CA2096009A1 - Premix compositions of polyol, blowing agent and optionally additives having improved storage stability - Google Patents

Abstract

Premixes of a polyol suitable for polyurethane or polyisocyanurate foam preparation, 1,1-dichloro-1-fluoroethane and optionally additives and/or auxillary blowing agents which do not require a stabilizer to inhibit reaction between the fluorocarbon and the polyol. These mixtures are useful for polyurethane and polyisocyanurate foam preparation.

Description

~g2/08756 2 0 9 6 ~ ~ ~ Pcrt~f~fgl/08032 PREMIX COMPOSITICSNS OF . POlfffYOL, BLOWffINfG AGENT
AND OPTIONAIiff~ffY ADDITIVEfS HAVING IMPffROVED
~lffQRAG~ S~E~I~ffIl'Y

This application is a. continuation-in-part of f.-o~nonly assigned Application ~f~rial ~o.: 251,730, filed October 3, 198~, and entitled Polyol-~flowing Agent Compositions With Impro~red Stora~ffe 5ftability which was recently allowed.
' .
ieId ~ f th~ v~n~ iC~A : .
.
This invention rfela~ces to impso~ed polyurethane and polyisoc:yanurate foam systems which eliminat2 the need for stabiliz~fr~ used in the past :
with certain chlorof luorocarbon blowing rfff~ffgents . The improvement stems f rom lchef disffrffo~r~sry that use of 1, l-dichloro-l-f luoro~th~nef (CC12FC~3 ) as the blowislg agent provide~ enhancéd chemical stability when the blowing ag~nt i~ ~tor~fd as a pre-mi~, i . e .

2 0 . . .. , -.. -. ~ .... r ~ . f ff blowing agent pre-blënded wffith ~:ertain other compol~ent~fff u~ed in polyurethane-type foifflm ~f manuf acture ~ ~uch asfff polyol~ . .

'?s~ J; ,~ L~-~5''s',~ ~J~'3 ~ J'Jtr~? ~
It i~ well known to tho32 ~killed in the art thi5lt polyurethane and polyi~o~yanurate foams can be prep~red by rsActing ana. ~oasning a misture of J, ~ t ~ 5~5p ~ ~,` . 5 1 ~ }i !, 30~ ng~r~e~d~ n~t~ C~n~s~8~iJn9 ~ins~g~n~al!of an or9aniC
polyisocy~nate (i~cluding ~iisocyanate) a~d an~
approp~riat~ a~moun~ ~ yp~ S~mi~lsxt~u~re r;P~yols~in ~:
;;: the pres~nce 0~a~vol~til~ liquid blowing a9ent~
,;"~ 5 ~ J . ~ 5~ ;3 ~lq .~ omi~?~5 : :
: ~` : : .

: ~ . ~ . . . :, . ` . : ~ : :

wos2/08756 PCT/US9l/08032 ~?, 9~ 9 which is caused to vaporize by the heat liberated during the reaction of isocyanate and polyol. It is also well known that this re~action and foaming process can be enhanced through use of amine and/or tin catalysts as well as surfactants. The catalysts ensure adequate curing of ~he foam while ~he surfactants regulate and control cell size.
In the class of foams known as low density rigid polyurethane or polyisocyanurate foam the blowing agent of choice has been trichlorofluo~o-methane, CC13F, also known as CFC-ll. These types of foamis are closed-cell foams in which the CFC-ll vapor is encapsulated or rapped in th~ matri~ of elosed cells. They of~er e~cellent thermal insulation, due in part to the very low thermal conductiYlty.of CFC-ll vapor, and are used widely in insulation applications, e.g. roofing systems, building panels, refrigerators and freezers.
Generally, 1-40 and4typically, 15-40 parts of blowing agent per 100 parts polyol are used in rigid polyurethane or polyi~ocyanurate formulations.

Fles~blè plyurethane foam~ on the othér hand are generally open-cell foamis and are manufactured using a diisocy~n~e and polyol along wi~h catalysts . andi oth~r~ additives~with`various combinations of : watnr, methylene chloride and CFC-ll as the blowing - J''2 ~ .r ~ i r~ t~ .t i~ 7r~ 7 "~ r ,~ ~l agent. The~s foam3 are widely u~ed as cushioning ma~erial~ in items ~uch~a~ ~'urniture, beddlng and au~omo~lë s ats~ 3 Tha~q~antity o CFC-ll ùsëd as an ~au~illary blowing agént in~le~ibie ~ am`manufacture IS;i ~.r, ~5 1~ æ ' ~ 3 ,~ .?.3 ^1~'; s7 ~3 .i ~ ) r~ ~ ic '~ r ~
~arles from 1-30 parts ~y we~ght per 100 pa~ts of ` ~polyol àccording`~to~t~gr ~ e''o`f~oam beingiprepared.
~-Yf,~E~ J~ 3 F ~ r! ~ r~

It is common practice in the u~etha~ foam i8yste~3 area to prepare so-called prs-mi~es o~ .
certain compon0ntB used to prepar~ the foam, i.e.
. .

... .. . . . , ~ . -. . .. - ... ~ . . . .

~092/~756 2 ~ ~ 6 ~ Q ~ Pcr/usgl108032 often the appropriate quantities of polyol, ~lowing agent, sur~actant, catalyst, flame retardant and other additives, are blended together and sold along~ .
with the stoichiometric quantity of polyisocyanate -component in two separat~ containers. This is convenient for the end user who then only has to combine the 'wo reactants in order to crea~e a foam.

It is also com~on practice for large foam manufa~turing plan~s to pre-mi~ the polyol with the - blowing agen't in bulk storage containers. This liquid mix~ure possesses a lower viscosity than the pure polyol and i9 therefore easier to pump and meter.:.
into the mixing zone of the ,oam manufacturing equipment. ....:.
. .
Special precaution~ must be taken when following these practices if '~he blowing agent is :~
CFC-ll, namely, the.CFC-ll..must have a stabilizer added to it in order to inhibit a.reaction which can ~ occur,between.the fluorocarbon and~the pol~ol -resulting in the pr~duction of acids such a~ hydrogen chlorlde and:other organic products such as aldehydes : . 25 ::and ketones. :The~e reaction products havelarr.~
- ; detrimental~ef~ect onithe reactivity characteristics of the foam ingredients wh`ich in the worst:casei r~8ults in no~oaming action~at~`all`~:;"Stabilizers found~u~e~ul in stopping~the~lreaction~between j:~
- 30 ~luoroc~r~on-and polyol`have'-been~disclo~ed,-:for ;.
;i e~ample, in U.S~ Patènt3i~3;~183,192 and 3,~52,7B9.
Use o such'stabilizer~ with!C~C~ polyol::based ~blend~ àlthough `succe~ul when~measured~in-~t~rms of fiuorocarbon?`s~abiiity,ihave-rdi~adva~ag~s~suc~ as added e~pen3e and som~ti~'s'~t~au~e~odor`problems-which p~r8i5t ~ven in th~ ~ini$hed foam.
ï For ~he 'above ~retasons~ it would be ~~
' -.

.

~ ., ' ' '' ~ . .'; ',' :' ''' ' ' :' . : . : . ~ .. .

W092/087~6 PCT/US91~0~032(-~96~ _4_ advantageous to identi~y useful fluorocarbon blowing agents which do not require stabllizers in the presence of polyols. Unfortunately, there does not appear.to be any relia.ble scientific basis upon which to predict such stability. The propen~ity for a fluorocarhon species to react with an OH contai~i~g species, like a polyol, is dependent, in the fundamen~al sense, on the elec~ronic and molecu.lar structures of the ~luorocarbon and the OH species involved. Studies of certain reactant systems, su~h as CFC-ll and ethanol by P.H. Wit~ens, ~J5LUi ~g~
Vol. 4, ~o. 12 ~December 1959), P.A. Sanders ~Mechanisms of the Reaction 3etween Trichlorofluoro-methane and Ethyl Alcohol~ u~. of the CS.~A 46th M~ Y~r ~e~tin~, ~May 1960), and J.M. Church and J.H. Mayer, ~,~9~ .~vl~:e~ , Vol. 6, No. 3 (July lg61), have. shown that the reaction products `` ;
include hydrochloric acid, acetaldehyde and CHC12F. ~Sanders, in ~ , (~ecember 1965~:has.shown that ~hese reactions are further:,promotediby the:prexence.of metal:and water.

;H.M. Parmele~. and R.C! Downing in Sn~
, Vol.!25, pp.ill4-119 (July 1950) have ~hown that.rfluoro~arbon3 such~as chlo.rodifluoro- ;
methane.:~C-22),~ difluoroethane (FC f 152a), a-l,l,l-chlorodifluoroethane ~5FC.-14Zb)l:and 1,1,2,2-tetrafluoro-1,2-dichloroethane "~FC_114~undergo r~actions~in:~aqueou~,a.nd ethanol and!,isopropanol ~solutions in the.pres0nce~,0~jsteel ~nd aluminum.
:Church .and~,Maye.r,~upra, stat0 that mise.d polyhalo-rl!genated:hydrocarbons ;containipg both.chlor~nejand ~ ~luorine:.jonnth@.~same,~carbon,at~o~jz.re le~s,stz.ble than 3 5 ~ s theipoly~1~oro d.2r lOY ati.V~ 8 -",,~ 3 h ~ * ~ 3 The molecular structure. of HCFC-141b [CC12FCX3).~suggests that HCFC-141b i~. amenable to , ~ .
':

::

... . . . ... .. . . .. . . . ....

~ 92J~8756 2 0 ~ 6 0 ~ 9 PCTtUS91/08032 dehydrochlorination due to the presence of hydrogen and chlorine atoms on adjacent carbon atoms, On the other hand HCFC-123 (CHC12CF3) is amenable to dehydrofluorination, a process requiring a greater activation energy. Therefore it would be e~pected that HCFC-141b would be less stable than HCFC-123.

The prior art evidence therefore suggests that 1~ chlorine and ?Eluorine substituted hydrocarbons as a class react with organic OH co~taining species such as alcohols and polyols. ~.
. ~ . . :. . - .
U.S. Patent 4,076,644 discloses that HCFC-123 may be used as a blowing agent and does no~ re~uire a stabilizer in the presence of polyols. Thus, HCFC~123 may be an e~ception to ~he rule that fluorocarbons require stabilizers.
..,~ '.. . _!. .. . .. .

. 20 However, .stability~tests on HCFC-123 in the presence of a.variety.of polyols show that HCFC-123 may not ~e stable in the presence of some polyols which are commonly used in th~ preparation of polyurethane.and.,polyisocyanurate foams.
2 5 ` ~ - ? . .; C .. ~ ," , ". ,, It i~ ~.accordillgly an~ object of thi i ~invention --. to ~iderltify ~ anoth~r ~. f luorocarbon ~ u~eful as ~ a blowing , ;"~ .ag~lt for po~ ?~eth~ane a~id~ po?yi~ocyanu?ra~tel~f~lo~ams zwhi~h~i~.8tabl~ n;the pre~ence of polyol8; and~
cptionallyJadditivè~ and ,auxillary blowing~j~gents.
.It i8~another,0b~ect o this~invention to id~ eniti f~y, such 3jaj1,f luioroc:a~bon,J w~ich ~ 8 ai~ . c~ ns idered " c.~P~J ~lCa~llY7S~a~f~ sU~b~ltut~ for CFC-ll 3 5 . ,which i s ~ thought ~jt~o~ jbe,!~a ~ coln~t"r!lbutor -.~t~o ~OJz~y ;, ^~ ~ depletion ,,and .91obai .gr~enhou~e~..warming . ~

`i ., Yet another object of thej ~invention is .to .~ .
.i ~ .
: , .
. . ~ . . , , ,: ~ -- - , ' :

,' ' ~ : -,, '. . ' ., . . ,' :

- . . - . : . .
- . .: . . . . .: :

W092~087~6 ~96~ -6- PCT~USsl/08032 identify such a fluorocarbon which may have a wider or at least different range of applicability to polyols than does HCFC-123.
I
Other objects and advantages of the invention will be apparent from the ~ollowing descriptis~n.
. ~_ .. .. . .
The invention comprises pr~mi2es of a polyol suitable for polyurethane or polyisocyanurate foam preparation, l,l-dichloro-l-fluoroethane and optionally add;tives and~or au~illary blowing agents ~ in proportions suitable for polyurethane or polyisocyanurate foàm preparation.
, . - . . : . .

~ HCFC-141b is a known material and can be : 20 ~ prepare~ by methods known to the art ~uch as :: ai sclosèd in U.S; Patën~ 3,~33,676.

~n~accorda~ce with the in~ent ion, %CFC-141b may be u~ed as described in the background portion of ~this dë~cription ! ~o prëpare a vàriety of~polyurethane ::
- -~ `a~ `polyisTscyanurate foàm~ by`standard techniques :'knawn~t~ ~ e art which'`may;inciude~t~e use o~various ~u~ àry blo~ng ;à~entsl: and 8tandarsd additives~such 30 'i3 a~ ily~, 8ur~actint~TJ5watèr~Tà~nd~other~Tr.~

*he amoun of HCFC-l~lb relati~e to the amount '' d' ~ r~id~`n~i~g'ùpon~"thë
;; applica~ on~,~'the~typ~`~of~oam being^ prepared, t'he . :.
identity ~ ~ ~i'poiyoi~an~othse~ ~ac ~ rs','but:cin reasdily bë'detë'rmirie~s~b~ '~nyonë'~skill'~d~'in`!`th'èiart.
enerally, ~rom about 1 to 40 part~T by weight of : HC~C-141b per~l00 parts^~y weight ~of polyol are ,': ' ':,' ~092/087~6 PCT/US9l/08032 ,`~ 209~009 employed, but preferably about 15 to 40 parts by weight of HCFC-141b per 100 parts by weight of polyol are used in rigid foam manufacture and abou~ 1-30 parts ~y weight of HCFC-141b per 100 parts by weight of polyol are used in flesible foam manufacture.

For purposes of this application, the term "storage stable premixes" shall refer to premises 1~ which have been stored for at least 30 days prior to use without any substantial delPterious effect on the rea~tivity characteri~tics of the foam ingredients.
For purposes of thi~ definition, "substantial deleterious efect on the reactivity characteristics of the foam ingredients~ shall mean that the reactivity of the foam ingredie~t~ decrea3es such that it produces a lOS increase in any of the following: cream.time, gel time and rise time.

This invention is further illustrated by the following esample~ in which part~ or percentages are ;`
by weight-unless other~i~e specified. ~
.. '' .' '':

::.
... ... In this set.of e~amples the stability.o~
HcF~-l4lb:~ith;thelvarious:~ipolyols listed in Table I
i'3 d~termined and ~ompà~ed withith~ stability o~
".:'CFC'lll~and:..HCFC-123.~w~th~i~the 3ame polyols.i~The polyoi~ selecEed~are~;some~oe the~most common polyol~
u3ed in the commercial foam indu~try. Th2 - fluorocarbon/polyol mistuirë~Jsimulate commercial ~oam ~ formuIations. ~oto~that ~he~fla~h po~t~ reported :~ : wer~i deter~ined.~:using~the ~ollowing.fla~h point methods: ~Pensky-~arte~-:Cup~T~st~lfo~the:Y~U~ACO~
polyols; Cl~veland~Open`Cup~or the TERAT ~ , CHARDO~ POLY- ~and NI~0 polyol~i~ SET~ Fla~ih ' ^t'l.~C'lo'~e~',Cup or`~th~`rSTEPANO~ polyol; TAG Closed Cup .
:~ -~:

. ,,. . , . .: . . . :

W092~087~6 9 ` PCT/VS91/~8032 ~

for the PHT4 diol; and Pensky~Marten Closed Cup for ~ ;
the T~ANOL~i and VORANO ~ polyols.

TA~E I

OH Viscosity Water Density Flash Polyol Number 25~C Content ~lb./gal.~ Point . . . _ (CD~ ._(%) . _ _ .
PLURACO~ 400 4,50~ 0.0S Ma~ 9.08@25 C >200~F
9751 :
: P~URACO ~ 390 10,S~0 0.05 Ma2 9.09~25 C 200CF

P~URACO ~ - 14,000 -9.24 200~F

TERATE~ 316 20,585 - Not 1.2 (typ)~ 156C
2034 ~ . . Detected STEPANOL~ 230- 2,000- 0.15 Mas 10.0@25C 200~F
PS-2502AS 250 4,000 CHARDO ~ 235 5,400 0.~(typ) 1.18(typ~* 250C
. ................... .336A6 .
(~) indicates speci~i~ gravity lPLURACO ~ .is a trademark.o~ BASF Inc. PLURACO ~
:: polyol 975~is a sucro3e-based polyether ~ polyol.
P~URACO ~ i~ a tra~ëmark of BASF~Inc. ~PLURACO
.'Ji~,;.i'~' S,. ~ ;; polyol~824~is.,an aromatic.initiator-based , PlYeth~r4~po~lyo~ J~ r 3P~U~A~O ~ is a:,trad~marksof~ SF~ c. i~r~P~URACOL~
~ 30: i ~ r~ 3sri~3~3~ PO.lYolt~ 4~i8 ajpolyather poly~

`' ,~J,r~ ,';TErE~,~jTE,'"~ TERATEd~2mo3kiio~aca~pelo~nndu5tbi8sd '~
poly~ster polyol.~ ,;., r ~ .i ; ~
5STEPA~Oi~;)'' i~ '~tr~ rk~ o'f ~ st~pa,n ~Co~npany'~ i~ ' ~; '' ~ ' ' "' ` 35~ f~ q .~`~rl~ Ic~STEpANOL~ PS-2502-A~ an aromati~-base,d I `'J '~ r d; p ly~ t1~ P~ 2~ 3~ 3 , 3 ~
5CH~Do ~ i~La:1tradèmark~ofr&ook:~omposi~is~and Polymers:.C ~ ~OL 336-A i9 ~a poly~thylene ~ .
` tere`phthalate-based polyeYter polyol l~

~ 92/087~6 2 0 ~ 6 ~ V ~ PCI`~US91/08032 _g_ TA~ I cont.

OHviscosity waterDensity Flash Polyol Number25C Content( lb . /gal . ) Point ~CO~ _ ~%) THANOL(~ 520-12,000- 0.1 Ma~c 1.12@25C~ 300'~ ;
R-350-X7 54017, 000 THANOL6 ) 440-- 22, 000 0 .10 1. 06@20C* 305"F
1~ 650-X8 460 POLY-GC;~ 3502,`500 0.08 Max 9.2@25C 3S6DF
71-3S7g ~ - `- -PO~Y-G/~ 4405, 000 0 . 05 9 . 2@25C 204C
7 5-~ 4 2 10 15 NIA~ 700100,000 0.1 Ma3: 1.05@Z0C~ 455~F

PHT4-- 220-90,000 0.~1(typ) 1.8@25CR~ 200~F
DIC)L12 23~__ _ _ _ _ _ ( * ) indicate~ specif ic gravity - (~*)in~licates den~ity (g/ml) 20 7THANOI;~;) is a tra emark of ARCO Chsmical Co .
THANOL~ R~350-~ is an aromatic amine-. . . b~ed`polyether polyol..
8T~A~O~ ;~i8 a~tra~emark~of ARCO Chemicâl:Co. ~
. -. . THA~O~ 650-X is a rigid polyol*a~.
2~ -9PO~Y- ~ :i is a`trademark of:Olin Corporation.~
PO~ j71-357 is a sucro~eramine based polyether polyol.
POLY-~ is a tra ~ mark of Olin Corporation. ,~
PO~Y-G 75-442 is a methyl glucoside-b~sad polyol.
llNIAX ~ is a t~demaxk o Union Carbide Corp.
s.l. !~NIAX~polyol:LA-700~refers.is:an amine- ..
t.;; . . ~:~ ba~ed r' polyeSher).polyol.
PHT4~ a reactiia~rominate~ diol~
~ DIOL~ manU a~tured by.Great~l~ak~ Chemical 35 .~ r r~ .} r~ c~o~ s~ cl~ t,j~ r~ r~ tr **The term ?~Eigid;~polyol?a!refer~to~polyols which ~ ~ are used to mak~ rigid polyuretha~e or ', . polyisocya~urat~ ~oam. ~ -., .
1 ~ ;
,, ~ : .

W092/087~6 i PCT/USgl/08032 ~

2~6~0~ -10-TABLE I cont.

OH Viscosity Water Density Flash S Polyol Number 25C Content (lb./gal.) Point (.t~2 2 ( %L
VORA~OL~;) 370 23, 000 0 .1 Max 1.11@25C~ 335~ F

VORANO~ ~00 17, 300 0 .10 8 . 75@25C 405"F
10 8ool4 FOAMO~ 302 28,400 0.13 1.2@25C* 145~C
3sonl5 _ _ (*) indicates specific gravity VoR~oL6~is a trad ~ ark of Dow Chemical Corp.
VORANOL 370 is a sucrose-based polyether polyol.
VoRA~o ~ iis a tra ~ ~ark of Dow Chemi~al Corp.
VORANO 800 is an amine-based polyether ` polyol. .. . ..
lS~ojAMO ~ is a trademark63of Jim Walter Resourc~s, Inc. FOiA~O 3500 is an aromatic 1 .polye~ter polyol.
The apparent pH-~of each ~lend is determined by mi~ing 20 cm.3.~of the ~luorocarbo~.blend with 80 .
cm3 of 0.1 ~ormal ~Cl soiution-made up in 3:1 :
methanol:water and,then measuring^;th~ pH of the~final~ ~
-- solution?with~a calibrated p~ meter. This type o~ :
mea6urement is believed to be accurate to within 1 p~ ùnit~ s;,~ s ~ ~

. After~measuring th~ it.~itial pH of the ., . q 1 .. ~l ., . i~ ~ .; :: .i ~ tl ~ t ~ ~J ~ iYls. :~ ~ t~
~mistures,~,theyxarQ~;depo~Sit~dlin!~sealed glas~ tube~ ~
and placed in~anj~ovë`n:~controllèd~at 54C ~ about 0.5C for a il2~week~.pzr~od.~At ~he~end of~,thi~:
eriod, !t~e:~p~o~t~e t,ni~ùre~'~'is~!again mea~ured. -The tcesults indicate that the HC~C-141b~polyol ,~
, mizture~ ar~ sig~ antly more stable ~han those of FC-ll or HCFC-123..~ S~e~fically,' the ~reduction in , ~ ~
,, :
' ': , ' " ' :.
~, . . . .

~092/08756 PCT/US91/08032 20~6~0~

pH is significantly less in the HCFC-141b~polyol mixtures than in those mistures employing CFC-ll and HCFC-123.

~AMPL~S B

This set of examples further confirms the enhanced stability of HCFC-141b/polyol blends over CFC-ll/polyol blends.and HCFC-lZ3/polyol ~lends using a different measure of the acidity chanye and a more real-life storage technique.
.
Polyol/blowing agent blends are prepared using :~
the polyols listed in Table I above at a 30 weight percent blowing agent composition. These compositions are stored i~ clo~ed, unlined tin-plated steel cans ~or 10 weeks at 54C. At the end of the aging period, a sample o~ the~mi~ture is diluted with ethanol and titrated against a standard solution of .
KOH in ethanol to a pHw9.S endpoint. The amount of :KOH used!is.~hen compared~wîth.the.amount of KOH
~: irequired to.neutralize the~un-aged.polyol. The ;:
~;,re8u}t~ indi~ates.~that HC~C-141b,results,inJ
substantially ~maller acid generation (i.e., the ; ~CFC-141b containing misture requires les~ ~OH than ~:~ Y~ ds;misture~ co~taining CFC~ or~HCFC-123)~in~all .'! ~ case3 relatl~ to~C~C-ll,"and~HC~C,1~3JLindica,ting it more ~tàb,l~.~in ~th~.presence~of,polyols than either - ~307~ ~.)C~C~ or ~CFC-123-,~ ,r ~ ~?,~

t~ Often polyol/blowing,;agent prem~xeæ contain , , ~,' aa~additi~e~ like surfa,ctants, ~ataly~ts,.,,a,n,,d~ 5/,~
up}emu~lsiEiers.[~c~or,~ample,~:rigid urethane ~oam .~ 35',J~ ormulations may ~ontain silicone surfactants :like .
Y DC~193, a silosanè,~,,manufactured by Air Product~ ~
Chemical~ Inc. of Alle~tow~, Pennsylvania, B8404, a polyzther modified polysilosane ma~ufactured by :

W092/08756 ~ 9 6 ~ ~ -12- pcT/uss1/o8 Goldschmidt Ch2mical Corp. of Hopewell, Virginia and L5420 a polyalkylenoxide methyl silo~ane manufactured by Union Carbide Chemicals & Plastics Co., Inc., Specialty Chemicals Division of Danbury, Connecticut. A surfactant has ~wo functions: it may act as a cell regulator, controlling cell nucleation and c~ll size; it can also act as an emulsifier. In this second capacity, the surf actant allows incompatible materials to be blended into a homogenous batch.

Amine catalysts may also be added to the premises. Some typical amin~ catalysts include dimethyl ethanol amine, DABCO 33LV~ which is a 33%
solution of triethylenediamine in dipropylene glycol - - and:POLYCAT~ 8, which is N,N-dimethy}cyclohe~yl-amine. DABCO 33L ~ and POLYCA ~ 8 are manufactured by Air Products & Chemi~als Inc.~ Amine catalysts control`the rate of the:urethane reaction.
~ . , ~ Metallic catalysts may al~o!b~ included`in rigid urethane foam:formulations;- T-12 orrdibutyltin dilaurate manu~actured by Air Produc~s & Chemicals DA~CO~33-~ ~ and PO~YCA ~8;are registered trademarks ~` o~;Air~Productsi&~:~ChemicalslInc~ r~ .J,.~3 a ..-~.~.i!~. Ty~ical~properties~ ` : D~8~0 33-L ~- '~ ~
Specific gra~ity: 1.03 e~24'C`'~ 0.8512 @ 20C
Boiling Point ~C): 174 160 ~756 mmHg ...
~'Vapor pre~ure e;38c:~ ;2 mmHg ',~ i 9.77 mmHg A~pearince '~ . '''` - '3~cl8a`r,~ ,'?1 ~ L x:tcolorless-t ~ J ~?~ olorles3 ligu.~straw;~liquid 35 7~;i Flash~poiht~ o~ 110 C rr~ .ir....... ,40.C:c(ASTM.,~.
A r ., ;,~ 3,~' ~ PP~!lCC ) - ,!,~,,t,`; ,; : ' D56--7~) (CC) , '. ''',,,.'.' .'. . '' ,, .. ,. "" '' ,".'' ,', ', ,.' . , ' '' ' .. ' ' . ' ., ' . ' '' ' ,: ",," ' .' ' ' ."" "' "'.'' '.' ' . . ' , ,,~092/OB75~ 2 ~ 9 ~ D ~ ~ P~T/US91/08032 Inc. an~ lead naphthanate are typical metallic catalysts. Metallic catalysts grea~ly increase the rate of the urethane polymerization. ~etallic catalysts are necessary, for e~ample, in spray foams where very short reac~io~ times are required.

Premi~es often contain at least one au~illary blowing agen~. The premix compositions in accordance wi~h the invention may ~ontain at least one ausillary blowing agent. The au2illary blowins agent used in these premi~es may be, for esample, a fluorocarbon, an organic liquid, water or any combination of the above.
- ~
Au~illary blowing agents are used in combination ~ith a primary blowing agent for a variety of reasons. : For e~am~le,::water is sometimes employed as an au~illary blowing agent to heIp reduce the consumption of the primary blowing agent. Water also produces improved strength properties in rigid foam. Other materials including:CFC'.~,.HFC's, HCFC's and organic liquid~ have also been used as~ au~illary blowing.ag~nt~.wi~h H~C-141b, for:esamp~e, to reduce consu~ption:of HCFC~ r~duco.;~foam costs,~..improve foam properties.and~or imprQv~.,foam processing. Some ., .
~of the mo~t common,CFC~, H~C~s,i-HCFC's::a~d organic liquids, employed.,~asTau~cillary~blowing agent~ clude : trichlorofluorome~ha~e (CFC-ll), dichloro--:~ 7di~1uoro~ethane-~l(CFC-l2);~methylene fluoride .
HFC-32),~-penta~luoroethane (H~C-125),-:1,1,1-,2-i;.tetrafluoroethan~ (HFCil34a),~^;chlorodi~1uoromethane (HCFC-.22),~Jl,l-di~chloro-2,2j2-trifluoroetha~e~
(HCFC-1~3).,.i11,2-dichloro~72,~2,2-trifluoroethane'':' 35~ (HC~C-123a),r 1-chloro-.1~2,2,2-tetra1uoroethane ~HCFC-124), methyl formate and~m~thylene chloride.

:

WO 92/087s6 9 PC~/US9l/0~032,--q~9 ~ -14- t :
In premi~ compositions utilizing a fluorocarbon or organic liquid as auxillary blowing :~
agent in conjuction with ~CFC-141b, HCFC-141b 5 generally comprises greater than 50 percent of the total amount of blowing agent us~d. In another embodiinent utilizing a fluorocarbon or organic liquid as au~illary blowing agent in conjuction with HCFC-141b in a premix composition, the HCFC-141b 10 comprises greater than 70 percent of the total amount of blowing agent used. In yet another embodiment utilizing a fluorocarbon or organic liquid as au~illary blowing agen~ in conjuction with HCFC-141b in a premix composition, the HCFC-141b comprises 15 greater than 50 and less than 70 percent of the total amount of blowing agent used.
.
~: In premis compositions utilizing water as the au~illary blowing agent in conjunction with - HCFC-141b, water generally comprises up to 2 parts by weight per lOO parts~by weight o~ polyol used i~ the ..foam formulation.

, . .O.In a preferred:embodiment, in premis -. - composition~:utilizin~ water a~ an ausillary blowing agent .in::conju~ction.with HCFC-141b, water generally ,.Si~comQri~e~ up'to } part~by~weight~per 100 par~s by J.~.wsight~of polyoIr.'used.~,'i;n,.the foam~formulation.:

~.. In~thi~ nest.::setiof Esi~mples the~:stability o~
: HCFC-141b-ausillary blowing~age~t~polyol~blen~s are .,r.i...u.'compared:'~with;~blend~;utilizing~CFC-~ and HCFC-123 with:.ith~.same.1ausillary blo~ing~agents~and~:pblyols.
The.~re~ults.;'co~fi~m~that.~ble~d~utilizing HC~C-141b are~isubstantially more~sta~1e than blends~utilizing.j;
~C~C-l~ or.v~CFC-123~ A.~.~ L~

'~ ~ ' ' ' ', ''.' .
., ' '' .

/~O9~/08756 2 o 9 6 o O PCT/US91/08032 ~L~

All possible blends o~ the polyols list~d in Table I above with the au~illary blowing agents listed in Table III below with each of HCFC-141b, CFC-ll and HCFC-123 are prepared and the stability of each blend is determined by repeating the experiment outlined in ~xamples A above. The results indicate that the HCFC-141b-au~illary blowing agent~polyol mi~tures are significantly more stable than those oE
CFC-ll or HCFC-1~3. ~pecifically, the reduction in pH is significantly less in the HCFC-lglb-au3illary blowing agent~polyol mixtures tha~ in those mixtures ~ :
employing CFC-ll or HCFC-123.

Eh~

Trichlorofluoromethane (CFC-ll) Dichlorodi1uorome~hane (CFC-12) Methylene fluoride (HFC-32) Pentafluoroethane (HFC-125) 1,1,1,2-tetrafluoro-ethahe ~HFC-134a~
Chlorodifluoromethane (~CFC~22) 1,1-dichloro-2,2,2-tri- ~-f~uoroethane ~HCFC-123) 1,2-dichloro-1,2,2-tri-1uoroethane ~HCFC-123a~
l-chloro~ ,2,2-tetra-- fluoroethanc ~CFC-124) Methyl Formate : M~thylene chloride ,~
~2 All pos~ible blend~ of the ~olyol~ and au~ilIary blowing agents`li3ted in Tables I and ~II~, respectively with each o HCFC-141b, CFC-ll and HCFC-123 are prepared and th~ stability of eaGh blend ~:.
is.determined by repeatin~ th~ esp~rim¢nt outlined in .~
. .
~":
; ' . I ' ,, . , , . . , ,. . ., . . . , . . , ., .. . .: .. .. . :, .::

W092t08756 ~ 16- PCT/V~91/0~03 E~amples B ahove. The results indicate that the compositions employing HCFC-141b result in substantially smaller acid generation in all cases rela~ive to CFC-ll and HCFC-123.indicating that HCFC-141b is more stable than CFC-ll and HCFC-123 in the tested compositions.

' :"

, ,. ..
';
1~ ... ..

..... . _ .... ... . . . .. . .... . . .. .. . . . . .
.. . . . . ...
' 2 0 r .. ..
... -..... ..
. . ,' i i; ~ ;

'~ .' ' `; .'. ~~ ,- . . - ' ' ~,: ". . ;.,", ... .

; P~ ,Yj`, ,,;:".j;~',il~,fC?`'~"'~, .' .:
:

. ~ ' : :-' ~ : ,;:
. .

Claims (90)

What is claimed is:

1. Storage stable premixes comprising a polyether polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyiso-cyanurate foam preparation.

2. Storage stable premixes comprising a polyester polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyiso-cyanurate foam preparation.

3. Storage stable premixes comprising a rigid polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

4. Storage stable premixes comprising a polyether polyol/polyester polyol blend and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

5. Storage stable premixes comprising a methyl glucoside-based polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

6. Storage stable premixes comprising a reactive brominated diol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

7. The premises of claim 1 wherein said polyol is a sucrose-based polyether polyol.

8. The premixes of claim 1 wherein said polyol is a sucrose amine-based polyether polyol.

9. The premixes of claim 1 wherein said polyol is an aromatic amine-based polyether polyol.

10. The premixes of claim 1 wherein said polyol is an aromatic initiator-based polyether polyol.

11. The premixes of claim 1 wherein said polyol is an amine-based polyether polyol.

12. The premixes of claim 2 wherein said polyol is an aromatic-based polyester polyol.

13. The premises of claim 2 wherein said polyol is a polyethylene terephthalate-based polyester polyol.

14. The premixes of claim 7 wherein said polyol is PLURACOL? polyol 975.

15. The premixes of claim 10 wherein said polyol is PLURACOL? polyol 824.

16. The premixes of claim 12 wherein said polyol is TERATE?203.

17. The premixes of claim 12 wherein said polyol is STEPANON?PS-2502-A.

18. The premixes of claim 13 wherein said polyol is CHARDOL?336-A.

19. The premixes of claim 6 wherein said diol is PHT4-DIOL.

20. The premixes of claim 9 wherein said polyol is THANOL?R-350-X.

21. The premixes of claim 8 wherein said polyol is POLY-G?71-357.

22. The premixes of claim 11 wherein said polyol is NIAX?Polyol LA-700.

23. The premixes of claim 3 wherein said polyol is THANOL?650-X.

24. The premixes of claim 4 wherein said polyol is PLURACOL? polyol 1114.

25. The premixes of claim 5 wherein said polyol is POLY-G?75-442.

26. The premixes of claim 12 wherein said polyol is FOAMOI?3500.

27. The premixes of claim 11 wherein said polyol is VORANON?800.

28. The premixes of claim 1 wherein said premixes additionally contain at least one auxillary blowing agent.

29. The premixes of claim 2 wherein said premixes additionally contain at least one auxillary blowing agent.

30. The premixes of claim 83 wherein said auxillary blowing agent is selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, methylene fluoride, pentafluoroethane, 1,1,1,2-tetrafluoroethane, chloro-difluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1-chloro-1,2,2,2-tetrafluoroethane and mixtures thereof.

31. The premixes of claim 94 wherein said auxillary blowing agent is selected from the group consisting of trichlorofluoromethane, dichloro-difluoromethane, methylene fluoride, pentafluoro-ethane, 1,1,1,2-tetrafluoroethane, chloro-difluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trlfluoroethane, 1-chloro-1,2,2,2-tetrafluoroethane and mixtures thereof.

32. The premixes of claim 83 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 50 percent of the total amount of blowing agent used.

33. The premixes of claim 84 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 50 percent of the total amount of blowing agent used.

34. The premixes of claim 83 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 70 percent of the total amount of blowing agent used.

35. The premises of claim 84 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 70 percent of the total amount of blowing agent used.

36. The premixes of claim 83 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 50 and less than 70 percent of the total amount of.
blowing agent used.

37. The premixes of claim 84 wherein said 1,1-dichloro-1-fluoroethane comprises greater than 50 and less than 70 precent of the total amount of blowing agent used.

38. The premixes of claim 30 wherein said auxillary blowing agent is chlorodifluoromethane.

39, The premixes of claim 30 wherein said auxillary blowing agent is 1,1-dichloro-2,2,2-trifluoroethane.

40. The premixes of claim 31 wherein said auxillary blowing agent is chlorodifluoromethane.

41. The premixes of claim 31 wherein said auxillary blowing agent is 1,1-dichloro-2,2,2-trifluoroethane.

42. Premises comprising a polyether polyol and 1,1-dichlor-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

43. Premixes comprising a polyester polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

44. Premises comprising a rigid polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

45. Premixes comprising a polyether polyol/polyester polyol blend and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

46. Premises comprising, a methyl glucoside-based polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or poly-isocyanurate foam preparation.

47. Premixes comprising a reactive brominated diol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation.

48. The premixes of claim 42 wherein said polyol is a sucrose-based polyether polyol.

49. The premixes of claim 42 wherein said polyol is a sucrose amine-based polyether polyol.

50. The premixes of claim 42 wherein said polyol is an aromatic amine-based polyether polyol.

51. The premixes of claim 42 wherein said polyol is an aromatic initiator-based polyether polyol.

52. The premixes of claim 42 wherein said polyol is an amine-based polyether polyol.

53. The premixes of claim 43 wherein said polyol is an aromatic-based polyester polyol.

54. The premixes of claim 43 wherein said polyol is a polyethylene terephthalate-based polyester polyol.

55. The premixes of claim 48 wherein said polyol is PLURACOL? polyol 975.

56. The premixes of claim 51 wherein said polyol is PLURACOL? polyol 824.

57. The premixes of claim 53 wherein said polyol is TERATE?203.

58. The premixes of claim 53 wherein said polyol is STEPANOL?PS-2502-A.

59. The premixes of claim 54 wherein said polyol is CHARDOL?336-A.

60. The premixes of claim 47 wherein said polyol is PHT4-DIOL.

61. The premixes of claim 50 wherein said polyol is THANOL?R-350-X.

62. The premixes of claim 46 wherein said polyol is POLY-O?71-357.

63. The premixes of claim 52 wherein said polyol is NIAX?polyol LA-700.

64. The premixes of claim 44 wherein said polyo1 is THANOL?650-X.

65. The premixes of claim 45 wherein said polyol is PLURACOL? polyol 1114.

66. The premixes of claim 46 wherein said polyol is POLY-G?75-442.

67. The premixes of claim 53 wherein said polyol is FOAMOD?3500.

68. The premixes of claim 52 wherein said polyol is VORANOD?800.

69. The premixes of claim 48 wherein said polyol is VORANOD? 370.

70. The premixes of claim 42 wherein said premixes comprise a polyether polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used in the foam preparation.

71. The premixes of claim 43 wherein said premixes comprise a polyester polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used in the foam preparation.

72. The premixes of claims 44 wherein said premixes comprise a rigid polyol and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used in the foam preparation.

73. The premixes of claim 45 wherein said premixes comprise a polyether polyol/polyester polyol blend and 1,1-dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used in the foam preparation.

74. The premixes of claim 46 wherein said premixes comprise a methyl glucoside-based polyol and dichloro-1-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used in the foam preparation.

75. The premixes of claim 47 wherein said premixes comprise a reactive brominated diol and 1,1-dichloro-fluoroethane in proportions suitable for polyurethane or polyisocyanurate foam preparation wherein said 1,1-dichloro-1-fluoroethane is the only blowing agent used the foam preparation.

76. The premixes of claim 70 wherein said polyol is a sucrose-based polyether polyol.

77. The premixes of claim 70 wherein said polyol is a sucrose amine-based polyether polyol.

78. The premixes of claim 70 wherein said polyol is an aromatic amine-based polyether polyol.

79. The premises of claim 70 wherein said polyol is an aromatic initiator-based polyether polyol.

80. The premises of claim 70 wherein said polyol is an amine-based polyether polyol.

81. The premixes of claim 71 wherein said polyol is an aromatic-based polyester polyol.

82. The premixes of claim 71 wherein said polyol is a polyethylene terephthalate-based polyester polyol.

83. The premixes of claim 28 wherein said auxillary blowing agent is a fluorocarbon.

84. The premixes of claim 29 wherein said auxillary blowing agent is a fluorocarbon.

85. The premixes of claim 28 wherein said auxillary blowing agent is water.

86. The premixes of claim 29 wherein said auxillary blowing agent is water.

87. The premixes of claim 85 wherein water comprises up to 2 parts by weight per 100 parts by weight of polyol.

88. The premixes of claim 85 wherein water comprises up to 1 part by weight per 100 parts by weight of polyol.

89. The premixes of claim 86 wherein water comprises up to 2 part by weight per 100 parts by weight of polyol.

90. The premixes of claim 86 wherein water comprises up to 1 parts by weight per 100 parts by weight of polyol.