Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3525F
BA~KGROU~D OF THE INVENTION
1. Field of the In~ention
This invention relates to cellular polymers and
intermediates therefor and is more particularly
concerned with novel polyol blends and their use in
a process for the preparation of cellular polyiso-
cyanurates.
2. Description of the Prior Art
Cellular polyisocyanurate polymers are well known
in the art for tneir use in various types of thermal
insulating applications. They are also well known for
their ability to withstand heat and flame; see U. S.
Patents 3,745,133, 3,986,991, and 4,003,859. Minor
amounts of polyols are sometimes added to the foam
forming ingredients to modify the foam properties. When
fluorocarbon blowing agents are employed the problem
of the incompatibility that may arise between the
polyol, particularly primary hydroxyl polyols, and
fluorocarbon in resin premixes is generally solved by
premixing most, if not all, the fluorocarbon with the
polyisocyanate; see the patents cited supra.
Polyisocyanurate foams find particular utility in
the production of laminated foam board stock material
which can be prepared with a variety of different
facer materials. Problems which can arise in the
production of such laminate material include 1.) lack
of uniform foam core strength; 2.) poor adhesion
between foam core and facer material; 3.) màintaining
good fire resistance in the foam; and 4.) keeping foam
friability at low levels. These problems have been
--2--
3525F
1$'~
overcome in the art by employing minor amounts of low
equivalent weight polyols, particularly diols, in the
formulation, combined with the heating of the formed
laminate product in an oven at 160 to 190F.; see U.S.
Patent 3,903,346.
However, the low equivalent weight polyols employed,
particularly the preferred diols (see column 4, lines
59-61 of U. S. 3,903,346) having only primary hydroxyl
groups, cannot be blended beforehand with the fluoro-
carbon blowing agent in a "B" side component because of
the low solubility of the diol-fluorocarbon pair.
This necessitates the blending of the fluorocarbon with
the polyisocyanate in the "A" side component. Further,
because of the fluorocarbon diol immiscibility, the
above patent teaches that a third component "C" is
required which contains the catalyst constituent
dissolved in a low molecular weight glycol; see column
2, lines 32-33 and the examples of 3,903,346.
Furthermore, a laminate preparad in accordance
with the patent noted above must be heated in an oven
to provide a product having a uniform foam core strength.
Surprisinglyj it has been found that high levels
of fluorocarbon blowing agent are completely miscible
with low molecular weight polyols containing primary
2S hydroxyl groups when novel blends comprisiny certai~ types
of amine or amide diols or amine triols with the primary
hydroxyl polyols are employed, Additional ingredients which
can be present in the miscible blends are surfactants,
catalysts, and the like.
Further, it has been found that the same type of
--3--
3525F
~'`
miscible primary hydroxyl containing blends as
described above, except that water replaces the fluoro-
carbon component, can be obtained.
Furthermore, it has been discovered that the novel
polyol blends above can be employed in minor amounts as
a B type component to prepare polyisocyanurate foams
characterized by low friability, fine cell structure,
good dimensional stability, and low flame spread, via
a two-component, i.e., an A, and a B side, process.
The fluorocarbon and water components act as the blowing
agents in their respective foam forming formulations.
Further, the certain types of amide or amine diols or
amine triols referred to above can be employed as the sole
polyol ingredient in combination with the fluorocarbon or
water, catalyst, surfactant, and other adjuvants to provide
polyisocyanurate foams in accordance with the present invention.
Quite unexpectedly, the presence of the amide or amine
diols or amine triols in the B side gives rise to excellent
reactant compatibility between the polyisocyanate and the
other ingredients. This gives rise in turn to faster
reactivity compared to prior art foams and very good reaction
exotherm. The hlgh exotherm is of particular advantage when
foam laminates are being prepared because it results in
excellent adhesion between foam and facer material thereby
eliminating the need of heating the formed laminate in an oven.
SUMMARY OF THE INVENTION
This invention comprises polyol blends comprising
(i) from about 20 percent to about 85 percent by weight of
sa~ blend of a member or mixture of members selected from
compounds of the formulae:
--4--
3525F
f CH2CHOt-H 1 ~ CH2CHO ~,H
R-N ~ ; R2-C-N ~ ; and
Rl R
I II
Rl
f CH2CHO~
R-~ ~ CH 2 ~HO~
CH 2CHO~H
R 1
III
wherein R is an aliphatic radical having from 8 to 18
carbon atoms, inclusive, R2 is an aliphatic radical
having from 7 to 17 carbon atoms, inclusive, each Rl is
independently selected from the group consisting of
hydrogen or methyl, x and y each independently have an
average value from about 4 to about 15 inclusive, x~
and y' each independently have an average value from
about l to about 3, inclusive, x" , y" , and z each
~ independently have an average value from about l to
about 5, inclusive, and n is 2 or 3; and (ii) from
about 15 percent to about 80 percent by weight of a
primary hydroxyl polyol (IV) characterized by a
molecular weight of from about 60 to about lO00.
This invention also comprises miscible blends
arising from the above polyol blends in combination
with a fluorocarbon or water blowing agent.
This invention also comprises miscible blends
arising from the above polyol blends in combination
with a fluorocarbon or water blowing agent and an
--5--
35~5F
isocyarlate trimerization catalyst.
The invention also comprises processes for the
preparation of polyisocyanurate cellular polymers which
utilize, as a blended component, a member or mixture of
members selected from compounds of the formulae (I~,
(II), or (III) above wherein the values of x and y can
have independent average values of from about 1 to
about 15 but preferably from about 4 to about 15, with
x', y', x", y", z, n, R, Rl, and R2 having the
definitions set forth abovel in combination with
a fluorocarbon or water blowing agent and a
trimerization catalyst, and, preferably, the blended
component additionally containing the polyol (IV) in
which case the diol (I) is defined as above witll the
narrower range of x and y of about 4 to about 15, in
the reaction with an organic polyisocyanate.
The invention also comprises the cellular polymers
produced in accordance with the above process.
The invention also comprises a laminate panel
having a polyisocyanurate foam core made in accordance
with the improved process in accordance with the
present invention.
The term "aliphatic radical" as it relates to R means
alkyl and alkenyl having from 8 to 18 carbon atoms inclusive.
Representative of alkyl are octyl, decyl, dodecyl,
tetradecyl, hexadecyl, octadecyl, and isomeric forms
thereof. Representative of alkenyl are octenyl,
decenyl, dodecenyl, -tetradecenyl, hexadecenyl, octa-
decenyl, and isomeric forrns thereof.
The term "aliphatic radical" as it relates to Rz
35~5~
11~0~;~5
means alkyl and alkenyl having from 7 to 17 carbon
atoms inclusive. Representative of alkyl and alkenyl
in this case are the same as above except for the
lower carbon atom range beginning at heptyl or heptenyl
and ending at heptadecyl or heptadecenyl and isomeric
forms thereof.
The polyol blends in accordance with the present
invention can be used as the polyol ingxedients in the
preparation of polyurethane foams. Polyurethane foams
are well known in the art for their use in a wide
variety of applications including thermal and sound
insulation for both industrial and residential buildings.
The polyol blends find particular utility, as set
forth herein, as minor constituents in the preparation
of polyisocyanurate foams particularly those polyiso-
cyanurate foams prepared in foam laminate machinery
and by spray foam equipment. Such foams are well known
for their heat and fire resistance and are used in
making laminate boards and foam bun stock which are
both used in building construction for thermal and
sound insulation,
DET~ILED DESCRIPTION OF THE INVENTION
The polyol blends in accordance with the present
invention are prepared simply by mixing together, in
the proportions by weight set forth above, the amine
diol (I), amide diol (II), or aminé triol (III? and a
primary hydroxyl polyol (IV) defined above, in any
suitable mixing vessel, holding tank/ storage vessel,
or the like. Preferably, (I), (II), or (III) is
employed within a range of from about 25 percent to
~7-
about 60 percent by weight of the blend while the
primary hydroxyl polyol is employed within a range of
from about 40 percent to about 75 percent by weight.
Preferred members of (I), (II), and (III) have the
formulae set forth above wherein Rl is hydrogen in all cases.
A most preferred diol is that which has the formula
corresponding to (I) wherein both Rl groups are hydrogen,
and x and y each independently have an average value
from abo~t 5 to about 10 inclusive.
10A most preferred amide diol has the formula
corresponding to (II) wherein both Rl groups are ~ ;
hydrogen and x' and y' each independently have an
average value from about 2 to about 3 inclusive.
A most preferred amine triol has the formula
corresponding to (III) wherein all the Rl groups are
hydrogen, and the x", y", and z each have an average
value from abo~t 3 to about 5 inclusive, and n is 3.
The amine diols (I) are prepared using standard
reactions known to those skilled in the art and in
` some instances the amine diols are commercially
available. Typically, the amine diols (I) can be
prepared by reacting the appropriate dialkanolamine
~ith the appropriate aliphatic halide (R-X) compound,
or mixture of different R-X compounds where all the
aliphatic groups (R) fall within the definition above
and X is halogen preferably chlorine or bromine. If
the desired number of alkyleneoxy groups are not
already present in the dialkanolamine prior to
-8-
3525F
~14~5
reaction with the aliphatic halide they can be
readily added afterward by reacting the alkylated
dialkanolamine with the appropriate number of moles
of ethylene oxide or propylene oxide, or mixtures
thereof, to provide the amine diols of formula (I).
Preferably, the amine diols (I) are prepared ~y
reacting the appropriate primary fatty amine R-NH2 or
mixture of fatty amines wherein all the R groups are
defined as above, with from about 2 to about 30 moles,
preferably from about 8 to about 30 moles, most
preferably 10 to 20 moles, of ethylene oxide or
propylene oxide per molar proportion of fatty amine;
see Bulletin 1294, entitled Ethoxylated Fatty Amines,
Ashland Chemical Company, Division of Ashland Oil Inc.,
Box 2219, Columbus, Ohio 43216 for a detailed teaching
of the preparation of the subject amine diols.
Illustrative of the starting fatty amines are
octylamine, decylamine, dodecylamine, tetradecylamine,
hexadecylamine, octadecylamine, and isomeric forms
thereof. Illustrative of the alkenylamines are octenyl-
amine, decenylamine, dodecenylamine, tetradecenylamine,
hexadecenylamine, octadecenylaminej and isomeric forms
thereof. Further illustrative of said fatty amines are
mixtures of alkyl- and alkenylamines, for example,
cocoamine which consists of the following mixture in
approximate percent proportions by weight: 2% decyl-
amine, 53% dodecylamine, 24% tetradecylamine, 11% hexa-
decylamine, 5% octadecylamine, and 5% octadecenylamine;
soya amine in the following approximate proportions:
11.5% hexadecylamine, 4% octadecylamine, 24.5% oleyl-
3525F
amine, 53% linoleylamine, and 7% linolenylamine; and
tallow amine in the following approximate proportions:
4~ tetradecylamine, 29~ hexadecylamine, 20~ octadecyl-
amine, and 47~ octadecenylamine. Further illustrative
of the starting fatty amines are the halogenated fatty
amines, particularly the chlorinated and brominated
fatty amines, which, illustratively, can be made by the
chlorination or bromination of cocoamine, soya amine,
tallow amine, and the like.
A particularly preferred group of fatty amines
consists of cocoamine mixture, soya amine mixture, and
tallow amine mixture. A preferred member of this group
is cocoamine.
The amide diols (II) are prepared using standard
reactions known to those skilled in the art. Typically,
they can be prepared by reacting the appropriate
dialkanolamine with the appropriate fatty acid, fatty
acid ester, or fatty acid chloride according to the
following equation
ll
~CH2CHO~-~H
R2COR3 + H ~ x ~ II + HR3
yCH2CHot-~H
Rl
wherein R2 , Rl, x', and y' have the same definition as
above and R3 represents -OH, -OR4, and X wherein R4
represents any typical esterifying group such as lower
alkyl, aryl, cycloalkyl, and the like, and X is halogen
preferably chlorine or bromine. In the event that
diethanolamine or diisopropanolamine or a mixture
thereof is the starting dialkanolamine, and it is
--10--
3525F
6~
desired to obtain amide diols in which the values of
x'and y'are greater than 1, then the intermedia~e
dialkanolamide is simply reacted in a one molar propor-
tion with from about 1 to al~out 4 molcs of ethylcne
oxide or ~ropylene oxide, or mixtures thereof. Sec
sulletin 1295, entitled Varamiclc ~lkal~olamiclcs,
Ashland Chemical Company, Division of Ashland Oil, Inc.,
Box 2219, Columbus, Ohio 43216 for a detailed teaching
oE tl~e preparation of fatty acid dialkanolamides.
Preferably, the amide diols (IIjare prepared by
converting the fatty acids to the corresponding fatty
acid amides(R2CONH2) and reacting the amide with from
about 2 to about 6 moles, per mole of amide, of
ethylene oxide or propylene oxide, or mixtures tl~ereof.
Illustrative of the starting fatty acids (from
wllicll the corresponding esters, acid halides, and amides
are also derived) are caprylic, capric, lauric, myristic,
palmitic, stearic, and isomeric forms thereof. Illustra-
tive of the unsaturated fatty acids are decylenic,
dodecylenic, palmitoleic, oleic, linoleic, and isomeric
forms thereof. Further illustrative of said fatty
acids are mixtures, for example, the fatty aci~ mixture
derived from coconut oil which consists of the
following mixture in approximate percent proportions
by weight: 8.0~ caprylic,7.0~ capric, 48.0% lauric,
17.5% myristic, 8.2% palmitic, 2.0% stearic, 6.0%
oleic, and 2.5~ linoleic; the fatty acid mixture
from soybean oil: 6.5% palmitic, 4.2% stearic, 33.6%
oleic, 52.6~ linoleic, and 2.3% linolenic; and the
fatty acid mixture from tallow: 2% myristic, 32.5%
3525F
palmitic, 14.5~ stearic, 48.3~ oleic, and 2.7% linoleic.
Further i~lustrative of the starting fatty acids are
the halogenated fatty acids, particularly the chlori-
nated and brominated fatty acids, which, illustratively,
can be made by the chlorination or bromination of the
coconut, soybean, and tallow fatty acid mixtures
described above.
A particularly preferred group of starting fatty
acids and fatty acid amide intermediates consists of
the coconut, soybean, and tallow oil mixtures described
above and the corresponding cocoamide~ soyamide, and
tallow amide mixtures. Preferred members of this group
are the coconut oil mixture and its cocoamide mixture
derivative.
A preferred group of amide diols (II)are the
cocoamide diol, soyamide diol, and tallow amide derived
diol mixtures wherein each Rl is H and both x'and y'
have a value of about 3. A preferred species within
this group of amide diols is the cocoamide diol mi~ture
above and identified by the chemical name of N,N-
bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture.
The amine triols (III) are easily prepared using
standard reactions known to those skilled in the art
and in some instances the amine triols are commercially
available.
Generally speaking, the mode of preparation of the
amine triols having n equal to 2 will differ slightly
from those amine triols having n equal to 3. The
former amine triols can be easily prepared according
to the following scheme.
-12-
3525F
[NH3]
RNH2 ~ C ~ - CHRl - ~ RNHCHRlCHRlOH ~ RNHCHRlCHRlNH2
V VI
E.O. or
P.o. or
mixtures
~II ~
wherein R, and Rl are defined above. The amine starting
material is reacted with an equimolar amount of ethylene
or propylene oxide to form the aminoalcohol (V) which
can be easily transformed into the diamine (VI~,
typically by reaction with ammonia, followed by the
reaction of a molar proportion of (VI) with from about
3 to about 15 molar proportions of ethylene oxide or
propylene oxide or mixtures thereof to form the amine
triol (III).
Amine triols ha~ing n equal to 3 are typically
prepared by the following scheme.
[H]
RNH2+ RlCH=CRlCN ~ RNHCHRlCHRl-CN--e RNHCHRlCHRlCH2NH2
VII VIII IX
E.O. or P.O.
or mixture
wherein R, and Rl are defined above. The amine starting
material is cyanoethylated with the appropriately
substituted acrylonitrile (VII)to form (VIII) which is
reduced to the diamine (IX) , followed by alkoxylation
with from about 3 to about 15 molar proportions of ethylene
oxide or propylene oxide or mixtures thereof to form (III).
The starting fatty amines are the same as those set
forth above and exemplified in the preparation of the
amine diols (I).
-13-
` -
9~i
Illustrative of the acrylonitrile compounds which
can be used in the preparation of the amine triols in
accordance with the present invention are acrylonitrile,
~-methacrylonitrile, ~-methacrylonitrile, ~,~-dimeth-
acrylonitrile, and the like. Preferred is acrylonitrile.
A preferred group of amine triols (III) are the amine
triol mixtures derived from cocoamine, soya amine, and
tallow amine mixtures wherein all the Rl groups are hydrogen,
the value of n equals 3, and the value of x", y", and z each
equal from about 3 to about 5. A most pre~erred species is
the amine triol mixture derived from cocoamine wherein all
the Rl groups are hydrogen, the value of n equals 3, and
the value of x", y", and z each equal about 4.6.
The primary hydroxyl polyol (IV) can be any
primary hydroxyl polyol having a molecular weight of
from about 60 to about 1000, preferably from about 60
to about ~00, and most preferably from about 60 to
about 600. Included in the polyols (IV) are diols,
triols, and tetrols. The preferred polyols are diols.
Included in the class of primary hydroxyl contain-
ing polyols are the various primary hydroxyl containing
diols, triols, and tetrols disclosed in U. S. Patent
3,745,133 which meet the molecular weight
limitations set forth above. The preferred
~5 classes are the polyester polyols prepared
from dibasic carboxylic acids and polyhydric alcohols
including those based on chlorendic anhydride, alkylene
diols, alkoxyalkylene diols, polyalkylene ester diols,
polyoxyalkylene ester diols, hydroxyalkylated aliphatic
-14-
3525F
monoamines or diamines, the resole polyols (see Prep.
Methods of Polymer Chem. by W. R. Sorenson et al.,
1961, page 293, Interscience Publishers, New York,
N.Y.), and polybutadiene resins having primary hydroxyl
groups, (see Poly Bd Liquid Resins, Product Bulletin
BD-3, October 1974, Arco Chemical Company, Div. of
Atlantic Richfield, New York, N. Y.).
The most preferred classes are the alkylene diols,
lower alkoxyalkylene diols, polyalkylene ester diols,
and polyoxyalkylene ester diols.
Illustrative, but not limiting, of the preferred
classes of polyols in accordance with the present
invention are ethylene glycol, 1,3-propanediol, 1,4-
butanediol, glycerine, trimethylolpropane, pentaery-
thritol; diethylene glycol, the polyoxyethylene glycolsprepared by the addition of ethylene oxide to water,
ethylene glycol, or diethylene glycol, etc., which
provide triethylene glycol, tetraethylene glycol, and
higher glycols, or mixtures thereof such that the
molecular weight falls within the range set forth above;
ethoxylated glycerine, ethoxylated trimethylolpropane,
ethoxylated pentaerythritol, and the like; bis(~-
hydroxyethyl)terephthalate, bis(~-hydroxyethyl)phthalate,
and the like; polyethylene succinate, polyethylene
glutarate, polyethylene adipate, polybutylene succinate,
polybutylene glutarate, polybutylene adipate, copoly-
ethylenebutylene succinate, copolyethylenebutylene
glutarate, copolyethylenebutylene adipate, and the like
hydroxy terminated polyesters; polyoxydiethylene
succinate, polyoxydiethylene glutarate, polyoxy-
. -15
3525F
6~i
dietllylerle adipate, polyoxydiethylene adipate glutarate
and the like; diethanolamine, triethanolamine, N,N' bis(~-
hydroxyethyl)anilin~, and the like.
The most preferred diols are diethylene glycol,
and the polyoxydiethylene adipate glutarate polyester
diols having a molecular weight from about ~00 to
about 600.
Particularly preferred are blends of from about
30 percent to about 50 percent by weight of diethylene
glycol with from about 50 percent to about 70 percent
by weight of a polyoxydiethylene adipate glutarate
polyester diol having a molecular weight from about
400 to about 600.
In the preferred polyol blends in accordance with
the present invention a fluorocarbon or water blowing
agent is also present in the blend with the fluorocarbon
beiny the preferred blowing agent.
When the blowing agent is a fluorocarbon the
unexpected and advantageous features of the polyol blends
Of (I), (II), or (III) with (IV) can be realized fully
Accordingly, there can be obtained miscible polyol
blends comprising at least about 20 percent by weight
of a fluorocarbon blowing agent and the balance being
the blends within the proportions set forth above.
The particular percentage of fluorocarbon to be
dissolved in the bl~nd will govern the proportions of
(IV) and of (I), (II), or tIII) to be employed in any
given instance and these proportions, falling within
the range set forth above, can be easily determined by
one skilled in the art by trial and error methods.
-16-
3525F
~4~
Miscible polyol blends comprising greater than 50
percent by weight of fluorocarbon and even up to 90
percent by weight can be readily obtained with the blends
within the proportions set forth above in accordance with
the present invention and depending on the choice of
blend ingredients. Generally speaking, the lower the
molecular weight of the primary hydroxyl polyol (IV)
the greater is the amount of fluorocarbon which can be
dissolved in the blend at a given proportion of polyol
(I), (II), or (III), as opposed to a blend with a
polyol (IV) of higher molecular weight at the same
proportion. In this connection, the alkylene diols,
and lower alkoxyalkylene diols having molecular weights
of less than 400 are preferred polyols of formula (IV)
with the latter lower alkoxyalkylene diols heing most
preferred.
The particular proportions of polyol (I),(II), or
(III) to polyol (IV) to be employed in any particular
polyol blend to obtain maximum miscibility with fluoro-
carbon can be determined by a process of trial and error.
Generally speaking, when the amine diol (I) isemployed with (IV) there are obtained miscible polyol
blends comprising from at least about 25 percent by
weight to at least about 65 percent by weight of a
fluorocarbon blowing agent and the corresponding 75
percent to about 35 percent by weight being the blend
` of (I) and (IV).
When the amide diol (II) and (IV) are employed
there are obtained miscible polyol blends comprising
from at least about 20 percent by weight to at least
3525F
.
about 60 perc~nt by weight of a fluorocarbon blowing
agent, the corresponding 80 percent to about 40
percent by weight being the polyol blend of (II)
and (IV).
Andr when the amine triol (III) and (IV) are
employed there are obtained miscible polyol blends
comprising from at least about 20 percent by weight
to at least about 50 percent by weight of a fluoro-
carbon blowing agent and the corresponding 80 percent
to about 50 percent by weight being the polyol blend
of (III) and (IV).
When water is the blowing agent it is present in
the proportions of from about 1 percent to about 6
percent, preferably from about 2 to about 5 percent by
weight with the balance of 94 percent to 99 percent
and preferably 95 to 98 percent comprising (I), (II),
or (III) with (IV).
The fluorocarbon blowing agent can be any of the
fluorocarbons known to those skilled in the art and
which can be used for blowing polymer mixtures into
cellular polymers. Generally speaking, such blowing
agents ar~e halogenated aliphatic hydrocarbons which
are also substituted by chlorine and/or bromine in
addition to the fluorine content and are well known to
those skilled in the art; see U. S. Patent 3,745,133,
column 11, lines 25 to 38.
-18-
J 3525F
In a preferred embodiment of a polyol blend
in accordance with the present invention which
finds particular utility in the preparation of
polyisocyanurate foams, there is additionally
present, in the blend of blowing agent and
components (I), (II), or (III) and (IV), an
isocyanate trimerization catalyst. The
isocyanate trimerization catalyst component
will be discussed in detail below. The
isocyanate trimerization catalyst is
advantageously present in the proportions of
from about 2 to about 20, preferably from about
2 to about 15 weight percent, with the balance
of about 80 to about 98, preferably about 85
to 98 percent, comprising the ingredients set
forth above.
Surprisingly, the blowing agent and the
polyol blend which includes the primary hydroxyl
containing polyols are completely miscible in
each other with no separation occurring upon
storage, which miscibility is due to the
presence of the amine diol (I), amide diol (II),
or amine triol (III). Aside from the advantages
arising from having a stable, miscible blend of
primary hydroxyl polyol and fluorocarbon or
water, the beneficial effects of having the
nitrogen containing diol or triol present
as a minor constituent when preparing
polyisocyanurate foams have been noted above.
Other optional additives can be added to the
--19--
~ji 3 5 2 5F
,. .
polyol blends without detracting from the
miscibility and stability of the blends. Such
additives include other optional polyol components
such as secondary hydroxyl containing polyols,
dispersing agents, cell stabilizers, surfactants,
flame retardants, and the like which are
commonly employed in the process of the invention.
In the preparation of polyisocyanurate foams
in accordance with the present invention, the
amine diol, amide diol or amine triol
described above can be employed as the sole
polyol component in admixture with a fluoro-
carbon or water blowing agent and a trimerization
catalyst to form a B side component for reaction
with an A side comprised of an organic polyiso-
cyanate. In this event the values of x and y
in (I) can have the broader ranges as noted
above of from about 1 to about 15.
The percent by weight proportions of the
blend ingredients are the same as those set forth
above for the proportions of catalyst to be
blended with blowing agent and polyol component.
That is to say the B blend is comprised of from
about 2 to about 20, preferably from about 2
to about 15 percent by weight of a trimer-
ization catalyst and from about 80 to about
98, preferably about 85 to 98 percent by weight of
~I), (II), or (III) and blowing agent~ In the event that
a fluorocarbon blowing agent is employed it is present in the
-20-
- 3525F
proportions of about 20 to about 80, preferably from
about 20 to about 50 percent by weight in respect of the
(I), (II),or (III), which latter, accordingly is present
in an amount from about 20 to about 80, preferably from
about 50 to about 80 percent by weight.
In the event that water is employed as the blowing
agent it is present in the proportions of from about
1 to about 6, preferably from about 2 to about 5 percent
by weight in respect of the (I), (II), or(III), which,
accordingly, is present in an amount from about 94 to about 99,
preferably 95 to 9~ percent by weight.
The B side blend is advantageously employed in an
amount falling within the range of from about 10 parts
to about 120 parts, preferably ~rom about 10 to about
80 parts, most preferably from about 20 parts to about
60 parts by weight per equivalent of polyisocyanate;
provided the total hydroxyl equivalents present in said
blend (B) are within a range of from about 0.05 to
about 0.5 equivalent, preferably about 0.08 to about
0.4 equivalent, per equivalent of said polyisocyanate.
Preferably there is also present in the B side
blend a minor amount of the primary hydroxyl polyol
(IV) described above. This combination in the blend
not only gives rise to the stabilized miscible blends
discussed above, but, additionally,provides polyiso-
cyanurate foams having the optimum advantageous proper-
t1es discussed above, including the preparation of foam
laminates which require no oven heating in order ~o
achieve maximum foam strength and adhesion to the
laminate facers. In this event the values of x and y
-21-
S
in (I) have the narrower ranges as noted above of
from about 4 to about 15.
The blend containing the amine diol (I), amide diol (II),
or amine triol (III), with primary hydroxyl polyol (IV),
blowing agent, and trimerization catalyst is also employed
in an amount falling within the same range of parts per
isocyanate equivalent set forth above for the B blend with-
out (IV); and with the same proviso set forth above
for the range of total hydroxyl equivalents per
equivalent of isocyanate. The pro~ortions of each
ingredient in the blend in percent by weight of the
blend are the same proportions set forth in the description
of the polyol blends. The amine diol (I), ami~e diol (II),
amine triol (III), primary hydroxyl polyol (IV), and blowing
agent, all have the same significance and scope set forth above.
The trimerization catalyst employed can be any
catalyst known to those skilled in the art which will
catalyze the trimerization of an organic isoc~anate
compound to form the isocyanurate moiety. Further, a
combination of urethane forming catalyst and trimeriza-
tion catalyst can be employed if desired.
For typical isocyanate trimerization catalysts
see ~he ~ournal of Cellular Plastics, November/December
1975, page 329; U. S. Patents 3,745,133, 3,896,052,
3,899,443, 3,903,018, 3,954,684, and 4,101,465.
Preferred as catalysts are the ones disclosed in
U. S. 3,896,052, and 4,101,465. The former reference
discloses the catalyst combination of (a) an alkali
~ ~4(~6~i
metal salt of an N-substituted amide with (b) an alkali
metal salt of an N-(2-hydroxyphenyl)methyl glycine ana
optionally (c) a tertiary amine trimerization catalyst.
The latter reference discloses the combination sf the
same (a) and (b) components above with a hydroxyalkyl-
trialkylammonium carboxylate salt component.
The organic polyisocyanates which can be employed
in the preparation of the polyisocyanurate foams in
accordance with the present invention can be any of the
organic polyisocyanates conventionally employed in the
art for this purpose previously. Advantageously, and
in order to obtain foams having exceptionally high heat
resistance and structural strength, the preferred poly-
isocyanates are the polymethylene polyphenyl polyiso-
lS cyanates, particularly those set forth in U. S. Patent3,745,133. Also preferred are the polymethylene poly-
phenyl polyisocyanates treated with a minor amount of an
epoxy compound to reduce acidic impurities in accordance
with U. S. 3,793,362; and the polymethylene polyphenyl
polyisocyanates which contain high levels of the
2,4'-isomer as typically disclosed in U. S. Patent
3,36~,979.
A most preferred organic polyisocyanate is a
mixture containing from about 30 percent to about 85
percent by weight of methylenebistphenyl isocyanate)
and the remainder of said mixture comprises polymethylene
polyphenyl polyisocyanates of functionality higher than 2Ø
In carrying out the preparation of polyisocyanurate
-23-
6~5
foams in accordance with the process of the invention,
and, in particular, polyi60cyanurate foams for the
preparation of ~oam laminates, the procedures and
aquipment conventional in the art are employed (see
patents cited supra); for a detailed teaching of the
mode of preparation, and utility o~, polyisocyanurate
foam laminates see U. S. Patent 3,896,052.
The following examples describe the manner and
process of making and using the invention and set forth
the best mode contemplated by the inventors of carrying
out the invention but are not to be construed as limiting.
Example 1
The following five polyisocyanurate foams (Foam A
through E) were prepared in accordance with the
followlng procedure.
The foams were prepared as hand-mix samples by
blending together the A and the B side ingredients (in
parts by weight) set forth in Table I below, in 1 qt.
cups. The polyisocyanate ingredient was the sole
component of the A side while the B side ingredients
which are listed in Table I were premixed and observed
prior to being reacted with the polyisocyanate. The
blending operation was carried out by thoroughly mixing
the A and B sides in the cup with a high speed drill
press motor equipped with a stirrer blade. The mixture
was rapidly poured into a cardboard box and allowed to
rise freely and cure at room temperature (circa 20C).
Foams B and E are in accordance with the present
invention while A, C, and D are not because the amine
-24-
B
3525F
diol component had values of x and y below that called
for. The B sides in all of the formulations were clear
with no evidence of turbidity. However, in the case of
A and C, secondary hydroxyl polyols were present which
are known fluorocarbon solubilizers while in C there
was present additionally the phosphate plasticizer.
Foam D also contained the plasticizing ingredient.
Maximum foam properties with respect to the
combination of maximum reaction exotherm with rapid
firm rate and low core and surface friability were
observed with Foam E.
The surface blush in respect of a rising foam
sample is the point when the shiny and moist unreacted
surface of the rising foam becomes dulled or blushed
lS and indicates that an efficient curing or reaction has
occurred at the surface. All of the foam samples
showed a good surface blush.
TABLE I
.
Foams A B C D E
~0
Ingredients(pts.by wt.)
A side:
Polyisocyanate I100 100 100 100 100
B side:
Diethylene glycol 5.7 5.4 6 6 8
Varonic~ L-202 5.7 - 6 6
Varonic~ K-2153 - 23.5 - - 8
Pluracol~ GP-73045.7
Pluracol~ PEP-6505 - - 6
Tris(dichloropropyl- 7.2 18 18
phosphate)
-25-
3525 F
TABLE I ( continued)
Foams A B C D E
Propoxylated polyol6 _ _ _ 6
L-54207 1.25 1025 1.25 1.25 1.25
Fluorocarbon R-llB25 25 25 25 25
Catalyst I 3 3 3 3 3
NCO/OH index- about about about about about
4 4 4 4
Appearance of B clear clear clear clear clear
component and and and and and
not not not not not
turbid turbid turbid turbid turbid
Foam reaction
exotherm (F) 339 313 294 298 345
Firm rate rapid slow medium rapid rapid
Core friability high low high high low
Surface friability none none none none none
Surface blush yes yes yes yes yes
Footnotes to Table I
lPolyisocyanate I is a polymethylene polyphenyl polyiso-
cyanate containing about 45 percent by weight of
methylenebis(phenyl isocyanate) and the remainder of
said mixture consisting of polymethylene polyphenyl
polyisocyanate having a functionality greater than 2;
the isocyanate equivalent = 133.
2Varonic~ L-202 is the soya amine adduct obtained by the
reaction of a 2 molar proportion of ethylene oxide with
soya amine; amine equivalent wt. about 360; hydroxyl
equiv. wt. about 180; supplied by Chemical Products
Division, Ashland Chemical Company, Columbus, Ohio.
3Varonic~ K-215 is the cocoamine adduct obtained by the
reaction of a 15 molar proportion of ethylene oxide with
cocoamine; amine equivalent wt. about 885; hydroxyl equiv.
wt. about 442; supplied by Chemical Products Division,
Ashland Chemical Company, Columbus, Ohio.
4Pluracol~ GP-730 is a propoxylated glycerine product;
hydroxyl equiv. wt. = 243, and is supplied by BASF
Wyandotte Chemical Corp., Wyandotte, Mich.
-26-
3525F
S
Footnotes to Table I (cont'd.)
5Pluracol~ PEP-650 is a propoxylated pentaerythritol
product; hydroxyl equiv. wt. = 148 and is supplied by
BASF Wyandotte Chemical Corp., Wyandotte, Mich.
6Propoxylated polyol is the product obtained from
propoxylating a mixture of sorbitol and toluene diamine
to a hydroxyl number of 360, viscosity of 2500 centi-
stokes at ~5C, and specific gravity of 1.072.
7L-5420: A rigid foam silicone surfactant having a
hydroxyl number of about 119 supplied by Union Carbide
Corp., Tarrytown, N.Y. 10591; see Union Carbide
Bulletin F-43565, December 1971.
Fluorocarbon R-llB is monofluorotrichloromethane blowing
agent stabilized with allo-ocimene and supplied by DuPont
Chemical Corp., Wilmington, Del.
9Catalyst I comprises a combination in the following
proportions of A.) 1 part of a solution comprised of (a)
45 percent by weight of potassium N-phenyl-2-ethyl-
hexamide, (b) 27 percent ethylene glycol, and (c) 28
percent dimethylformamide; B.) 3 parts of a solution
comprised of 50 percent by weight of sodium N-(2-
hydroxy-5-nonylphenyl)methyl-N-methyl glycinate in
diethylene glycol; and C.) 1 part of a solution comprised
of 50 percent by weight of 2-hydroxypropyltrimethyl-
ammonium formate and 50 percent dipropylene glycol; and
D.) 1 part of a polyethyleneglycol (MW = 200).
Example 2
The following foams were prepared in accordance
with the procedure and apparatus described in Example 1
except as noted below. The foams of this example set
forth a comparison of the prior art method (Foams F
and H) versus the method in accordance with the present
invention (Foams G and I).
The ingredients of the A and B sides are set forth
in Table II below. The F and G pair contained a
different polyisocyanate from the H and I pair. ~he
A side of Foams F and H contained the fluorocarbon
blowing agent in accordance with the prior art. When
the same amount of the fluorocarbon was mixed into the
B side to test miscibility, in both cases, the
-27-
~ 3525F
fluorocarbon separated from the other ingredients,
namely, diethylene glycol, surfactant, and catalyst.
In the case of Foams G and I which contained the
ethoxylated cocoamine in the B side, the fluorocarbon
and other ingredients were completely miscible with
the diethylene glycol component.
A comparison of the foam rise times between F and
G, and H and I, clearly show a much faster rate for the
foams in accordance with the invention (G and I) over
the respective pair in accordance with the prior art
(F and H). The dramatic rate increase clearly indicates
the increased compatibility between the A and B sides
which leads to better reaction between the two hence
the faster rise times over the formulations of the
prior art. While the ethoxylated amine used in Foams
G and I is a tertiary amine, these types of high
molecular weight tertiary amines are not strong bases
and were used in G and I in very small amounts based on
amine equivalents, iOe. 0.009 equivalents in each case.
l`hi~ low level of weak amine would not be enough to
explain the dramatic rate increases of G and I over F
and H respectively on the basis of amine catalysis alone.
TAB~E II
Foams F G H
Ingredients (pts. by wt.)
A side:
Polyisocyanate I 100 100 - -
Polyisocyanate II - - 105 105
Fluorocarbon R-llB21.5 - 22.5
-28-
3525F
.~ , ,
TA~LE II (continued)
Foams F G ~ I
B side:
Diethylene glycol8.3 8.0 8.3 8.0
Varonic~ K-215 - 8.0 - 8.0
L-5420 1.25 1.25 1.251.25
Catalyst I 3.0 3.0 3.0 3.0
Fluorocarbon R-llB - 23 - 24
NCO/OH index 4.6 4.2 4.6 4.2
Foam rise time(seconds)
Cream 75 19 59 21
Gel 104 42 96 41
Tack free 116 49 106 47
Exotherm (F) 341 336 318 316
Core density, pcf1.76 1.74 1.791.75
Dry heat age 300F/24 hrs.
% ~ volume +4.6 +4.1 +2.9~2.4
Core friability, % 31 30 22 19
Surface friabilitynone none nonenone
Surface blush yes yes yes yes
Footnotes to Table II
See Footnote 1, Table 1.
Polyisocyanate II is a polymethylene polyphenylpolyiso
cyanate containing about 35 percent by weight of methylene-
bis(phenyl isocyanate) and the remainder of said mixture
consisting of polymethylene polyphenyl polyisocyanate
having a functionality greater than 2; the isocyanate
equivalent = 140.
3The friability is the percent sample weight loss over a
10 minute period and determined in accordance with
ASTM Test method C-421.
-29-
3525F
~4~
Example 3
The following two polyisocyanurate foams J and K in
accordance with the present invention were prepared in
accordance with the procedure and apparatus described in
Example 1 and using the ingredients in the proportions
by weight set forth in Table III below. The B components
were clear in both cases.
Both foams were very fine celled in structure with
no surface friability and a good surface blush was
observed. The foam exotherms were good and the rapid
rise profiles indicated the fast reactivity for both
foams.
It is noteworthy that the catalyst mixture employed
in both J and K contained a very minor amount of the
lS Varonic~ K-215 amine diol which acted as a compatibiliz-
ing agent for the various other catalyst components. In
the absence of the Varonic~ K-215 the other catalyst
components are not completely miscible.
TABLE III
-
Foam J K
Ingredients (pts. by wt.)
A side:
Polyisocyanate IIIl 135 135
B side:
Varonic~ K-2052 37
Varonic~ K-215 - 75
DC-1933 1.5 1.5
Fluorocarbon R-llB22 27
Catalyst II4 3 3
NCO/OH index 4.5 4.5
-30-
- 3525E'
i ~
TABLE III (continued)
Foam J K
B mix appearance clear clear
Foam rise tirne(seconds)
Cream 5 6
Gel 20 20
Tack free 30 40
Rise - -
Exotherm (F) 328 305
Surface friabilitynone none
Surface blush yes yes
Core friability low low
Appearance very fine very fine
cell cell
Footnotes to Table III
lPolyisocyanate III is a polymethylene polyphenyl poly-
isocyanate containing about 45 percent by weight of
methylenebis(phenyl isocyanate) and the remainder of
said mixture consisting of polymethylene polyphenyl
polyisocyanates having a functionality greater than 2,
the isocyanate equivalent = 135.
2Varonic~ L-205 is the cocoamine adduct obtained by the
reaction of a 5 molar proportion of ethylene oxide with
cocoamine; amine equivalent wt. = about 445; hydroxyl
equiv. wt. about 222; supplied by Chemical Products
L)ivision, Ashland Chemical Company, Columbus, Ohio.
3DC-193 is a silicone surfactant supplied by Dow Corning,
Midland, Mich.; see Bulletin 05-146, February 1966.
Catalyst II comprises a combination in the following
proportions of: A.) 1 part of a solution comprised of
50 percent by weight of sodium N-(2-hydroxy-5-nonyl
phenyl)methyl-N-methyl glycinate in diethylene ylycol;
B.) 0.50 part of potassium acetate; C.) 0.30 part of
water; and D. ) 0.50 part of Varonic~ K-215 which is
described in Footnote 3 of Table I above. It should be
noted that this catalyst blend is completely clear and
miscible. Preparation of the same catalyst blend but
without the K-215 component yields a turbid and cloudy
mixture.
-31-
3525 F
Example 4
The following two water blown polyisocyanurate
foams L and M were prepared in accordance with the
present invention using the procedure and apparatus
described in Example 1 and using the ingredients in
the proportions by weight set forth in Table IV below.
The B side in both cases formed a clear miscible blend.
The foam rise characteristics were found to be
very rapid with a quick tack free time in spite of the
foams being water blown. High foam exotherms were also
observed attesting to the excellent conversions. The
resulting foam physical properties were good.
TABLE IV
Foams L M
-
Ingredients (pts.by wt.)
A side:
Polyisocyanate III 135 135
B side:
Polyol blend I 23 30
L-5420 2 2
H20
Catalyst II 3 3
NCO/OH index (includiny ~l2O) 3 2.5
B mix appearance clear clear
Foam rise time(seconds)
Cream 15 13
Gel 31 26
Rise 48 48
Tack free 35 30
-32-
~ 6~ 3525F
TABLE IV (continued)
Foams L M
Exotherm (F) 376 3 83
Density (pcf) 2.65 2.81
K-Factor in
BTU( ft.2)(hr.)F/in.:
in 1I dir. 0.190 0.201
in 1 dir. 0.189 '0.193
Compressive str.(psi)
¦I to rise 39. 5 42
1 to rise 30.0 20
% ~ Volume at 70C, 100
relative humidity after
24 hrs. -7.7 ~4-7
300F Dry Age~Volume(%)
after 24 hrs. -2.9 +3.0
Footnotes _ Table I
~olyol blend I comprises a blend in the following pro-
portions of A.) 40.8 pts. of a polyoxydiethylene adipate
glutarate polyester diol of M.W. = 500; B.) 28.6 pts. of
diethylene glycol; and C.) 30. 6 pts. of Varonic~ K-215.
2K-Factor is a measure of thermal conductivity of materials
by determining heat flow in accordance with ASTM Test
method C-518.
Example 5
This example sets forth a hand-mix polyiso-
cyanurate foam N prepared in accordance with the
present invention using the procedure and apparatus
described ;n Example 1 and the ingredients set forth
in Table V below.
The B side of sample N contained a mixture of
primary hydroxyl triol and diethylene glycol with a
41~ by weight proportion of fluorocarbon yet the
blend stayed clear with no turbidity.
3525F
-
The foam had fast rise times with a good exotherm
and good friability characteristics.
TABLE V
Foam N
Ingredients (pts. by wt.)
A side:
Polyisocyanate III 135
B side:
TPEG-990 8.5
Diethylene glycol 6.5
Varonic~ K-215 10
DC-193 1.25
Catalyst II 3.0
Fluorocarbon R-ilB 20
B mix appearance clear
no turbidity
~ R-llB in B mix 41
Foam rise time (seconds)
Cream 13
Gel 30
Tack free 35
Exotherm (F) 349
Surface friability none
Surface blush yes
Core friability low
Footnote to Table V
TPEG-990 is a primary hydroxyl containing trifunctional
polyethylene glycol having an OH E.W. a 333; and is
supplied by Union Carbide Corp., New York, N.Y.
Example 6
The following high temperature and flame resistant
~34-
3525F
polyisocyanurate foam laminates were prepared in
accordance with the present invention using the foam O
which was prepared from the ingredients set forth in
Table VI below.
A Viking laminating machine was used with "A" and
"B" component temperatures of 73F and 70F respectively.
Throughput was 15 lbs.~min. through a low pressure
impingement mixing head. A pour lay down technique
was used instead of a nip roll. The conveyor speed was
10 ft./min. and the curing oven temperature was at
ambient (70 to 90~F).
Two inch thick laminate was prepared with 0.0015"
aluminum foil facers and also prepared with asphalt
facers. The foam properties reported in Table VI below
are for the foam core material after the facers had
been removed. Therefore, the facer material itself
has no affect on this data. The adhesion between
facer material and foam was excellent.
The component B, although containiny the primary
hydroxyl polyester and diethylene glycol and a 43% by
weight content of freon (R-llB~ was clear with no
turbidity.
Tlle laminates were prepared without the necessity
of oven curing at a high temperature because of the
rapid reactivity of the formulation. The rapid
reactivity also was reflected in the rapid rise
profile and the fact that foam friability was found to
be very low in spite of the lack of a high temperature
cure step. Good facer adhesion, as noted above, was
also observed.
3525F
6~i;
The overall foam physical properties were found
to be good including the very low friability, good
fire resistance, K factor, and h~nid age data.
TABLE VI
Foam O
-
Ingredients (pts. by wt.)
A side:
Polyisocyanate I 133
B side:
Polyester dioll 9
Diethylene glycol 6.3
Varonic~ K-215 6.7
DC-193 1.25
Catalyst II 3.0
Fluorocarbon R-llB 20.0
B mix appearance clear
no turbldlty
% R-llB in B mix 4
NCO/OH index 4.9
Foam rise time (seconds)
Cream 19
Gel 40
Tack free 47
Surface friability none
Surface blush yes
Core friability low (6~)
Overall density (pcf) 2.0
Core density 1.8
Compressive str.(psi)
ll to rise 31
-36-
3525F
6~
TABLE VI (continued3
Foam
-
Compressive str. (psi)
1 to rise 21
Cloced cells 94%
K Factor in
BTU (ft.2)(hr.)F/in. 0.14
Humid age (15BF, 95~ R.H.)
~ Vol., after 1 day +6%
7 days +6.5%
28 days +7.0%
ASTM E-84 Test on 2" thick
samples:
Flame spread rating 38
Smoke 187
Footnotes to Table VI
lPolyester diol is the same diol described in Foot-
note 1 of Table IV under A.).
2Closed cells are determined by the air pycnometer
test in accordance with ASTM Test method D-2856.
~xample 7
The following polyisocyanurate foam P was prepared
in accordance with the present invention in accordance
with the procedure and apparatus described in Example 1
using the ingredients in the proportions by weight set
forth in Table VII below.
The B side was clear without evidence of turbidity
in spite of the combination of the fluorocarbon with
the primary hydroxyls of the amide diol.
The foam produced was characterized by a very fine cell
structure with no surface friability and with a good surface blush.
-37-
3525F
6~
The foam exotherm was good and the rapid rise
profile indicated the fast reactivity of the foam.
TABLE VII
Foam p
Ingredients (pts. by wt.)
A side:
Polyisocyanate III 135
B side:
Varamide~ 6-CM 49
DC-193 1.5
Fluorocarbon R-llB 23
Catalyst II 3
NCO/OH index 4.5
B side appearance clear
non-turbid
Foam rise time (secs.)
Cream 8
Gel 42
Tack free 52
Rise
Exotherm (F) 328
Surface friability none
Surface blush yas
Core friabilitymoderately fxiable
Appearance ~ery fine cell
Footnotes to Table VII
Polylsocyanate III is the same polymethylene polyphenyl poly-
isocyanate defined in Example 3j Footnote 1 of Table III.
Varamide~ 6-CM is the cocoamide adduct obtained by the
reaction of a 6 molar proportion of ethylene oxide with a 1
molar proportion of cocoamide; amine eq. wt.= 290~ OH eq.
wt.=193; supplied by Chemical Products Div.,Ashland Chemical
Co.,Columbus,Ohio.; and otherwise identified by the chemical
name of N,N-bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture.
3Catalyst II is the same catalyst combination defined in
Example 3, Table III, Footnote 4.
-38-
3525F
~L4(~
Example 8
The following polyisocyanurate Foams Q, R, and S
were prepared in accordance with the procedure and
apparatus described in Example 1 and using the
ingredients set forth below in Table VIII. Foams Q
and R are in accordance with the present invention
while Foam S is not.
The B side components in the case of Foams Q and R
were clear with no evidence of turbidity in spite of
the mixture of the fluorocarbon with the primary
hydroxyl containing components in both blends.
The A side of Foam S contained the fluorocarbon
blowing agent in accordance with the prior art. When
the same amount of the fluorocarbon was mixed into the
B side to test miscibility the fluorocarbon separated
from the other ingredients, namely, diethylene glycol,
surfactant, and catalyst.
A comparison of the foam rise times between Foams
Q and R on the one hand with Foam S on the other,
clearly shows a much faster rate for the foams in
accordance with the invention(Q and R) over the prior
art (S) . The dramatic rate increase clearly indicates
the increased compatibility between the A and B sides
which leads to better reaction between the two hence
the faster rise times over the formulations of the prior art.
TABLE VIII
.
Foam Q R S
.
Ingredients (pts. by wt.)
A side:
Polyisocyanate III - 135
-39-
3525F
,
TABLE VIII (continued)
Foam Q R S
Polylsocyanate Iloo - loo
Fluorocarbon R-llB - - 21.5
B side:
Polyester diol2 9
Diethylene ~lycol 8 6.3 8.3
Varamide~ 6-CM 8 6.7 ~ -
L-5420 1.25 - 1.25
DC-193 - 2
Fluorocarbon R-llB 25 22
Catalyst II 4.5 5
Catalyst I3 - _ 3.0
NCO/OH indexabout 4 about 4 about 4.6
B side appearanceclear clear
non-turbid non-turbid
Foam rise ti~e(secs.~
Cream 16 lÇ 75
Gel 40 35 104
Tack free 45 4Q 116
Rise 54 48
Exotherm (F? 344 351 341
Firm rate rapid rapid
Surface friabllity none no~e
25 Surface blus~ yes yes
Core densi-ty(pcf)1.55 2.06 1.76
Core friability(~) 38.5 32.0 31
300F Dry Age,
~ Volume ~/24 hrs. +7.4 +5.0 +4.6
-40-
3525F
Footnotes to Table VIII
_
lPolyisocyanate T iS the polymethylene polyphenyl poly-
isocyanate defined in Example 1, Table I, Footnote 1.
Polyester diol: a polyoxydiethylene adipate glutarate
polyester diol of MW = 500, and OH # = 211.5.
S Catalyst I is the same catalyst combination defined in
Example 1, Table 1, Footnote 9.
Example 9
The following polyisocyanurate Foam T was prepared
in accordance with the present invention in accordance
with the procedure and apparatus described in Example 1
using the ingredients in the proportions by weight set
forth in Table IX below.
The B side was clear without evidence of turbidity
in spite of the combination of the fluorocarbon with
the primary hydroxyls of the amine triol constituent.
The foam produced was characterized by a very fine
cell structure with no sur~ace friability and with a
good surface blush.
The foam exotherm was good and the rapid rise
profile indicated the fast reactivity of the foam.
TABLE IX
Foam T
Ingredients (pts. by wt.)
A side:
Polyisocyanate I~I; 135
B side
KD-2141 56
DC-193 1.5
Fluorocarbon R-llB 23
CatalySt II 2.5
~ 3525E'
~l~LOff95i
TABLE IX (continued)
Foam T
NCO/OH index 4.5
B side appearance clear
non-turbid
Foam rise time (secs.)
Cream 4
Gel 17
Tack free 50
Rise
Exotherm (F) 323
Surface friabilitynone
Surface blush slight
Core friability low
Appearance very fine cell
Footnotes to Table IX
~ D-124 is the ethoxylated mixture obtained by
reacting ethylene oxide with a cocodiamine in the
molar proportions of about 14 to 1 respectively,
and wherein the cocodiamine is obtained by reacting
cocoamine with an equivalent of acrylonitrile and
reducing the cyanoethylated cocoamine mixture to
the cocodiamine; amine eq. wt. = 290; OH eq. wt. =
193; supplied by Chemical Products Div., Ashland
Chemical Co., Columbus, Ohio.
-42-
; , . ;
3525F
Example _
The following polyisocyanurate Foams U, V, and W
were prepared in accordance with the procedure and
apparatus described in Example 1 and using the
ingredients set forth below in Table X. Foams U and
V are in accordance with the present invention while
Foam W is not.
The B side components in the case of Foam U and V
were clear witll no evidence of turbidity in spite of
the mixture of the fluorocarbon with the primary
hydroxyl containing components in both blends.
The A side of Foam W contained the fluorocarbon
blowing agent in accordance with the prior art. When
the same amount of the fluorocarbon was mixed into the
B side to test miscibility the fluorocarbon separated
from the other ingredients, namely, diethylene glycol,
surfactant, and catalyst.
A comparison of the foam rise times between Foams
U and V on the one hand with Foa~ W on the other,
~0 clearly shows a much faster rate for the foams in
accordance with the invention(U and V) over the prior
art(W) . The dramatic rate increase clearly indicates
the increased compatibility between the A and B sides
which leads to better reaction between the two hence
25 the faster rise times over the formulations of the prior artO
``` ` ` T~BI,E X
` Foam U V W
Ingredients (pts. by wt.)
A side:
Polyisocyanate III 135
-43-
3525F
TABLE X (continued)
Foam U V W
Polyisocyanate I 100 - 100
Fluorocarbon R-llB - - 21.5
B side:
Polyester dioll - 9
Diethylene glycol 8 6.3 8.3
KD-214 8 6.7
L-5420 1.25 - 1.25
DC-193 - 2
Fluorocarbon R-llB 25 22
Catalyst II 2.5 2.5
Catalyst I - - 3.0
NCO/OH index about 4 about 4 about 4.6
15 B side appearance clear clear
non-turbid non-turbid
Foam rise time (secs.)
Cream 16 15 75
Gel 39 42 104
Tack free 46 50 116
Rise 56 60
Exotherm (F) 331 337 341
Firm rate rapid rapid
Surface friabilitynone none
Surface blush yes yes
Core density (pcf)1.67 2.27 1.76
Core friability(%)18.8 33.1 31
300F Dry Age,
~Volume %/24 hrs.+10.8 +5.3 +4.6
Footnote to Table X
lPolyester diol: a polyoxydiethylene adipate glutarate
polyester diol of MW = 500, and OE~ # = 211.5.
-44-
3525F
, :.
LO~
Example _
A series of blends of fluorocarbon R-llB (monfluoro-
trichloromethane) with two typical primary hydroxyl
polyols of the present invention were prepared. The
proportions by weight employed, including the amount
of amine diol(I) when present, varied according to the
values set forth in Table ~I below. The blends
were observed for their miscibility and clearness or
their turbidity,and separation of the fluorocarbon
from solution.
Blends A through D contained diethylene glycol
with fluorocarbon and in the absence of amine diol,
i.e., 100% diethylene glycol, the maximum fluorocarbon
solubility was 15~ by weight. The addition of 10 per-
cent by wt. amine diol was not sufficient to impartfluorocarbon solubility at the 25% by wt. level whereas
a 20 percent amine diol content (blend D) did result
in a clear miscible solution at 25 percent fluorocarbon.
Blends E through J contained a polyester diol
defined above wherein the pure polyester diol was
capable of dissolving 20 percent by weight fluorocarbon
but not 25 percent. The break for 25 percent fluoro
carbon solubility started at about 10 parts by weight
of the amine diol (blend G) while at the 20 percent
level of amlne diol the fluorocarbon could xeach up to
31 percent by wt.
Blends K through M were observed to have maximum
fluorocarbon levels of greater than 90 percent and up
to 67.5 percent for diethylene glycol and the polyester
diol respectively when a maximum of 85 percent by
-~5-
3525F
63~1$
weight of amine diol was employed.
Blends N throu~h Q were observed to have maximum
fluorocarbon solubilities of 60 percent and 50 percent
respectively for diethylene glycol and polyester diol
when the primary alcohol-amine diol blends were 50/50
percent by weight.
~0
-46-
H I ~ ~ ~ ~ ~ ~ miscible
:~: I ~ ~0 ~o ~) ~o u) misecarible
o o ~ o o ~ clear
miscible
r~
o ~ o o ~ turbid
~ ~ ~ ~ ~ separates
o ~ o o o clear
~ I o I ~ ~ ~ miscible
x a ~ ~ ~ ~ ~ ~ mlisecarible
o o ~ o o ~ turbid
E~ O a~ I ~1 o~ ~ ~
~ separates
o ~ o o o turbid
m ~ I I ~ ~ ~ separates
o ~ o o ~ clear
miscible
~ ~ ~d O ~ '
0
o
:~ ~I P:; 0 0 h
Q. ~1 0 ~ O
-- ~ ' O h Ei ~I h
~Q o Q Q~ 0 ~ (d
h aJ
~ ~ ~ 0
O ~1
3 ~ 3
aJ ~ ~ ~1 o ~ ~ ~ ~
R ~ .4 ~:
m ~ a ~ 0 0~O 0~O
~7-
~SZ5
-
O O O O O ~ turbid
separates
o o o o o o clear
~ I u~ In o
~ miscible
o o ~ o o ~ turbid
o ~ I ~ ~ ~ ~ ~ separates 4
_ ~9 ~
~ z ~ ~ clear ~ H
~I misclble H
~ a
O ~1
~ ~ o turbid
separates
H ~`I ~1
X O ~
clear ~ $
~ ~ ~ ~ ~ ~0 ~ ~ ~ miscible
E~ ~ ~ ~o ~
o
~o ~o
clear ~
a~ mlsclble ~1
.,~
o o o o o ~ 1 d
1~ I ~ c ou y ,~
al H
~ ,~
O
3 ~ H ¦ 3 3
m ~ 'o~
rl (d a
~ 1 ~ r~
U~ ~ ~1 I h O a) .4 U~ E3
a) 1
Ql ~1 0 ~3 ~ O ~ E~ ~
~ O S lE~ i O O rS
u~ 5 ~ tL~
~ a) u~
a~ E~
o 3 3 3
a) U s~ o u~ u~
~ ~ ~ ~ ~ o
,~ ~ ~ a
m ~ ~1 o I ,~ a~ o
~ a ~ ~0~ ~ O E~
H m
~48-
~ZSE
3525F
~ . ~,
Example ~
A series of blends of fluorocarbon R-lls (monfluoro-
trichloromethane) with three typical primary hydroxyl
polyols of the present invention were prepared. The
proportions by weight employed, including the amount of
cocoamide diol (II) when present, varied according to the
values set forth in Table XII below. The blends were
observed for their miscibility and clearness or their
turbidity and separation of the fluorocarbon from
solution.
Blends A through D contained diethylene glycol and,
in the absence of any amide diol, the maximum fluoro-
carbon solubility did not reach 20 percent by weight.
The addition of 10 percent amide diol (blend B) was not
sufficient to impart fluorocarbon solubility at the
20 percent level. It was not until at least 15 percent
of amide diol (blend C) did the blend remain clear at
20 percent fluorocarbon, and, obviously, was clear
at the 80/20 blend level (blend D).
Blends E througll G contained ethylene glycol and
at least 20 percent of amide diol was required to
maintain a 20 percent fluorocarbon solubility.
Blends H through L were prepared from a polyester
diol and it was observed that while 20 percent fluoro-
carbon solubility was possible with the pure diol that
25 percent was not. ~hen the amide diol level was 20
percent (blends J through L) the highest fluorocarbon
level attainable was about 31 percent
~lends M through O were observed to have maximum
fluorocarbon levels of greater than 90 percent and up
-49-
3525F
06~
to 60 percent by weight for diethy~ene glycol and
the polyestex diol respectively when a maximum of
85 percent by weight of amide diol was employed.
Blends P through S were observed to have maximum
fluorocarbon solubilities of 55 percent and 45 percent
respectively for diethylene glycol and polyester diol
when the primary alcohol-amide diol blends were 50/50
percent by weight.
-50-
~ 36~ii
o o o o o U~ 1
, c ear
oo
~ o o `~ ~urbid
HI I ~ I ~ ~ ~ separates
o~ o o o clear
$ I I oI ~ o ~
~1 ~
~ o o o clear
I o~ I ~ ~ a:) ~ ~
o turbid
separates
o ~ o o o turbid
separates
H
H o O ~ clear
X ~ oo I I ~
E~ Il~ n o 1 _ ~
c~e~_
o o ~ o o o turbid
m ~ separates
o ~ o o o turbid
separates
~o
3 8 o
m ~ ~o
o ~ ~ ~c~
u~ V ~ ~ Is~ o a~
O ,1 ~ 1~a~ h
Q~ _I V 0 ~3 ~ O ~::
u~ a~ ~/ ~,Q h 1~3
S~
Q) ~ a) ~ . . .
~1 ~ ~ O
.~ o 3 3
Q~ ~ O
-l
m ~ o I ~ a~
~ a ~ O d~ 0~O
H
~3: SZS~
I I u~ u, o u~ ul ui turbid
~ separates
o o ~ o o u, clear
~; I I u, u, u, u, ~
o o o o o o turbid
Oi L~ I I U~ U U) U) ~ separateS
~='.
~ O O u~ u~ ui clear ci
r-l . H
_ o u ~ ~ u, u, u, turbid
separates
ui u o u, u, o clear
o~ ~ miscible " ~
H ~ Ci
X ~ ~ I I ~ O ~ ~ ~ clear ai O
mlscible O O
o
o o o o o ~ turbid
separates
~
.~ .~
o ~ o o ~ just R
~4 I Io~ ~ ~ ~ ~ ~ 1
c ear ~ ~
3 ~ H¦ ~ o
~i X ~ c
ui ~, O ~ ai ~ ul
u., ai ~ h Q ~ ~ ai ~ ¦ Q~ a
s ~ ai ~, . , , ~ ul a
~i r~ i V ~ ~ U~
~i ~i ~ r~ N 3 3 3 ~ 0 U,i
~ a) l~ o
,-i h a~ 1 ~ R Q ~ ~ ~ a
m ~ O I ,~ o o ~ I
~ a ~ a ~9 E4 o\ o\o~ r-i O
H al ~4 r l ~`I
~SZS~ _5~
3525F
Example 13
A series of blends of fluorocarbon R-llB (mon-
fluorotrichloromethane) with three typical primary
hydroxyl polyols of the present invention were prepared.
S The proportions by weight employed, including the
amount of amine triol (III) when present, varied according
to the values set forth in Table ~III below. The blends
were observed for their miscibility and clearness or
their turbidity and separation of the fluorocarbon from
solution.
Blends A through D contained diethylene glycol and
in the absence of any amine triol the fluorocarbon
solubility could not reach 20 percent by weight. The
addition of 10 percent amine triol (blend B) was not
sufficient to impart fluorocarbon solubility at the 20
percent level. It was not until at least 15 percent of
amine triol did the blend remain clear at 20 percent
fluorocarbon.
Blends E through G contained ethylene glycol and
at least 20 percent amine triol was required to maintain
20 percent fluorocarbon solubility.
Blends H through M were prepared ~rom a polyester
diol and it was observed that while 20 percent fluorocarbon
solubility was possible, 25 percent fluoro~arbon
solubility was not with the pure diol and thàt at leas~
15 percent by weight~amine triol was required to
maintain 25 percent fluorocarbon solubility (blend K).
At a 20 percent by weight content of amine triol t~e
maximum fluorocarbon solubility was about 28.6 percent
by weight.
-53-
3525F
~L3L4~6~;
Blends N through P were observed to have maximum
flurocarbon levels of greater than 90 percent and up
to 50 percent by weight for diethylene glycol and the
polyester diol respectively when a maximum of 85 percent-
by weight of amine triol was employed.
Blends Q through T were observed to have maximum
fluorocarbon solubilities of 50 percent and 40 percent
respectively for diethylene glycol and polyester diol
when the primary alcohol-amine triol blends were 50/50
percent by weight.
--54--
6~
O O ~ O O ~ turbid
~ I I ~ ~ ~ ~ ~ ~ separates
H I ~ o I ~ o ~ turbid
~ ~ ~ separates
r~ .
o ~ o o o clear
I I O I ~ ~ N miscible
o o ~ o o o clear
miscible
I ~ ~ ~ ~ o turbid
separates
~ o o o turbid
w I ~ I I ~ ~ separates
H
HH ~ clear
x a ~ ~ ~ ~ ~ ~ ~ ~ miscible
o clear
miscible
O O ~ O O O turbid
m ~ I ~ ~ ~ ~ ~ ~ separates
O ~ o o o turbid
separates
o ~1 o
:~ O O R
~ ~ m
R O r-l ~ O a)
~ U ,1 ~1 1 ~ o C)
u~ ` ~ O ~I P~ h
O ~ O '~
~
~o 0 ~) R h
~: ~ a) a) ,~ . . .
~ ~ ~ ~ ~ U J~
ra .~ ~ o 3 3 3
~a ~ ra
a~ ~ ~ ~ ~ ~ o
R
m ~ o ~
H ~ m
~5
~S Z S ~
O O ~ O O ~ turbid
separates
o o o clear
miscible
~ .
o o ~ o o ~ turbid
separates o
x
o o o o o clear H
a ~ ~ ~ ~ ~ ~ ~ ~ miscible
~ ~ . turbid
~ ~ ~ separates ~ Q
~ ~ o ~ ~ o clear
_ o ~ ~ ~ ~ ~ ~ ~ ~ miscible
~ o'
o ~ ~ o clear ~
o z ~ ~ miscible
_ ~ a~
H O O ~ O O ~ turbid
H ~ I I ~ ~ ~ ~ ~ ~ separates
~D
o o o ~ ~o ~ clear .
clear
miscible
~ od ~ O HX¦ ~ ~
~ O ~ , ~~ o a~
Q",~ ~ 8 ~ ~ ~~ ~ $1 ~ ~
."
''~ r g 3 ~ 3 d ~ td
Q .4 .~ ~ ~: K
S C~ K
~SZ5
.
