printed and bound by Kösel, Krugzell
Printed in Germany
Acknowledgment
Theauthorsgratefullyacknowledgethemanysuppliers,compoundersandplasticsprocessors
whoprovideduswithhelpfulcommercialliteratureonflameretardants.Wealsothankthe
Supresta (ICL-IP) management for providing means for searching patents and non-patent
literature.We are particularly indebted to our colleagues who read drafts of our chapters
and provided useful comments.We thank ICL flame retardant experts,specifically Pierre
Georlette,SieghardGoebelbecker,AviBen-Zvi,YoavBarYaakov,AndyBakerandRonyShamir
for reading drafts and providing feedback. Paul Moy at the Supresta research center had
substantialinputintothePVCchapter,andwasacoauthorofourearlierreviewonthistopic.
Günter Beyer (Kabelwerk Eupen) was helpful on this chapter and on the polyolefins.Dan
ScharfandJimInnesgaveususefulcommentsonthepolyolefinchapter.RonDombrowski,
JimJohnson,Prof.DickHorrocksandProf.CharlesYangprovidedhelpfulinputforthetextile
chapter. Michael Masciantonio (Bayer), Marcelo Hirschler and Jürgen Troitzsch provided
helpful critiques of the test method chapter,Bruce King (Dow) likewise with the styrenics
chapter,andProfs.AlexanderMorganandGiovanniCaminoinregardtoseveralclassesof
plastics.Prof.WeilthanksAnnBolek(UniversityofAkronLibrary)whohelpedhimobtain
scarce wire and cable literature.Prof.Menachem Lewin deserves credit for organizing the
BCC Flame Retardancy conferences which are a rich source of useful information on all
flameretardancytopics.
Finally, editorial advice and encouragement from Hanser Publishers, in particular from
ChristineStrohm,isappreciated.
ThiscoverpicturewasprovidedbyAndrewPiotrowskiofICL-IP.
Preface
For several years, the authors have taught a short course on flame retardancy under the
auspicesoftheBusinessCommunicationsCorp.Thiscoursehasbeenfoundusefulbypersons
enteringthefieldofflameretardancyorwhowerefacingparticularproblemsofflameretard-
ingplastics.Oneofus(S.V.L.)presentedanintroductorylecturediscussingmodeofaction
of main classes of flame retardants and one of us (E.D.W.) presented a survey of flame
retardantsincommercialuseoradvanceddevelopment,discussedpolymerclassbypolymer
class.The present volume is a much-extended coverage of flame retardants from the same
practicalpointofview.Itisintendedtobeofuseespeciallybyplasticscompounders,textile
technologistsandbyR&Dworkersinthisfield.Ourcoverageismainlychemistry-oriented
andformulation-oriented.
Wehavenotincludedflameretardantcoatings,“firestops”and fire-barriermaterials,flame
retardantsforwoodorpaper,andinherentlyflameresistantpolymers.
We have made an effort to reference much of the information presented,but in the many
caseswherereferencesarenotcited,itcanbeassumedthatthesourceissupplier’sliterature,
supplementedbydiscussionswithsupplierswhereneeded.
Contents
Acknowledgment ............................................................ V
Preface......................................................................VII
Contents .................................................................... IX
1 Introduction ............................................................. 1
2 FlameRetardantsinCommercialUseorDevelopmentforPolyolefins......... 3
2.1 Introduction ........................................................ 3
2.2 Generalizations ..................................................... 4
2.3 EndothermicAdditives(MainlyMetalHydroxides) ...................... 4
2.3.1 Alumina Trihydrate (Aluminum Trihydroxide,ATH;Mineral
Name:Bauxite) .............................................. 4
2.3.2 PropertiesofATH ........................................... 5
2.3.3 ATHModifications .......................................... 5
2.3.4 SynergistsandAdjuvantswithATH ............................ 6
2.3.5 MagnesiumHydroxide(MagnesiumDihydroxide,MDH) ......... 6
2.3.6 SynergismofMDHwithZincBorate .......................... 7
2.3.7 OtherSynergisticMDHCombinations ......................... 7
2.3.8 Ultracarb®(Huntite-HydromagnesiteMixture) .................. 8
2.3.9 Talc ........................................................ 8
2.4 HalogenatedFlameRetardants ....................................... 8
2.4.1 Chloroparaffins ............................................. 9
2.4.2 DechloranePlus® ............................................ 10
2.4.3 BrominatedAdditives ........................................ 11
2.5 AntimonyTrioxide .................................................. 15
2.6 PhosphorusAdditives ................................................ 16
2.6.1 IntumescentPhosphorus-BasedAdditiveSystems ................ 16
2.6.2 RedPhosphorus ............................................. 19
2.6.3 OtherPhosphorusAdditives .................................. 19
2.7 ExpandableGraphite ................................................ 19
2.8 Co-Additives;HinderedAmines ....................................... 20
2.9 Nanocomposites .................................................... 20
X Contents
2.10 PolymerModifications ............................................... 21
2.11 BlendsofPolyolefinswithChar-FormingPolymers ...................... 21
2.12 SiliconeSynergists ................................................... 21
2.13 SiliconeModificationofPolyolefinsbyAdditionorCopolymerization ...... 22
2.14 LayeredPolymerApproach ........................................... 22
2.15 SpecificApplications ................................................. 22
2.15.1 WireandCableInsulation .................................... 22
2.15.2 Wood-PolyolefinBlends ...................................... 23
2.16 FlameRetardantElastomers .......................................... 23
2.16.1 GeneralComments .......................................... 23
2.16.2 DieneElastomers ............................................ 24
2.16.3 ChloroparaffinsinElastomers ................................. 25
2.16.4 ZincBoratesinElastomers ................................... 26
2.16.5 BromineCompoundsinElastomers ............................ 26
2.16.6 PhosphorusCompoundsinElastomers ......................... 27
2.16.7 ATHandMDHinElastomers;LowSmokeFormulations ......... 27
2.16.8 ClaysinElastomers .......................................... 28
2.16.9 (Poly)chloropreneandotherHalogen-ContainingElastomers ..... 29
2.16.10 ChlorinatedandChlorosulfonatedPolyethylenes ................ 29
2.17 FutureTrends ....................................................... 30
3 PolystyrenesandThermoplasticStyreneCopolymers ....................... 35
3.1 Introduction ........................................................ 35
3.2 GeneralCommentsontheFirePropertiesofStyrenicPolymers ........... 35
3.3 CrystalPolystyrene .................................................. 36
3.4 ExpandablePolystyreneandExtrudedPolystyreneFoam ................. 36
3.4.1 Hexabromocyclododecane(HBCD) ........................... 36
3.4.2 Tetrabromocyclooctane ...................................... 37
3.4.3 Dibromoethyldibromocyclohexane ............................ 37
3.4.4 OtherBromineFlameRetardants .............................. 38
3.4.5 TheFlammabilityEffectoftheExpandingAgent ................ 38
3.4.6 SynergistswithBrominatedAdditivesinPolystyreneFoam ....... 38
3.4.7 Phosphorus-BromineCombinationsinPolystyreneFoam ........ 39
3.4.8 Non-BromineSystemsinPolystyreneFoam ..................... 39
3.4.9 The Recommended Fire-Safe Use of Extruded Polystyrene
Insulation .................................................. 40
3.5 HighImpactPolystyrene ............................................. 41
3.5.1 Bromine-ContainingFlameRetardantsforHIPS ................. 41
Contents XI
3.5.2 Non-HalogenFlameRetardantsforHIPS ....................... 47
3.6 FlameRetardedAcrylonitrile-Butadiene-StyreneCopolymers(ABS) ....... 47
3.6.1 BrominatedFlameRetardantsUsedinABS ..................... 48
3.6.2 ChlorinatedAdditivesforABSorHIPS ......................... 50
3.6.3 Non-HalogenFlameRetardantsforABS ........................ 51
3.7 FlammabilityRequirementsandTests .................................. 51
3.8 MechanisticConsiderationsasaGuideforFlameRetardationofStyrenics .. 51
3.8.1 VaporPhaseMechanismsinStyrenicsandSomeImplications ..... 52
3.8.2 TheSmokeProblemwithStyrenics ............................ 52
3.8.3 CondensedPhaseMechanismsinStyrenics ..................... 53
3.9 SummaryandFutureTrends .......................................... 53
4 FlameandSmokeRetardantsinVinylChloridePolymers–
CommercialUsageandCurrentDevelopments ............................. 59
4.1 Introduction ........................................................ 59
4.2 Plasticized(Flexible)PVC ............................................ 60
4.3 AntimonyOxideandRelatedProducts ................................. 61
4.4 HalogenatedPhthalatePlasticizers ..................................... 62
4.5 ChlorinatedParaffins ................................................ 63
4.6 InorganicFlameRetardants,SynergistsandSmokeSuppressants ........... 64
4.6.1 AluminaTrihydrate(AluminumHydroxide,ATH) ............... 64
4.6.2 MagnesiumHydroxideandRelatedMagnesiumMinerals ......... 66
4.6.3 MolybdenumCompounds .................................... 67
4.6.4 CopperCompounds ......................................... 68
4.6.5 ZincBorates;BariumBorate .................................. 68
4.6.6 ZincStannates .............................................. 69
4.6.7 ZincSulfide ................................................. 69
4.6.8 CalciumCarbonate .......................................... 70
4.6.9 SmokeSuppressants–GeneralComments ...................... 70
4.7 LowFlammabilityPlasticizers:PhosphateEsters ......................... 70
4.7.1 TriarylPhosphates ........................................... 71
4.7.2 LowTemperatureAlkylDiphenylPhosphatePlasticizers .......... 73
4.7.3 ComparisonofSomeFlame-RetardantandNon-Flame-Retardant
Plasticizers ................................................. 73
4.7.4 ComparisonofVariousCombinationsof PlasticizersandOther
Additives ................................................... 73
4.8 FormulatingforSpecificApplications .................................. 74
4.8.1 CalenderedVinyls ........................................... 74
4.8.2 PlenumWireandCable ...................................... 76
XII Contents
4.8.3 CoatedTextileApplications ................................... 79
4.8.4 VinylFlooring .............................................. 79
4.9 PVCfromaSafetyandEnvironmentalPointofView ..................... 79
5 CurrentPracticeandRecentCommercialDevelopmentsinFlameRetardancy
ofPolyamides ........................................................... 85
5.1 Introduction ........................................................ 85
5.2 Additives for Polyamide 6 and 66 in Engineering Thermoplastic
Applications ........................................................ 86
5.2.1 ChlorinatedAdditives ........................................ 86
5.2.2 BrominatedAdditives ........................................ 88
5.3 MelamineCyanurate ................................................. 91
5.3.1 OtherMelamineAdditives .................................... 94
5.4 InorganicHydrates .................................................. 95
5.4.1 MagnesiumHydroxide ....................................... 95
5.4.2 AluminaMonohydrate ....................................... 95
5.5 PhosphorusAdditives ................................................ 96
5.5.1 RedPhosphorus ............................................. 96
5.5.2 AluminumDialkylphosphinates ............................... 97
5.5.3 HypophosphiteSalts ......................................... 98
5.6 DripRetardingAdditives ............................................. 98
5.7 TreatedGlassFiberReinforcement ..................................... 99
5.8 TextileFiberApplications ............................................. 99
6 FlameRetardantsforThermoplasticPolyestersinCommercialUse
orDevelopment ......................................................... 105
6.1 Introduction ........................................................105
6.2 PolyethyleneTerephthalate ............................................105
6.2.1 TextileFiberFlameRetardancebyMelt-SpinningAdditives .......105
6.2.2 Dihydrooxaphosphaphenanthrene Reactant in Polyethylene
Terephthalate ...............................................106
6.2.3 PhosphinateStructureinPETBackbone ........................108
6.2.4 ModeofActionofPhosphorusFlameRetardantsinPolyethylene
Terephthalate Fabrics and Materials which Interfere with this
Action .....................................................108
6.2.5 Bromine-ContainingFRinPETFibers .........................108
6.2.6 Flame Retarding Polyethylene Terephthalate Fabric by a
ThermosolFinishingProcess ..................................109
6.2.7 FlameRetardingPolyethyleneTerephthalateMoldingResinbyan
AromaticDiphosphate .......................................110
Contents XIII
6.2.8 FlameRetardingPolyethyleneTerephthalatebyotherPhosphorus-
ContainingAdditives ........................................110
6.3 PolybutyleneTerephthalate ...........................................110
6.3.1 PolymericandOligomericBrominatedFlameRetardantsinPBT ..110
6.3.2 PBTwithotherBromine-ContainingAdditives ..................113
6.3.3 PolybutyleneTerephthalate/PolycarbonateBlends ................113
6.3.4 Non-HalogenFlameRetardantPolybutyleneTerephthalate–
PhosphorusFlameRetardantAdditives .........................113
6.3.5 Non-HalogenFlameRetardantPolybutyleneTerephthalate–
PhosphinateSaltAdditives ....................................114
6.3.6 Non-HalogenFlameRetardantPolybutyleneTerephthalate–
AromaticPhosphateAdditives ................................115
6.3.7 Non-HalogenFlameRetardantPolybutyleneTerephthalateUsing
MelamineCyanurateorSulfate ................................116
7 Flame Retardants in Commercial Use or Advanced Development in
PolycarbonatesandPolycarbonateBlends.................................. 121
7.1 Introduction ........................................................121
7.2 Bromine-BasedFlameRetardancy .....................................122
7.3 Anti-DrippingAdditives ..............................................123
7.4 Non-HalogenFlameRetardancy–GeneralComments ...................124
7.4.1 Phosphates .................................................124
7.4.2 OtherPhosphorusCompounds ...............................125
7.4.3 SulfonateSalts ..............................................125
7.4.4 OtherSalts .................................................128
7.4.5 Silicone-BasedSystems .......................................128
7.5 Polycarbonate-ABSBlends ............................................128
7.5.1 HalogenAdditivesinPCBlends ...............................129
7.5.2 PhosphorusCompoundsinBlendsofPolycarbonatesandABS ....129
7.5.3 OtherPhosphorusCompoundsinPC-ABSBlends ...............132
7.5.4 OtherFlameRetardantSystemsforPC-ABSBlends ..............132
7.6 Polycarbonate-PolyesterBlends ........................................133
7.7 OtherPolycarbonateCopolymersandBlends ...........................133
7.8 StructuralApproaches(Laminates) ....................................134
7.9 ModifiedEndGroups ................................................134
7.10 Conclusions ........................................................134