MARCH 24 - 27, 1996

FLAME RETARDANTS - 101:

BASIC DYNAMICS Past Efforts Create Future Opportunities

THE F IRE RETARDANT CHEMICALS ASSQ'CIATION

Pspers Presented At:

BALTIMORE ~w{RIOTT INNER HARBOR HOTIEL BALTUIORE f MARYLAND

-r /) ztt; b r )' 11 /;I'

FLAMI!\l: REIIf'.ARDANTS- 101: BASIC DYNAMICS P'ast Efforts Create Future Opportuniti.es

1996, SPRING CONFERENCE

THE FIRE RETARDANT CHEMICALS ASSOCIATION

TABLE OF CONTENTS

"Flame Retardant Ma.rkets, Products, Regulations, A Historical Perspective"

Louis O. Raetber

Market ing 'Technic al Serv lces fIne ..

"Mechanis.rusfor Flame Hetardancy and Smoke Suppres sian - A Review"

Joseph Green

FMC Corporation

"Fire Test .M.ethods for Fir·e Retardant Polym'ers" Javier O. Trevino

Omega Point Laborat.oriesl Inc.

"Fire Safety Codes and Regulations" Robert S. Strength

FRCA consultant (Product Safety Management, Inc.)

"Flame Retardants and Their Market Applications" James D. Innes

Flame R.etardants Associat·es Inc.

"A Review of Phoaphor'ua-Cent a.i.n.i.nq Flame Reta.rdants'~ Joseph Green

FMC Corporation

.. Chlor fne Containing Flame Ret.arctan t s " Rona.Ld L. Markezich.

Occidental Chemical Corporation

"Brominated Flame Retardants" Mary G. Harscher

Great Lakes Chemical Corporation

"Antimony Flame Retarder Synergists" Irving 'I'ouval

Touval ASSQC La t·es Inc.

"Boroo Compounds as Fire Retardants" Kelvin K. Shen

u.s. Borax Inc.

1

13

31

41

61

11

89

105

117

137

"Mineral Hydroxides-Their Manufactun!:! and Use as Flame Retardants"

William E. Horn, Jr.

Alcoa :Industrial Chemicals

147

.. Engineer ingT'hermoplas tics" * Ari Hochberg

LNP Engineering Plastics, Inc.

"'HIPS/EPS 11 '*

Robert M. Sw,et t

Huntsman Chemical Corporation

ABS &ABS!PC*

Thoma.S L. Eva.ns

General Electric Company

"Flame Retarded Vinyl Formulations: Their Contributions to Fire Safety"

A. Will.iam Coe kez , Ph.D. A Coaker and Associates

161

"Flame Reta.rdant Po Iyo Le fLne r Key Facto.rs in Developing Eng ineer,ed Commodity Res in Systems"

John. Moritz

The Gitto/Global Corporation

171

II' F 1 arnruabi li ty and lola te,r ia1 Trends in t.he Furnish ings I ndua try" Hll Gordon H. Darnant

Inter-City Testing and Consulting

"Future Flame Retardant Tr,ends/Require.rnents 195

at Texas Instruments"

Herb Moltzan

Texas Instruments

"Construction/Federal Requ.irem,ents - Private Needs"-)/:

David Harris

National Institute of Build~ng Sciences

"Future Trends Involving The Use of Fire Retardant Chemicals 21.5

in Wire & C.able Applications ,.

Doug Terry Furon Company

I'Transportation/ Amtrak Design Iii Mat'erialsActivi ties II * ,James Gour ley

Ceasar Vergara

D. Karan

Fire Safety Group/.Amtrak

'"

Papers not available at, publication tim.e

CHLORINE CONTAINING FLAME RETARD.ANTS

RONALD L MARKEZICH

Oedd,ental. Cllemiea[ Corporation Technology Center

Gra1i1d Island" New York 14071

Chlorinated flame retaroanlts can be divided into wee groups: al~phat[c., aromatic, and cyclealiphatic.

The type of organic chJorine compound will determine processing llmltations and, to some extent, the application of'these flame retardants,

Important properties aad characteristics of a commercialflame retardant shoeld indude:

,. High molecular weight; many of the additiveflame retardants in this class have molecu lar

weights above 600.

• High chlorine, content greater than 50 percent.

• Thermal stabm~: greater than 27(lPC for addition to. engineerirrgthermoplastics,

• Nontoxicity.

• White or 1igbt color: many plastics applications require white or light-colored flame retardants for aesthetics,

~ Compa:tibiUty with polymers: once a. flame retardant additive is compounded into a polymer. it must not bloom during use, even at elevated temperatures,

• Low volatility: flame-retardant additives must be essentially nonvolatile; they must not vaporize during processing or evaporate from parts during their useful ] ife,

Iron icelly, one property highly desasble for prccessing-stheemal stabHity=- is not desirable for flam e retardaney, Restated. if a compound is too thermally stable at flame temperatures, it wDU be a poor flame retardant, Figure 1 shows the general relationship between increasing flame-retardant efficiency and increasing thermal stability for aromatic, alicyclic or cycloaliphatic, and aliphatic flame retardants.

Increasing Rame Retardant Efficiency

ft<' ~·t

c-c

I I

H H Ii;

CI

CI

CI

Gl

AnClfCllc

A~liphatic

Jncreaslng Th,e.rma.1 Stability

Figure 1. General relafi;onship between flame -retardan t effldency and thermal stability for the three groups of chlorine-.conlaini:ng .Rame retardants.

8.9

The aliphatic chlorine compounds, which must be processed under ] 75GC

Alipbatic Chlo:ri:oe Compounds

The most efficient c:]3!SS of flame' retardants; the aliphatic ch!orine compounds, is represented by lite chllomparaffms, which are emp~oyed as flame-retardant additives for a yarie~ ofpol)'Mers,. includiIng flexib~e vinyl PVC ~sinkerendly flame retarded by virOO.e of <156 percent ehloriae oom-en~ and rigid PVC is sometimes blended with other resins for this feah.lrre. With plasticizer ,addition ,es.sential for flexible viny~ arppUcartkl'r.!s, however, ~he iralterent flame retardancy is lost and must be restored by flame~retaId.a:nt additives such as antimony oxide, ehloreparaffins, and phosphorus p~astidzers.

Aro;matie Chlorine Compounds

The chlorinased bi- and poly-phenyls arre the prindpal members of the chloroarematic group. The simplest member--deca.chl.orodiiphenyl,--is sbown run Figure 2. These cQ_pounds have never

CI

CI

CI

CI 0,1 (11'% 'QI)

eil

Figure 2. Decachlo'l"odiphenyl, simplest chlol"oar-omatic.

found great acceptance as flame-reta::rdant additives because they are too thermally stab le (F igure 1)"

(::ycloaliphatic Cblorine Com,o'l!luds

The cycloaliphatic or alicyclic chlorine compounds areinterraediate in both thermal stabHhy and effi cn ency, as has been shown in Figure l ,

For die Most part, the only compounds in this group that have re-ached commercial importance are based on derivatives of hexaehloroeyclo pentadiene, shown in Figure 3.

CI

o

CI

CI

CI

CI Het Anhydride (a.50 acid)

CI

CI

CFR "Dechlorane P~ulse;"

Figure 3

90

~ve 'types ,Ofrn.lIere.st ~re center on (hJo:re:nW.c~a:Wlydrlde- or Hct-aerd·!based a~h::yclic cOM]]rnmdis.

H~~o pentadicne is oon:ve:rtOO into fUllCI.100ail dmv,atives by 'reactruo:!!! with UI1saturated. cOMpounds seeh as maleic anhydride to ,gjve~~ het anhydride or het ac[d, The: main eeenmeecial outlet for sllch oompounds OO~ prepru:,atiol1l. o.f ftII;MDe-~atdoo. polyester re~~ns.

Dochloranc Pluill. pNldluoodi by OcddmlaJl ChemiCIl] C,ctpOrOOcm. calmed CPR lA dl~s paper. has been used for year,s as a flame retar:dan~ in valrimas polyme>m, This flame relMdllltco:nt:a~1lS 65% by weight eWoline ~[Id is the o~ chIDori_~ted name relan!!ant that lS stable arough to b~ ~ iathe engineering pol'ymers. The structure I(lf CfR is mown below'.

01

eRR IdQ!'IIU3i 65%, CI

Ffgwe4

To, iMpart :O!am.e ~tiU'dam;yoo, ,:Iaslics. most h4:!logen iIl~. re~ require 'the Ee: (l,f lmUntQQ.Y ,o;.cide as the synagWL CPR can. be used in nylotl!lad epoxies: to :achi'l}ve n$.le retardan~ usimilg synergists ~1;l1 ~W1 ruWmony oxide, 'I"he ,CIlI:Wr S}~tsrhat can. be ~sed ~nd~de Zln\> borate. zjij;C o~e. l.in(;, s~aw. and. the ~nmJ oxides.

1M fR~mliYI.oll Fj)maulialfons shewn in, Tab~e .~ alJ'C alloou dripp~ and. cffer flame rewdantmtmgs or UL-94 v..ij dbwllllO 0.4 1:tlDi" .By us-g Ii!. nUxt:uwe .0£ zinc bomteud .utim.aI1Y oxide with CFR.,a UL.:94 '1,-,0 is oclliewd, "ithjs~ I 22%fR s:ys~em loading. hon oxide,. in ,uombma:lion wim, zinc borate, is the most effective synergist It gives I V ~ nliatenal 'wilth an FR system Lcailing ,of only IS%. The zinc bora.wl.antimony oxide ,com_ion P¥eS· a ma~ Viima CTI of 450 Violts.,. while ilie cn of the iron oxidelzmc boraresysm is on~y 3S0'l!"oLls:.

91

TableI, fR~Ny]on ,66 Using D~ffe:rellt: Synergists

EQllDl! la~i O:ml
(We~gln%) I 2 3 4 S 6
Nyl@n66 70 78 70 70 82 ,8:5
CfR 20 ]6 20 20 14 [2
SbO 10 2
z 1
Zinc Borate 4 10 .5 1.5
Zinc Oxide 5
IronOxide 4 1.5
~rfom1ance

Ul.-943.2 mm (WIn V-O V-O V-o V~O V~O v.e
L6 mm (1/161') V~O Va(} V-o v.o V-o V-o
0"8 mm (] 132.") \1-0 v-a v-o V~O v-o v-o
0.4 mm (Ini4") v-o v.o v-o v-o v-o V~O
II Tensile Strength (MPa) $8.0 67.] 59.3 56.9 7] .6 70.2
(PSI) 85119 9744 8603 :8264 10376 lOli'3
en Kc (Volts) 175 450 300 :3.15 17:5 350 .

#

CFR can also 00 used ~o flame retardant g~3SS reinforced nylon 66 using different synergists, as shawT] in Table 2. The synergist Most often used with the halngenated flame retardants is antimony oxide (formulation #1), which is UL-94 V-O dOWl1lO 0.4 rum and has a CTI of 225 volts. The Z~fIlC synergists. oOf<:lh: <lind oxide, give a m sxi mum en of 375 volts but the flamm abil ityproperties are not as good. The mOS~ 'efficient .syau:r~i:st in th~s case is the iron oxide,providing a ULr94 V-O 00\1l,1[li. to 0.4 mm \!ii'im only 120/0 f arne retardant <lind 3 % synergist,

Tsble 3 shows the results of glass-re irn forced ny~on 66 using mixed synergists. The combination of antimony oxide wuth zinc borate and CFR gives a UL·'94 rating ofV~O down [0 OA rnrn and a en cf350 volts. Using taemixedzinc boratcJiromi oxide system. One obtains a V -0 at 0.4 ram with olDlly 13% total flame retardant loading (tlaJ:FnC retardant plus. synergist),

..

Re 5 u lts 0 f us I ng zinc stanaatein 1;;:0. biaation w ith other syne rgi S·lS and eFR i n grnals~Heinforc~d nylon 66 are shown in Table 4. Wrut:h ~4% of the name re1r.aMaJnt and 4% oFthe mixed synergists, a CTI of up to 41:5 volts and a UL-94 V~O down to 1.6 mm cal] be obtained.

EQrmulatiQn
(W,~~gb~ %)1 2 .3 4
Nylon 66 49 48 4,g 60
I
Fiberglass 25 2.5 25 25
CFR 18 18 1:8 11
Sb,.O~ g
Zinc.Bonue 9
Zi~cOxide 9
I F erric Oxide 3
B!i;rfQml an!;;~
UL-94 3"2 m.m {US") V-1O v-a v-!o v-O
1.6 rnm (U16") '1 .. 0 V~O v-o V-O
0.8 mm ( lif32''') V-O V-I V-I V-O
OAmm (liM") V-O V-I NC V~O
Tensile Strength (Nlfa) ]22..8 1113 9'7,2 983
(PSI), ]7800 175'90 ]4080 141250
I ell Kc: (Volts} 225 375 325 225 93

2, 3 4
4119' 601 ,62
.25 25 25
18 12 10 Nylolili66

55

4 1.$ ],:5
4
15 L5 I. Fi,oorgLass

.25

CFR..

16

Zinc BOrnite

2

Zinc Ox:~d~e

PerfoIDIance

T rII' _ 9Al '2'. ' .. - c. 'l/<lW) UiJl.r - "I .:l<. m.m. \ Q •

~ ,,6 ME (U~ 6,"') 0.8 •• (U32"') 0.4 M. (~/64~i)

Tensile Strength ,(1VtP:a)

(PSI)

! en Kc (Volt'!:)

V~O V~O V~{1 V~O
V-o v-o v-o v-a
v-o NC v-o v-a
v-o Ne v-o V~O
124.3, ]03.3 1 ]2.2 ] l4.4
18050 15000 16260 ]6580
350 375 225 225 'fable 4. FR~Nyl.cn 66 (25% 'Glass-Reinforced) Using Zinc Stannate

.Fcm:mu lalion (Weight %)

2 3 4 5
51 59 57 57 Sf
25 25- 15 2S 25
14 12 ]4 14 4
2 2 2 l
:2 2 2
2 2 Nylon 66

Fioerglass

CFR

Zinc Borere

Zinc Stannate

Zinc Oxide

PedQrmanc@:

Ulr94 3,.2 mm (118 'I) 1.6 mm (1116")

(Mfa) (PSI}

CT] Kc (Volts)

v-o V·O V-o V-o V~O
V-o V~O V-o v.o V-O
123.0 ] 23.3 ]033 r03,7 103.4
]7860 ]7900 15000 ~:506D 15020
32.5 125 275 425 375 The use of CFR 'to flame retard nylon ,6 is shown in Table 5. F omliula!ion #: i ~sing antimony OXlGe synergist, gives a Ul-~M V-O at 1.6 mrn and 0'3! en of 325 volts. By using the mixed synergist techrlol.ogy. form 1.1 lations #2 and #3 also giv,e, 11. V -0 material down to ],6 mrn =but the difference shows. .~[l the en values, with 425 volts for #2 and 375 valls fOJ #1, Formulation #4 demonstrates that zinc borate is not effective as asynergist ~o achieve any' level of flame retardanc:y in nylon 6. But as. shown earlier, when form U larion #4 us usedwith roylon 66,3 ut,..;94 V-O material down to 0'.4 mmis obtained. As is the C,1lSe of nylon 66., the iron oxidesarethe most effective synergistsia nylon 6.

Table 6 snows the use ofthe different synergist to flame retard 25% glsss-reinforced nylon 6.

95

-

FOJimJu~art~(mj
{Weight %) I 2 :3 4: S
NyJofl.,6 73 14 76 70 75
CPR ]8 21 16 20 20
Sb~O~ 9 25 6
Zinc Borate 2_5 2 ru,o
Iren O:dde 5
Perfomn;;m.oe
UL-94 3_1 IIll1:t (US") V..!O '1-0 v-a NC v.o
1.6 rum (1116") v-o v.e V-D NC v.o
Tensile Streng[h (MPa) 47.4 50,,1 51Ai 52.,6 52.,5
(pSI) 6869 7150 76Hl 7606 7026
CTI. ICc (Volts) 325 425 375 NA 27 96

Table 6. FR-Nylon 6, (25% G]3iSS-Reinfotted) Using Different Synergists

f'Olmly)atiO!
(We~~t%) 1 2 3
Nyfon6 51 51 54
FiOOrgLass 2-5 25 25
CFR 16 16 16
Sbz°3 6
Zinc- Borate 2 6
Zinc Stannate 2
Iron Oxide .5
.Ped'ormanoo
lJL..94 3.2 rum (1/8") V~O V-o v-o
1..6 mm (1/1611) v~ru v.e V~·O
Tensile Strength (MPa) 116 114 86
(pSI) 168,80 rn658,O 12540
eTI Kc (Volts) 32.5 350 200 97

CFR 'CM also be used to flame reGm:l elhy~e v.irnyl aoota~ lEVA) wire aad esble materials. '1l.esc P,REVAfmrmilatioos ~'D. in Tsble 1 and have dlJ.u-forming M.d Ron4rippimtg c~!'!:ncs. Po~ylene may 00 wOO ~ a Sin:'liWM formulahon ~o gffive n .i1allleretaffied, mattrialw:lth an crXYS9 mdex. ,of 2TVo,. \\iti,ch amso eM pass tffile UL-44 VW ~ 1 flame rest.

Tab]e 1. FR.-EVA W&c

fomndation ,(YIeight %)

.EVA

CFR

Tra!IlSliiM.-31 (Clay)

1 :2
41.9 ,4,7..9
25.0 18 . .0
5.0 9'JII
20.0 23 .. 0
0.1 0.7
L4 1.4 Tensile Str-e-ngth (lvWa)

(P'S])

98

27 27
pass pass
rn.2 .. 1 14.0
Ul46 203·4
298 262 NmJ\daltkllJ (parts)

EPDM (Nomel. 2721 [Dupon~])

90

20

CFR

33

12

Zlne O:dde

5

2

Leperox 50G-R (P~rmdde)

Ox.ygen Index. (%)

3

26

UL 44 VW-l Harne 1',e.s.t

pass

frvtPa) (.PS~)

~ 1.0 ~,600

Elongation (%)

290

When using eFR to fleme retard glaas-reinfcreed P.BT~ one ~ey 10< achievw~g lew levels of flame retardents is usiwg Teflo:l1li 6C 101 stop dlrillpp~n,g.Fo:nnulat~on #1 versus it2 shows ~heaffeet oHU % Teflon. Only 8% CPR with 6%illl.lwmofiY oxide .-d. OJ% Teflon g~ves. a V-O maool.i.al down to 0"8 mNi. Formulations #3 _d #4 do no~ use l'e1flijD bllllt use~. di.ff~rle'n~ mmlo' ofCfR ttl Mt~n:tony oxide.

99

Table 9. FR-.PBT

EO[N,Jation (Weight%)

2

80.9

PBT

l5.75

15.2

ern

5.25

3.8

Teflon 6C

0.1

e.t

PerfQIDIance

UL-94 3.2 mm 0.8") 1.,6 mm (U~6 H) O.S mm (1!32M)

v-o V-o V-o

v-o V-O NC

{MPa) (PSI)

Tensile Strength

41.2 6848

47..2 6844

Table 1 u FR~.rB,[ (Glass-Reinforced)

EQirm uiatjQ@ (Weight%)

:2 3 4
S6 55.9 S:6 54
30 30 30 30
8 8 1 ] 1.2
6 6 3 4
I)J PBT

Fiberglass

CFR

Teflon 6C

Ul~94 3.2 mm (J IS") 1.6 mm 0/16") OJ~ mm (U321~)

v-o V-I} V-o V-O
V-ON~2 V~O V-J(I V-O
V~2 V-O V-I V-O
98.9 98.7 ]03.2 100.0
14340 U300 14960 1452,0
150 250 225 225 Tensile Strength (MPa)

(PSI)

I CTI Kc (Volts)

100

Table 11 shows improved FR.-polypropylene fomulations us~ng SFR-I 00 as a co-synergist The use of this silicon material lowers the level of tke flame retanftlant package by ,6 to 7%.

Ta.b~e n, FR-Polypr-opylene

Forum Ialian
(Wdght%) ] 2 3
Polypropylene S5 ,61 I 62 I
CFR 35 I 30 28.
I SbiOJ 4 6 ,6
Zinc Boraee ,6 4 2
SFR-]00 -- I 2
Pe-rfo:nn ance
UL-94 3 .2 mm (]/8."), v.o V~O v-o
1.6 mm (11]6,") V~O V_,O v-o
I
I Tensile Strength % Elongation 25 I 23 4fl .un

-

1 :2 1
HI is.s 19'.5
5 _j
2
6
.5
2 . .:5 4 S
!.9.S 7'
2.5 1 eFR

5

10

Iron Oxide I(Red)

Zinc EI orate 415

Am

6

E:erform Inee

26 27 29.5 28,.:5 30
v-o V""O V""O v.-o V~O
600 600 32.5 350 375
Mite Red YeUow Y,dlow Y'eHow lJL.94 3.2 mm

eTI Kc (volts)

I Co~or

The epoxy used was lipan 828.&om SheU ChemicaL The coWiringage11l~ was trieayh,~~e-retraMi1te (TETA)a,ta 13 phr,

102

ne :~o~lowhl1g three tabl~ are I!Jpp]i!~tlm15 of chlQrifla;tm p3in.lJffii!i!s. c,~ 70 rOO~tains 70% CI, Md Cf76· contaiss 74% C1.

.Additilf'e;

I'woil

CP-70

20 .. 2

6.9

'9.3

Red Iroa Oxide

.AIItl.o:ny Oxide

4.8

]0

6

'9J

T;otal. So~id -.5 G%in Minern] Spirits

103

TaMe: 14. FlU1J.eRewdmlt P!:>lyelhyle.ne Using CP-70 and CP-16

AddiU",-CJ;.

CP-10

rua;t&mQrry Oxide

1 2
66 n
24
20
10 8: UL-94 ll8" (3.2 mm) I Oxygeon ll1dex %

I PlliIysi.cal. Propeg;i.es Te:tls~~e Strength

(MPa] (PS~)

Heac Distortion

2M psi 66 psi.

v-a

2,4 .. 0

HU l-t·60

10.7 1548

40'lC 50~C

31DC 48~C

Addli.t~ves

PotyP.ropyl.ene

CP-16

Antimony Oxide

I 2
62 60
27' 29
10 10 27 .. 6 4{WO

27.0

StaJbiliz:u

UL-94 liS" (3.2 mm) Oxygen Tndex %

27.0

Physica] Propcrties

Tensi~e Strength

(MPa) (PSI)

10·4

.BROMI.NATED FLAME RET,ARDANTS

MARY G~ HARSCHER

Great Lakes Chemical Corporation west Lafayette, Indiana USA

INTRODUCTION

Since it was first isolated in 1825 by A. J. Balard(l) , the manuf act.ure Q f bromine and bromina tea organi c compounds have evo.Lved simul taneouslywi t h the identification and growth of end-use markets. Simple organic alipha.tic and aromatic compounds can be readily brominated. The discovery of app Lt ce t f on s for these brominated compounds in ,a variety of industries has created a chemical industry around the isolation of bromine and the manufacture of broad spectrwn of bxorai.nated compounds. Applications areas for these compounds include reactive intermediates, pharmaceuticals, fuel additives, drilling fluids, agricultural chemicals, and wa.ter t rea tment chemicals. Our focus here is bromina ted flame retardants, which in 1994 accounted for 47% of the global bromine consum:ption(2)~

The evolution of the fire safety codes is the driving force for the use of flame retarda.nts. To meet these codes var Lous :f 1 ame r et.ardant cherni cal s a.re formula ted into a myriad of organic polymer systems. A diverSified growing flame retardant chemical industry has resulted. The demands of changinq fire codes, safety new processing requirements and new finished property targets in these resin systems ensur-e a continuing need for new flame r et.ardant formulations. Th.ese new opportun.ities will require development of new brominated flame retardants. This review wi 11 id,enti fy maj or c l as ses 0 f commercia.lly a va i Lab l e brominated flame retardants and their uses.

BROMINE EXTRACTION

Bromine is found as bromide salts in brines and in the ocean. Inland brines, have higher coricen t rat t ions as do was te brine st.reams from potash pzcduct Ion and waste bitterns from salt production. Concentrations vary from grams per liter in these brines t.o less than one gram per liter in t.he ooean. The development of an efficient process for bromine extraction is credited to H. H. Dow and K+ Kubierschky(3).

10.5

.Brines are hea.ted to approximately 90t'OC and chlorin.e is used to oxidi.ze the bromine ions. There f'o11owsablowolllt procedure depending upon the concerrt.rat Lon of the source brine with steam or ai.r to sepalr.at.eelem.ent.al bromine fr,om

the brine(4). -

It is eas Le r to ship bromina ted compoundsend, there fore I the el.enen tal bromine is often conve-cted to. br-omi.ne containing compounds near the sight of the· bromine

ext.ract Lon .• Therefore Great Lakes Chemical" Albemarle and .D8ad 'sea. Brom.ine, who accoun tfOlb 95% of thebrom.ine

product ion in the world, have hromi na ted. flame retardant or bromine de r i. vat i ves manuf act.uz; ing s i t.es at or near their bromine manufa.cturing facilities (5) .

CQMPANY

SOURCE

Table 1 BROMINE PRODUCERS

Great Lakes Chemical

Well brines

Albemarle

Well brines

Dead Sea Bromine

Sea Water bitterns from salt production.

Well brines & seawater

Former USSR State Owned State Owned

'Tosoh

seawater

El f .Atochem.

seawater

La.izhou Bromine

Well Bri.nes

Dow Chemf cal,

Well Brines

( 6)

106

Fire in the vapor phase is a free radical process involving H* " OH* I 0* and HO:;: 'llano many others. Brominated flame r,eta.rda.n t s act in the vapClr phase as free radic.a.1 traps (Figure 1) (1) .

CCIIIIJIJS11(IN OF GA$EOI.lS m'DfIOCMElORS

• (III ... ACIU, 4 )Ii m::ta .... II2CI

RCItiI' ~'.OI 1:.,4 RCHO"+ '.

IlIIr

A ~ ,ar.

4) RCIit2 '''1iIBI A" IDD ......

FigiUre 1

T:he polymer substrabe has a t.empez akuz-e at which it will ignite with the application of flame or auto-ignite without direct flame con.tact. From the above mechanism the b~ominated flame retardant must release the bromine into the flame front '. Th.e most e,ff,ecti,ve flam~e r,eta.rciant for a.

part icula.r organic pol ym.er system wi 11 re Lease the bromine ear lyin 't.he fire scenario, as th.e subs tcat e is beginnin'g to burn, If the bromine is r'sleased lat'er it will be much less effective.

'rhermogra,vim,etric ana lys ls {TGA) is one w.ayto n::pr,esent t.he tempera.ture rang'8 .averw.hich the bromina.bed flame reta.rda.nt decomposes.,

107

ThermograVimetric Anal~s~s

WI!I~I!ht,% 1~~~~~~"~~~========~====~ ~HBCD

-l'BEltPA

-DB~DPO

- TIilBPAPE

-POBt;

H '.-,.- -'-- -.----.--.--.--.- ..

20 -.--.- -- -.-- .. -~-.--~ -"-.,- - --.--.-.-- ..

~. IHBCD

oL_------~--~~~~~~~~--~

" 100 200 300 400 500 700

Temlleralure (C)

I"iqu.re 2

The majority of th.e bromina.ted flame retardan.ts deco.mpose between 200QC and 400QC. This range correlates well for the ignit.ton. temperatures of a broad spectrum of' organic polymer systems.Ca) The selection of flame retardants for an organic polymer system often involves matching the decomposition temperatures.

Figure 2 shows the 'temperature ranges wh.ere significant bronu.ne release occurs to r five different hr onu.nat.ed flame retardants. For a res.i.n systemwhicb bas a low .ignition temperature such as polystyrene o.r polyolefinj choices might include hexab.romocyclododecane (lIBCD} or tetrabromobisphenol PI. (TBBPA} as pot entLall y the mos t e f fie Lerrt • Polydibromostyrene (PDBS) would likely be more appropriate for materia 1 s with higher i gni t ion temperat u.res such as nylon.

The TGA data in Figure 2 also is a guide fOr"" selection of flame reta.rdants where the resin. system is thermoprooessed. such as in compounding of a thermoplastic or curing of a t.hermoaet . The .bromine mus 1: not be r,e leased from the bromina.ted flame reta.r-dant during t ha.t processing.

108

''r.here.fore one would .not use BBCD in a nylon whi cb peocee sea at 240°C - 300~C. PDBS has sufficient thermal stability ~or nylon p~oce8s~ng temperatures •

.l[ tis a common p.ra.ct i ce to u.s.€' s yner- g is t s in f o rrnu I a t; i ons to improv'8 tne f lamma.hi 1 i ty pe.'riormanc'e 0 f bromina ted f 1 arne r€ta~dants. The most broadly used synergist for brominated flame retardants is antimony trioxide(9).

BR.QMINA.TEDFLAME, RETARDANT'S

One view of bro'iO.ina.ted f l.ame re t ar dant s Ls that their funct.i,on. is to c,arry the ac t i ve component, bromine, in tea. formulaticm,. Conceptually one would look. fo.[ molecul,e:s W'h.i.ch, might car ry the hi ghes t we i gh t pe rcen t 0 f bromine in a usab.Le form which would be incorpora.tedas an additive. Representatives of this type of family are shewn in Figure 3{(0)<.

Br IBr Eiir I~

' ... ~. ___X_.O·.·.·.... .".__/R\_.O .. · •·.• .. · •.. ·· .. r OO>CtlbroModiphi""~ 'O!lill1o: ... _ M .. ~_~~,_ [] "!~ OJr 8;'U MP' 30!i1~l5 c

IBr Br Br !iii!'

~o~

.~ 11

Octttll!'@m.(H!li[l)h.llm1yl OlI'.ida O/~ Oil: 71U, Mill 7\1lI-~!JjB C

~~

~ y

(,1It+1I"!i )

Penb.br'OlflQd~,hiQn~ oxIIde ~~ Sf 71'1.:8 U'll1! id

Figure 3, Diphen.yl. Oxide

Pentabromod.iphenyl oxide is us ed in pol yurethane .sys t ems where a. liquid additive is desirable. Oct.abromodiphenyl oxide is used in acrylo.nitl'.ile butadiene s t.yr ene copolymers (.ADS) as itmeltble:nds Int o the resin giving better physica.l

properties. Decabromodiphenyl oxide is used for polyethylene baoaus 8: of the high bromine cont.en t .. This f' ami 1 y of f Lame retardants is used in different applications ~ased on their unique features.

109

Another approach is to brominate a. reactive building block of the polymer. ,An example bisphenol A can be

brcmi.na ted. to make tetrabromobisph€:nol A ( Fi gurelJ! ). '["his is reacted in to epoxy res ins commonI y us ed in cd.ncui, t boards o.r used. in ABS s ys terns as an. addi t.ive f 1 arne retardant. It is further converted into families of brominated epcxy oligo.mers and bromina.t,ed carbonat.€: oligomers. These a.re used ina variety of thermoplast.i.cB fr·om. .ABS to po l.ybuty'l ene terepbthalate IPBT). Other aerivatives ~nclude the bis d.lbropopropyl ether deriv8i.tive to efficiently flame r,etard pol ypropyl erie ( PI?) .

TlOItfabrolmobrlllphQno~ A bi8(2,3.-dibr~mo',ptoPJII ,athQ~)

,.. Elr 67,7 MP 9.100 C

Br

Sr TBP

C H2 =©_ ' ... 0"'0"':::;::

B,rJ

Tetra'brom.Qphthaii.c lBS

Anhlmlr~de

Figure 5 Reactive

liD

\

Other react! ve f'Lame retarda.nts commer ca all y ava.i 1 ab l e are shown in Figur,e 5,. One 1.9 tribromaphenol which is a. reacti VEl: building block for a family of flame retardants including an oLi'gome'r used in nylon and a phenoxyebhane de I' i va ti ve fc)r more TN stabl'E! styrenic appl icat: ions 't Figure 6).

PoEy-dibromt'!phQllilyienfi Oxide

% Sf' '62.0 MP21 0'-240 C

Bromostyrrenics, d.ibromostyrene (DBS}, and tribromost.yrene ,(TES), can be copolymerized, horaopo Lyme.r Laed, or grafted to various resins. Reactive flame retardants remain the focus o:f developmental programs for at broad spact.rum of pol ymers and app lLcat.Lons, Putting the bromine rnt;o the backbone of an, organic polymer sys t.ems patent i ally 1 ead to bet ter physical properties, processabi I i ty and per forraance , A. family of brominated polystyrene flame retardants are u.sed in nylon and other engineering thermoplastics.,

Pentabromoacrylate is a reactive flame retardant which could be used as a building block for the creation of new :flame zet.ardarrt s or copolym.erized into a.polymer backbone. '']'h,e homopolymer is proposed for use in the rmopl a st Lc polyester and nylon.

'Tetrabromoph t heL Lc anhydride is reacted into the unaabur at.ed polyestler by the re s i.n supp l Ler to CT'sate 131 b!>omina ted, resin syst.em ( 11). It is al so the key bui Ld Lnq bl,ock f,or additive type,s shown in Fi,g1l.lre 1.

111

~.*Br ~'

Bra c .. oc. H2. c c H. ,OCH,CH,oH

H_ COCH2CHC'HJ,

01 II I

_' 0 OHI

Totrabromop hthal'ate d j,DI % Sr 46.0 UqUid

a-oco.Bro 0crg.... .0. lif Br

r. .. ...N-CHP'l2-N .. .... .

Hr·. ...... / . . Sr

- " -~ ~

Br 0 0 8.r

Elhylonobicftotmbromophth:al ~miklo % Br 67.2 MP 445-458 C

Figure 7 Te,tr'ab,ro:moph th,alate Deri va. ti yes

The diol derivative finds significant use in rigid polyurethanes. The bisimide derivative is used in

pc.l.yo Lef.tris , st.yrenics and 'fiBT where bloom, uv stability or thermal stability are required. There is also a phthalate ester derivative finding use in PVC wire and cable applications.

Figure 8 shows two aliphatic materials with significant uses, HBeD and dibromoneopentyl glycol {DBNPG).

Elf I

Br c-c Bf

-" 1 1,

c-c c-c

... !-~ c-l

lar - 1 I"er

C-C-'Sr

Hexabrom:oeyclododeea,ne % Dr 74,.7 MP 18&,197 C

CH20H II

Brirt!C 4-CH20H

CH28r

DiU) rn mooeope my I g'l:ycol % Br 60.5 MP 109 C

Figure 8 Aliphatic

112

Aliphatic bromine generally releases from the mOlecule at lower temperatures than aromatic bromine ~ HBeD is successfully used in expanded polystyrene ...tow' temperature release Ln polystyrene foam. res'!]] ts in high efficiency. Peroxide synergists can be used as part of the system to hasten the degradation of the polyme~r.

DBNP{i is reacted. into po lyurethanesiillnd unaat; u.ra.ted polyester systems. A mcno funct.Lona I alcohol., tribromon.eopen.tyl alcohol, TBNPA., is al so ava.i Lab l s ,

Many of tbe abcveraa t er La La, whethe'lL reacted into, the polymer ,ori.ncorporated into resin systems as additives, are used in comb.i.nat.Lon with other flame r et ardent.s , These are often based upon phosphorous, chlorine, boron~ and/or anhydrous minerals to meet specific performance needs.

The body of formulations kn.owledge and the changing needs fO.r flawnability and pr'oper t Les of the f Lnd she'd goods provide t he 0PPo.rtuni ti es fo r future f 1 arne r'e tar darrt s . Brominated flame retardants will continue play a significant role in that future.

MANUFACTURERS

The list of hrominated compounds used E:I.S fLams r at ar dants grolws as new requiremen t e -are identified in tbe

ma.rke tpt.ace . Table I I shows some 0 f the ro.aj or bromtnat eo flame ret,E:i.rciant supp.lt.er-s . Some are velrtica.lly i.nt,egra.t,ed. back to the extraction of bromine while others see opportunitHls from t.hei r raw materials base or their

techno logy base , Other compan i.es , such as FMC, not included in this list see opportunity in offering in single molecules the combination of b.romineand phosphorus.

This is the. le.raJ. of globalization wherlethe compounding or fo rnlula.t ions creve lopmen t may ta ke pI ace in the same community or in another part of the world. The suppliers are continually challenged to respond to this globalization while remaining responsive to regional requirements.

113

(' 6)

'T',able II

Bromipa.t,sd. pllameR.etardillot :lhl.pplis!rs, Great Lakes Chemical Corporation

Albemarle

Dead. Sea Bromine (JUne,ribrom)

Ferro

I •

El t' At.Qch.em

DIC

DKS

Teijin.

Tosoh

Supplie,rs gen.erally offer formulations recmnmendatio.ns for use of their flame retardants to achieve certain levels of both flaImirlability and ot he.r pez fozmance criteria. It is fI"om the. dialogues among the. end-user, the formulators, the regulatory bodies and the flam€! retardant manuract.ur-er s that new oppo rtunt.t t es ari se , A change in availa.bili ty of a resin such as polycarbonate or other k~y raw material such as glass can cause a sh if t in demand. fOlLa, specific type of flam.e retardant. Manu.facturers remain alert to. these changing demands and continue to participate in this ever changing marketpiace.

114

1. Jolles, Z.E./Edt~ Bromine And Its Comeounds, pp3, Acad.em.fuA:= Press, New York,. 19"66.

2. Lyda.y" .P. A. i tlB,romine Annua.l .Revi.ew 1994, ill ppl, U. S . Uepartment 0 f the Inter for Mineral Indus try surveys, Washington, D.C~ 1995.

:3. ,Jo,ll,es I Z. E,. I Edt .. Bromin,E! And I cs. Compounds $ pp2 (}I ~ Acao'emicPr,e.ss I - New y,ork, 1966.

4,. Bromine, pp119.1000C,. Chem.ica.lEcono.mics Handbook, SRI

International~ 1995. .

5. Lyda.YI P . A., uBromin.e .Annual Revi.ew JL 994 it, pp l, tlI • .s . Depa.rtment of the Inter.ior Miner,al Industry surveys, Washingtonl D.C. 1995~

,6. Bromin,E!'t pp719. HU::UJE-H,. Chemical Economics Handbook, SRI

Internationalj 1995. .

"l , Lyons, J. W ., The Ghemi.s try And Uses Of Fi ire Retairdan ts ,. pp15, Wiley~IDterscience, New York, 1970.

B .. Cullis, c. F.,. nBromine conpounds as Fla.me Reta.rdantsiJ, P~acedin.s International Conference Fire Safet, pp310,

'9 ~ L.yons, J.w .. , 'Tbe Chemi.str And Uses .of Fi re Ret.ard.an.ts,. pp17,. Wil€!y-Int.eI"s.(~]_ence, New Yor' I _

101. Nametz~R~C., uBromine CompourrdsiF'Qr Flame Retarding Polymer Compositions Part!: Thermoplastics If, Plastics Compounding, pp2 6-3·9, July/August f 1984.,.

11. Nametz, R, C. r "Broml.ne Compounds For Fl ame Retarding P'olymer c.ompos.i t rons P,8i .. rt! I: Thentlo.sets'~ f Plast.ics - Compoundin.g,. pp54-'6,6, g,eptember/October, 1'9:8·4 ~

115

\

------ ~--~~~~~~~~~~~~~~~~~~=======--

BORON COlVIPOUNOS AS FIRE RIEl' ARDANTS

K K SHEN, Ph.D. and D. J. FEIUvI U. S. Borax Inc.

20871 Tuurney RJd ..

Valeucia, C a]ifumia

~NTRODUCTION

B oron compounds such as borax and b erie acid are wen known fire rerardanas for cellulosic products (1,2.). Howeves, the use orb O:llon compounds such as zinc berate, ammonium pentaborate, boric oxide, and other metallo-b orates ~n the plastics. industry has become prominent on]y since the late 1970's. This papew Mil review the manafaemring, cbe.rruc!.dand physical properties, end-use app]ic.ati,ons., as weU as mode of actions of major in o'l!:amic boron compound s as fire retard ants,

TIIE ORIIGIN OF BORON

Boron. is present in the earth's crust at alevel of only 3ppm, but there are areas where it is ccnceotraeed as bo rate salts (saJ]t of oxidized form. of elenlerrutlllW b oron) in substantial. volume FOT..wmng. The United States, and Turkey supply 90% of global borate demand. U_S. Borax Inc.ithe largest U.S. borate prodacer, operates an open p~t mine and rdinery complex at Boron in the Mojav1e Desert of California. The princ~]lal minerals in the deposit are tineal and kernite rr.abrne I} u. S. Borax produces so diuHI. borate products (borax decahydrate; pentahydrateaad anhydrous borax) from tineal ores. Ke:rnite is used ~o produce boric acid and boric oxide. Et~ban k, a. state-owned Turkish mimnga!rld baddng group. effers burate rnsnerals (colemanite and ulexite) and. refined berates.

THE PRODUCTS

Table II lists properties and applications far various types of berorr-containing fire reta rdants,

131

Bor,a!X Pmtahyd rate ( NalO· 2B;;iD1· 5"20 )~ Commerc.iaUy b OfaJX pentahydrate is produced by c<1IfllwnuonaJ eootraction and reerystallization from the sodium borate rninera:l~imcaffi

( NalO'2BtCb ·10IhO). Due to its low deh.ydr3i~ion temperatnre and water solubl~ity {4.4%)j it has been used mainiyllISa fire retardant in ,c;e~~u]os~c products, (F~g. 1). Its u seas a 'ririe retardant in urethaeefosms was also reperted in seve:r~ patents (3). The anhydrous form of the mil!~eria1 ( N a,zO· 2IbOJ) is also coramercially availabte, bu~. its pctentielas afire

il"letllifil! .. t inplasl!ic.s has, net bee~ fully explored.

138

Boric Acid" B(OHh )- Boric acid is an important precursor ofodiler boren-containing fire retardaets, It is p~oduood by reac~~nga borate onerail such as keoote I( N aliO- 2E:203 -4H20 ) or cole~mllirut.eMm sulfuric acid.

Due to its loW' dehydration tJem;p eratuee and wa~e:i so.~ub~~~~y (41.7%,)' boric add is mostly used as afire retardantin cetlulos.i!c pm ducts saeh as eellelosic insulation. cotton baJuing, and medl~um density fiberboeed Its use in ulie·th~ne foams has WSiO been reported.

:Boric Oxide (13.203)- Boric oxide, abo known as anhydrous boric acid, is produced commercially by calcining boric acid. This msterial has been reported to beaa

260~· 300 -c

2B(OHb---~

eil[ectivlc fireretardamt ~n le~gjnoodng p~astics such as hiigh impact p o~)'sty:iene, polyetherketone, and polyetherimide 1(4). MO[1e recently, boric oxide, when usedin conjunction with Fled. phosphceous, was al so reporred to be rut effectivef lie retardant in fiberglus reinforced nyrnol1l 6~6 (6). Boric oxide softens at ~bOllt 325 0c. It is, however, hyg~osoopic 3111d can aJlt~oib wateraad revert back to boric acid butwithout losing its fire n~lardmJt efficacy.

Djsodium Oc~abma:te '[_etra:h~drate (' N.a.~O·4Ih!D3·4H10)- This sodium borete ~s produced fto,"'~ a SIOhJtion (Jf boric acid and borax. Hi s all amorphous material and 'thus can be d:i.ssdved into wa~er mpid1y (soLub~~~ty 9.1wt.% at room tesnperature). Itis used mal]n]y as a fire retMdanrt for cellulosicmaterials.

.Ammo~ilJlliI P,entaib orate ( (Nlt):iO· 5.B·lOl· 8HJO )- Tbe produet cam be produced by read~ng ammmruium hydrolxide and boric acid. I~ has been used as a fire retardant m.ostlyi n urethane foam and epo'x-y. This material releases its w,ater of hydr.a:~ion beginmng at about ~20°C :Ind. releases aenmonia beginning at about 220°C (piS. 2). Its usage ~n polymers, hCllw'ever~is limi.ted by its high water sO]IU~bj]ity (~0.9%) and low dehyldr.am~on tempellalure"

,Barium MetaJbor2!~e ( HaO'Bi03'H10 )~ It caffi'l be produoedfrom borax Mldi barium su]fide~ Mid finds use primarily as a corrosicn il'illhibitor and fungi.s~a.t~c pigrnelilit ~n coatings, ThJ s material is also clammed to be afire retardant ~n plastics, but i~s efficacy ~s not aJS good as that of zincboeases, Its usage ~n pi astics isalso limited 10y its low dehydfa:~i(Nltellllperatuife (200°C).

Zinc Berates- This ~s the most important class of b oron compcunds used as ,~. fire retar-dant in~ihe plastics :and rubber ~mldllJ:mies, Zinc borate was the esseeti all ingred~ent m a. US Navy linseed oil-based fireretardant palot specification. during Wodd War n,. but thereafter this use Japsed un:t~~ zinc borate of differing eompositienwith a much betterthermal stability became oomme:rcial!~y avaihilb~e_

Zinc borate is commercially produced by reacting ei~her boric acid or sodium bonaewith zinc oxide. Depending om the reaction coeditions, a host of zinc berates with d~ffe:rent mole ratio of ZnO:EhO;3:lhO CUI be produced. in ,ekly 1'970~ U",s.Borax diseeveredaad pateeted a unruque form of zinc boraue with aJ. mo~ec'lJ.lar formula of2ZnO· 3 BzOj' 3 _ 5"20 (or 4ZnO·,6BtOJ·1f[20) (Fig. 3), In contrast to other commerda] zinc berates such as 2ZnO·2BzOJ.·3H2Q, it is stable u.p to 290°C MIdis suitable fur use even in engineering plastics: suoh assylons (6-9).

Recently U. S ,. Borax dlscovered another unique zinc b orate- 4ZnO' B2,03, -HiO - which is &tab~e up to 4f ~ 5 °C aad suitable for use in eng~neerirng plastics processedet temperature above 290°C (to).,

FtRE RETARDANT lME-CHANISM OF BORON COMPOUNDS

For ,ceUu~os~c systems, borate fise retroFd~Fllts (such as boric acid, borax pel]!ta!ll:Iydrate. and di sodium. octabor,a~e teiuahydrate) act by endothermic release of Wi3Itf\f and melting to form scdium boraee or boric oxide coating, Chemically. b on-rutes aIDso can react wilth the C6- hydroxyl group of cellulose polymer to give a borate ester and blocking the release of flamm ab~e C-6 fragments, In addition, dehyd.ration of atcohol s is enhanced by boric add> which aeeounts fOf the larger 'q uan:tfu~ies of char produced when borate tre-ated cellulose is burned.

B eric oxide! or any precursors such as boric add wbich can form boric oxide under fir,e conditions, is weill~ known tcredoce aftergrno,w eombusnons. It is geReir.ailI~y believedtbat boric oxide,3i low melting glass, can cover the char and inhibit oxygen permeafion, and thus prevent oxidat ion ofthe Cl:ulf. Another school, of thought belseves that effectiveness of bowie

139

ox! de in aftergJow suppressi on is related to its high ionizati on ,energy/Qf electron &ffinity~ active sm~es for oxygen ad serption on the char surface may be deactivated by boric oxide vi a electron traasfer (11) .

. Ammo.urn pelnltab orate, upon then1lla] decomposition, can evolve large amou~~s of water, a:rnmOr:l~a, and boric oxide which is a glass former .. Ammonium penraborMe funerioesas both an inorganic blow~ng a.ge,n,t and a glass forming fire retardant.

uo - 450°C

2NH3 + 9fbO + 5B201

ZiQC borate, ~n halogenared systems such as flexible PVC, ~:s, know!1to markedly increase the amount of chali formed during polymer combustion; whereas the addition of antimony oxide. a. vapor phase flame retardant, has little effect on char formation A..naJysis of the char shows thet about. 80'~95% of the amimony is volatilized, whereas the majority of boron and zinc from the zinc horete remain irnthe chaJI (80 and 63%, respectively) (] 2)_ The fact that the majority of the boronremains in the condensed pbase is in. agreement with the fact that boric oxide is a goo d afte:rg~ow suppressant, The zinc sp eeies remaining in the condensed phase can alter the pyrolysi so chemistry byc~tllllyring, the dehydm- halogenation and promoting cross-linking, re su~~~ng in increased char formation and a decrease in boOth smoke preducti em and Halring combustion. The bode oxi de released cam promote the formation of a strong char and, more importmt]y, can stabilize the char,

In halogee-free systems, it was reponed that zinc borate in oonj u nction with alumma trihydlrate promctes the formation of a perous ceramic residue during polymer combustions. Thi s residue is an important thermal Winsu later for t he underlying substrate or unburned polymer. Both D,itIer'emI~ial Scanning Ca~orimetr:ic- 3Jl.d Differential Thermo gravimetric ana~yses. as well as char yield analysis suggest that pastial :rep]acemen~ of alumina trihydra te with zinc borate ina halogen-free polymer such as etbylene-vinyl acetate 'can favorablyalter the oxiidil!ltffive-p)'fo~ys~s chemi stry of the hadoge]}~free base polymer (7)_

PRODUCERS AND TRADE NAMES

140

T ab1e 1m 1i sts maj or U _ S. producers and trade names of boron-based fire retardants,

REFERENCES

L Lyons, J.W .. ~ The G.b:¥miarornd Uses of Fire Retard.ants:. W~~ey-Interg,cien0e> Nl! 1970.

2. Sprague" R. W. and K K Shen, Joumal of Theon al II] s!.datiQn. 2,161

(Aprit 1919)'

3. Ismkawa, Td:asm, lap.} KokaID, 76~ 124~ 195) (l97S).

4 .. Lobmeijer, J.H.~ etal., lEuro'pean Patent ADP~ication 0 364 129Al (1990).

5. SyIDvie, Bodrero and Rene Dien,French Patent 93 04093 (1993).

6. Shen, KK. and T.S. Griffin, ACS Symposium Series 425~ «fire all;ld Polymers" p .. lS?

(1990).

7. Shen, K.K.~ Plastics Compm.mding. (Sept/Oct. 1985)1.

8. Shen, K.K.. Pi.astics Compounding. (Nov.~Dec. 1988).

9. Ferm, D.l .. and K.K. Shea, Pmceedings. Intemationa:l Confenmoe 0111 Fire

S,afety. SanFrancisco, n. 242 (i 992).

10. Schubert, D. > u. S. PaJtent 5,342,533 and 5>412,644 (l994). 11" Rakszawski, IF.. and W .. E. Parker, Carbon,. 2) 53 (1964).

12. Shen, KK. and RW. Speague, Journa[ QfVil1ly~ Technology." NO._1.110 (982).

Table 1 Principal. B orate Mineral s

Ore Name

Fermula

Tineal

36.5 United States, Turkey

Colemam~e

50.9 Turkey

50.9 United States

43.0 Turkes Cht]·e

. -"i. .•

H yodmb oracite

50'.5 Argentina

Szarubelyit.e

41.4 Russia

* Theoretical maximum p ereent,

vn

Teble II. Boron Based Fire Retardant Products

Chemical Name

StMting Dehydration Temperature °C

Water Solubility (wt.% around 20° C)

Applications

Borax Pentahydrate (N a20·2Ib03·SH20)

65

4,4

Paper pmducts and wood composite board.

Boric Acid (HsBO!i.)

70

4.1

Paper products; cotton hatting and wood. composite board.

Boric Oxide (B20;;)

2,6

EngLneering plastics

Disodium Octaborate T etrahydrate (Na20'4B203+4HzO)

40

9,7

Paper prcducts

Ammonium Penteborate (~4)2()·5IJ2()3·8J12(»)

120

]0.9

Urethane, ,epoxy and other coatings.

Barium Metaborate (BaO·B203·H20)

200

0..4

Flexible PVC and coatings.

Zinc Berates (2ZnO~3B203 .. 3.5H20)

290

0..2

PVC, polyolefins, nylon silicone, urethane" unsaturated polyesters, and elastomers. PVC

Engineering plastics Enginee,ring pJasti.cs

(2ZnO"2Eh03+ 3H20) (4ZnO·B203• H20) (2ZnO,,3B20:;)

190 4] 5

0.2 0.05 00.2

/

Tehle Ill, M.ajorU.8. Produerers of Boron-Based fire Retardants

Trade Name

Producer

Compos~t]on

Ammonium Pentaborate

us. Borax

Hone Acid

u.s. Borax. NACC

Boric Oxide

U'S. Borax

Bulab Flamebloc

Buckman Lab

Firebra.ke® ZB .

u.s. Borax

u.s, Borax

Firebrake® 500

u.s. Borax

Neobor'®

US. Borax

Polyb.(J'*

us. Borax

ZB-467

Anzon

Z.8-223

Anzon

v-aor

NACC

143

~oo

-

ff.

-

50

Fig. 1. TGA of Borax Pentahydrate and Boric Acid

Borax Pentahydrate ( NalO·2~Ol,·5HtO )

Boric Acid { 8(OH)J')

Heating Rate SOCtmi n.

Temperature, (°0)

50 : U,eati.ngRate 5~C/min

90

Fig,., ,1. TGA Analysis. of Ammonlum Penta bora te

Ammonium Pentabora'te «NB4hO·'SB20J,~IUllO )

40 ~-_--II-~---'p"--'-'-_-"'--_-"--_-"""' """'I""'!_~_'"

0100

200

300

400

500

Temlperature (OC)

Fig. 3, Thermogravimetric Analysis of Zin e Berates

100

'Beating R.ate 10De/min.

100-

300

400

SOD

600

Temperature ('oC)

700

MINERAL HYDRQXIDES- THEm MANUFACllJIRE AND 'USE AS FLAME .RET.ARDANTS

WILLIAM E. HORN. JR .. AND TER.RANCE R. CLEVER.

Alcoa. lndustdal Chemicalls

Alcoa Technical Center. Alcoa Center, PA and Arkansas OpemU0l1!S~ Bauxite, AR

INTRODUCTION

Mln.eraJ hydmxides3ire am. Importam class of flame retardants, accounting for more than 50% of tlK volume: (by wejght) of flame relaro.3IlI.Its sold in the world U,2). This is due in p.art: to meitm' relatively low cost, but also because they are easily haedled and relailive~y nontnxic. Mineral hydmxides prov.~de flame retardant fonnu~atioFJis~at meet the :l!ppwprla:1:e SIlMldru:di tests for the aiPp~ication (3-5) and proouce combustioa products oflow opacity. wxic~ry and COlTOSivity {4~6). When properly compounded (J ,8). formulations containing these flame retardanas o.ffelr III eost.effeetive means to achieve low smoke. flame remrdant. fonnulations w~m a ~ow propensi~y fOF nonlhermal:fire damage (9JIO). The two ma~or m~nerarn hydroxide FRs are ail.uminLmll tribydroxide_d magnesium, hydroxide. Smal]e,r amcuets of bruci~ buntite and hydromagl1&s:i.reare also sold for this purpose,

ALUMINUM TRJHYDROXIDE (A TIl)

Aluminum tmlydmxide" or ATII, is appmpriarely wriuen as Al(OI03. Sometimes tl\!is marerial is called. alumina tribyd:mw m: hydrated alwnina and is wriuten as AbOJ,.3H20. Thiis, is erroneous M .ATH is nc~th& an alumlna nor a hydrate.

Aluminum 'I:ribydjroxide is usually obta~mled frt>m bauxwre ore using am extractio» process

(I l-Id), B auxite oreciQl1Itairns40~70% alu minum. minerais consisting mostly of Gibbsite and HoohmHe. Gibhshe is a crystalline form of A TH. Boehmite is aluminum. hydroxide oxide. OAI0H. These, ores also contain many mineral impurities includ~ng sHicates,iJron and ti,tanium comlPou~ds and organic compounds especially humaees, The Bayer process, developed by Dr. KiwI Joseph Bayer { 15), isa low C 05t procedure widely used to extract caustic sd.ubl.e ruuminlWl compounds from lfIe baux i te.. It invol ves d~gesting crushed biMlxire ore with eoneenerated SOO~UIl. hydrodd~ solutions at ~e:mpe.ramrlecs OOtwoon~25'°-280QC. The chemical reaetioas involved are:

Al(OH,h + NaOH ~ A~(OH) 4 + Na* OMOH + H20 + NaOH ,;!!' Al(OH) :4 +- N,3J+

147

(

I

The sodhan aluminate solution obtained in the Bayer process ~s fiJ tered to remove solid hnpuridea, The ATII is precipitated by cooling the stirred solution,. The specifics of me process vary among the various manufacturers of A 1H. The general process is outlined in Figure 1.

Crush BauxilC .. -----1 ......

Wash

Dry

M.eta'lllllfgicaf __ ~_lfi_'n_-II'" Bayer

BaIlllliLe .... Baaxhe

SCI'" ~ N.oH UqJlIDl ... 41 .... --- Digestale

Seed

Filter J

Produot ...... __ --- PrecipitalC ~

Dry Cod

Filter

Figure 1

Bayer Process to Manu.facture A.TH

The product obtained is a coar-se Gibbsite with a panicle size of ~ SO urn which can be used as iis or sold for chemical uses such as the production of alum. grou nd to produce finer partide sizes of A 'fA (grnund Bayer hydmte} or redissolved and precipitated 00 produce a more high1y purified grade of ATH precipitate (white hydrate).

Ground B,Slyer hydrate represents the largest volume of ATH sold to the flame retard ant market, The ATH can be ground [0 partie le sizes ranging from 1.:5 to. 35 .!-LID depending on the grinding andelasaification equipment used. '(14,16.1'1).

Either wet or dry milling Is used to produce ground Ani. A wide variety of mills can be used depending on the prutide size desired. Classification produces materials with narrower particle size distributions for specific applications. Blending is done to further customize products when necessary. A small percentage of A TH is surface treated to improve dispersion characteristics and the properties of the plastics that employ them as flame retardants. The more finely ground products are usuany surface treated.

Ground B,ayef products can vary in color from relatively dark to very lightly colored depending on the source of the bauxite and tlle process used to produce the ATH. The major impurities are soda, organics. sillcaeesand iron, Ground products tend to have broader particle size distributions and higher surface areas than precipitated materials,

Finely precipitated white Am is a purified f0111l of Bayer hydrate. II is the second largest segment of the A TH market. It is usually precipitated in particle sizes between 0.,25 to 311m. although 8 um products are also available commercially (16,~. 7). These products are v,e·ry whi te and have (ower impurity levels than their Bayer counterparts. Organk and iron contents are greatly reducedas _5 the soluble soda level of these materials. Precipitated products tend to have very Darrow particle size distributsons and low surface areas, compared to ground products of similar median particle sizes. These products are used. where color and low soluble soda eontenrare lmportanr,

Ground white A 111 is also a vailable, It is used where ,a white product is necessary or lower impurity tevels are required and where a precipitated product is too costly or produces a forrnulatiou with too much viscosity.

A TH is MI. excellent name retardant for materials that are processed at temperatures below its decomposition point (1900-230,oC) depending on panicle size (1-6-20), It finds uses mn

148

elastomers, thermosets and thermoplastics. A major use is st.yrene .. butadiene m boor ~amx used fiQr·tJhe f'rnmme retardation of carpets. ATH is used. in rubber insulatedcable, insulating foam, oon.veyor beldng. roofing and hoses. It is abo used to f!Iam.e retard unsaturated polyester used for laminates, sheet molding compound (SMC) and bulk molding compounds (BMC). SlliCh polyester's find uses in bathroom ware and enclosures. decoJ'ative wall pane'ls, applianoe housings, 3U*oIlO'live hoods and decks, molded seating, truck: fmnt ends ~ and electrical applications such as standoffs, insulators and circuit ooards. Pal truded prOOuc~ eomplny A TH as a fJam.e (Il!Wdiml in PJioduc-ing profiles for constraction appHcauons ..

ATH is used in epoxy and! phenoliicresins for electricalrelectronicasd construction applicati,ons including adbesi ves,lamin3Jtes. circut t boards, pottingcompounds and profiles, ATH is p'anjcularly effeclive in producing materials with excetlen~ arc-uackieg resistance, Crnss-lioked acry~ic I!es:ms employ ATH fer decorative and flame retardant applicetions, The usa am mostly in ccasencdoa for eouneertops and sinks. bathroom panels. deeorative surreends and wall pme1s.

Am is used. in a wide variety of themuoplasdc8~~c;luding flexible and rigid poly( ¥iny 1 chloride) (PVC), ,ethyle.ne-propylene rubber (BPR), ethy~ene~propylene dime monomer cross-Iinsed rubber (EPDM), ethylene-vlnyl acetaee (EVA)~ emylenlXthylacryhlJ1te, (EEA)'.,. low density polyefuyJene (LDPE), high a:ens:i{y polyernylene (HOPE), Hflei3ir low density polyethylene (LLDPE). b1ends ofpo~yeth.ylene and polypr'Opylene, and ~he new classes of plastomers and flexomers created by metaillilocene catalyst 'lechnology. Geaeral epplications include wire and cebles, cendaits.applianee housings, adhe...,iws" censtrueuon ~amin3!tes and.

insul_ngfo.ams (16-20.28), ,

ATH ilsa hrug,hly useful flam.e retardant having a wide range of applicability. Iaadditioa to its FR properties, A rn provides FR form u]ations with low smekegenesation and a low order of to'xic.ity and ,cormmv.~ty to, com~u.s~~on produc~. Its range of use is 5-65:% dcpendil1l!g, on me polymer and app~icatioro. Itis usually used in mhe 40s65% ramge in non-helogeaated s:y.srems. These levels of usage can sometimesIncrease the yisCOSl'ty of the formulation. The use of appropn,aw ,compounding agents •. resin b~endin.g techniques.aedadeqnate d~spe:.rni vel

~ -

distributive mixing usually can minimize most of these effects, Property surface treaied

A THs can also minsnizeihe effectsassociated with h 19h load lngs, but do add 10 the material cost (21.28). A wide range of products are com merdally available to meet !!IImost every applicasion need ..

MAGNESIUM HYDROXIDE

149

Magnes.~um hydroxide, Mg(OH)2, is the second largest selling mineral hydroxide flame retardant, Its volume is only a fractlon of those for AlB, however. Itis more thermally stata,le th am A TH. decmnposing attemperatures above 30(fe and finds ~,t8 largest use in eWlgineering resins (1l.22).

Millignesium hydroxide is produced from magnesium COlilta~ning ores. such as magnesiJte (MgCOJJ<. dolomise (CaC03.MgC03) 'Or serpentinite (M&3[SiJOs](OH)4),amd from brines ,or seawater. Some ores such as boodle (Mg(OHh). huntite (Mg3C:!J.(C03J4) and hydromagnesite {3MgC03.Mg(OHh.3H20)o can be used as flame retardants themselves or converted mID mllignesium hydrox1de. MagliLe:s~um hydm.~ides used as flameretardams

generaJIly need io be of high purity and are often obtained from seawater or brine, ahhough ore sourced productsare also of high purity (1,2.,22-24).

Magnesium. hydroxide is produced from seawater or brines with high magnesium cement, The magnesium is preeipitated as the hydroxide using slaked lime or dolime, Seawater is pretreated with sulfuric acid to remove bicarbonate sa.llts.. The preeipi tate is washed .fihered and dried. This product CM be used asis, purified furth.er orcaleined to Mgo. The oxide ,obtained can also be hydrolyzed eo yield a. purer form of the hydroxide. Variations ofmi~ process .are practiced by numerous magnesium hydroxide producers (2,23.24). 'The general process is shown in Figure 2. The chemical reactions involved are:

CaQ.M.gO + 2H20 ~ Ca(OHh + Mg(OHh Ca(OH2) + Mg,(OHh + MgC12 .-+2Mg(OHh + CaCl2

Seawater or

Reaol '..... .Brine

Dolime + IIp ----~ ..... ,. .. Stlked Dolime .-~-~......... Mg(OH)2 Slurry

!seUle

R~te,r

Wash

Mg{OIJ)l·... ..

Filter .[}(y

. Crude Mg(OI~

Figllr.e 2

Production. of' Mg( 0 Un trom B rille or Seawater

The Aman PFOCesS uses iii concentrated MgC12 brine solution as its magnesium source.

The solution is hydropyrolyzed to produce a mixture of magnesium oxide and aUtaIJi chloride salts. This mixture is treated with water to produce magnesium hydroxide, hydrochloric acid and soluble alkaline salts. The Mg(OHh is filtered. washed and dried. The hydrochloric acid is used. for other chemica] processes. The alkaline salts are returned to the brine source. This process is practiced by Dead Sea Periclase (22-24). The process is shown in Figure 3. The chemical reactions invol ved are:

MgCb + H20 ~ MgO + 2HCI

6()Q·C

Hydropoyro~ysis

MgC~ Brine - ............... -.;~ ...... / Crude MgO + ACl 4> Ca. K. NaCl

Aman Reactor .

. 1 Jly_",i.

Se.ttle t Fiher

Mg(OH)1 .. - Crude Mg(OI.f'I

- Dry .....

Figure 3

Production of Mg(OH}2 'y the AmaJ1 Process

150

\

i

!

Mg3[SiOS](OH)4. + 6HCI -4 3MgCI2 + Sl~ + 5HZO 3MgCh'" 3H20 ----+. 3.MgO + 6HC]

H~

The Magnifin process u ses serpentinite as its magnesium source. The mineral ]s leached with hydrochloric acid to convert the magnesium into the chloride. The impUlrities are removed by precipitadon andthe p~ln:ifled magnesium chloride liquor ~s roasted to produce MgO which is h ydrolyzed to produce purified magnesi urn hydrox.ide. The hydrochloric, acid is rec,ycled to the process. The process is shown. In. .Fig.ure 4. The reactions involved are:

3Mg:O + 3H:l;O --;. 3Mg(OHh

Eigure 4

Production of' Mg( 0" h from S erpenti De

The magnesiarn hydroxide used for flame retaedant alPpHcations is gen.e~a] ly of high purity.

Most FR grades are white powders rangin gin median particle size from 0..5 ~:5 ~JLm. Surface areas can range from 7 ~o greater th. illS m2/g dependieg on [he particle shape and 8~7:.e. Most magnesium hyd])oxides sold [or flameretardant applications Me surface treated to improve dispersion and physical property retention, LUre A TH, magnesium hydroxide is used at high loading levels usuaUy between 50 and 10% (2,22-25.28). Because of their high purity and surface treaenent req ulremenas, flame retardant grades of m agnesium hydroxide are more expenslve than precipitated A TIL

Due to their higher decomposition temperature and cost, magnesium hydroxides H~ generally USiOO in thermopl astic and thermoset resins that are processed above 200'" ~ 225°C. They find use in polypropylene :mdPP blends, polyamides and polyamide 'blends, ABSand AB S blends, in fluorocat'l'bonpolymer b]ends'j in polyphenylene oxiddpo~y styreil1e alloys, in polyimides and in lite. aliphatic polyketone, Carilon® (Cartlon ~s 3!. registered ttademark or Shell) (29).. End use applications are in wire and cable, appliance housing, construction ]am~Ii1.are..s. pl~ping and electrical components. As with ATH. a wide variety of magnesium hydroxides are commercially available to meet the requirements of me application,

lL51

DTHER.FLM1E RETARDANT MINERAl.S

In addition ~o Am and Wllagnes ium hydmxid.e., other mi nerals are usedas flame rel:arilamlts.

These materials are mined, crushed, ground amd classified. They may be beneficiated or refined further to improve color or remove unwanted impurities such as iron. They can be

surface waled to improve pol ymer compatibm~y. Such treatments are generally kept to a minimum as dlese products are aimed at the ~ower cost appllications.

Brucite is a naturaUy occurring form of magnesium hydroxide. Its cokir and purity vary depen<ting on the q uali ty of'the ore. It is usually not as thermally stable as refined magnesium hydroxide because of the impwities present in tlte mineral, It is also less costly. It is usually used where color is not critical~ though high whiteness brucites are available (2.22.23).

H ydromagneshe is a mixture of magnesium ,caroonate and magnesium hydroxide (3MgC0).Mg-(OH)1.3H20). It is a naturally occurring mineral found in Greece. It is sold commercially in combination with huntite, H ydromagneslte decomposes between 220o-240cC. but the mixtures are somewhat more stable (2~30).

Huntite is a mixed magnesium calcium carbonate (Mg3Ca(C03)4) which is used for high temperature FRappUcations. It is stable to 450~C. Being a carbonate. it does not possess the same flame retarding characteristics of a hydroxide but can be used for applications where thermal stability is :important Huntite-bydromagnesite mixtures are commercially a vailable and finding .1];8W FR applications. Vanum blend ratios are available depending on the supplier'. Surface treated grades are also available (2.30).

Gypsum is hydrated calcium sulfaee (CaSO.;l.2H20). It is usedasa flame, retardant in unsaturated polyester tub and shower enclosures 0).

FLAME RETARDANT MECHANISM

The mineral h yd!l'oxide flame, retardants decompose when heated. releasing water into the vapor phase, This elimination of water is endoiherm ic and allows the substrate to remain belO'w its i.gnitiO'n eemperatnre for the duration of the hydrate decomposition. The water is released into the vapor phase along wi til other gases of decomposi lion" diluting the amount of fuel available (2.26). The decomposition of the hydrous materials produces an oxide residue which has a reman vel y hi~h heat capacity, reducing the amount of thermal energy a vaiIab~e to furthe,r degrade the substrate (16,26,32).

2AI(OH)3 ~ AJ203 + 3H2,O Mg(OH)2 --7 MgO + H20

1500 JI g

1600 Jig

The residual oxides form a ceramic-type layer w hlch further protects the substrate (26,,32).

The oxide also is a good adsorbent and has potential catalytic acuvi~y. To achieve good flame retasdant.response, the mineral hydroxides are usually used :u Wevels above 50% by weight of me subsnaee, This aliso reduces the amount of ' comb us db le materia) available for degradation. The result is. an overall nell reduction in the mass burning rate of the substrate containingltle hydroxides (3-5.33).

In addition to inducing flame retardant properties to pol ymers, the mineral hydroxides also reduce the amount 'Of smokegeneration exhibited on burning, Although not thoroughly understood. this phenomenon is associated with 'the adsorption of carbonaceous materials on the surface of the oxide residue and subsequent oxidation to CO2 (26.,32), The presence of an increased amount of water vapor in the combustion gases rna y also playa part in the oxidation of carbon to CCh. Because wa ref is the only product of combustion, m ineral

152

hydroxides do not add significantly to the corrosive nature of the· smoke generated during. the combustion of polymers oonuJn~ng rnem (6,9,10).

Because high loadingsase required for hydrous m inerals to be effective es flame retardants, com binaaons w~th other flame retardant materials were examined to assess the potential synergy of dte mixtures.

Theuse of small amounts of antimony oxide in com bination with: hydmus FRs am effective in reducing the amount of loading levels in flexible PVC wire and cableformuladons (34" Combinations of ATR and zinc borate are also e.ffocll1ve in accomplishing similar reductions (34.,35). In general, tern pans of ATH can replace one to two pam of antimony oxide, Adjusting the mos .of me two additi ves provides the optimal FR/physical propenyJc.ost performance, Zinc borate can replace ATH at a simHar one ~o ten part replacement, This general ruleis operative foe both halogen and non~halogen containi_ng formulatiens.

A THana magnesium hydroxide give improved performance when used together OWl a wide range of mltios (28,44). The effect ~;S: thought to be due to the increase in the range, of ,endoltlerm and release (If water into the vapor phase, The resulting mixed oxide residue may abo play animportaat rok in this syneil:gy.

Combinadons of hydrous minerals with molybdenum corn~ai:ning compounds reduce smoke emissions aadincrease flammability reslstanee, especially in PVC (31.34.35).

Similae reports are made for com binations of mineral hydw-.ddes and tin compounds (36.,.31).. ATH and magnesium hydroxide coated. with tin compounds are reported to be particularly effective .in flexible PVC (31).

A'fH and red phesphorus offer potential synergy. While red phosphorus is used aJ,t low levels (3~ 5 %)~ the addition of A TH increases the FR performance (38).

Comblnations of siliecnccntaining compounds and hydrous mineral FRs reduce tbe amount of additi ves required to achieve name retardant formulations (39,40) in a variety of po~ymeritc susbstretes. Themechanism of theinteraction is not weU understood.

MANUFAC11JRERS OF HYDROXIDE FLA:M:E REf ARDANTS

ATIJ

153

/

The Aluminum Company of America (Alena) is the largest manufacturer of Am in the world. They manufacture both Bayer and white hydrates for internal use and sale to grinders. Alcoa produces precipitated ATH in the 0.25-2 micron particle size range. They grind ATH producing both Bayer and white ground productsin the 3-45 micron lange. Alcoa operates facilities around the world

Othee primary manufacturers of Am in the United States include Kaiser, Lakoche and R£ynolds Chemicals. These producers sell Bayer hydrate. to grinders. Alcan AJ uminum produces both Bayer and wh~.te A TH in Canada and Ole U OJ ted IGngdom.

Primary A Tn producers MOund rtle world include Marl1nswe:rke. VA W. Pechiney, Alusuisse/Lonza, Nabehec, Showa Denko, Sumhemo and Nippon Light Metal, Most produce precipitated andground products.

J. M. Huber's Engineered Minerals Division is a major grinder ofAlH in tile

U nited States. Other companies grinding A 1M in the U.S. include Alnchem, R. J. Marshall,. Georgia MarMe. Franklin Minerals, Hitox and Custom Grinders. Ineemin is a grinder of

Am in Europe. AU offer a wide, variety of products and most have surface treated grades. Other oompanies also supp~y ground ATH.

Magnesium Hydroxide

The major producers ofmagnesiem hydroxide for flame retardant applications are Kyow.aJ.

Chemicel (Japen), Magnifm (Austria) and Dead Sea Pe.ric1asdDead Sea. Bromine Israeli joint vemture. Mmton International produces magnesium hydroxide and magnesium lfydrox.ycaroonate in the U.S. Martin Marlena. now has a line of magnesium hydm:dde fIIame retardants jn the U.S. (2).

Incemin (Sw~tldland)~ Mean Chemicals Europe and Solem Division of 1 M .. Huber Enginoemd Minerals are major grinders of megnesium hydroxide. Smallercompanies aliso offer ground magnesium hydroxide.

Other Mineral Flame Retardants

Incemm ofters ground bruclee, bundle and hydromagne,siWlbuntire mixtures. Mic:rofme Minerals also grinds a hydromagnesiteJhundw b1el'lld. The blends produced by Iacemin and Microfme Minerals have dijfJerent compositional ranges aad find .appli.cation in different markets (30). R. McMinerals offers ground brucite in the U.S. Monon Ineernational offers magnesium hydroxycaroonate ..

LATE DEVELOPMENTS

Although mineral hydroxides have bee.n. used as flame retardants since the ] 9608, their use is growing as polymer producers and compcuedersJook for al temalives to conventional flame retardants. The demand for improved performance has spurred the development of new grades of existing products, the developraent of new compositions of matter and an increase in thennm ber cfcompanies offering .FR grades of mineral hydroxides. The b~ending of A1lIs: to produce materials iliat develop, less viscosity on compounding and the introduction of new surface treatments that offer improved physical property reteminnand improved p,oocessibiUty are examples of such imprnvemeets (18,28).. Martin ~delJta. has introduced their first FR grade of magnesium hydroxide (2.41). Queensland Mews Corp. Ltd. and Mines de Lucette have formed a joint vensure to produceand market magnesium hydroxide. PremieePericlase Ltd, has just announced they are entering the same market (2).. A new chemic.illy modified Am, wbichis smbleto 33CfC, has been developed by Alcoa (42.,43). All mate-rim are currently being test marketed,

CONCl.USIONS

Mineral hydroxide flame re:taroafJts offer a wide variety of materials for applicadoninalmcst every market. They can be used. in thermosets, thermoplastics.elastomers, engineering resias, paints. caulks, adhesives. backcoating, mastics and paper products, They can be used

154

at prooessin! temperatures of up to 400QC. All are re~atiye~y .non~oxic. Mmeral hydroxide flame reWdanm provide exceHe;nL flame retardant pmpeme.s when used .a~.3ippmpria;re concenerations, .MaJre:rims oontainingllhis class of Ilame retardants produce little visible smoke on combustion. These materials also exhibi t m inimal nonrhezmal fire damage. such as oORosion.When properly formulated and compounded, resins using these flame retardant'S offer cost -effective soludons to most FR peobleras,

REFERENCES

L Loughbrouch, R., "FlameRetaedants - Legislation F~res Markels/, Industri aJ Minerals. p'. 35 (May. 1'991).

2. Bo~ger .•. R., ~ Flame. RCJumdanllWine:rals. ~ In.dusjriatM~nem18. p. 29 (January. 1996) ..

3. Betle~t. D. W .• "Reduction of File Hazard Using Fire Retardant Chemic,aJls. ~i (a review of N13S Special PmlbUcation 149). Are R~tardrult Chemical Associath'm Publisher~ Babrauskas, V., R H .. Harris. Jr., R G. Gann,. B. C.l.evin. B .. T .. Lee, R. D. Peacock. M. P.aabo.W.T:wmey. M.F. Yoklavlch MId H. M. Clark. ~'Fjre Hazard Comparison of Fire-Retardedaad Non-Pire-Retarded Products," NBS Special Publication 74l9t National Bureau of Sbmldards (July, 1988).

4. Harris,. 1 F •• R. H .• V. B abrauskillS" B. C. Levin and M .. P:aabo" "Date fm Fire Hazard Assessment of Selected Non-Halogenated 8.I1Id Ha]JogeniJJmd. Fire Retard~nts; Report.of 'fest. FR 3983,'" NlSTR 4649, National Instimre of Standardsand Technology (Ocmber. 1991).

S. Hirschler, M. M., "Comparative Analysis of Effectiveness of Fire Retaedaens Using Heat Release Calonmetry,' inFlame Re'tlrdants '96, S. 1. Grayson, Ed. {L-ondon~ UK:

Interscierree Communications Ltd .• 19%,), p'. 199.

6.. RlmathandtMI. S., "LJw-SmokelHatlogjen.~Free Compounds." Wire Yechnol. INt. p. 3 ~ (Maa:h. 1995}.

7. McMurrer~ N., ~Updare:Bquipme:!lt fOf Ccmpounding FR Materials," in "Fire Safety Advances in High Perfoemance Plastic Products." CEIQ!;_eed.~Dgs of tile ~1994 Spring Conf'erem:e Df the Fire Reltaroant Chem.kaJs AsSloci.auon, San Amonio. TX~

March 13~ 16, l'994) (Lancastes .PA: Tee hnonicPebli suing Co., 1994). p, ill.

8. Mielcarek. D. E. "Technology Advaeces in ~e Compowding or Flame Remrdmts." lllliL,. 1". 25.

9. Tewarsen, A .• "Bffectiveness of fire Retardants in RedudngffiHminatlng NOf[l~Therma1 Fire Dam ag.e. "~n the E1ec@nk Inform at]on Age and] rs Dem arn"ld on Pi re Saf¢lX CProceec!ings.__oLtbeJ:295 faU C-onfcrence of the FireRetard·oo~ Cbe;miclILAssDcruation. Rancho Mirage. CA.Ck~ober 29-Nov,ember CU. 1995) (Lancester, fA: Technonic PuMish~ng Co., M'99S), p .. 79.

10. Tewarson, A.. "Non-Therm.al Fire Damage:' IT Fire Science 10. 188 (1992).

1 ~. Sleppy.,. W. C. ~ "Aluminum Compounds," in Kirl.-Odlmer EmcyclQmWrua of Chemical l'echnolQ~}!~ F'ourtllilEdition. VoL 2. I. Krooscll witt and M. Howe-Grant, Eels.

(New York. NY: John Wiley and Sons. 199U. p .. 252.

12. McMichael, B., "Alumina Markets, H Indlllluial Mincrws. p. 19 {Decem her. 1989). 13.. Wefers ~ K .• "Nom enclature, Preparation and Properries (If Aluminum Oxides. Oxide Hydroxides, and 'Trihydmloxides," in AllIlrnruna Chemicals: Science and IedmQ~Q<ji:Y

155

Hand.'OOQK. 'L. D. Han. Ed. CN es.tervitle. OR: l'he AmencWl CeTmni:c Sociay ~ lnc., 1990), p. n.

Vt Musselman, L. L .• !!PrOOuction Processes, Preperties, and Applications for Aluminmn Containing Hydroxkles,M in. I.hid., p. 75.

15.Bayer~ Karl Josef~ Germea Paseat 43.911 {August 03~ 1888).

16.. Sobolev, I.. E. A. Woycheshln. !! Alumina Trihydrare." Chap~r 16 in Han.dhook; of Fmen furl!lasti.cs. H. S. Katz. and J. V. Milewski, Bds, (New York, NY: Van Nostrand RcinhQtd. Co\.. 1. 9B.1) .p. 1..92.

1.'7. Mus~m3fi. L. L. • "Alumina, Chemkalsas Mdilives[or Paper. Dentifrices"Pt'lints.

Coa;b~,gs;~~liIb~rs, and :lastic8 With an Bmphasis on Rre-Remrdaflt Preducts," in

IS.. ~unuml Cbemlcals: ScIence and IechnoIQu:Handbook. OJ}. Cit.. p, 195.

Kirnchb~um. G. S.t "Aluminem Hydroxide for Noa-Halogen Compounds - WeD KflIown -and Stilll~very Young," .in FJame Rourdants '94. The British Pia.~f1cS FedeDt~on •. Ed. {London, UK: lnrerscimce Communicauons, LuL 1994).p. 169.

19~ Bmwn~ 8. C .. and M~ L Herbert, jjNew .Developments in .ATH Technology and Application..s:/' in Flame R.e,mrdant5 -92, The Plastics and Rubber Institute, Ed. (London. UK: Elsevier Applied Science. 1992), p. 100.

20. Szahlowsk:a. B. and 1 Pelica, "Fire Proofed Floor Coverings on the Basis of Polyoleflns," in Flame Retardantlj;j '96. O~. Cit, p. 241.

21. Goodman. R. "Sueface Modific~~on of Mineral Fillers," Industrial Minerals, p. 49 (February, 1995).

22. OTJriscolt M .• "Caustic Magnesia- Markets - PlayingWNh Fire," [mdustriijI Minera.ls, p. 23 {March, 1994}

23. Seeger, M .• W. Ono,W. Flic.t, f. Bickelhaupt and O. S .. Ackerman, "Magnesia Compounds." in UUmann's Encydopedia:. of Industrial Chemisny. Vol. 15A. B. Elvers, J. F .. Rcuasavilleaed G. Schultz, Eels. (Weiobeim, Germany: VCH Verlagesellschatt rub",. 1990).. p .. 595.

24. Jackson, L. C .• S. P. Levings, M. L. Maniocha, C. A. Mintmeir, A. H.Reyes. P. E.

Scheerer, D. M. SmIth, N. T. Wajer. M. D. Waltet aad J. T. WItkow:sld~ "Magnesium CompowuJs,~ in Kirk~Otbmer EncycJqDOOia of Chemical Technology, fourth Edition. Vol. 15, J. Korschwitz and M. Howe-Geaot, Eds. (New York, NY: John WHey and Sons. 1995). p, 675.

2:5.. Hatke Vande, Ven, S. and A 1. Dallavia, "Flame Retardance of Pol ypropy leae - Additives Based on Magnesium Hydroxide;" in Pmceeding of tile Annua~ TechnicaID. Conference of the Society of Pi i3!stics En gineers (ANTECl, Atlanta, G A, April 18-20. 1988 (Lancaster; PA: Technomlc Publishes, 1988.) t p.. 1415.

26. Homsby.P, R. and C. L. Watson. "Aspects oftbe Mechanlsm of Fire Retardancy and.

Smoke Suppression jn Metal Hydroxide RUed Tbermoptastics," lOP Shorl: Meetings,. Series NQ, 4. (London. UK: Institute, of Physics. April. 1987). p. 17; and Hornsby.P. R. and C. L. WaL<ron, ~M3gnesium Hydroxide, - A Combined Flame Retardant and Smoke Suppressant Filler for Thermoplastics," Plastics R.ubber Process. AI!W!&." ,6: 169 « 1986).

21. Ziegan.,. 0 .. and H. Hijndesher,g~ "Magnesium Hydroxide: Effective Flame Retardant for Rubber and Thermoplastics," in Fh~me RetMdaQts_:22,. Op. Cit., p. 120.

28. Kiirschbllum, (t S .• "Recent Developments in A TH and. Magnesium H ydroxldes ~ A Challenge to Traditional Materials," ~n The ~ctron]c InfoonatiQn Age and Its Dew and on Fire Safety, QD. Cit, p. 145.

156

...

29. Lenda, M .• R. P. Gingrich, B., G. Kormelink and M. G. Proctor. "Development of Non-Halogenated Flame Retardant Aliphadc Polyketone Compounds," Ibid ..• p'. 157.

30. "New Huntite Site Expands Applications Possibilities for FR." ~n ,Functional Finer News" K.. L. Govanuccl, Ed. (November 20, 1995)1. p, 1.

31. Groen, J .• H. S. Katz and 1., V. Milew ski, "Miscellaneous Flame Retardants and Smoke Suppressants." Chapter 18 in Handbook of Fillers for Plastics. OJ?. Cit. p. 3-64.

32. Hornsby, P. R. and C. L. Watson. "Mechanism of Smoke Suppression and Fire Retardancy in Polymers Containing Magnesium Hydroxide Filler, ~ PJaslks Rubber Process. Applic .. Hip, 45 (1989).

33. Whitely, R. H. and P. J. Elliot; l' A Cone C~orimeter Study of the Effects of Alumina Trihydroxide and Magnesium Hydroxide on tbe Burning .Behav.iorof an Ethylene-Vinyl Acetate Copolymer." a paper presented at the 2nd Fire and Materials Imemational Conference. Crystal City, V A (September. 1993).

34. Moore. F. W. and W. J. Kennelly. "Effect of Co-Additives. on the Flame/Smoke Suppression Properties of Zinc Borates, It J, Vinyl Tcchnol. 13 (3): 169 (1991).

35. Shen, K .• "Use of Zinc Borate in Electrical Applications." in The Slactronic InfQRnaUOD AGe and Its. Demands on Fire Safety, Op. Cit.. p, 129.

36. Chaplin. D., "New Improved Flame Retardants of Low Hazard," in Harne Retardanrs ~ • .D.». Cit. p. 198.

37. Cusack, P .• "Cone Calorimeter Studies of Pnlymers Containing Tin-Based Fire Re-tardants," in Flame Retardan ts '96, Qp. Cit. p. 57.

38. Staendeke, H .• "Red-Phosphorus - Recent Developments for Safe and Efficient Flame Retardant Applications, H in Dynamics of Currernt Devdopment in fire Safety of Po.lxmers. Proceedings of the Spring Conference of the Fire Retardam Chemicals Association. March 20-23. 1'988,. Grenelefe, fL (Lancaster, PA: Technomic Publisher Co .• 1988). p, 32,.

39'. Chavez, M. J. and D. J. Romanesco, "Fire Retarded Plastics: Computer Manipulation and Video Cone Calorimeter Data. It in The Electronic Information ABe and Its Demand of F'we ~. ~ (}p, Cit.. p. 1 '69.

40. Huber, M. S., "Non-Halogenated Flame Retardant Systems for Oietlns," in Internationa~ Conference on Fire Safety - Fire Retardant Technology and Marketing, Proceedings of me Spring Conference on me Fire Retardant ChernicalsAssociatirm, March 25-28, 1990,. New Orleans, LA (Lancaster. PA: Technomic Publisbjng Co., 1990). p. 237.

41. "Legislation Could Drive Demand for Magnesium Hydroxide FR, n in FlI!ncttonal Filler ~~ K. L. Govanucci.Bd, (December 1.8. 1995), p. 1 .

42. Horn. W. E. and J. M. Stinson, "Thermally Stable Aluminum-Based Flame Retardants for Use Where Processing Conditions are Too Severe for A TIl," in Fire Safety Advances in Hi gh Performanoe P~astics prOOucl'IJ. Op. Ci t.. p. 91.

43. Stinson, J. M. and W. E. Hom, "Flame Retardant Performance of a Modified Aluminum Trihydroxide With Increased Thermal Stability," 1 Vinyl Additive Technol. 1(2):94 (1995).

44 Kirschbaum. G. S., "Halogenfreier Flamrnsehutz," Kunststoffe. 79: 11 (1989).

157