Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2182714
, .
Fl~-re~i~ta~ isi~ fo~m.~ ~a~d c:~r~ Jc~an~,te
;
l'he invent.ic~n r*l2t.e~ ~.o ~ ne-r~i3tant V1g~d ~lcln~ aRRd. cn
5 i~cy~Lnat~ and al~o to ~ pr~c~ss f~r pr~.~cing thefie
re~i~t.~nt rigi~ fo~m~ .sed ~n 1socy2~n~t:e ~y rk~ctirly
~ o~aric 3nd~or mc~l.ifi.c~ ~rg2~nic pol~i~c)cy~n~l;;~s wi.th
10 ~ 'c le~et o~le COI~O~ collr~t~ir~tJ hy~ ge;~-~ a~c~ reaat.lve
tcJwartq i.eOCya~a~c!~: ~T~d, i~ desixed,
C~ ?w m~ c~ .ar w~h~ chaiD exte~;~de;c~7 ~rldJur- cr~fi3.1ink~r.
15 i n ';h~ F,re~ ce a~: -
d~ blowinSr ~ent~,
2) c~t~lyY:
~1 ~t le~a~ ~ne blo~nina- con-aitl7~cl flam~ ~t~rd~nt
des ired.
g) f urt-.her ~uxi1i~ an~i/o:r ad~it..ives .
'25
The ir~r~r~ n fur~.her relat ~ th~ use o~ the ri~,id ~o~n~s b~ .d
ocyanate an~ pr~du~e~ l~y t~is ~ ooe~d a~ 1us~la~ n
m~ ri ~16,
30 ~i~id oam~ ~*~c~d c~n ~ 30~yar,~e, i:n ~a:~ticulax pulyu~eth~ a.n~
i ~o~y~ ura.~e foamfi, hA~ beerl kno~. fo~ ~ ].o~lg ~ k and are us~d
predomir~n-tl~- fe~;r heat or cold ~n3~ula~ion. e.~r.. in re~rig~rati on
aI~pliances, irl ~uildln~ or~st;;t;ucticF~ L h~t wat~f Btorage t~nks
and lon~-ai~t.a~ he6tir~ piF,es.
A ~lumm~ry ov~r~rie.w of t.he ~rodu~ti~n and us~ o~ rigid fo~m~ ha~e~l
~n i~o~anate h~ be~ p~li.shed, ~or exa~ple, in Pol~t~ es,
st~toffharl~buch. Volu~d 7, l~e E~dlti~n l9~fi, ~ e~ by
R. ~iowQ~ and A. H~chtlen, 2nd }:dition lg83. ~di~ Y G. O~tel,
A~ and 3rd ~ .ion 1993, ~:ait;?d by l:. E3~cker 9nd. I~. Br~u~, C~r. l
i~aF~ r V2rla~, Mu~ich, vi.
Ttnt.il r~co~ly. ~ ing agentl~ u~ fO~ o~ucin~ th~s~ ~o~m~
hav~ b~en ctlloro~luoroc~hon~ (C~,S), pa;cticularly trichl~r~
~5 1UOrOm~th~n~ Owing to thq~i~ de~t~u~ e ac~ n or Ch~ glc~
o:zor~ layq~x, ~he~ c~F~s h~v~ t~ b~ ~epl~ee~ ~y m~tkri~l~ whi~h d~
not hav*. thi~ Po~ tial f~r ~maging ~che ozone ~ ~yer and have ~;
2182714
~ow ~ P~ le ~ ~r~e.rillou~ ef~e~. In a~dit~ n, ~ t i~ to b~.
ex~ec~e~ that, ~t ~ t. ir~ ~ f~W yea_s, only ~he us6 e:~ h~lo~r~-
fFeQ blv~7ing ~gent~s or blowln~ ~eht mix~ures will h~ ~lLowe~.
5 Th~ L-~pl2~cem~t ~f C.FCs by alterr.at:Lve .l~lowin~ t~ ~uch a~
~ICF::s, HFCs, C:~ and hydrocar~ ns ~lake~ it ~nore ~l~.fia-l~.t to
obtai2J ~n equally go~d f~r~.-r~tar~ t ac~iorl. This is refl~tec~.
in the hiqher amoun~ f .~lam~ r~t.~rd~nt~ ~hich h~e to 4~:? acld.~c~
to ~he ~:orntulati on~ . The se~rch fo~ e~ .r ~ ~larne re~a~d~ s is
10 th~xefo2~e ~ i ot tar~ du~r.i.al ta~:k .
Apart from c~hlorinQ and ph~s~phor~ ~omPound~ b~oml.ne compoun~;
arç~ hi~hly ef~e~ive fl~er r~t.ard~rlt~ for ri.qi.cl fo~m~ ;ba~. O~l
yar~ate~ owi~g ~o ite high bromlne ~orltent, trik,~omonec:peHtyl
l~i alahhol ~-hromc~ethyl-2~ lrc,x~nethyl-1, 3-fl.i~ro~nnprc~anel is a
partl~ularl~ ef f ~3atl~re ~oh:pou~d . Tril~romc~n~opentyl alcoh~
k~ow~ a~ ~l~Le reta~dAnt ~c~.r palyur~th:~n~ 0~3m~ f.~ t~e ~a~es~t~
5 ~ 3 ~, DE ~A --15 !~ ~i g l 4, D.E;--A- ;2 7 3 2 ~ ~a 6, E ~ 2 4 0 8 ~! 6,
~P~A-OSll; 5811. U~3-A-~g3~541~ A-4052346;, U~ 419406~ ~nd
2~ US~ 5116e~. A di.sadtra~Lta~e i.n the u~e c~f tri~ n~o~erl~y:~.
al~ohol ~8 ~lame ~et:~r~ dir~ly and al~o e.~ s~r~t heti~
4~ diny b]C~Ck or othe~ Elallle r~tardsAts is i~s lc:w function~
al ' ty ~s monool, whlch le~d~ te) chain t~2r.nirl~l; iOI~ bo~ h in t ~;.e
tiOL~ wl-~.h i~c)cy~n~t.~ ~nd also, ~or exan~pl~, in th~: esteri.-
at~n?L ~l~h pc~lycarb~xYli~ i~cids Tlli6 re~ult.s in r~duc~d
m~ hAni cal stre~ths ~f ~h~a cur~ad foam~ and, in p~rtic~ r,
~on~i~erable retard~tion of the cur~n~ pxoc~3~c during fvam
ro~lu~ticn~ T}IQ latto~ d~.flcien~y in part~ lead~s t~ a:l .; t:y
~roblem~ ar~d ~r~duativity 1066e~: in ~at~hwl~ anA c~tinuo~
~0 proceQe~s Pur ~roducinSJ i~ul~tic~n mar.eri.a.l . ~hi~ ef ~ect i~
p;~r~l~ul~.rly ~erlo~ in ~hP c~se of ~ igid ~oa~ns b~sed on
i.~o~ e ~nd blown without u~in~ ~.F~s, ~n w~i.bh a conwarati.-rely
bi1.~h amv~nt. o~ fl~me r~t~r~lsnt ha~ ~o ~e useA.
35 ~ ~ ohj~ of ~he~ pr~e~t inv4n~.iul~ to ~rovide fl~me-
re~ tant rlgi~ fc~amA ba~:fl on i~oay~ w~ with~ u~lna
~FC~ and u~ing b~omin~-~containi.ng fl,~m~ l~et.ard~t~, iD. whic~h r..h~
dis~dv~t~e~ o~ the p~lO~ re l~rg~ly A~vi ded ond ~he
met~ c~l ~n~ phy~ie~l pro~e~ti~s ~re nc~t adv~ e].y ~ffected,
40 without the ~rnin~ ~ha~icsr ~ing~ in~air~d.
W~ have four~d th~t ~hi~ object iB ~e~Ji.e~r~l by 4~in~ predom~ nt:~
tribL~ -n~c~per,tyl alcohol ~s bro:nine-con~ai~ing 1ame retaz~d~n~:
~c:r ~l~mepro~fing rigld ~o~mo baoed on i~ocy-nate ~n~ ~y tl~
45 c:ro~slin~cing ind~x of all compou~d~ cont~ining hydr~gen atort.s
2182714
r ~ 3
r~ac~ tbw~d isocyanaL~s inu:tudin~7 the br: ,~nine-~nt~in~nr7
~lame retard~n~, b.~ing at le~st 3 . o.
i
qlhe ln~,~entio~ acc~rdi~ly ~o~riele. :Fl.~n~e-resi~t.~nt rigid -E~ms
~5 b~$èd on i~oc~a~ te and a proce~s l~or produ~in~ t.he4:~ flArn~.-
~e~i~tant rl~d fc~ ed ~ oc3rel~t~ r ~e~ct iny
a1 . or~anic ,and~-r rno~ d ~ry~ntc E~olyisb~ ya~AI;~s with
, .~ b~ leaet one avn-,puu~.d cont~l ni~lg hydrogen a~.om6 re~oti~7e.
toward i~cy~ana~c~9 ant~ ed,
C!) low molecu~2r wei~ ch~irl exte.n~ers ~Jor ~ro~ Lkers
lS :i n th.~ pre~OEnc~ of
d) . ~ ring ~ t~,
e~ catalysts
ZO
f ) ~ t one brGmi~ o~ n~ r.lam~ rd~rl~ ~nd, i~
d.~ir~3d,
rt;her ~uci li.a~ ar,dJor a~di tiv~
.~5
wh~rein tr~brc~tno.ne,t)~an~y~. aL~ ol i~ :Dr~ol~;n~n~ly u6~.d. ~8
b~omin~-~ontair~rls ~ xe~r~ , ~d l:h~ cros~ kin~ inA~
all cornpc~ s c.c~nt~ hydr~g~n atom~ r~ctive towar~S.
isocyanat~s, incllldLnc~ t.he b~nih~-co~t.qinin~ ret~r~r., i
30 at Lea~t 3 . O .
'~'h~ in~Tenti.on fu~ther pr~v~de~ ~OL~ the use ~f ~ e ri~:~.d ~o~ns3
base~ on isocy~nate -,?roduc~d by thi.s pr~ce~ as inqu~ ation
m~L~er~
It wa.~ rpri~ g ~h~t fc:~m form~l~t ion~ flO ~ .h~ a ai~ e
de6~ ed dis~dvaI~.ta~;re~ of th~ ~io~ ax~ whe~, in ~ddi ~lo~l tQ ~h~
us~ c~f ~ri~L~ *~ent~l al~hol ~ ~rominb-cont~ining fla~
r6,~r~ane, th~y havQ a p~t~cularly hi~h c!ro~ lng in~ex ~c
4.~
Fbr the ~urpofies ~ he 5~re9e~t in~ tio~, the crc~s~linki~ in~L~x
is ~ dim~n~iorle~ er ae~c~i~îns the croa~.inkins cal?abiïity
~f ~11 a~mp.~u..d~ bea~ g hydroger~ ~tornY ca~e~}e of ~eac~ing wi~h
t~he is~yarla~e comporlen~. ~r~3 a~o~.inkinq i~e~c Ic i5 c~l~ul~t~ed
~5 by the followiny foni~u~:
21827l4
.
~` ~rn~ Z1 ~1 ' m~ Z~ n Zn ~ f:n)
C , --.,^ .. _ ._ . .. ......... , _.. .
~m~ 12 ~ n ' C-n )
whe~ h~ ii~idu~l s~n~ have th~ f~3 l~wil~g me~l Ln~3
Ic c~.s61illkil~s indi?~xr
0 mL1~ rn~, .. r~.~ prop~r~i.on hy ma.~ 11 compo~ bearin~
h~drog~L Atom3 c~p~ react~n~ with th~
ise)t,~yana '~ mpc~ st,
Zl, Z~ hydroxyl llumbe~s ~f ~11 ct~mp:~ulld~ b~ario~
~6 bydrc~en ~tOIU~ C;d~F~ ac~iILg ~i th the
i.s~cyf~uate co;~ol~e2~t,
fl, f~, - - ;En ~ t~i~ena3~ i*s ol~ all l~omp~ur,d~ b~r~
h~d;~oca~n ~toma ~p~hlq~ c~f rea~t~ t~ ~t th the
~0 i~cyArate c:~n~on ar~t .
on the~ hasi~ o~ ex~eri.cnce, it would have ~eeD expected th~t the
~r~n~e of th~ l~ont~fu~tl~ t.~ r~monec~ent~yl ~lcoho]. in th~
fo~ onni.ng ~:ea~ti.~n mix~ure ~ul~ pair, iIl partic~ul~2, the~
25 c~ur ~ nq co ~ an extent that ;pl-o~er ~roc~in~ of the oa~
F~y~"em ~7QUlC~ not ~ o~ or ~v~ible~ c~nly wi~:h gr~at
di f ~ ic~ll tv .
~refe~n~.~ 15 ~ n to ~o~mulatinr~s in which ~he :brom~.r.~-
30 ~ontaiI~in~ fla~n6~ ;ce~a~nt. contai~s a~ ~a~t ~0 9~ by ~igh~ anc~
part.icul~l~r pxefer~bly at leA~t 515 ~ by w~ ht c~ t~iDromo-
~neopentyl ~ ohQl ~nd ~he ~ro~li.nk.ir~ ex i~ at :lea~ 3 . 2. an~g.
particu.'~arly ~r~ ar~ t 1.~.a~ .3s.
~1~ E~i~id ~ Uit~ or the flalne~oofing ~xe~ n~ o~ th~
pr~3nt in~ tion are in prin~i~le ~11 thoaQ oun~ k~own ~e~ ~Q
ba~ed on i~oc~anat:~ and whieh ~n be produce~ by c1latomary
mQ~hod~ kno~.m per ~ lnn~ a8 th~.y h~ve the c~osslinkin~ index
~3~ at l~c 3 . O requi.~d a~ r~inçt to ~h~ p~ t in~r~3nti.0~l .
40 P~tic~ rly adv~tRseo~ ~e~ h~ een o~a i.n~d in the ~a~;e
o~ polyur~th~n~ ~ncg i~o~yan!ur~te rigid ~wLm~
~G}~ ~r~lu~ a th~ riyid i~o~ls bac,ed on i~o~yan~t~ ~y th~ ~o~e~s
c~ thc ~r~Y~nt .~n~nti.~, uAe i~ made, v~ith the e~cçeptivn ~ the
C5 ~l~e :Fe~aan~ tf), o.~ ~he~ f~ ti~r~3 cr ~r~nt~ kn~wn p~r ~e~
res~rdin~ whlch the ~ollow~ng de~ils ~ay be yi~ren~
21827t4
a~ Sui~ak:la or~anic andfor suodi~ie.d olgani~ ~ol~i~ocy~ t~ ~a~
~x~a the ~li.ph~ti~" ~:ycl~ali.phati;~ ~r2,1.~hatic ar.,d E~:e~e~
the ~ mati~ ~blyi~ln~ n~l i80c~y~nate& h~ow~l p~r se.
S .sp~ei.~i e ~x7~ ples ~re.~ yl~ne ~.i;.is~yanate~ l~eLv~g f7-~m
to 12 c~rbc~n atc~ in the ~13cylene radical, ~r e}~an~
dodec~ diisoc~ a~e, ~--e~hyl~et~ t~-ylene 1, 4-~ii su-
cs~anat~s, 2--methy'l pent:~Lethyl.e~e 1, ~-diiao~yan~te, te~tr
nLethylene 1,4-dl~ocy~n~te ~rld pr~er~ly he~c~eehylen~
'10 1,~-dii.s~cy~n~tet cy~loaliphatie di~i~oeyanat~ ~uch a~
cyc~ohexAne 1., ;- a~d 1 4-dii~ocyanate a~d any mi.x~ure~ ~f
th~ o~nere~ ocyu~.at~-3, 3, 5-er~me~h~y~ o-
me~hylcy~lohex~rl4 ~ ;7horons dii ~oryan~t~), h~x~h~dxo ~
tc~lyl.Qne 2, 4- and ~, 6-dii~cy~.nat~ an~l th.e ~o~er~33pondil;g
i.~omer ;~.ixtur~, dicyc.lohex~lmeth~ne 4,4'-, ~,2'- ~n~
2, 4' -d i~ocvana~e ~td ~.h-?. c~rr~!~pon~;n~ isomer rnixtu~e.~, a.
p~e~extlh3~r ~rbm~le..iC di.i.~ n~te~ ~hd pe:lyi~oc~anat~ fiuch a~
tolylen~ ~, 4- an~ 2, ~-di i~ocy~n~t~ ~nd the c:c~rre!spondinq
is02ner mixtur-3s, diph~lmeeh~ne Q,4'--, 2,4'- and
:10 ~ dli3~cy~t~t~ arld thP cc~rr~3sp~ di~lg i~omer mixt~x~s,
mixtures o~ herl~lm~thaIle 4,4'~ a~d ~,4r-dii~o<~y~
}~ol~hYr3ylpo~ thy~n~ pc~ly~ ~:cl~y~Atos, mi.xture~
diphenylmeth~ne ~,4'-, 2,4'- and 2,~'-diisocyanates an~
polypher~ylpoly~nethylen~ pol~ cy~ ~e~ (~aw ~DI) a~d
2~ mi~ct~ra~ ~f ~ ~ ~d tolrl~n~ dii~ ~an~t~. ~h~ ~;7r~a~i~
dilso~:y2Ln~tes ~nd pol~ ooy~nate~ ~:an be us~d indi~i dual ly or
i~ t3~ ~onn ~ he~ ~nixtu~-es~
U~o ic ~r~r.au~tly als~ mad~ oE ~no~i~ied ~c~ f~ lc)~l
i~ocyanate~ . produc~t6 which are obt.~i.necl by ch~micf~l.
r~c~lon ~f oroanlc ~iis0cy~Lna~e~ andJc:r polyi~ocyanate!3.
. Examplee whi..ch may be me~ion~d ar~ diiso~yarlRt~s ar,d~er
pol.yi~oayana~ on~a~ini~q qE~ , uxea, 1 iurot, ~l loph~at6a,
~h~A~ imid~, ;.Lo~:yanur~, u~P~.di.on~ and/or t~ t han~ ~nu.~ .
~5 spee~fi.~ example~ of ~u~ta~le cf~m~ound~ are: organic, ~re~x-
~ly ~r~Je~atic pc~ ocy~r~at~ei coIltain;.ng ure!thane ~rou~?.c and
~ing N~0 cont~nt~ of from ~3 . 6 tc~ 15 s~ by w~i~ht, ~refer-
~bly rom 31 t o ~1 Sls b~ weight, base~ on the. tot~ h~,
~or ~xample dipke~nyl~nQth.~n~ 4, 4 ' -dii.60~yarlatQ modif led w:i ~h
4f) lo~v moie~ular weight diols, t~.iols, di.~lkyle~ gLyools,
trialkyl~ne ~1YÇ D o~ }~ol.yoxy~lk~lene ~lycols ha~ri nçr
molectllax w~ight~ u~ to 6V0~, in ~articular ha~7in~
molQcular w~i;rhtA of up to lS00, mbdified ~i~hen;rlme~h~ne
~,4~- ~nd ~,4'--diisocya~ate m~xture~ or modi~ied ra~ Mr~r or
tclyle~oe ~ Or 2,6-dii~yanate, wi~h eY~mples o~
diA lk.yle~ or pol y~c~a:~k~l en~ ~lyt!Ol ~, whi ~h Q~l h.3 ~1~ ed
i~ldividu~Lly ~r ~3 ~i~tu~os, bçi~; dLie~ hy]e~e glYc~
21827i4
hi1propy.l.ene o l~"t~ q l~oxy~thyl~e, polyox~pr~yiene and
p~lyo~ p~opyle~e-polywcyq:~hyle~e ~lyc~l~, t~r iols ar~/o~
tetrols. ~lgo ~uitable ~re! NCC!-cvntailling ~re~olym~r~ h~.vir
i~CO c~,~ntent~ o~ ~:rosQ 25 to 3~5 ~ by we~ght, pr~e~ably ~rc~n
:~1 to ~4 ~i by weiyht, ba~ed or~ th~ tQt~l we~gnt, p~-epa~e~
fro~ t~.~ pc~ly~ .r andfor prcf~r~ly polyeth~r polyols
dea~r~l~e~l ~elow and di~hen~Tlmethane A,4'-dii~oc~anz~te,
mixtllr~3~ o~ di~h~nylm~tha.nf~ ~, 4 ~ - and 4, 4 ' ~ cyanate~
tc~lylT~a! a,4- an.dJnr 2,6-dilsocy2lIlates or raw ~I. Oth~
~ompo~l~da which have beer. ~und to be u~eful ar~ l.i guid
poly~.~o~y~n~te~ con~' n; n~ carbc)~iimid~a group~ O:F
i~ocy~nu~at~ riDs~ and h~vln~ NCo contentfi of ~rom 33 . ~ to
15 96 h~r we~ ~ht, pre~erA~ly from 31 to ~ by w0igh~ a~d
on t.he~ tota~ weiç~h~, for ~c~m~l~ on ~he b~0i~ c f d~Ph~tlvl-
lS tnetha~ 4,4'-, ~,4'- an~or 2,~ o~,yanate an~l/or tolylene
Ln~ r l, 5~ ocyaqate.
~h~ modified p~ly~ an~t~ an, i de~ , be mixed wi~h
c~nQ ~T~othe~ or ~i th n- - '; i~d c: x~ p~ly~ ~ac~y~n~te.~ ~uch.
as dil?h~3nylm~tharl~ ~,4~- andJor 4,4~ lisocyanate~, raw ~I,
tolyl~n~ 2, 4- and~r ~ diisocy~n~te.
ya~.~te~ which h~ve ~ee~ fc)urld to bQ c)articularlY usn.~ul
~r~ dl~henylmethanQ diis~cyar~ate isoml3r rnixtur~!!; o~- r~w ~I
a5 and. in par'ciaul~r, ~b~t MDI. h~.v~.n~ a ~ het~ylmethar~e :!lii&~-
cya~ate 1sorP~r- content of I~er~l 33 t~ 5~ gG by wei~, ~d a1so
pc~lyi~c~cya~a~e mixt.u~es b~oed OQ diDhe~rl~etha:n~ dii~oa.y~ t-a
~ontain.ing urethane grou~q ~nd h~ing an ~C~ cor~tent os f~om
1~ to 3 ~ y w~i~ht;
'~ Suitabl~ onlP~nd~ ~bj con~.ininC~ hydro~n atom~ r~a~ti~re
~ow~r~. i.s~.yem~tee ~re tho~e whi~ ear two or more r~ ti~re
group~ FQleG~d from l~mong c~H group~, SH g~bt~p, l~I grbUp~;,
,t~lH2 g;~p~ a~,-3 CY7~ id rJr~UE;~ 1 n ~.h~ mol~uL~.
Use i~ ad~Jlta~eo~l~ly n~d~ of ~hose havi~lg ~ furlc:tion~ r o~
frcmn ~ to ~, preferaLbly fro~ 3 to ~, and a me~n mole~ular
wei~ht o~ ~om 250 ~o 80U0~ p.referably from 300 ~o ~000.
Compound~ whi~ re heen fo~Lnd t~ b~ u~ful ~re, for
4~ ~.xAn~ple" polyetheIp olyaun~e ~nd~or pr~fer~bl~ polyol.~
~el4c~Qd ~bm t.he group ~onci.ctin~ of n~l~e~he~ polyol~,
polyAster poLyol~ olythio~thkr polyols, polye~eerarnlç3e~,
hy~roxyl--con'cair.ins~ eta 1~ ~nd hy~l~oxyl~ cln~1 n~ n~
~llphatîc ~QlY~arho~at~s or mixture~ o~ at lea~t two o the
~5 ~poei~i~d p~lyhlel. ~J8~ i9 .~rQf6i~rnb~ lneldU of~ pol~,re8t.er
~clyol.~ and~or ~olye~er p~ly~l9~ ~.h~ hydro~rl mlmb er of the
2182714
p~lyhy~oxyl ~ompo~md~ i~ h~rFe ge..nkr~:l ly ~om 15U to ~;0 arld
. prefrar~bly from 2~ to 6qO.
Suita~ ol~e~e~r pol~vls ~rl be pr~p~.red, f~r ~ mpl~, f~om
or~rliQ d:ic;~r.boxyl.ic aci~ ha~ fr~ to l~ car}~orl ~tom~;,
pr6,f~r~hly alipll~tic di~arbox,~rli~ id~: h~virlg fro~ ~
~arbon ato~3, a.nd po.l.yhy~ al~ohols, ~r~ra~ly liol:~,
h.~rin~ f rom a t:o 12 c~arborl at~m~ . pr~?~erahly f rom 2 ~o ~i
c~a~on ae.o~A. Su.tt~ dic!~rbc~x~ c a~i.d~ are, i~or e:xample:
~ucclnie ~ , ul~t~ric a~i~l, a~ ic aoi.d, suheri~ ~icd,
a:rel~ c1.cl, ~e~cic ~cic~, dec~ne~ r~oxylic a~id, maleic-
acid, ~rlc acid, ;ph~halic a~id, i~ophthalic a~id arld
'ce~eph~halic ac~d. The di~a~boxylic ~nid~ . b~ used ~lth~r
~ ndiv~ ally or iIl a~nixture with one a.~ot:her~ In pla~e of
th~ free di~rboxY~lic ao~.d~, 1t i~ so po~ le to u~e the
c~rro~pon~lin~ dic~.~bclxyli~ ~i.d de~rivative~ ~uch a~
dl~arbc~xylic ~est~r~ o ~lcoh~l~ h~in.~ from 1 to 4 car}~on
atom~ or di~a~oxyli~ ~nh~dri~e~. Rrq$er~no~ ren t.c:,
u~lA~ di~ oxrlic acid mixtures o~ s.lcc:~ n~ lutari~ ~nd
a0 EL~lipi~ ac~ de in w~ ht rati.oc ~f, fO~ ~Y~ 0 - 35 : .~S
50: ~0 -- 3~ d in psrticul~ adipi~ id. E~xample~ ~f
dihydric a~.d polyhydr3~c ~ h~ n parti.~ular diol~, are:
o~ha~ediol, di~thyl~n~ glycol, 1, 2- or 1, 3-p~p~3ne~; ol,
~iprc,pyl~ne ~l~aol, ~, 4-~ut~n~d~ c~l, 1, 5-~en~ edi~l,
1, ~ Y~n~l ol, 1, l O-dQc~nediol, glyc~rol and txim~thy~
p~o-~ne. P~ofc3rer~cq i~ ~iv~n to UI;in~ ethanedi.ol, di.~hylPnÆ
glycol., 1, 4-bue~ llol, 1., 5-pe~ntanediol, 1, 5 --hexanedit~l or
mi.xturc~s c~f at 1 e~ast ~ ~o o$ the d~ol~ ~peci~ied, in
p~rtlcul~:c ~ixturl2æ ~f 1 ,4-hutanediol, ~ ;pentanediol an,1
l,~-h*~an~iol ~t 19 al~ p~ le ~o U8~! polye~ter ;p~lyols
~ror~ lac~onf~s, eg. IE--caDrolac~tvne, ~r hydrc)xy~rbox
ac:i.d~, eg cl-hydroxyc~2~0ic a~id~
To :~r~P~r-3 th~3 poly~ tr pvlyc~l~s, ~he organt c ~ f o~ q~.~op~ e
~S A3~0~natie and ~refe~ral~ly ali~ha~ic, polyc:arbc:xylle uc:ia3 ~n~,~
or deri~a~ re~ and ~ol~,7h~dric: i~lcohol~ oan ~. po~yeon~n~fed
in the ~ s~nt;~ e~t~ r t ~r proe~erhhl~ i.n t:he3 pr~ence of
e~terifl~ati~n ~alyst~, ~dv~ntaseou~;ly in an ;L~mosphsr~ c~.
inert ~aæ ~lch aa nitro~n, ~ on monox~de, heli.u~, ar~on,
4~ e~ta~, in the melt. atc f~om 150 to ;250 C, ~r~e~ly ~ m l~o
to ~O~C, ~t ~.o~heria sre~ re or unfl~r reduc~,ed ~ressure,
- t:o th~ ~ r~d. Acl.CI nu~ er ~h~ ch i~ ad~ ti3qQo~sly le!~s ~h~n
10, ~re*rAb1y le~8 than 2. Accordir~g to z~ prefe.rred e~d~
~e~t, th.e e~te_ if ic~tionL ~ix~llr~a i~ poiy~ondenfie~ ZLt ~he
~n~re temperae~ro~ ~o ~n aci~ nllmhc~r of ~rom B0 to 30,
pre~a~ly ~ror~ 40 tC3 30, under atmo~pherlc! ~?r~3s~u;~o ar~
3l~sequentl~r unde~ ~ ~re~a~lre of less ~hAn ~0() mbar,
21827~4
p~efer~bly f~ow. 50 to 150 ~r. ~;uit 3bl e esteri.~iicar:ion
.~a1:;alystS ~re, L~,r P~xi~mp~ ~, iroJ~, cac3r.~ium, c-i~al t, le~l,
ælnc, au~imony, m~ i.um, t.itarlium an~ J~'caly~ts ir~ the
~onrl 4f m~a:l.6, metal oxide~ or m~t~ lt~. ~owever, t:he
S v~ly~ondensa~ion aa~ o bR c~ri~d ou~ ln ~ uid phYse
in the prese~lce o Ai.lu~nte a~d~o ent~ rs ~iuc~ as
h~nzene, ~olueI~e, xylene~ r c;hlorobqn~el ~ t~ az.~c~tropically
ti ll o~f the wat~r of ~.onde~tion .
l.O ~rn p~ep~r~ 'ch~ p~l ye~t~ pol~rol~, the~ o~n.i~. polycarboxylic
~c:id~ and~or d~ ve~ and pol yhyar~ c a~cotLol~ aro adva~.a
u~ly polyc~ n~ed in ~ molar ratio o~
pre~ rably 1 . 1. oS
lS ~ o:Lye~t~ y~3~ hta.ined pxefe:~eu;~ have. a .~lmc~ n~l-
.ity of frc~lu 2 cn 4, in partlaular fr~m a ~o 3, ~d ~ molar
w~ight o~ frb~n 25~ to ~000, Pr-3fer~bly .~rorn 300 to 2000.
'~n particulal~, h~.we?~e~ ;h~ polyolo. used ~ e polyether
pcl~-ol~ .p~r~ by krlo~n m~!.th~ds, f~r ex~ple l:~y a~ionic
polyme~l~a~ion ~ ~lk*li met~l hydre~xi~ uch ~ ~o~iu~
o~ pot~s~;i~n l ydrvxido ~r Ff.lkali. me~ lkoxid~fi ~uch ~
sodl~m m~thoxi~ odium or potass;ium ~tlloxi~l~ br pota~iurn
i.~opLoyVXia~ ~6 c~t~.lyæt~ Nnd with a~iti.on of at le~Yt one
ini~ia~or mol~ le ~-on~ca.ining fxom ~ to ~, pxefe.r~ly ,~om ~
to ~, roa~tlve hydrogen a~m~ ih b~n~e~d f~~[Lt or by c.ationio
pol~e.ri.~tion usins ~w~ ids ~uc~h as Antimor~y ~ent~-
~hlorid.e. boron ~3~ubx~fle etherAte, et~. ~ or ~L~hing e;3~th~
af~: c:A~ly~t6/ rom on~ o~ mo~ alkylP~ oxit3.e6 h~vi.n.l7 f~om
to 4 c~bon ~tom~ in t~e ,~ n~ r~di.caLl~
~it~le ~1.kyler.e c:,xi~e~ are, ~o~ example, tetrahydr~u~n,
l, 3-~ropylQ~e oxid~, 1. a- or a, ~-bl~tylq~ >xid~ yron~
oxide ~nd ~f~albl.y ethyl~n~ c)xide ~d L~a-prcpyleIle oxide.
The alk~ n~ oxl.~ s ~Rr. b~ ed individu~:lly, ;~ltel;-nat~ely i.n
succ~r~ion or a~ mixtur~ ui~ahlo initi~ or m~ ul~ ar6~,
or exarn;ple: ~ater, orqar~ic dicarbox~ id~ ~UC!h i~,11
s~c~ir~ l, A~ a~ pht;~ali~ acid ~1~ t~erephtha.l ic
a~ia, ~liPh~tic and aromatic, un;~ ted or ~-morlo41kyi~ted,
~, N- or N, ~' -dl~lkylated ~i~mine~ h~in.~ rom 1 to 4 car~o~
~tc~ he alkyl radi4~1, ~u~h a~ llnalkyla~A, ~o~O-
e.lk~l~ted Ol~. ~alk~latefl Qthylenediomin~, ~lethylenet~i~ine,
t:riethylenetet~r~m~n~ ~,3-p~o~yl6!~ledi.amin~. 1,3- or
1, 4-butyll3ne~lamine, 1, ~-, 1, 3-, 1. 4-, 1, 5- ~nd ~, 6-hex2-
4~ r~e'chyl~nedismine, Dhenylen~ i.aminqs, ~,3-, 2,4- And
2~827~4
.~ ~
2~6-t~'uylerle~d.i~minP~ and ~4r_~ 2,~ - a~d A,2~ Linc~-
dip~enylsnetha~o .
~h~r ~uit~ initi~t:or nwl~ul~ ~r~ ~l lca~loi ~ir~ su;~h a~
ethan~lamiIle, N-nl~thyl~eh~ol~nine ~nd N-ethy1 ethar~olami~
dialkanolbm~.nes sucl~ a6 di~'~h~nol~sn~ e. ~-m~3t}lyldi~h~llt~ï-
amine and. N-~thyldi~t,hanol amin~r a-nd tri alkar.~ ~mines such ~s
~:rieth~ll017llsi~ nd alr~mcjni~. Pl e.fer~nce i~; gi~r~ u~,ing
polyhyc~.ri~, in p~.ic~ll.a~ dihydr~c a~l~sior ~-~lhydri~ alc~h~l~
1~ ~u~h a~ nc~fli~ arld 1, 3-pco~lpallQdiol~ ~liethylo;ne
~ly~c~l, di~;sroI~ylolle ~ly~ l, I, 4-~ut~ne~liol, :L, 6 -hexanedio ~ )
~lycero1. trimq~th.V~ o1Pro~anQ~ pe.ntal~ry~hrito1, ~orbitol and
suc:ros~ .
t~ Th~ po3ye~h~r ~o1y<~1~, p~ r~ p~1y~ o~y~ene a.r~ poly
ox~ro~Y16~ pn1~0x~r~thy1~ne po1yolfi, have a iunctic;~la1it~, of
p~e~e~ra~ly ~ro~ 2 to a ~n~ i.n ~a-rticulax f:rc,m. 3 to .5 and
mo1e~tl1~r wQighta ~ from 250 t.c~ 8000, ~r~fer~1y f~om ~00 tc~
1500 a~c~ in par~c~lar ~r~!n 3s0 ~o 11.00, ar~l ElU~ ..e noly-
~n oY.y~etr~e~l~e glyc~ ha~e. a mo1e~:~13~ w~i~Jh~ o~ up to
abc;)ut 3 5 ~ 0 .
~urt:her 6ui.~1e ~1yq~he~ poly~l~ ar~ pc~ uer-mvdif i.ed p~]. ~ -
et:he}r polyol~, p~ rzlbly g.r~ft polyet.her polyols, irl ;pa~tic~-
~r, Ul~F tho~e kb~dd ~ ~tS~rerle and/or ac:rylonitrile ~lich ~e
p~ep~r4~d. I~y i.r~ ~itU ~ ri.~tioh ~ cr~10ni.tl-11e~ styr~ne
o~ pre~rably mixe~rea o~ ~tyrene and a~ylc)ni~.~ilç, eg. in
w~ight ratio o from 90: 10 tc~ 10: g~. ~ref~r~bly ~Dm 7C):
.~0 to 30: 70, ac~.v~ntageo~ ly irl t.he abvv. rti~ned Eloly~.th~
3C polyol~ in~ a m4thod ~imi.lar t:~ ~ho~e. gi~en in the C:erman
PQten~; 1.1 11 394, 12 22 ~65 (IIS 3 3~4 273, ~ 3~ 51, 3 $il.3
Og3), 11 S~ 53fi ~t:a 10 40 ~) a~d ll ~2 5~ G~3 98'7 61~,
and c~ o pc~1y~h~r polyc~ dispersions ~Ont~.n~r~g ~ pers~d
~h~ ually 1~1 arl am~unt o~ ~rom 1 t.t~ 50 ~ b~ ~igh~,
5~ ra~1y ~om ~ ~o ~S q6 bi~ w~i.gh~ for 4xa~ lQ p~1yureas,
po1yhy~ id.~s, po~ th2u~e6: ~nt~ n~ nded ter~-Ami~O
S~rol~.p~ ~nclJo~ me1am1n~, ~a ~hich are de~c~rihed, ~o~ exa~Dle,
~n ~ 011 75a (U~ 4 ~04 'J08), US-A-4 374 203 ~nd
I~E A--3~ 31 4~7.
4~ .
The p~ly~ther uol:y~ c~n, 11ke tlle poly~te~ ~olyo1~, ~e
~d indi~id~.a1L~ hr in rh~ form ~ mixt.ut R~; . Fur~hermor~e,
they c.~n be mixea wlth t~e ~r~f t polyether ~ol.yol8 or poly-
este~r ~?oly~ r wi Lh ~he hs~ro~yl-~!~ntai~in~ po.lyes;~er -
~m~de~a, polyac~t~lç, pol~ra~rhon.~t~te: ~ndior ~olyetherl~oly-
~lliiS1~3S ~
2182714
~ 10
$ui~ 1e hy~oxyl-cor t;~ in~ l.yac~c~.g ~re, for ex~znp]~,
t~h~ m~t~nd~ wh~.eh ~a~ he E~re~i~.re~ ~r~L ylycols s~i-h ~#
.~ieth.yl~no ~ly~ol, tri~hy'l.~n~ qlycc~l, 4,~r-~ihYd.~t.~xye~.hox~r-
~iphenylt~im~thylm~sh~7 ~, h~.DxAnY.alol an~ ~ hyde.
Su.ir~hle poly~cet~l~ car~ bt-~ Elr~ r~d l~ ~o~y~r.e;ri.zal i~n
o~ c~rcli~ e,
SuitAbl~ 2~ydr~xyl-cont~lnin~ pol~:arbc~l~atec~ are thos~ c,f ~.h~
type kn~wn per ~e hThic.h c:an }~ ~rep6r~d, f~r ex~n~ e, by
1~ re~c~ln.~ ~iols BUc~. ~6 1., 3~rt~p~n~.~iol, 1, 4 -hut~ne~ bl ~nt~c~r
e~C~nQ~li4l, ~ thylQn~ cp71ycol, trlethy~ e~e gly::ol o~
te~aethylen~3 gly~ol with diaryl aarb~h~t~s, eg. ~ hQl~l
c~arbo~a~e, f~r pho~
l.S ~'he. ~c~1ye~tçr~ ~x in~ de, ~nr example, t~ ?, p:Ck~ mi n::lnl~ly
' line~r conden~;ate~ ob4~;n~ frbm po1ybas~ aturate~ ~n~ r
uns*t~rat~d c:~rboxy1ic r~cid6 or t~ arlhydxia~ L po1~y-
Lçtional c~tur~!at-ld and,~hr un~;at~at~d ami noalc~ r
mixtUrel; of ~olyhydrlc rllc~hc~ inoa:L~h~ r
;;20 I)oly~nines.
Slllt-~le polyet:4~rpoly~nin~ n ~e px~.p~re~i ~r~m th~.
;~rementio~e~d pclly~thcl~ poly~:ls ~y l~ow~l methodA ~x~npl~
whi~h m~y be mentlonc~d ~re the cyAno~l lcylatic~. bi~ pol~ox~7 -
S aLk~Jlen~ polyolE~ and suh~Q~uent h~d~o~en~ti-J~n of Jche ~ i ~r 1 l ~
orme~1 ~US 3 267 OS0~ or th~ P~rti~l or com~lete amir~ on ~f:
p~l~.oxy~lkyl~ne p~lyol~; with æmines vr a~ 7ni;~ in the
pr~se~nce o~ hydr;~qen and cat~ t~ tL)~ 1~ 15 373 ) .
It i.c also possi~le to llse ~}yols i~ w~ h the~ ~lydrox~l
g3~0up~ are re~la~ed at l~t par~ially ~y C~--A.~id ~rou~.
c) Th~ ri~ foan~ e~ oh i~y~nat~ ~n bf~ l~rodu~d wi~ r
-~ith~ut cone:o~tallt ut3e of ch~i~ ~cterlde~ a and~or cro~li2Lk
~ owkv~, the cld~ition ~ chain ~xt~r~dç~, R. cro,s6-
1 ink~ s ~r, 1~ d*~ired, ~i.xtu~ th~r~t,~ n ~ a~v.a~t~e~us
for mod1fying ehc n~eeh~antc~al pro~e~r~i~s~ e~. the h~rd~as.
C:hain. ex~endicrs andt~r ~o~lin1~e~ u~ed a~e d~ol~ an~Jc,r
triol h~vin~ mol~c~l~r we~ght~ h~n 250, 3:re~r~
4~ from ~0 to aon . ~c~n~ bf ~uit~le ch~ n extender~Jcro~ -
linkers ~re ~ h~L~.i.c, cy~.lo~ h~ti.~ ~fl~or a~aliphai:i~
d.iol9 n~vi~g from a to 14, ~r~ ly ~ro~n 4 to 10, c~bor~
at-~m.q, for e~am~le ~t:hylene ~ly~ol, 1, 3- p~pan~diol,
l,10-~e~ ne~d~o1~, c-, m- or p-dihy~roxyc~ ne, ~I..ethyl~
4S . gl~!o], c~ipr~ ne~ gl,~ol and prefercbly l.~-bl~e~
hQxa~ nd ~ 2-hy~oxs~et~l)hydro~uincnle~ t.~ iol~
s~ch a~ 1, 7., 4- or 1, 3, 5-tri.hydrc:xy~ hex~n~, q~ and
2182714
tx~iMethy~ rop~ne aIld 1~ molecular w~ ht
hy~r~ cO~t~in~n~ ~c~ly31k~1~n~a oxi~e~ based ~n ~thylelle
an~/or 1, 7.-propyle~ bX~ d~ a~ the a~ov~ iol~e~l ~i.ol~
~r~d,~o~ tri~lY ~ ~niti~tor ~nole~ul~s..
I~ ahain ~:x~en~t~rs, cro~slinker~ or rn.ix~:u~ thex~o~ ~r~ u~ed
for pr~uc i~ thta J~ polyur~th~ o~ , th~e ~re ~dY~m
t~g~u~ly use~ i s~ an ;lt~o~nt of from ~1 to 20 ~ s~y ~ei~h~,
, pr~erably f~ 2 to 8 ~6 by weigh~ 3sed on tht~ w~i~h.t o~
1~ 'ch~ relati~r~ly h~ah molQ~ular weigh~ comIo~ d~ (h)~
d) Blowing ~Cent~ ld~ whi.ch cRn be~ uOed for prt~ducing th~. ~igid
~ me ln~ de, ~c,r examp.le, whter, whic~ ~e~t~ ~rith
i~cyan~te: lJro~s ~o fonn carbon d.iox*de, ~ or phy~ic~lly
ac~ing ~lowi~ ~ee~ Suita~le '~lowing asrents ar~ auicl~
:~hl<~ e i~ert towafri the nr~nic, n~oalled ~r ~ mr~ -ied
polyisoGyan~te,~ ~nd h~vd~s boilin5r pt~ir~,s ~ w 100 C t
pre~era~ belo-~ 5VD~') 1n partàaul~r 1~ro~ -50~C t:o ~O~C, aLt
pheric pr~sure, ~o eh~t ~ y e~r~orz~e ~r~d~r th~ act.i~n
hç exofGhe~nic ~oly~lelition re~.tlo~. Ex~;71es o~ .~Lut!h
p~efe~ y u~ed liquid~ are ~lka~ such a~ hept~ne, h.exhne,
n- and iso-p~rn~a~, pre~2r~Iy lnd~trial mixture~ of n- an~
i~o-p~rtane~, n- ~nd i.60-hu~ane an~ rop~ne.~ ~.y~ k2n~s
s~ h ~ cyclopcm~ ~nd/or cycl~heLx~ne. elilers ~uch ~S
~5 fur~n, dimo~hyl ~th~.r ~nd die~hyl ether~ ke~nee ~uch a~
~etone a~-~l mc3thyl e~h~l ketc~ lkyl car3~ox~1ate~ U~
me~hyl ~or~ate, din~Qthyl ox~l~te a~d eth~ et~ It i~
al~o F~oE;~ibl* tcl u~;~ mixturcs c~ the~Q l~w-boiling li~id~
w.ith on~ an~ther andJ~;?r with o~he~ ~uh~ ut.~d or tln~ub&~i-
~0 t~lted hydrc~ rbon~. Othe~ e~Lit.a~le comPc~1mds ar~ gAnic:
carboxylie aeicl~ ah ~ :~onnie z~oi~, aeetie acid, oxalie
aeàcl, rieinolei~ ~eid an~ e~r.b~ eontaining ~omp~un~lo~
Pr~.Eer~d blowing ~gents a~ w~t~r, ~r~;ia~ u~ol.,
:35 ¢~.~.rhoxyl i.~ s. i~ rtleuLar formic a~.id. low-boi:Ling
licEuids such A~ h~.r~, e~te:~, keton~, and hyd~.o~rbo~, in
p~rticu1~ n-pen~arlc, iY~-P~tEIne~ cyclo~ent.a~o ~n~l
2 . ~-dim~ylprop~A~3. .
40 e) Catalys~t~ ) u~ed ~r ~r~u~lncr the ri.~Tid i~J~ms are, in
~'cicul.ar, c~ ~lu .dE~ wh1ch s'cr~n.gly Accel.~Ya~Q th~ rea-~tion
ol~ ~h~ mpound~ o~ ~he ~omponent ~ nd, if usQd, lc:~
co~ta1nins reacti~rc hyd~c~g~n atoms, in p~rti.cula~ hy~r~xyl
group:~, with the org;~nlc, mc~dii~d or un~nodiE~.e~i polyi~o-
4~ cyarlat~s la)~ Suit~le eata1yst~ are org~1c meeal a~mE~
pref erably orge~ic ~in colrpoo~ uch ~ tin ~ IX) ~ t~3 ~f
c,rg~nic car1~ox~rlic~ a~ids, eg. tin ~ etate, tin (~
218271~
oc~at.e, t~intlr) e~ lhexarlc~a~e~ ~nd tir~XI) l~ te, and t;~J~.
dialk~i~in ~IY) g~llt8 ~1~ o~ ic c~ axyl~ c ~ g.
dibutylt.in di~cetate, di~u~ltirl di~c~ur~te, dib~Tyl~.bn
dimale~te and di.~C'-y~ tin di~¢e~.ate. Th~- ~r~anic n~et:~l
S cc,mp~ n~ls ~re US~sd ~l~n~ 0~ .urefera~ly ~n cc~mb'natioll with
~r~ngly I:~SiC! aminEs~ Exan~16~ ~,Yhich ~nay b~ ~r,ent;i~:~neca a~
3midine.s ~uch ~Is ~!, 3~ .eth~Tl- 3, 4, ~, 6~ rahydro~yrimi~ e,
terti~ry ~mine~ su~h. ~ ~riethyl~nlne, t~ibut~l,~ln~r
dimHthylb~nzylAmirle, 2J-me~hylmo3~pholin4 . N~ h~lmor~holine~
N- cycl oh~x~Tï.mon~hol. i~e, N, ~, ~ ', N' - tet r~methyl ~sthylenedi aminc
N,N, N' ,~'-tetrarrLQth~lb~tanc~dj.~ni~e, ~3,N,N' ,N' -t,etr~net~
h~ ne--1,6-d.ismine, pe~t~ne~hyldiethyl,~an~triamine,
bl8 ~im~thylamino~t~hYl~ ather, bie~dim~t~ylami~opro~yl)~rea,
~imethyl~ire~in~ --d ~thylinlid~ol*, l-~zabicyclo--
1.5 ~,3.~]o~t~e and p~efe~ly 1,~-dia~abia~clo~2 ~.~loctan~,
and alka~ ~ine olapounds ~uch as triet}la~lol~in~,
tr~so~-op~nol~mine, ~-~et~yldietharlolamin~ an~
~-eth~laie~h~nol.~.~lne ~ d~l~thyletharl~la~in~
O~her sui~a~le ~At~ly~s a~e: tri~dlalk~l~nin~alkyl)-s--hexa-
hydrot~i4~inee, in ~arti~.ular tri~lN.N-di~ethylaminh-
~ro~ hexAhydrotriazlre, ~Rtra~lkylammuni~n ~alts su~ a~
N.~ trimethy~ 2-hydr~y~ro~ylr A ~i um o~ate. ~,N,~-tr
m~lhyl-~7-~-hydrox~prop~lammonium 7.-~thylhexan~ate, t~a~
2~; alky'l;~m~non;um hydroxi~leg ~uan ~ te~ram~h~rl9"~m~niust~
hy~oxide, ~lk~ll metal hy~xide~ ~uch ~s sodi~ hydroxide
a~d ~lkali ~etal alkoxi~e~ h a~ sod.~u~ ~etho~ *r~d
yOtas~iu~ ~o~o~ide, and ~ lXali metal saLt~ or
~lk~ e ~ar~h m~tsl s~lts of fatty ~ci~ vlng ~r~m l to
20 carbon ~o~Y and, i~ d4~ d, lateral OH ~o-~p~.
Preferenc~ iven t.v ~Isin~ ~t~rtiary ~mincs, t~ ~d ~i~n~t~
c~mpouncls, alkali ~etal an~ alkali~o ~r~h ~e!~al c:i~rb~:~y-
lat~3~, c~atern~ry ~noni~ 6~1t~, 6~x~h~d~0~ 2in~s ;EInd
3~ ~r~ ~ (di~lkyl~ninom~thY1) ph~
Pref~renc~ ia ~iven tCi u6i~ rom 0,001 tc~ 5 ~ ~y ~7~ightJ. ir~
:~art~ ~ular from ~ . 05 tv 2 ~6 ~y weight, o~ r:at~ly~t or caca-
~yfit cc~mhi.nation,- b~.~e~ on th~ w~lghc ~ thle oomPone~t (~).
Ac~ordin~5 t~ t.h~ pre~ . i~vellticn, ~he fla~lle ~etardi~n~ u~3d
16 pr~m~nt;~ t~ib~om~n~ope~yl. ~l~nh~l B~o~iI~e~ tai~-
l~m~ ~etard~ts whi~h ~an be UQQA in ~ url~s in
~ditiG~ ~0 t~ib~ neopen~l Al~hol ar~. for QxamPle, ~ea~
4~ tion produ~ts of tr~ m~n~o~tyl alcohbl. di~romone~entyl
~ly~l a~ ~t~ r~actlon ~roduc~ ibromo~utenediol ~n~ i~s
r~ction Ylo~uct~ 2~3-di~mop~o~ l an~. lt~. rea~ei~n pro~-~
21&27~4
uct~ tral~romophth~l ~ c ar.L~yd~ nd it;s re~tic~r~ px-odu~c~,
tri~o~bph~r~ol and .i~ r~:a~ion l?rodu~tfi~ ~tlabrom~bi~ L~n~l
a it~ ~action prodl~t3, ~r-vmin~ ;n~ng pho~hc)~:~c
q!~;t~r~ a~lcl brominat~i:d ~lydrocar~c~nfi~ l;
s
Ap~rt f~orn the hromine--~c~n~ y flam~ ret;~aar~ t i x;
aLso p~ss~le t.o U~e ~h~ o~her n-)n--brom~.~,e~ ~ta.ir~in~ i~l arne
r~et~3rda~ knowu ~or th~ produ~ t~ xigld ~ m6 ~as~d ~n
i ~o~yana f~ .
Suital~le fla~ne re.~3r~antY~ ~Lret ~or e~xa~pLe, di.ohenyl c~e~7
phat~, tricr~s~l pi~osp~.~t~, trie~;h~l ox tri.butyl
E~hc~ph~t~, tris ~2- chlorc)eth~,rl ) pho6I?hate~ ~;r~s ~2--chlo~o
. propyl) pho~h~te, tr~ ~ ~1 r ~ -di~:hlvr~opro~yl) ~ho~ ~hate,
c~ral~ 2 c~,hlo~o~thyl) ~til~len~ dipho~h~te, di~hrl
eth~ hv3~ll0n~e, diethy;l dieth~ol~ln; ~ th~lph~phon~te.
B~ Le~ the phos~n~ com~o~ds alrea~lsr ment.ioned, i~
a~so po6~ 1e to use inor,O~i~: or c~rg~nic f ~ b retar~nt~
~0 ~uch as rqld pho~phor~r h~lr~tocl alumirl~un oxide, ~ntirQony
tri.oxidc, nrsenic oxide, ~ vl,~phosphate ~d cal~i~m
lf~te, expa~aed ~raPh.it~ or ~ranuri~ tl C~e~ atiYe~5 13UCh
~,s m21~nine, or mixtur~s of al; l~ t two fl~utl-3 ret~rd~ts
such ~.~ ~nmoniw~ polyDhn~ph~te~ and mel~Q~in~ cq al~o~ lf
desi:red, mai~ tArch or ammor~ ol~ho~p~at~, m~la:mi.~ .an~l
n~d graE~hite ar~d,~or Fo~.~ l,y arorn~Lti~ poly~ter~ r
fl~m~proo~ing th~ polyisc~ n~te ~olyz~dditio~ rc~ducts. L~
h~3 gç~er~lly h~ n fo~ o bo ad~ 0us t~ ~ tc~al o~
.~om 5 tc~ l5n p~rt-s by weis~ht, pre~Rrably ~rom 3~ t~ 10?
~rts by weight, oi~ flame ~etardan~ for e~c~h. 100 ~arts hy
~ei~h~ o the com~o~ t tb~.
g~ ed, ~ r~h~r ~ i1iarieE a~d~or 3dditive~ Ig~ oa~ e
inocr~ ted l~to ~he r~ ctlon InLxt.:ur~ f;c~r p~oducil-q the
rigi.~l ~8~ h~se~ n~t~ es wElich ma~ be
~u?~t ~ f rl are ~ur~aco-~tive ~ nc~ fc~ t:lbil:L2~r~;,
cell rogulator~, fil1br6, dye~, piqmene3. hy~lr~lysi~
1l~hibitor~. f~Ln6i~t~tic an~ h~cterio~at:ic ou~t.~n~e~s.
S~lit~l.e~ ~urfac~-a~tiVe sub~n~:es are, fQ~ ~camp1e,
co~ound~ ~hich s~re to aid t.he hO~no~eniz~t~i.Or~ o~ t~
stllrtln~ materi~ls Ar~d m~y a1so be 6uit~hle ~or regul~tin~
~h~3 cEa11 stru~ ur~ of th~ ~la~tics. ~am~l~s ~hich may ~e
menti~ned a~e emu1.,i~iers s~h ~ he sodiun ~altY c~ cas~or
oil sulfate6 or of f2ltty ~c1~8 ~nd al~o ~.ine g2.1t~ of fattir
~id~, ~g. diethy1amin~ ole~t~, diethanolami~e ~t:ea~aee,
~11eth3n~1ami~e ricinole~te, salt~ o~ oni~ ~cidq, ~
~ ~ ` 14 2182~14
~l.k~ t~l o~ amrnc~i.um ~;al~ oi~ ~od~,cylbenæP~ne- ~r
di.na~hthyl~m~thalledi~t~lfvni~ aci.d and ric~inc;l~.ic ~cid; ~æn
stabilizer~, in };a~ icular th~ b~d ~7n 51 li~.c~e, !,uch as
~iloxane- ~x~alkYl~ne coPol~ne_~ and o~;h~ar or~ opolysilo~-
ane~, ethoxylat~ ~lkylphellol~, ethc~xylate~ f~ ~ a.lcoh~
p~raffin oil~. cast,or ~ ter~ or r.i~i~ol~ic ~ t~r9, 'rurk~y
r~d c~il arld pe~.u~ oil, ~d cell requl;~tor~ h ar
~ra~fi~ al:t.y alaohol~ and dim~thylpoly~iloxane~ Th~
abo~e de6~ribed olis~ ylate6 ha-~in~ prJ;L~oxyalkyl~e
~n~l fluoro~llcAne radi~ A~1 ~ide g~ups arql al o ~uit~hle
or lm~ro~i~g the ~ yin~ ~c~ion) the c~ ructure a.r~d~'
or s~zbilizl~ the ~oam. 'rhf3 ~lrface~ .tive .~ 3tanc~s are
u~ Lly u~ea i~ a~ountg c~ ~.ft~m O . Cll t~ 5 part~ by w~i~ht,
7c~s~d o~ 100 p~iLrtf; l~y t`141ght of ~ne cc~ c
F~r th~ urpos~s o~ the ~resent~ j.nv~r~tion, ill~r~, i.n
~art1c!u1.ar ~ein~o~cin~r ~i ller~, are 's.he cus tom~ry ~rganic ~nd
i nc~rq~ni~ ~iller~, ~ei~orcem~ts, ~.c, kno~.m p*x 5C.
Sl~eci~ ex~mpl~ no~q~ic fill~r~ ~uch a~ lee~us
.o minera~ or ~xample ~hQet ~ilio~t~ ~u~h a~ antigo~$te,
s~r~tin~, he rrtble~-le~. P~h~ole6. chrys~ils, talc; met~l
c~xi ~lea ~uch ,~s; kaolin, ~llumi.num ox.ides, tl~anil~n oxide~q ~n~
i~on ~ , met~l ~alt~ h a~ ch~lk, barit~ ar~ inorg~rLi~
pig~ s such as ~a~ ul~'ide, 2in~ ~ulf iCle and ~12L~S,
~5 etc, ~re~er~ce is gi-~e~ t:~ using ka~lin ~ehin~ clay~,
alumillum sill~te. ~ opr~.ipitat~s of ~ariunL sulAte ~ld
a,l~hi~wn sillcate ~n~ al~o rlatu~a~. ar~l syn~he.tl~ ~ibrc~u~
minerzll~ such a~ woll~t~nite., m~tal an~, ~n particula~,
~la~E~ flbors of ~-aribus len~th3, wh~ h ma~y, i.~ des.~r~d, b~
coa~e~. Example~3 o:~ 6uit~bl~ orga~iç 4111e~ are: e~rb~t~,
m.elamine, ro~in, ~y-~lo~ent~d~yl r~6~in~ a~ld srr~t polymer,~,
and ~l~o cellulo&o ~iher~ 'l.ynmid~, ~olyac.~ylon.it~ei.le~
J?olyurethan~ or prblye~t.e~ ~14~F~ b~eed r~n ~ ti~ d~or
~li phat~ c ~lc~rbo~lie e~er~ r ~ii ~n partiaular céLrbbn.
f i.b6lr~
~he ~ ~rg~nïc ~s~d or~ani~ r a c~arl bc~ u~;ed iI~di~ lu~l ly ~x
a~ m~xtu~e.~ ~nd a~ ad~r~nt~gql4usly incr.~rporated ~.nto t~i2
re~c!tion I~ Ct~Fe i~ P~mo~3nt~l of~ rom O.5 ~.o 3~ ~ hy wei~rht,
~0 ~r~f~3~abl~ ~rC~m 1 tO 15 g4 ~ we.i~}l~, ha~d C)~ e weiC3~ of
t;he comp~n~:~t~ ) to (c~ ut wi.th the c:ontellt of rn~c~
wo~ren~ a~d ~ro~en ~abr.ic~ ~f n~tu~al elIld syr~t~et~ f i~e~3
bein~ le to r~ah va~ o~ uP t~ 80 S.
45 D6s,.alilc of the aboY~ ~ ti~r~e~ and ~s~rthQr ~Arti~ m~teria1~ ~:an
~e foun~ the ~ liYt late~ u.r6~, f-~ exampl~ the n~ono~rr~ph
by J. ~. 3Aurlae~ d ~ c. rr l~ch ~High Pc~ rs" Vc~ me x~,
` ~ 21&271~
Pol~ur~thanea, par~ an~i 7., Ir~te~cl~no~ Pu~ h~r~ 1~6~ ~n~
19~4 or Kun~ l vf~.handl~ hr P~l~ur~ha~e, ~olum~ 7, C~rl-HaIls3e~l
~erl~g, Muni~h, Vie~n~, J.-t, ~d and 3~d Edition, 1366, ~9g3 and
~ .
.~
T~e iE;o~ran~ -b~ed ri~id ~oam~s or t~h~ pr;~sqn~. in~e~tic-n ~re
~peciall~r th~ cQnt;.aining ur¢thane a~cl/or i.~o~y~ r~te and~/or
hiu~et ~d~r al.l~han~te anc~/or u~er~ 3n~ ~nd~'oY ~Irea an~l~o
ç~r`bo;liit~ide 53roUp3 a~ ac~ris~ic oheml c~1 st.r al
10 eïe;~e~t~.
p~od l~e the ri.~ o~ns b~e~d on i.~c~ ate . 1:he o~ nic
d~or mocli ied org~a.nic p~1yi~oa~anatqs (a), the c:ornp~ur~4
~onta~ n.i ~g hyd~o~e~ a~oms rQacti~e! to~d isocya}~tes and, i~
15 ae5~xed~ eh3~in ex~ç~.nde~ ~n~ox croe~1~nker~ (c~ ar~ reactec~ .~r
~;urh ~o~:Ln~ ~h~t ~h~ ~.quiva~ence rat~ o of NCO Y~bup6 or th4
lyi6c~c~yan~.t~ ~a~ to ehe ~um of thc r~;ti~re hydrog~3n ato~n~ o~
.he component~ ~b) ~nd, if ~d, (e~ i~; O.~S - l.2~:l, prefe~r~y
n . ~5-1. 15 1 ~nfl in p~rt icu1, r 1-1. OS ! 1~ If tne ri~id ~ns
ao c~n~in ~ l*a~t ~ome ~on~-d i~o~yanura~e ~rouE~, u~e is ~lsu~lly
mad~ o~ A xPtio of ~C~ rou~ f ~h~ pOlyi800y~1~1tes3 (~1) tO thc
~uun of the re~cti~ J. o~ atom~ ~f thQ ~ompon~nt (~) and, ~f
us~ c:) o~ l.S-~:o:l, p,.çPfer~bly 1~
~5 Riy~ o~ms base~ on is~anate o.re p~Q:t;~ hl.y prc:~ducetl h~ the
casting v~ ~pr~yin~ proce6~;. I~ ~rti2u'~r, us~ i~ here r~Lade o~
f~.rnins~ into ~lc rk~ ox ~ i~ss or o~ con~.in~lou.~ n~n~f~ctur~ ~y
~he ~ou}~l~e conv~or }~01t prc~ae~ It ha~ bee~ o~nd ~o b~
~rtiaula~l~ a~vaDt~.çrec~us to u6s the two-~ompone~t p coce~s ~nd
30 co~i~: the ~orm~ ve ~om~ one~t~ d), (~ na, i
de~ired, (~ ;1 (9) into th~ ne~t (A) and ~c e~nplo~r th~
orçJ~nic pol.yi~oa~anate~, nwdi~i~d polsri~ocy~at~ la) or m~xtur~
of ~.he zpe~ ed ~lyi~ocyar~'ce~ and, ~ ~ de~ired, blowiny Ocen~;
(d) a~ c- _ or)~n~ ~B)
T)~ s~ component~ ~e mix~d at ~rom 15 tc~ 5~ c, pref~ra~l~
~ro~ 20 ~o 60 C ~nd in kart;i~ula.r f~om 20 ~ 35 ~, and intro~luc~
into t~e opes- h~ol~ e~, If ~3.e~i~e~ nder ir,c~ e~ p~ef~re i~r,~
th ~ c l o ~ ed me~l d .
I~ c] o~e~ molfi~, it i~ o Po~lble to ul3e r~?r~ fo4m- .~or~
re~c~tio~ ture tkan i~ xe~ d ~:o cvmplet~l~r fill t.he m~ld.
~'hi.æ gives ~ompacted oaln2:.
2182714
The ri~ld ~;o~ or ~ol~e~ ri~id ~anl~ p.~roduc~sd hy ~he Dro~e~s
th~ pr~s~nt inVftnti~n hav~ a de~it~ of ~m 0 . 0~ to 0 . 7~ ~Jc~
prefera~ly ~rcn~ o.oa5 to O.~A ~m~ ~n.c~ t.:LCu~ from 0 ~03 t o
~ . 1 gJc~r,3
Tney ar~ partie~ularl~ hl~ a9 ~ ulat~Gl~ Tnat*rrial in th~
b~.ildi~g ~ecw~, e~. ~s ~nte~ne~liat~ laye~ r sandwich ~ ~r.
or as iIl~3ulatio~ ho~l-ds fox ~h~ the~nal insul~tiorl o~ f l oor~3,
w~lls, ~eilillg~ ovi~ and l~iP~'S. rIl vehi~l~ c~r~aoruc:tlon, is~.
1.0 p~r~.icul~r in t.h~ cunstr~ ion c~f rail ca~;, road vehi cl~ and
ohi~, th~ fo~ c~ln iikewLse he used for i~s~ 'cion ~wE~oa~
Tho pr~dur~s ~ar6~ prefQIa~ly used ~ h~r~ally ix~ la~Lin~ b~ in~
m~t~ri~
T~ inv~ on is ill.u~tr~.et~ in the ~x~npl~ b~lor~r,
Th~ ollowlng def initlol~s a~ y ~ the ,St~tiI~g tu~t3rlals us~
0 uo~vl 1~ Pol~-eth~r ~lcohol ba~d c~n ~uc:rQoe, ~'.yc~rc~l and
E~ropyl~ne oxi~t~
Polyo~ Polye~ht~r alc:ohol- k~fietl o.n suc~:o~. t~l.yc~erol ~ri~
pr~}~yl~.ne oxlde
Pc~lyol 3 ~ lyreth~3r al~ohol base~ ~n trimethy~ prova~e ar
lpro~yl~ oxide:
P~l~ol 4: Pol~efiter alcohol hased on pht~ it~. h~ yd:C~d~A an~
~ 3th~l.ene ~tlyc~ol
Polyol 5: POl.yhtheI ~ ohol bal~a~ ou ~or~it~l, pro~ylene ~l.y~
and P~opy~ e oxid~
~5 ~l~ne r~t~rdant l: Pcl~eth~r ~lcohol c~or.~ininq ~hlori~e ~nd
~ mine (I~ 51 f~rom SoJ.va~r~
r:Lame~! r~ d~2~t 2: Tri~ (chlorop~-o~yl~ phogpJLa~:0
40 F~o.~ fs~ l ize,r ~ or~ano~i] ~ c~ a.. ~d suff;~:t~n~.
(OS 340 ~ron~ :E ay~r A~)
Exalqple~ and ~,ornJparati.ve Exa~nplea ~
4~i ~h~ n~ r 1 b~ ~olyol mixtur~ u~e~ ~Lre sunr~arlz~. in
Tabl e 1~ The ~ ol ~nixture~ ~ch h;~d a hydrclxyl ~ r c~ abou~:
320 m~ XoEIJs~
2182714
17
A b~t~.h o~ aoo kg wa.~ pre~a~ n a s~ir~d ~re~æe1 ~rom e,~ OL~
thC~ fo~m~llPtions ~h:~wn iD r~ . 'rhe ~i~tu~e W-16 ~tirred un~cil
the trihrc~rnnr~o~3nt~1 al c-~hul wa~ cc~np~.~ate~iy di~olved and wA~
then fi. tered. Proce&5inç wb.~, c~r~ d OU~ on a 1~ rn ao~
S ~cln~ or bel'~ unit ~cord~ng t~ t.h~ ~1~ 4wi.~(~ r~c:ip~r:
LOr) P~ y ~eight o:E polyol ~ ur~,
g ~a~-ts b~ ;rei.~ht:: o~ ~lo~ing a:,~nt dic3~ rof '.u~ro~t:h~ 4l~,
150 part~ by wei~ht t~f ~aw diphenyl~ t.h~ oc~y~nat~ lNC~
co~ 31~ osity: 512 mPas),
Boar~i product hav.ing ~ t~hi.~:kn~s~ ~f .~L5(~ mm was ~roduced. T~
15 ~s~ c~ th.e e~p~rim~lt~l r~slllt~, th~ curi..~ Ol'A leaving ~e ~ blç
con~3y4r ~lt. a~ ths ~u~ ty ~o c~a~.kin~ ~fter c~tti~.g
~c.he~ ho~Lrd~ to l~ngth were o~erved. In :~t~i~ion~ the h~YrLi.-
~beh~io~ o~ ~he r~id ~oam w~s te~ted in acc~rd~ with I~I~
410 ~ ~ The ~e~ult~ are ~.ari zec~ irL l~a~ 2 .
2a
~xam~le 7 ~nd Co~par~i~e ~ L~ple 5:
trhe ~c~nn~latibn?~ ~vr the ~cJlyol mi~tl~res U~h~d a~ d i n
Tab1~ 3, ~he poly~l. mix~llre~; eac:h had a h~drox~l nurnh~ a2::out;
2S ~0 m~ ~0~
A '~a~ah of ~0~ kçr ~ ~re~;~red iII a stirre.d. ~5~l from ~ac:h of
th~: ~rm~ tio~s ~ew~ in ~a~ rhe mixtur~ wa~ st;.r~d un.ti.l
the tr~romone~pe~yl alG~ol ~a~ comple~el~ ~is~o~ed arld W1
~0 t:hen filt~r~d. Pr~ce~sing w~ rried uut C~:rl :1 L ~ m dou~le
..varoY ~elt ~ ce.ordin~ the f~;llc~win~ r*cil e:
100 ~arts by weigh.t ~ mi~ure,
;pa~c.~ ~.y w~ight o~ owin$~ n~c ~ic~hlc~Lofluol-o~thane [1~ 1.41i~!,
13~ part~ }~y w~j.ght of ra~ diPh~nyl thane d~isocya~te ~NCo
con~r~t: 31.1 ~6, ~i~c~itY: 5:L~ ~P~6).
40 -i3o~rd E~rod~t ~avlng a r.hic,kllP~s o~ 150 mm w~; produc~3d. q''t,,~,
~5~ he ~a~erimc~t:al r~3su1ts, tht~ c;ur~F~g on l~viTJg ~;he t~o~le
con~eyor belt ar.d th~ ~u~;a~ti~ y to c~a~king~ ~f er ~ut~1r
thR b~6r~1Ei to len~th w~t~e o~ red. In a~ditior~, the bu~nir,g
behavic:~r of ~he rigid fo~m ~g te.~ced ~.r &ccor~ wlth ~I~
4i~ Th~ re~lts ~e ~m~rizc~d in Tahle ~.
2182714
r-
r~ O O Ut~ ~ ~ ~ , ,.
C-J t-
'.D O O . C;~ ~ O
";, Ul ~ t~ ~ ~ '~ ~ C t~
u~ ,r, c~ ~t ~ o I
q r~ o
r.~ ~ ~r, r--I ~ r~i O
~ ~ O o m o nt7
r'
c~ o o ~ o ul ~ o o
~'1 0 ~ ~ ~ ~ ~ ~ ~, '
.~ r~ Ot~ ~ O C~ O t,~
er ~ Mt,~ ~ r~- ~t t~- C`l
h
t~t O ~
H
1 ~ r,
L
.rl
r .~
~r~
~ o ~ o ~
~le ~ Gntimla~ n~ r
~ydroxyl ~-mc~ionali~y C~nFar~ti~re' C~p~ratilre~~ ~ ~r~t~re I ~ -ra~ e
nuobe~ tZ~ ~f~ 1e~ample 2 Bxan~ple ~ 8xas~ple 4
Pol~t~l 1 39~ 4 . ~
Polyol 2 4g~ 4.~ , ~5.2 ~3.2
~lyt~ ~ 4~ 1 .0 lC.C 5~ . û 5~. 6
Y~1YQ1 4 2~ 2.0 25.0 ~5,0
~O1YO~ 5 433 5.3
Trib~l _ ty~ L'72 1 .Q L2.~ 2.
alcobol
. Fl~o~.e I~ta ~-' t 1 3~ 3 0 2 . 0 25 . 0
Fl3~e ret~rdi3nl: 2 27,0 27 0 2'~.0 ; i~.0
C'ycerol 1~û5 3 .0 6 .47 4 .~, 5 ; .o
~ba~ st~ili~sr 1 ~ 1.0 1.~
r~imeth~rlcyclo~exy~ ine 1. ~ 1.5 ~ .5 i. 5
W~ter 6Z30 2.0 ;.~ .9 1.9
To~al lO0 .01~0 .0 lO0 .0 100. 0
Cr~P~11.,ki"9 i~ ~) I a.~ ~.7~ 2.~3 2.77
~abLe 2
. .
Examl?leExampLe~xas~leExa~npl e Exa~ple E~an~ple
2 ~ g 5 6
~urning beharior ~IIt B~ a2 B2 ~2 ~2 ~2
~l ~2
Curin~ at ~e end o~ the çood ~ood good good lrery good good
bel t
Susc~pt~ y to nor~en~llenoneD~ne n~ne none
c~a~k;rl~
e 2 ~ col-~ti~ t~or~
Compa3;ati~P Compar~ti~.e C~paxati-~re ~o~ arative
Example 1 E~salTple 2~cample 3 Exam~le 4
B~.~rnic~g bel~or ~IN B~ B~ B2 ~2
~1~2
Curing at the end of tne low lo~ lc~w low
bel t J
Su~ce~tibility to at ~he sa~ cut 13 t:he ~oeun in the foam ~n th~ Loam
~rack~ng
_2~
r~rfie 3 ~,
E~ydroxyl nw~er FunctionaLity ~f i~ Ex~pl~ 7 .Compara~ive
' Ex~mpl e L
Eo~yo} 1 3g7 4 } ,~5 5
Polyol ~ 1~f5 4 . 3 23 .
P~lyol ~ 24~ 2.Q ~2 ~
~_bro~.cfneo~entyl ~ 172 1. 0 15 . 0 15 . 3
a~ c~hol
e1ame r~tar~an~ ~ . 30.0 ~r.o
G~yceroL lg~' 3 . 0 4 . 5 S . 3
~Qa~ tab~ }~ze~
~i~ethyLcyclohexYlf~ e ; 2 . O 2,
W~e~ ~2~0 ~ 1.7
motal ' ~ ~ . O 1~0 . O
Cr~ g Lndex ~Ic~ ~ . 2~ 2 . 34
~.
Tab~ e 4
~x~up~e 7 ~or~aracive Example 5
Bur~,~r.~ ~h~vior ~lr3 4~0~ ~2 B2
Curing at the end of 'h~ ~ood low
~e~t
S~1sceptibilit~ ~o cra~k~ng nonc in the Fca~
00
